•

SOLID
\
-.
STATE
PHYSICS ,
~
~;;f'

By

ADRIANUS J. DEKKER
DEPARTMENT OF EI,ECTRICAL
ENGINEERING, UNIVERSITY OF GRONINGEN

LONDON
MACMILLAN & CO LTD
Copyright © A. J. Dekker ]952
•
First Prentice-Hall edition 1957
First edition in the United Kingdom 1958
Reprinted 1960,1962,1963, 1964,1965,1967

Published hy
MACMILLAN & CO LTD
Little Essex Street London WC 2
and also at Bombay Calclltta and Madras
Macmillan SOllth Africa (Publishers) Ply Ltd Johannesburg
The Macmillan Company of Alistralia Pty Ltd Melbourne
The Macmillan Company of Canada Ltd Toronto
SI Martin's Press Inc NClV York

PRINTED IN THE NETHERLANDS BY JAN DE LANGE N.V., DE VENTER

--/---

f':
PREFACE

THE purpose of this book is, to introduce the reader to the study of the
physical properties of crystalline solids. It is based on notes which I used
for lectures in the Physics Department of the University of British Colum-
bia, Canada, and in the Electrical Engineering Department of the Universi-
ty of Minnesota.
My aim has been to write an introductory text suitable for senior under-
graduate and beginning graduate courses on the solid state in physics,
engineering, chemistry, and metallurgy. Also, I have attempted to make
it suitable for self study by scientists in industrial laboratories interested in
the physical properties of solids. The widely varying background of the
anticipated groups of readers has affected the organization and presenta-
tion of the subject matter. The general level of presentation has been
kept elementary, with emphasis on the physical reasoning underlying the
interpretation of the physical properties of solids. I have made an effort,
however, to remain as rigorous and up-to-date as possible within the limits
imposed by the level of presentation. The first eight chapters deal with
subjects which, at least in an introductory text, can..'be discussed without
,

reference to the details of the electronic structur€' of solids. Prerequisite

for understanding this part of the book is an elementary knowledge of
statistical thermodynamics and of the quantized harmonic oscillator.
Chapters 9 through 20 deal with the electronic properties of solids and
require familiarity with the elements of wave mechanics, although in a
number of chapters no explicit use of wave mechanics is made. As a
consequence of the organization of,the material outlined above, the degree
of difficulty tends to increase as one progresses through the book. This in
itself does not compel the reader to follow the order in which the various
subjects are discussed. In fact, the chapters are organized in groups which
could be taken up in any order suitable to serve the particular needs of the
instructor or reader.
To some extent, my own interest and taste have determined the choice of
v
vi PREFACE ,.
material; however, with the possible exception of Chapter 17, the material
is basic to a great variety of subjects in the field of solid state.
I am indebted to W. Opechowski for constructive criticism during the
preparation of Chapters 10 and I I, and to A. H. Morrish for his comments
on other parts of the manuscript. I also wish to acknowledge the coopera-
tion of numerous publishers who kindly permitted me to reproduce il-
lustrations. I am grateful to F. L. Vogel, W. G. Pfann, H. E. Corey, and
E. E. Thomas for a micrograph of a lineage boundary in germanium.
Finally, I wish to thank my wife for typing the manuscript and for her
encouragement.

A. J. Dekker
CONTENTS

1. The Crystalline State 1

I-I. The crystalline state of solids ....................... .

1-2. Unit cells and Bravais lattices ...................... . 4
1-3. Miller indices .................................... . 8
1-4. The diffraction of X-rays by a simple space-lattice ac-
cording to von Laue ............................ . lO
1-5. X-ray diffraction according to Bragg ................ . 13
1-6. The atomic scattering factor ........................ . 14
1-7. X-ray intensity and atomic configuration of the unit cell .. 16
1-8. Experimental methods of X-ray diffraction ........... . 19
1-9. Diffraction of electrons by crystals .................. . 20
1-10. Diffraction of neutrons by crystals .................. . 21
1-11. Interatomic forces and the classification of solids ...... . 23
1-12. Anisotropy of the physical properties of single crystals .. . 27

2. The Specific Heat of Solids and Lattice Vibrations 32

2-1. The specific heat at constant volume and at constant
pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2-2. The various theories of the lattice specific heat. . . . . . . . . 34
2-3. The breakdown of the classical theory. . . . . . . . . . . . . . . . 35
2-4. Einstein's theory of the specific heat. . . . . . . . . . . . . . . . . . 36
2-5. The vibrational modes of a continuous medium. . . . . . . . 39
2-6. The Debye approximation. . . . . . . . . . . . . . . . . . . . . . . . .. 41
2-7. The Born cut-off procedure. . . . . . . . . . . . . . . . . . . . . . . . . 45
2-8. Elastic waves in an infinite one-dimensional array of
identical atoms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2-9. Vibrational modes of a finite one-dimensional lattice of
identical atoms ...... '.' .......................... ' 49
2-10. The equivalence of a vibrational mode and a harmonic
oscillator. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2-11. The specific heat of a one-dimensional lattice of identical
atoms. ....... ... ... .............. .............. 53
2-12. The vibrational modes of a diatomic linear lattice. . . . . . 54
2-13. Vibrational spectra and specific heat of three-dimensional
lattices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
viii • CONTENTS

3. Some Properties of Metallic Lattices 60

<3-1. The structure of metals ............................ . 60

3-2. Lattice defects and configurational entropy ........... . 62
3-3. The number of vacancies and interstitials as function of
temperature .................................... . 65
3-4. The formation of lattice defects in metals ............ . 67
3-5. Interstitial diffusion in metals ....................... . 70
3-6. Self-diffusion in metals ............................ . 74
3-7. Chemical diffusion in metals; the Kirkendall effect. ... . 76
3-8. The elastic constants of metals ...................... . 78
3-9. Plastic deformation of metals ......... " ............ . 81
3-10. The interpretation of slip; dislocations .............. . 83
3-11. Motion of dislocations under influence of a uniform shear
stress; dislocation density ........................ . 86
3-12. Edge and screw dislocations ........................ . 88
3-13. Stress fields around dislocations. '" ................. . 91
3-14. Interaction between dislocations .................... . 93
3-15. Estimates of dislocation densities .................... . 96
3-16. The Frank-Read mechanism of dislocation multipli-
cation ........ " ........ , . . . . . . . . . . .. . . . . . . . . . . . 99

4. Some Properties of Simple Alloys 104

4-1. Interstitial and substitutional solid solutions. ... ....... 104

4-2. Mutual solubility as function of temperature. . . . . . . . . . 105
4-3. The Hume-Rothery electron compounds. . . . . . . . . . . . . . 107
4-4. Superlattices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4-5. The long-distance order theory of Bragg and Williams.. III
4-6. Short-distance order theories ...........• , . . . . . . . . . . . 114

5. Lattice Energy of Ionic Crystals 117

5-1. Introductory remarks ..... " . ....... ... ...... ....... 117
5-2. The fundamental assumptions of Born's theory. . . . . . . . 117
5-3. Calculation of the repulsive exponent from compressi-
bility data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
5-4. The repulsive exponent as function of electron configu-
ration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5-5. Calculated and experimental lattice energies ........ " . 121
5-6. Stability of structures and ionic radii. . . . . . . . . . . . . . . . . 124
5-7. Refinements of the Born theory...................... 128
CONTENTS IX

6. Dielectric and Optical Properties of Insulators 133

Part A. Static Fields

6-1. Macroscopic description of the static dielectric constant. . 133

6-2. The static electronic and ionic polarizabilities of mole-
cules. . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . 134
6-3. Orientatio\lal polarization .......................... , 138
6-4. The static dielectric constant of gases ................ , 140
6-5. The internal field according to Lorentz. . . . . . . . . . . . . . . 141
6-6. The static dielectric constant of solids. . . . . . . . . . . . . . .. 144

Part B. Alternating Fields

6-7. The complex dielectric constant and dielectric losses. . . . . 148

6-8. Dielectric losses and relaxation time. . . . . . . . . . . . . . . . .. 150
6-9. The classical theory of electronic polarization and
optical absorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 154

7. Ionic Conductivity and Diffusion 160

7-1. Lattice defects in ionic crystals ......... , ......... , . .. 160

7-2. The hydration energy of ions. . . . . . . . . . . . . . . . . . . . . . . . 164
7-3. The activation energy for the formation of defects in ionic
crystals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 166
7-4. Example of self-diffusion in alkali halides. . . . . . . . . . . .. 168
7-5. Interpretation of diffusion in alkali halides. ........... 171
7-6. Ionic conductivity in "pure" alkali halides. . . . . . . . . . .. 175
7-7. Ionic conductivity in alkali halides with added divalent
impurities ...................................... , 178

8. Ferroelectrics 184

8- I. General properties of ferroelectric materials. . . . . . . . . .. 184

8-2. Classification and properties of representative ferro-
electrics ............ ',' . . . . . . . . . . . . . . . . . . . . . . . . . .. 186
8-3. The dipole theory of ferroelectricity. . . . . . . . . . . . . . . . . . 192
8-4. Objections against the dipole theory. . . . . . . . . . . . . . . . . . 195
8-5. Ionic displacements and the behavior of BaTiO a above the
Curie temperature ........ '" .. '" .. , . .... .. ...... 196
8-6. The theory of spontaneous polarization of BaTi0 3 • • • • • 198
8-7. Thermodynamics of ferroelectric transitions.......... 20 I
8-8. Ferroelectric domains. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 207
x CONTENTS

9. Free Electron Theory of Metals 211

9-1. Difficulties of the classical theory ........ , ......... " 211
9-2. The free elect~n model. .............. '. . . . . . . . . . . . .. 212
9-3. The Fermi-Dirac distribution. . . . . . . . . . . . . . . . . . . . . . .. 213
,9-4. The electronic specific heat. .... " . . . . . . . . . . . . .. . . ... 216
9-5. Paramagnetism of free electrons. . . . . . . . . . . . . . . . . . . .. 217
9-6. Thermionic emission from metals. . . . . . . . . . . . . . . . . . . . . 220
9-7. The energy distribution of the emitted ele~trons. . . . . . .. 223
9-8. Field-enhanced electron emission from metals. . . . . . . .. 225
9-9. Changes of work function due to adsorbed atoms. . . . . . 228
9-10. The contact potential between two metals ........... " 230
9-11. The photoelectric effect of metals. . . . . . . . . . . . . . . . . . . . 232

10. The Band Theory of Solids 238

-10-1. Introductory remarks..... . .. . . .. . . . . .. . . . . . . . . . .. .. 238
\' 10-2. The Bloch theorem. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 240
10-3. The Kronig-Penney model .... " . .. . . . . . . . . . . . . . . . .. 243
10-4. The motion of electrons in one dimension according to
the band theory. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 247
'. 10-5. The distinction between metals, insulators, and intrinsic
semiconductors ................................. 250
v1O-6. The concept of a "hole" . . . . . . . . . . . . . . . . . . . . . . . . . . .. 252
10-7. Motion of electrons in a three-dimensional lattice. . . . .. 252
10-8. The tightly bound electron approximation... . . . . . . . ... 257
10-9. Application to a <simple cubic lattice. . . . . . . . . . . . . . . . .. 260
'- 10-10. Brillouin zones; density of states; overlapping of energy
bands ....... '" .. ... ........................... 263
10-11. The zone structure of metals. . . . . . . . . . . . . . . . . . . . . . .. 266
10-12. The density of states and soft X-ray emission spectra. .. 268
10-13. The Wigner-Seitz approximation and the cohesive energy
of metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 269

11. The Conductivity of Metals 275

11-1. Some features of the electrical conductivity of metals. .. 275
11-2. A simple model leading to a steady state; drift veloci~y
and relaxation time ............' ................ " 276
11-3. The Boltzmann transport equation. . . . . . . . . . . . . .. . . .. 278
11-4. The Sommerfeld theory of electrical conductivity... . . .. 281
11-5. The mean free path in metals. . . . . . . . . . . . . . . . . . . . . . .. 283
11-6. Qualitative discussion of the features of the resistivity. . .. 285
11-7. Thermal scattering described as electron-phonon col-
lisions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 289
CONTENTS xi

11-8. The electrical conductivity at low temperatures. . . . . . .. 292

11-9. The thermal conductivity of insulators. . . . . . . . . . . . . . .. 295
11-10. The thermal conductivity of metals. . . . . . . . . . . . . . . . . .. 299
II-II. The Hall effect in metals............................ 301

12. The Electron Distribution in Insulators and Semiconductors 305

12-1. The Fermi distribution. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 305
12-2. A simplified model of an insulator. . . . . . . . . . . . . . . . . . . 306
12-3. Improved model .for an insulator and intrinsic semi-
conductor... . .. . .. . . . . .. . .. .. . . . . . . . . . . . . . . . . . .. 308
12-4. Models for an impurity semiconductor.... . . . . . . . . . . .. 310
12-5. Thermionic emission from semiconductors. . . . .. . . . . .. 314
12-6. Electronic degeneracy in semiconductors. . . . . . . . . . . . . . 316

13. Nonpolar Semiconductors .·r.. '1,,' ,./w".:·d 319

. ..1 .
13-1. Introductory remarks... . .. . .. . . . . . ..... . . . .. . .. . . .. 319
13-2. Some lattice properties of the elements of the fourth
group ..................................... ,. ... 320
13-3. Conductivity and Hall effect in semiconductors with a
single type of charge carrier. . . . . . . . . . . . . . . . . . . . . .. 326
13-4. Mobility and Hall effect as determined by different
scattering processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 329
13-5. Comparison with experiment. . . . . . . . . . . . . . . . . . . . . . .. 331
13-6. Constant-energy surfaces and effective mass in silicon and
germanium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 334
13-7. The lifetime and diffusion of minority carriers. . . . . . . .. 341
13-8. Intermetallic compounds. . . . . . . . . . . . . . . . . . . . . . . . . . .. 344

14. Rectifiers and Transistors 348

14-1. Rectifying properties of a barrier layer between two
metals.................... .... .......... .... .... 348
14-2. The Schottky theory of a metal-semiconductor contact. . . 349
14-3. Single-carrier theories of rectification. . . . . . . . . . . . . . . .. 351
14-4. Surface states on semiconductors. . . . . . . . . . . . . . . . . . . .. 354
14-5. The two-carrier theory of rectification. . . . . . . . . . . . . . .. 356
14-6. The p-n junction rectifier.. . .. . . . . . . . . . . . . . . . . . . . . . .. 357
14-7 . Transistors........................................ 361

15. Electronic Properties of Alkali Halides 366

15-1. Optical and thermal electronic excitation in ionic crystals. 366
15-2. The upper filled band and the conduction band in ionic
crystals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 369
XlI CONTENTS

15-3. The ultraviolet spectrum of the alkali halides; excitons ... 371
15-4. Illustration of electron-hole interaction in single ions ..... 375
15-5. Qualitative discussion of the influence of lattice defects on ,
the electronic levels .............................. 375
15-6. Nonstoiehiometric crystals containing excess metal ..... 377
15-7. The transformation of F centers into F' centers apd vice
versa ........................................... 383
15-8. Photoconductivity in crystals containing excess metal .... 386
15-9. The photoe1ectric effect in alkali halides ....... , ....... 390
15-10. Coagulation of F centers and colloids ................. 392
IS-II. The Hall effect and electron mobility ................. 393
15-12. Color centers resulting from excess halogen ........... 393
15-13. Color centers produced by irradiation with X-rays ..... 394

16. Luminescence 398

16-1. General remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 398
16-2. Excitation and emission.... . . . . . . . . . . . . . . . . . . . . . . . .. 399
16-3. Decay mechanisms ........ " ... '" ....... ,. .. . .. . .. 402
16-4. Thallium-activated alkali halides. . . . . . . . . . . . . . . . . . . .. 406
16-5. The sulfide phosphors. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 410
16-6. Electroluminescence................................ 413

17. Secondary Electron Emission 418

17-1. Secondary electrons ......... , ......... '" . .. . . . . . .. 418
17-2. Experimental yield curves. . . . . . . . . . . . . . . . . . . . . . . . . .. 420
17-3. Elementary theory of secondary emission; universal yield
curves ................ " ...................... " 423
17-4. Comparison of the elementary theory with experiment.. 426
17.. 5. Variation of the secondary yield with angle of incidence. . 428
17-6. Baroody's theory of secondary emission for metals. . . .. 430
17-7. Wave-mechanical theory of the production of second-
aries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 434
17-8. Interactions to be considered in the escape mechanism;
factors determining high and low yields. . . . . . . . . . . .. 438
17-9. The temperature effect of the secondary yield in in-
sulators ....................... " . . . . . . . . . . . . . . . .. 440
17-10. The possible influence of donor levels on the secondary
yield of insulators .............................. " 442

18. Diamagnetism and Paramagnetism 446

18-1. Introductory remarks... . . . . . . . .. . . . . .. . . . . .. .. . .... 446
18-2. The origin of permanent magnetic dipoles.. . . . . . . . . . .. 448
CONTENTS xiii

18-3. Diamagnetism and the Larmor precession. . . . . . . . . . . .. 451

18-4. The static paramagnetic susceptibility. . . . . . . . . . . . . . . .. 454
18-5. Comparison of theory and experiment for paramagnetic
salts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 457
18-6. Nuclear paramagnetism. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 458
18-7. The Hamiltonian for an electron in a magnetic field. . .. 459
18-8. The principle of adiabatic demagnetization. . . . . . . . . . .. 460

19. Ferromagnetism, AntiferrQmagnetism, and Ferrimagnetism 464

Ferromagnetism
19-1. Introduct-ory remarks .............................. . 464
19-2. The Weiss molecular field .......................... . 466
19-3. Comparison of the Weiss theory with experiment ..... . 468
19-4. The interpretation of the Weiss field ................. . 472
19-5. Qualitative remarks about domains .................. . 475
19-6. The anisotropy energy ............................. . 478
19-7. The thickness and energy of the Bloch wall ........... . 480
19-8. Coercive force and hysteresis ....................... . 481

Antiferromagnetism
19-9. Introductory remarks......... . .. ... ... ... .... .... .. 483
19-10. The two-sublattice model. . . . . . . . . . . . . . . . . . . . . . . . . .. 484
19-11. Superexchange interaction. . . . . . . . . . . . . . . . . . . . . . . . . .. 488

Ferrimagnetism
19-12. The structure of ferrites ...... " ................ '" .. 491
19-13. The saturation magnetization........ . .. . .. . ......... 491
19-14. Elements of Neel's theory ............. '" ...... ..... 493

20. Magnetic Relaxation and Resonance Phenomena 498

Paramagnetic Relaxation
20-1. Phenomenological description. . . . . . . . . . . . . . . . . . . . . .. 498
20-2. Relaxation mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 499
20-3. Spin-lattice relaxation. : . . . . . . . . . . . . . . . . . . . . . . . . . . .. 501
20-4. Spin-spin relaxation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 504

Nuclear Magnetic Resonance

20-5. Nuclear magnetic moments ....................... '. .. 505
20-6. Conditions required for resonance absorption.... . . . . .. 506
20-7. The Bloch equations and the complex susceptibility. . .. 508
xiv CONTENTS

20-8. The influence of molecular motion on the relaxation

times. '" ......... '" .. ............. .... ........ 51 I
20-9. Some applications to solid state physics. . . . . . . . . . . . . .. 513
20-10. Determination of nuclear magnetic moments. . . ... .. .. 516

Other Resonance and Relaxation Effects

20-1 I. Paramagnetic resonance. . . . . . . . . . . . . . . . . . . . . . . . . . .. 517
20-12. Ferromagnetic resonance and relaxation ..... " . . . . . .. 518
20-13. Frequency-dependence of the initial permeability in
ferrites ..................... '.' . . . . . . . . . . . . . . . . .. 519

APPENDIX 525

A. Thermodynamic conditions for equilibrium. . . . . . . . . . .. 525

B. Particle in a box, according to wave mechanics. . . . . . .. 526
C. Indistinguishable particles and the Pauli principle. . . . .. 527
D. Fermi statistics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 529
E. The Boltzmann relation ........................... " 531

INDEX 533

j"
I
I

.'

..
Chapter 1

THE CHYSTALLINE STATE

l;-

1-1. The crystalline state of solids

The elements and their chemical compounds generally occur in three

states of aggregation: the solid state, the liquid state, and the gaseous
state. In solids and liquids the distance between neighboring atoms is of the
order of a few Angstroms, i.e., they contain 1022_10 23 atoms per cm3 •
This may be compared with a density of about 2.7 X 1019 molecules per
cm 3 in a gas at room temperature under one atmosphere, corresponding
to an average distance of approximately 30 A between molecules.
In crystalline solids the atoms are stacked in a regular manner, forming
a three-dimensional pattern which may be obtained by a three-dimensional

lui rb)
I
Fig. 1-1. Schematic illustration df the difference between a
crystal (a) and a glass (b). [After W. H. Zachariasen, J. Alii.
Chem. Soc., 54, 3841 (1932)]

repetition of a certain pattern unit; two-dimensional examples are given

in Fig. I-Ia and Fig. 1-3. When .the periodicity of the pattern extends
throughout a certain piece of material, one speaks of a single crystal. In
polycrystalline materials the periodicity of structure is interrupted at
so-called grain boundaries; the size of the grains in which the structure
is periodic may vary from macroscopic dimensions to several Angstroms.
When the size of the grains or crystallites becomes comparable to the size
of the pattern unit, one can no longer speak of crystals, since the essential
feature of a crystal is its periodicity of structure; one then speaks of
J
2 THE CRYSTALLINE STATE [Chap. t

"amorphous" substances. For most solids the crystalline state is the

natural one since the energy of the ordered atomic arrangement is lower
than that of an irregular packing of aioms. However, when the atoms are
not given an opportunity to arrange themselves properly, by inhibiting
their mobility, amorphous material may be formed; an example is
amorphous carbon formed as a decomposition product at low temperatures.
Certain polymers are composed of very large and irregular molecules and
in such cases a crystalline packing is not easily obtained. In other cases,
the solid state may correspond to a supercooled liquid in which the
molecular arrangement of the liquid state is frozen in; because of rapid
cooling and a high viscosity of the liquid, crystals may not have had time
to grow and a glassy material results (see Fig. I-I b). Upon annealing,
such glassy substances may crystallize (devitrify), as is well known to any
experimentalist who has worked with quartz. In this book we shall be
concerned essentially with solids which are generally regarded as crystalline.
Although one usually thinks of a solid as an arrangement of atoms in
which the atoms occupy fixed positions relative to each other, this is not
necessarily the case. Of course, in any crystal the atoms carry out a
vibrational motion about their equilibrium position; this topic will be
taken up in Chapter 2. However, in certain solids particular groups of
atoms may have rotational freedom to some extent. For example, in KCN,
which has the well-known NaCI structure (see Fig. 5-1), the CN- ion is
rotating even at room temperature;1 neither the carbon nor the nitrogen
atoms occupy fixed positions in the lattice, but are spread over a number
of possible positions. Similarly, long-chain molecules may rotate about
the longitudinal axis and disk-shaped ionic groups such as NO,; may
rotate in the plane of the disk. The three-dimensional regularity is, how-
ever, maintained in such crystals. One might F'erhaps say that such crystals
are partly melted. At sufficiently low temperatures the rotations are
inhibited.
In another class of crystals, there is only two- or one-dimensional
regularity,2 viz., in the "liquid crystals." Such substances actually flow
and will rise in a capillary tube. Normal crystals exhibit flow only under
influence of external forces (see Chapter 3). A few hundred examples of
liquid crystals are known, most of them being organic compounds, such
as ammonium oleate Cl,H:J:lCOONH~. They will not be discussed in this
volume.
Although we shall ass4me in the present chapter that the crystals under
consideration are "perfect," the reader will have ample opportunity in the

1 See, for example, C. W, Bunn, Chemical Crystallography, Oxford, New York, 1946.

pp. 329-331.
'J. D. Bernal and W. A. Wooster, Ann. Repts. Chem. Soc., 28, 262 (1932); J. T.
Randall, The DitFaction of" X-rays and Electrons by Amorphous Solids, Liquids ami Cases,
Chapman and Hall, London, 1934; W. Voigt, Physik. Z., 17, 76,153 (1917).
Sec. I-I] THE CR YST ALLINE STATE 3
remainder of this book to realize that a large number of properties of
solids are determined by lattice imperfections such as impurities, vacant
lattice sites, atoms in positions where they "should not be" according to
the crystal structure, etc. However, since we shall be mainly concerned

N
24
t
16
_. -,
8

_riA)

o 2 4 6 8 10 12 14
(a)
.03 fir)

t
.02

.01

o 2 4 6 8 10 12 14
Ib)

Fig. 1-2. The number of K atoms in metallic potassium is repre.

sented in (a) as function of the radial distance from a given K atom'
(20'C); in (b) the fully drawn and dashed curves represent the
density of K atoms fCr) in the liquid at 70"C and 395T, respectively.
[After Thomas and Gingrich, ref. 3] ; ,;

in this chapter with crystal structures and their determination, such

defects may be neglected temporarily.
In liquids, the atoms or molecules are in continual motion, and a
crystalline structure is therefore absent. On the other hand, this should
not lead one to believe that the arrangement of atoms is completely
random. Even in liquids there is a certain amount of order, but it extends
over a relatively short distance. To illustrate the difference between the
"long-range order" in a crystal and the "short-range order" in a liquid,
let us consider potassium in the solid and liquid states. Potassium, like
the other alkali metals has the body-centered cubic structure (Fig. lAb),
the cube edge being 5.344 A at 20°e. Taking the nucleus of a given K
atom in the crystal as origin, suppose we were to plot the number of nuclei
of other K atoms as function of the radial distance r from the central
atom. We would then obtain a number of vertical lines as in Fig. 1-2a at
4 THE CRYSTALLINE STATE [Chap. I
specific distances from the origin. For example, there are eight atoms at a
distance ~aV3, six atoms at a distance a, etc. In the liquid state the
situation is rather different. Suppose the origin of the coordinate system
is attached to a given K atom and moves with this atom. At a given
instant there will be a certain configuration of the other atoms, but the
configuration changes continually with time. Taking the time average of
these different configurations, one could then plot the average number of
nuclei as function of the distance from the central atom. Such information
may actually be obtained from X-ray diffraction experiments. Thus, in
Fig. 1-2b the fully drawn curve fer) represents the density of K atoms per
Aa at 70°C as function of the radial distance from an arbitrary K atom in
the liquid;3 the dashed line corresponds to 395°C. Note that the set of
discrete lines of Fig. 1-2a has been transformed into a continuous curve.
Also, only the first few "shells" of other a4>ms are distinguishable in the
70°C curve, whereas in the 39SoC curve only the first two are somewhat
pronounced. For distances larger than ,-,10 A the curves show little or no
structure and the density becomes independent of r; for the crystal,
however, the discrete lines extend over the whole piece of material, at
least when it is a single crystal. It is of interest to remark that the integral
of 47Tr2J'{r) over the first peak determines the average number of nearest
neighbors of the central atom; for the alkali metals we find that this is
approximately equivalent to 8 nearest neighbors, as it is in the solid (only
there, it is exactly 8).
1-2. Unit cells and Bravais lattices
We shall now discuss somewhat further the periodicity of structure,
which is the fundamental feature of a crystal. Consider part of a two-
dimensional crystal, the atoms of M
which are arranged in a pattern
as illustrated in Fig. 1-3. Each
cluster of atoms (in this case a dot
H ' B
j----j---- ----'j
G
___ ___ !'V _ --o.k
/
/

ill'(- -
and two open circles) will be E F / ;'
referred to as a pattern-unit. It is D ' C( /
observed that when a parallelo- -of- -- ~
gram such as ABC D is repeatedly b /
translated by the vectors a and b, ----~----
A
corresponding respectively to AB -----a-B K

and A D, the whole pattern may be

obtained; thus ABCD is called a Fig. 1-3. Two-dimensional crystal and
various unit cells.
"unit cell." The choice of a unit
cell is by no means unique; for example, EFG H or KLM N would serve the
purpose just as well and so would many others. All three unit cells
3 D. E. Thomas and N. S. Gingrich, Phys. Rev., 56, 415 (1938); for a review of this

topic, see N. S. Gingrich, Revs. Mod. Phys., 15,90 (1943).

Sec. 1-2] THE CRYSTALLINE STATE 5
mentioned contain one pattern-unit, since each of these units located at
a corner belongs to four neighboring parallelograms and each pattern
unit located at an edge belongs to two parallelograms. The areas of all
unit cells containing one pattern-unit are equal. It is usually convenient to
choose as a unit cell a parallelogram with the shortest possible sides.
In three dimensions, a similar procedure may be followed by stacking
parallelepipeds in a regular manner; a convenient unit cell then contains
again pattern-units only at the corners. In some cases, however, there

1Il1, (bl

Fig. 1-4. The true (fully drawn) and compound (dashed) unit
cells of the f.c.c. (a) and b.c.c. (b) lattices.

are reasons, to be given below, for choosing a "compound unit cell"

which contains more than one pattern-unit. Consider, for example, the
arrangement of atoms in a crystal of nickel, illustrated in Fig. 1-4a. The
true unit cell corresponds to the parallelepiped based on the translation
vectors a, b, c; it contains Ni atoms only at the corners, i.e., there is one
atom per unit cell. On the other hand, the lattice may also be divided
into a system of cubes with atoms at the corners and at the centers of the
cube faces. It is convenient to consider a cube of this kind as a new
"unit cell," even though it contains four atoms and has a volume four
times as large as the "true" unit cell. One refers to the face-centered cube
loosely as the "unit ceIl," although strictly speaking this is not correct
since it is a combination of four unit cells. The most important reason
for choosing the face-centered cube as a new unit cell is that the symmetry
properties of the atomic arrangement in nickel are the same as in crystals
which have a cube as the true unit cell. In fact, the essential symmetry
elements of a simple cube (atoms only at the corners) are four threefold
axes running diagonally through the cube; whenever the cube is rotated
about any of these axes over 120°, it is brought into a position indis-
tinguishable from the original position. The same symmetry is seen to be
possessed by the face-centered cube. Another reason for choosing the
compound unit cell is the fact that cubic axes provide a more convenient
reference system than those corresponding to a rhombohedron.
In a similar way, the structure of the alkali metals represented in Fig.
6 THE CRYSTALLINE STATE [Chap. 1

] -4b is described as body-centered cubic (b.c.c.); in this case the compound

unit cell comains two atoms and is twice as large as the true unit cell
based on the vectors a, b, c. The b.c.c. structure also has the required
four threefold symmetry axes. The three cubic structures mentioned here
(simple, f.c.c., and b.c.c.) are the only possible cubic structures. For
example, a cube with atoms at the corners and at the centers of one or
two pairs of opposite faces would not have the four threefold symmetry
axes, and thus no cubic symmetry.
In order to describe the structure of crystals, Bravais in 1848 introduced
the concept of the space-lattice. A space-lattice is a mathematical concept
and is defined as an infinite number of points in space with the property
that the arrangement of points about a given point is identical with that
about any other point. For example, the intersections of the two dashed
sets of parallel lines in Fig. 1-3 represent a two-dimensional space-lattice.
The intersections of these lines are the lattice points. From symmetry
considerations of the type indicated above for the three possible cubic
structures, Bravais showed that there exist no more than fourteen space-
lattices in three dimensions. In order to specify the arrangement of points
in a space-lattice, one introduces a system of axes such as indi'cated in
Fig. 1-5. One distinguishes between seven systems of axes or crystal
systems, depending on certain specifi-
z
cations about the lengths of the axes
and the angles between them; the
seven crystal systems together with
the essential symmetry elements are
given in Table 1-1. Although we shall
not discuss the symmetry properties
of crystals here, the elements occurr-
ing in the table may be defined. 4 A
crystal is said to possess an n-fold
x
rotation axis when rotation over
Fig. 1-5. Crystal axes. (360/n) degrees brings the crystal into
self-coincidence. When a plane can
be drawn in the crystal, which contains the center of the crystal, such
that one half of the crystal is the reflection of the other half, the crystal
is said to have a plane of symmetry. A crystal possesses an inversion
center when for each point located at r relative to the center there exists
an identical point at -r. A rotation-inversion axis exists when the crystal
can be brought into self-coincidence by a combined rotation and inversion.
The fourteen Bravais lattices or space lattices are represented in Fig.
1-6. Certain unit cells contain only points at the corners; they are
, See, for example, A. Schoenflies, Theorie der Kristall Struktur, Borntrager,
Berlin (1923), or W. Voigt, Lehrbllch der Krista/lphysik, Teubner, Leipzig and
Berlin, 1910.
Sec. 1-2] THE CRYSTALLINE STATE 7

/ /
c

{3 b

I/a
2
V
!.. .

4 5 6 7

10 11

12 13 14

Fig. 1-6. The fourteen Bravais lattices: (I) triclinic, sinjlle;

(2) monoclinic, simple; (3) monoclinic, base centered; (4)
rhombic, simple; (5) orthorhombic, base centered; (6) ortho-
0"'0-
rhombic b.c.; (7) orthorhombic rc.; (8) hexagonal; (9) rhombo-
hedral; (10) tetragonal, simple;' (II) tetragonal, b.c.; (12) cubic,
simple; (13) b.c.c.; (14) rc.c.
8 THE CRYSTALLINE STATE [Chap. I
Table 1-1. The Seven Crystal Systems and Their Essential Symmetry

System Essential symmetry Unit cell specification

f-----

Triclinic No planes, no axes a "" b cF c; oc 'F {J "" Y "" 90

0

Monoclinic One 2-fold axis or one plane 0

a "" b "" c; oc = f3 = 90 " " Y0
Orthorhombic Three mutually perpendicular a "" b 7" c; oc =~ {J = y = 90
(rhombic) 2-fold axes, or two planes
intersecting in a 2-fold axis
Tetragonal One 4-fold axis or a 4-foJd a = b '?" c; oc = {J = i' = 90
0

inversion axis
Cubic Four 3-fold axes a = b ,~ c; oc = fJ = )J = 90 0

Hexagonal One 6-fold axis Three equal coplanar axes a at

I 120°; fourth axis c 1. to

Rhombohedral
(trigonal)
One 3-fold axis I
I these; c i' a.
u~d~". ~ fl~y~, 90'

referred to as "simple." Others are compound unit cells and contain

points at the center of the body or at the centers of faces. One might
think at first sight that there are more space-lattices than the ones given
in Fig. 1-6. For example, in the tetragonal system one might suggest the
absence of a face-centered type. However, the reader may readily convince
himself that such a lattice would, upon choosing a different set of axes,
be identical with the body-centered tetragonal lattice of which the edges
are 11"/2 times those of the original lattice. The reader may consider
other examples himself.
It must be kept in mind that the lattice points in a space-lattice do not,
in general, represent a single atom but a group of atoms. Consider, for
example, the diamond structure represented in Fig. 13-1; it may be
represented by an f.c.c. space lattice in which the lattice points are
associated with two atoms: one in the lattice point itself and another in
a point determined by a translation of t, t, i. This leads to the typical
configuration in which any given atom is surrounded by four nearest
neighbors occupying the corners of a regular tetrahedron. A discussion of
the crystal structure of particular elements or compounds will be postponed
until the physical properties of such materials are being considered .

.'
1-3. Miller indices -, '

The lattice points forming a space-lattice may be thought of as

occupying various sets of parallel planes; some examples of dividing a
lattice into such sets of planes are given in Fig. 1-7. With reference to the
axes of the "unit cell," each set of planes has a particular orientation. In
Sec. 1-3] THE CRYSTALLINE STATE 9
order to specify the orientation, one employs the so-called Miller indices;
these are defined as follows: Suppose a particular plane of a given set
has intercepts pa, qb, and re with the crystal axes (Fig. 1-8). The Miller
indices of the set of planes are then given by three numbers h, k, I such that
I. : k : 1= I/p : I/q : I/r (1-1)
with the condition that h, k, and I are the smallest integers satisfying (I-I),
i.e., h, k, and I have no common factor> I. We shall adhere to the rather
general practice of using the notation (hkl) for a particular set of planes.
We emphasize once again tha.t these indices refer not to a particular plane

Fig. 1-7. Various ways of dividing a Fig. 1-8. Illustrating a plane with inter-
square lattice in atomic planes; the cepts pa, qb, and rc; ON is the normal
Miller indices are indicated. to the plane.

but to a set of parallel planes. One or more of the indices may be negative
when the corresponding intercepts are negative; they are represented in a
form such as this: (likl), (hkl) etc. Miller indices for some planes are
given in Fig. 1-7.
When the indices are shown enclosed by braces, such as {hkl}, they
refer to planes which in the crystal are equivalent even though their Miller
indices may differ. For example, in a cubic lattice all cube faces are
equivalent; in order to specify this group of planes, one writes {100},
which includes the planes (100), (010), (001), (100), (010), (001).
In order to specify a certain direction in a crystal, one employs three
indices u, r, w enclosed in square brackets [u, v, w]; the indices are
integers and have no common factor larger than unity. The direction
specified by this symbol is obtain~d as follows: Move from the origin
over a distance ua along the a-axis; vb along the b-axis and we along the
c-axis. The vector connecting the origin with the point so obtained is
then the direction specified by the symbol [uvw]. Thus, in a cubic crystal
the direction of the x-axis is indicated by [100], the y-axis by [010], etc.
A full set of equivalent directions in a crystal is represented by a symbol
of the kind (uvw).
We may note here that the Miller indices of a set of planes are related
IO THE CRYSTALLINE STATE [Chap. I

to the direction cosines of the normal to these planes. Denoting the

angles between the normal ON in Fig. 1-8 and the crystal axes respectively
by (X', fJ' and y', one obtains the relation

cos a' : cos fJ' : cos y' = (llpa) : (llqb) : (l/re)

= (h/a) : (k/b) : (l/e) (l-2)

Also, the distance between successive planes in a set (hkl) is determined

by the Miller indices. It is evident already from Fig. 1-7 that as the value
of one or more of the Miller indices is increased, the distance between the
planes is reduced. For a cubic lattice the reader may show that the distance
between successive planes is given by
. \
( 1-3)

Thus the distance between (100) planes is a, between (110) planes a/V2,
between (Ill) pianes a/V}, etc. For other crystal systems similar relations
may be obtained."

1-4. The diffraction of X-rays by a simple space-lattice according to von

Laue
It is well known that when a beam of light passes through a screen
containing a regular pattern of holes, interference phenomena may be
observed if the distance between the holes is of the same order as the
wavelength of the light employed. The diffraction of X-rays by the atoms
in a solid is a completely analogous phenomenon, the wavelength of the
electromagnetic radiation in this case being of the order of interatomic
distances in solids, i.e., of the order of I A. The u"e of X-rays as a tool
for investigating the structure of crystals was first suggested by von laue
in 1912 and was later further developed by W. H. and W. l. Bragg. The
principles of X-ray diffraction will now be discussed briefly.
When an electron is subjected to a monochromatic beam of X-rays,
the electric field vector of the radiation forces it to carry out vibrations of a
frequency equal to that of the incident beam. As a consequence of the
acceleration of the electron, it in turn will emit radiation of the same
wavelength in all directions. Thus, in an atom all electrons contribute to
the scattering of X-rays in this fashion. (Inelastic scattering will be taken
up in later chapters.)
A few remarks about the scattering by a single atom may be in order.
It is obvious that when the wavelength of the incident radiation is large
compared with the dimensions of an atom, the wavelets emitted by the
.; Sec for example C. S. Barrett. Structure o{ Metals. 2d ed., McGraw-Hill. New York,
j 952, p. 633.
r
I
Sec. J-4] THE CRYSTALLINE STATE II
electrons in the atom are nearly all in phase. However, X-rays used in
diffraction work have a wavelength of the same order of magnitude as
the atomic diameter (this is necessary to obtain a diffraction pattern).
Thus the wavelets emitted by the electrons in an atom are in general out
of phase. Consequently, these wavelets will partially cancel each other by
interference and the amplitude of the radiation scattered by an atom
containing Z electrons IS less than that scattered by a free electron times
the number of electrons in the atom. We can, however, consider the
atom as a scattering center with an effective atomic scattering factor Is
which is given by the ratio of the amplitude of the wave scattered by the

t Zero order

Ix Incident waves

Fig. 1-9. Reinforcement of scattered waves producing diffracted

beams of different orders.

atom and that of the wave scattered by a free electron (for the same
incident beam). This problem will be discussed further in Sec. 1-6.
In crystals we are concerned with the scattering by a large number of
atoms arranged according to a particular pattern. For simplicity, let us
consider a one-dimensional row of atoms with interatomic distance a.
Assuming the incident wave crests to be parallel to the row of atoms, we
obtain a picture such as Fig. 1-9. The envelope of the wavelets emitted
by the individual atoms forms new wave crests and we see that besides a
beam propagated in the same direction as the incident beam (zero-order)
there are a few diffracted beams of other direction (first-order, second-
order, etc.). Thus, even though th~ individual atoms scatter radiation in
all directions, there are only a few directions in which these wavelets
reinforce each other. The condition for such a diffracted beam to exist
may easily be found as follows: In Fig. 1-10, suppose that AB is a \\,ave
crest of the incident beam, and CD is a wave crest of the diffracted beam.
Then, because a wave crest is an assembly of points of the same phase,
we must require that the path difference (AC - BD) shall equal an integer
12 THE CRYSTALLINE STATE (Chap. I
times the wavelength of the beam. Thus a diffracted beam is observed
only if
. a(cos Cl - cos ClO) = eA, with e = 0, 1,2, 3, ... ' \ (1-4)

For given values of Cl O' a, A, and e there is only one possible value for Cl.
We note that such a value exists only if at the same time cos ex ~ I.
Suppose then that to a certain value of e there corresponds a value IX.
The direction of the diffracted beam then forms a cone of directions with
the row of atoms as axis, as indicated in Fig. 1-10. Thus a monochromatic

Fig. 1-10. For reinforcement AC-BD should be an integer

times the wavelength. The vectors So and s are unit vectors in the \
direction of the incident and diffracted beams. Because the atoms
emit spherical waves, the possible directions of s form a cone
about the array of atoms.

X-ray beam falling on a row of atoms gives rise to a family of cones

representing the directions of diffracted beams.
Equation (1-4) may also be written in vector notation; if So and s
represent unit vectors, respectively, in the direction of the incident and
scattered beam (Fig. 1-10), and if a represents the translation from A to
D, we have
a • (s - so) = eA (1-5)

For a two-dimensional space-lattice, two conditions of the type (1-5)

must be satisfied. Each of these conditions gives rise to a set of cones for
possible diffracted beams. Hence, if both must be satisfied, only those
directions for a diffracted beam are possible that belong to one cone of
the first group and to one of the second group. Thus the second condition
strongly limits the number of possible diffracted beams, viz., to directions
determined by intersecting lines of two direction cones.
Conditions become even more stringent for a three-dimensional lattice.
Consider, for example, a simple space-lattice with a unit cell defined by

•
• Sec. 1-4] THE CRYSTALLINE STATE 13
the primitive translations a, b, and c. Then, for diffraction to occur, the
following equations for the path differences must be satisfied:
a(cos C( - cos C(o) = a • (s - so) = e},

b(cosfJ - cosfJo) = b· (s - so) = I}. (1-6)

c(cos y - cos Yo) = c . (s - so) = g).
where e,f, and g are integers; c(o, fJo, Yo and C(, fJ, y represent, respectively,
the angles between the incident and scattered beams and the axes a, b, c.
These are the von Laue equati.ons. It must be noted that for a given value
of ;, and an arbitrary direction of incidence so, it is in general not possible
to find a direction s which satisfies (1-6). In other words, for a mono-
chromatic X-ray beam falling on a crystal with an arbitrary direction of
incidence, in general no diffraction is observed. This may readily be
understood by remembering that for a two-dimensional lattice there
exist only specific directions for a diffracted beam and these directions
are in general not part of the direction cones determined by the third
condition required for the three-dimensional case. Thus only for particular
angles of incidence will diffraction be observed; it is exact Iy this limitation
that makes X-ray diffraction a useful tool for investigating crystal
structures. This point will become more clear when we discuss the Bragg
formula below. Before doing this, it may be useful to rewrite (1-6) for
the case of a simple cubic lattice. Assuming a = b = c, we obtain from
(1-6) by squaring and adding
2a 2(1 - cos C( cos C(o - cos fJ cos fJo - cos y cos Yo) = ).2(e2 12 + + g2)
Now, if cp represents the angle between the incident and scattered beams,
we may write
2(1 - cos cp) = 4 sin 2 (cpj2) = ().2ja 2)(e2 +12 + g2) (1-7)
In this form the von Laue equation is closely related to the Bragg formula.

1-5. X-ray diffraction according to Bragg

Bragg considered the problem of X-ray diffraction from a somewhat

different point of view. Although in itself it is not completely satisfactory
because it involves certain assumptions that are not immediately obvious,
it gives results identical with the Laue treatment and is therefore justified.
Bragg considers X-ray diffraction from a crystal as a problem of reflection
from atomic planes. In Fig. I-II consider a set of parallel atomic planes
of Miller indices (hk/), the distance between successive planes being d hk1 .
If we assume with Bragg that an X-ray beam is reflected by an atomic
plane according to Snell's law (i.e., incident beam, reflected beam, and
normal in one plane, and angle of incidence equals angle of reflection)
14 THE CRYSTALLINE STATE [Chap. I
we see that rays I and 2 can reinforce each other in the reflected direction
only if their path difference is an integer times A. This is necessary because
wave crests are points of equal phase. Thus from the figure we find as
condition for reflection from the set of planes under consideration,
2d"kl sin () = n}. with n = 0, 1,2, 3, '" (1-8)
The value of n indicates the order of reflection. This condition shows
immediately that for given values
of d"kl and A, and n having integer
values, only a particular angle ()
wouJd produce such a reflection.
Thus we arrive at the same con-
clusion as above, viz., that a beam
of monochromatic X-rays incident
on a crystal with an arbitrary
Fig. 1-11. Beams reflected from successive angle () is in general not reflected.
planes will reinforce each other if AB -I- BC Also, because sin () ~ I and d c:::
equals an integer times the wavelength; 10- 8 cm, we see that reflection can
this leads immediate:y to equation (1-8).
be observed only for Aof the order
of 10- 8 cm or less. It is for this reason that X-rays are used in these
experiments.
We shall now show that condition (1-8) as given by Bragg is equivalent
to (1-6) derived from the von Laue treatment. For simplicity let us
'-consider a simple cubic lattice, So that we must compare (1-7) and (1-8).
First of all it is evident from the definition of 1> and from Fig. 1-11 that
1>/2 = O. Furthermore, making use of expression (1-3) for the distance
between successive planes of Miller indices (hkl) in a cubic lattice, we may
write (1-8) as
2a sin () = An(h2 + k 2 + /2)1/2 (1-9)
Thus, identifying the integers e,J, and g, respectively, with nh, nk, and nl,
a diffracted beam detIned in the Von Laue treatment by the integers e, f, g
may be interpreted as the nth order reflection from a set of planes (hkl)
in the Bragg theory. The order of the reflection n is simply equal to the
largest common factor of the numbers e,J, g.

1-6. The atomic scattering factor

So far, we have considered only the condition for diffraction from

simple str'uctures for which only the comer points of the unit cell are
occupied. It will be evident that the intensity of a beam diffracted by
an actual crystal will depend on the grouping of atoms in the unit cell and
on the scattering power of these atoms. Conversely, the intensity of a
diffracted beam should provide information about the configuration of
Sec. 1-6] THE CRYSTALLINE STATE 15
atoms in the unit cell and therefore must be considered an important
quantity in X-ray diffraction work. In the present section we shall consider
the atomic scattering factor; in the next section the relationship between
the intensity of a diffracted beam and the atomic configuration in the
unit cell will be discussed.
In the beginning of Sec. 1-5 we mentioned that the atomic scattering
factor 1.: is defined as the ratio of the amplitude of an electromagnetic
wave scattered by an atom and that of a wave scattered by a free electron.
To calculate this factor for a given
wavelength}. we refer to Fig. 1-12.
Let A be the center of the a'tom
and let us consider an incident
and a scattered beam making an
angle of 20 with each other. We
may then choose the .:-axis of a
polar coordinate system r, 0, r/>
along AN, where AN is the normal B c
to the "reflecting plane" BAC. If
the electronic charge distribution
of the atom is assumed to be Fig. 1-12. Calculation of the atomic
spherically symmetric, a function scattering factor. A N is the normal to
p(r) may be introduced represent- the reflecting plane BA C'. The vectors are
all drawn in the plane of the paper, so that
ing the density of electrons at a the azimuthal angle cp has not been indi-
distancer from the nucleusA. Thus cated.
the number of electrons in a
volume element at r is equal to p(r)r2 dr sin 0 dO dr/>. Consider now the
phase difference between the rays scattered by this element of charge and
the rays that would be scattered if the same charge were located in point A.
From what has been said in the preceding section it follows that this phase
difference is determined only by z = r cos 0, and in fact equal to
cp =" (47TZ/}.) sin 0 = (471P.)r cos 0 sin (j (1-10)

On the other hand, the absolute value of the amplitude of the scattered
wave is of course independent of the location of the charge and simply
proportional to the amount of charge. The ratio of the complex amplitude
of the wave scattered by the element under consideration and the amplitude
of the wave that would be scattered by the same charge in A is thus simply
ei'l. The atomic scattering factor is 'therefore

j, = .Co t'~o .1::0 e;'(p(r)r2 dr sin {} df} dr/>

. Substituting (1-10) for fT, the integral becomes
(oo sin kr
/, = I, 47Tr 2p(r) - - dr with k = (417/,1) sin f) (I-II)
.0 kr .. '
...
16 THE CR YSTALLINE STATE [Chap. I

We note that f 41Tr2p(r) dr is equal to the total number of electrons Z in

the atom. Hence the atomic scattering factor is equal to Z only for
() = 0, and < Z for all other angles
2[\ of scattering. From (1-11) it follows
that a calculation of Is requires a
10
\ knowledge of the charge distribution
8 i\ in the atom. As an example, we give
f
t
6 \ in Fig. 1-13 the atomic scattering
factor for magnesium as a function

'"
of (sin ())/ A. The charge distributions
4 on which such curves are based may
~ t---... be obtained from a Hartree approxi-
2 mation or for atoms with a large
number of electrons (beyond rubid-

-
o .2 .4 .6 .8
1.0 ium) from a statistical atomic model
ainD developed by Thomas and by Fermi. 6
-),-
In some cases, viz., for solids
Fig. 1-13. Atomic scattering factor with simple structures, the atomic
for magnesium as function of (sin (j)/)., scattering factor may be determined
where ). is expressed in Angstroms.
experimentally from intensity mea-
surements. The agreement with the theoretical curves is generally good.

1-7. X-ray intensity and atomic configuration of the unit cell

To illustrate the problem to be discussed here, let us consider a particu-

larly simple example. In Fig. 1-14 let us suppose, to begin with, that
only the corners of the cubic unit cell
are occupied by atoms. For such a
simple cubic lattice, (which, by the
3
way, does not occur in nature) the
first-order reflection from the set of 2
planes (001) would be observed for a
particular Bragg angle 0, determined
in accordance with (1-8) by
2doOl sin () = 2 a sin () = A Fig. 1-14. Illustrating that the first-
order reflection from the planes {tOO}
For this reflection, the path difference is absent in a body-centered cubic
between rays 1 and 2 is equal to lattice. The path difference between
one wavelength. Suppose now, that 1 and 2 is ),; between I and 3 it is ).12.
the unit cell contains also an atom
at the center of the cube; we may then ask the question as to how this
• For values of the scattering factors of atoms and ions see R. W. James and G. W.
Brindley, Z. Krist. 78,470, (1931); il1ternationale Tabellen zur Bestimmlll(f{ vall Kristall-
strukturen, Vol. 2, Borntrager, Berlin, 1935.
Sec. 1-7] THE CRYSTALLINE STATE 17
will influence the intensity of the first-order reflection mentioned above.
Addition of an atom at the center of the unit cell is equivalent to inserting
planes halfway between the (001) planes; furthermore, the density of
atoms per unit area on these planes is exactly the same as that for the
(001) planes. Now, if the path difference between rays I and 2 is A, the
path difference between.l and 3 is Al2. From this, it is evident that the
intensity of the first-order reflection from the (00l) planes in a body-
centered cubic lattice is zero, at any rate if all atoms have the same
scattering factor. In other words, for an element crystalizing in a b.c.c.
lattice, the first-order reflection from planes such as (001) will be absent.
Similar considerations may be held for other reflections and other atomic
configurations. This leads to a number of characteristic absences from
which it is possible to draw conclusions regarding the atomic configuration
in the unit cell. If the central atom is different from those at the corners,
the intensity of the reflection under consideration will not vanish com-
pletely, but will give rise to a relatively weak line. For the second-order
reflection, the path difference between 1 and 2 is 2A, that between 1 and 3
is A; in that case, then, all rays will reinforce each other and this reflection
will be present in the b.c.c. structure.
The problem will now be discussed quantitatively. Let us consider
the intensity of an X-ray beam diffracted by a crystal with a unit cell of
primitive translations a, b, c. The conditions that must be satisfied for
the waves emitted by the atoms at the corners of this unit cell to be in
phase are given by (1-6); it will be assumed that these equations are
fulfilled. Furthermore, taking a particular corner atom as ongm, let
the coordinates of the other atoms in the unit cell be represented by
vectors of the type

In analogy with the von Laue equations (1-6) it then follows that the
phase difference between the beam scattered by atom k and the one
scattered by the atom at the origin is given by

where So and s are unit vectors, respectively, in the direction of the incident
and scattered beam. Substituting (1-12) and making use of (1-6), we

, obtain

It is convenient to introduce the structure factor F, defined in analogy

( 1-14)

with the atomic scattering factor as follows: F is the ratio of the amplitude
of the wave scattered by all atoms in a unit cell and that scattered by a
free electron for the same incident beam. In view of (1-13) the complex
18 THE CRYSTALLINE STATE [Chap. I

amplitude produced by atom k is hkei"1 where f,le is the atomic scattering

factor for atom k. Thus the structure factor may be written

(1- 15)

where the summation extends over all atoms in the unit cell. In con-
nection with this summation we must emphasize that an atom at a corner
belongs to eight unit cells, so that
such an atom in the summation
counts for only i. In other words,
all atoms at the corners together
produce only one term. We may
also look at this problem in this
fashion: if we add vectorially the
amplitudes of the waves scattered
Fig. 1-15. Showing the vectorial addition
by the atoms in a unit cell, we
of the amplitudes of the waves scatt<:red
by the different atoms in the unit cell. obtain a picture such as in Fig.
F is the resultant of the individual j,k'S. 1-15, where F is the resultant
amplitude. Each amplitude has
two components, j~k cos tpk and f,le sin tple and the intensity, which is
proportional to the square of the amplitude, then becomes proportional to

(1-16)

This expression is identical with IFI2

ceo FF*, where F is given by (1-15)

and F* represents. the complex conjugate of F. The values of the tpk'S

are given by (1-14).
For the particular case that all atoms in the unit cell are the same,
all hie's are equal and one may write
F = Is 'Z e2 "i(Uk e + vd+ wkU) (1-17)
k

A simple example may illustrate the conclusions one may draw from the
above treatment. For a body-centered cubic lattice of similar atoms, the
summations extend over the values u, l" IV = 0, 0, 0 and u, V, w :_ !, t, t
(all corner atoms together represent one atom). According to (1-14)
ffl = 0 and tp2 = 7T(e f + +
g). Hence, for a body-centered cubic lattice
of similar atoms we have, according to (1-16),

IFI2 = + cos 7T(e +f + g)J2 + sin27T(e +f + g)}

f~ ([I
We conclude that if (e +f + g) is odd, IFI2 = 0 and the corresponding
reflection is absent. On the other hand, for (e + f + g) even, we have
IFI2 = (21,)2 and the reflection is present. We leave it as a problem to
show that in a face-centered cubic lattice all reflections will be missing
for which the nu~bers e,f, g are mixed odd and even, such as 100,211, 324,
...
Sec. 1-7] THE CRYSTALLINE STATE 19
etc. The results of such considerations for cubic lattices of similar atoms
are represented in Fig. 1-16 in the form in which they appear as lines in

1,1 1.3 17 l~ ~1 _ (e2+f2+g2)

o 2 3 4 5 6 8 9 10 ,: 12 : 14 16: 18 : 20:22 24

I I I I I I Simple cubic

Body-centered cubic

Face·centered cubic

Diamond

Fig. 1-16. Powder patterns for different cubic crystals, illustrating

characteristic reflections and absences for each type. [By per-
mission from C. S. Barrett, Structure ot' Metals, McGraw-Hill
2d ed., 1952, p. 136]

a powder-method experiment. Because of the characteristic line pattern

produced by each of these structures, they are readily recognized.

1-8. Experimental methods of X-ray diffraction

Because of lack of space, it is not possible to discuss in any detail the

experimental techniques employed in X-ray diffraction work, but a few
remarks may be in order. There are essentially three methods which
may be employed, as may be seen from the Bragg formula (I-8). If one
uses monochromatic X-rays, equation (1-8) cannot be satisfied for an
arbitrary value of O. This has led to the rotating-crystal method, whereby
reflection occurs for a discrete set of 0 values. This method can of course
be applied only if single crystals of reasonable size are available. If this is
not the case, one can employ monochromatic X-rays when the sample is
in powder form and held in a fixed position. The reason that a diffraction
pattern is observed is that there are always enough crystallites of the right
orientation available to satisfy the Bragg relation. By a proper analysis it
is possible to identify the indices (hkl) of a particular reflection, and this
enables one to calculate the interatomic parameters when the wavelength
of the employed radiation is known. The characteristic absences, dis-
cussed in the preceding section, allow one in many cases to determine
the atomic configuration of the unit cell at a glance. Finally, there is
the von Laue method, in which the sample (a single crystal) is held
stationary in a beam of white X-rays. Each set of planes then "chooses"
its own wavelength to satisfy the Bragg relation. This method is not so
useful for the determination of lattice parameters as the other two because
the wavelength of a particular reflection is unknown. On the other hand,
20 THE CRYSTALLINE STATE [Chap. I

it is used in the determination of crystal symmetry. For a review of the

experimental techniques we refer to the references quoted at the end of
this chapter.

1-9. Diffraction of electrons by crystals

\
From a theoretical study of the relation between geometrical optics
and classical mechanics, de Broglie in 1924 suggested that particles may
be described by waves. He predicted that the wavelength associated with
a particle of momentum p = mv is given by
A =h/p (1-18)
where h is Planck's constant. One of the most direct pieces of evidence
of the wave aspect of particles was provided by the electron diffraction
experiments of Davisson and Germer in 1927.7 They concluded that if
one associates a wavelength with the electrons given by (1-18), the dif-
fraction pattern obtained can be interpreted in exactly the same way as
the X-ray diffraction patterns. As long as the velocity of the electrons is
small compared with the velocity of light, the wavelength of the electrons
may be expressed in terms of the accelerating voltage V as follows:
imv 2 = eV or A = hj(2meV)1/2 c::: (l50/V)1/2 (1-19)

where A is obtained in Angstroms if V is expressed in volts. Note that

only 150 volts are required to produce electrons of a wavelength of 1 A,
in contrast with X-rays, which require approximately 12,000 volts for 1 A.
Although Davisson and Germer in their original experiments used
electrons of 30-600 ev, modern diffraction equipment employs usually
voltages of the order of 50 kilovolts, corresponding to A c::: 0.05 A. In
such cases, a relativistic correction must be applied to (1-19); for 50 kev
electrons this correction lowers the wavelength by approximately
2.5 per cent.
The atomic scattering factor for electrons has been discussed by BomB
arid a simplified treatment has been given by Mott. 9 In contrast with
X-rays, electrons are scattered by the nucleus as well as by the electrons
in the atoms. For a spherical charge distribution one can show that the
scattering factor is given by
me 2 ..1 2
E(O) = 2h2 (Z - /.) sin2 0 (1-20)

Here Is is the scattering factor for X-rays, Z is the nuclear charge, and
() is the Bragg angle. As for X-rays, the scattering factor for electrons
, C. Davisson and L. H. Germer, Phys. Rev., 30,707 (1927).
• M. Born, Z. PhYSik, 38, 803 (1926).
9 N. F. Mott, Proc. Roy. Soc., 127A, 685 (1930).

'.
Sec. 1-9] THE CRYSTALLINE STATE 21
decreases with increasing values of O. However, there is a considerable
difference between X-rays and electrons in that electrons are scattered
much more efficiently by atd'ms than are X-rays. In fact, atoms scatter
electrons more strongly by several powers of ten for the energies involved.
At normal incidence, an electron of about 50 kev has a penetration depth
for elastic scattering of only about 500 A, while for the small angles of
incidence used in reflection techniques this may be only about 50 A
measured perpendicular to the surface. It is evident, therefore, that electron
diffraction is particularly useful in investigating the structure of thin
surface layers such as oxide layers on metals. Such layers would not be
detected by X-ray diffraction because the patterns obtained are
characteristic for the bulk material. We may note that diffraction of
electrons by gases requires much shorter exposure times than does X-ray
diffraction, again as a result of the relatively high efficiency of scattering
of electrons by atoms.

1-10. Diffraction of neutrons by crystals

( --

We have seen above that for X-rays of I A one requires energies of

the order of 104 ev, for electrons of 1 A about 102 ev. Now, the mass of a
neutron is about 2000 times as large as that of an electron, so that according
to the de Broglie relation (I-18) the wavelength associated with a neutron
is about 1/2000 that for an electron of the same velocity. Thus the energy
of a neutron required to give 1 A is of the order of only 0.1 ev. Such
neutrons can be obtained from a chain-reacting pile, and diffraction from
crystals may be observed. 10 Neutrons are scattered essentially by the
nuclei of the atoms, except when they are magnetic (see below). Now,
the radius of an atomic nucleus is of the order of 10-13 cm, and as a
consequence, the atomic scattering factor is nearly independent of the
scattering angle, because A?> 10-13 cm. Also, the scattering power does
not vary in a regular manner with the atomic number, so that light
elements such as hydrogen and carbon still produce relatively strong
scattering. The scattering of X-rays by light elements is in contrast, of
course, relatively weak. Thus the positions of such atoms in crystalline
solids may be determined from neutron diffraction experiments.u Another
important aspect of neutron diffraction is the fact that scattering from
neighboring elements in the periodic system may differ appreciably.
For example, neutron diffraction allows one to detect with relative ease
ordered phases of an alloy such as FeCo, whereas their detection by
X-rays is difficult.
10 W. H. Zinn, Phys. Rev., 70, I02A (1946); 71, 752 (1947); L. B. Borst, A. J.

Ulrich, C. L. Osborne, and B. Hasbrouck, Phys. Rev., 70, 10SA (1946); 70,557 (1946).,
II C. G. Shull. E. O. Wollan, G. A. Morton, and W. L. Davidson, Phys. ReI'., 73

830 (1948).
22 THE CRYSTALLINE STATE [Chap. J
A particularly important aspect of neutron diffraction is their use in
investigating the magnetic structure of solids. This is a result of the
interaction between the magnetic moment of the neutron and that of the ,
atoms concerned. In a paramagnetic substance, in which the magnetic
moments are randomly oriented in space, this leads to incoherent scat-
tering, resulting in a diffuse background. This background of magnetic
scattering is then superimposed on the lines produced by the nuclear
scattering mentioned above. In a ferromagnetic substance in which the
magnetic moments within a domain are lined up in parallel, this diffuse
background is absent. It occurred to Smart that neutron diffraction
(111) (311) (331 (511)
100

80 ,
\
60

80 K
0

ao=B.85A.

(100) (110) (111) (200) (311)

t t ~ t +

60
MnO 293'K
40 Tc=120'K ao=4,43A.

20

_ Scattering angle

Fig. 1-17. Neutron diffraction patterns for MnO at room tempera-

ture and at 80 o K. The magnetic unit cell is twice as large as the
chemical one. [After Shull and Smart, ref. 121

might provide a direct means of ~etec~ing antiferro~agnetism (see

Chapter 19).12 In an antiferromagnetIc sohd, the magnetIc moments of
particular pairs of atoms are aligned antiparallel and hence, fr.om the
point of view of the neutron, such atoms would appe~r to be different.
In Fig. 1-17 we show a neutron diffraction patter~ obtaIned for p?wde~ed
MnO at room temperature and at 80o K; the Cune temperature IS 122 K
and only below this temperature is MnO antiferromagnetic. The room
12 C. G. Shull and J. S. Smart, Phys. Rev., 76,1256 (1949).
Sec. 1-10] THE CRYSTALLINE STATE 23

temperature pattern shows coherent diffraction peaks as would be

expected from a lattice of the NaCI structure. The diffuse background of
magnetic scattering is also visible. The low-temperature pattern shows
the same peaks, but in addition strong magnetic reflections at positions
that one would not expect on the basis of the chemical structure of the
unit cell. If, however, one introduces a magnetic unit cell twice as large
as the chemical one, these reflections can be identified. Such a cell indeed
corresponds to an antiferromagnetic substance.
The diffraction of particles is, of course, not confined to electrons and
neutrons, but may also be observed for atoms and molecules, the corre-
sponding wavelength being given by the de Broglie relation. Diffraction
has been observed for example for H, He, H 2 , and other atoms. 13

I-H. Interatomic forces and the classification of solids

A few remarks of a qualitative nature may be made here about the
forces acting between atoms or molecules in solids. We shall not enter
into any detail since certain aspects of this topic will be treated in later
chapters.
From the very existence of solids one may draw two general con-
clusions: (1) there must act attractive forces between the atoms or
molecules in a solid which keep them together; (2) there must be repulsive
forces acting between the atoms as well, since large external pressures
are required to compress a solid to any appreciable extent. (Both con-
clusions also apply to liquids). In order to illustrate the importance of
both types of forces, let us consider the simplest system in this respect,
viz., a single pair of atoms A and B which form a stable chemical com-
pound. Without paying attention to the physical origin of the forces
between the two atoms, let us assume that the potential energy of atom B
due to the presence of atom A is given by an expression of the type

E(r) = -rxlr" + Plr'" (1-21 )

where r is the distance between the nuclei of the two atoms; rx, p, m, and n
are constants characteristic for the AB molecule. The zero of energy is
chosen such that for infinite separation E = O. The first term, which is
negative, corresponds to the energy associated with the forces of attraction,
the second (positive) term corresponds to the forces of repulsion. In
fact, the force between the two atoms as function of r is given by

• nrx
F(r) = -dEldr = - - n 1
r+
+ -rmp
m +1
( 1-22)

The energy and the force between two atoms A and B which form a
13 For a review see, for example, r. Estermann, Rers. Mod. Phys., 18, 300 (1946).
24 THE CRYSTALLINE STATE [Chap. I

chemical compound are represented in Fig. 1-18. The stable configuration

for the system corresponds to the minimum in the E(r) curve, which
occurs for a particular separation r = roo The corresponding energy
£(ro) is negative; thus the positive quantity D = -E(ro) is the dissociation
energy of the molecule, i.e., the energy required to separate the two atoms.
Dissociation may occur, for example, at high temperatures or as a result
of other processes in which the molecule can absorb sufficient energy.

E F
t t
Repulsive

(al (bl

Fig. 1-18. Schematic representation of the energy (a) and force

(b) between two atoms as function of their separation r. The
dashed curves are the sums of the attractive and repulsive curves.

The dissociation energies are of the order of one or a few electron volts.
Assuming that the energy curve exhibits a minimum, one may express
the equilibrium distance ro and the corresponding binding energy E(ro)
in terms of the constants t:I., fJ, m, and n by making use of the condition
(d£/dr),.~"rO = 0, i.e., r~t-n = (m/n)(fJ/r:x) (1-23)
According to (1-22) this condition is equivalent to the requirement that
the attractive and repulsive forces balance, i.e., F(ro) = O. Substituting
from (1-23) into (1-21) one obtains for the energy in the equilibrium state
E(ro) = -r:x/r~ + fJ/r3' = -(a/r3)(1 - n/m) (1-24)
Note that although the attractive and repulsive forces are equal in equi-
__~_. librium, the attractive and repulsive energies are not equal since n m. In *
fact, if m ~ n, the total binding energy is essentially determined by the
energy of attraction -alr~.
As one may expect already by looking at Fig. 1-18, a minimum in the
energy curve is possible only if m > n; thus the formation of a chemical
bond requires that the repulsive forces be of shorter range than the
Sec. I-Ill THE CRYSTALLINE STATE 25
attractive ones. This may be shown readily by employing the condition
that (d 2 E/dr 2 )r_r
- 0
> 0 if E(r) must have a minimum at roo In fact, this
condition leads to
-n(n + 1)1X/r~+2 + m(m + l)fl/r~'+2 > 0
which upon substitution of ro from (1-23) immediately gives
m>n (1-25)
Although the energy can in general not be represented accurately by a
power function of the type (1-21), the above treatment provides some
useful qualitative conclusions which may be extended to solids. An
application of this type of reasoning is given in Chapter 5 for ionic
crystals.
The forces acting between the atoms in solids are electrostatic in
nature; they are determined essentially by the way in which the outer
electrons of the composing atoms are distributed in space. The physical
properties of solids are determined to a large extent by the electron
distribution, and it is thus possible on an empirical basis to divide solids
into different groups corresponding to different types of electron distri-
butions. For a discussion of the nature of chemical binding we must
refer the reader to the literature.1 4 One may distinguish between the
following extreme types:
~ ,,'
1. Ionic crystals (NaCI, KF)
'_
2. Valence crystals (diamond, SiC)
3. Metals (Cu, Ag, Ma)
4. van der Waals crystals (argon, many organic crystals)
]t should be said from the outset that many intermediate cases occur
and in general one must be somewhat careful in employing very specific
labels.
I. Jonic crystals. In ionic crystals one or more electrons of one type
of atoms are transferred to another, leading to the formation of positive
and negative ions; for example, NaCI may be considered as to be built
up of Na+ and CI- ions. The cohesive energy of these crystals is to a
large extent determined by the Coulomb interaction between the hetero-
polar ions, as discussed in Chapter 5. At elevated temperatures they
exhibit ionic conductivity. Associated with the existence of positive and
negative ions is a strong optical absorption coefficient in the infrared.
Ionic crystals may be cleaved readily.
2. Valence crystals. In valence crystals neighboring atoms share their
valence electrons under the formation of strong homopolar or covalent
U L. Pauling, Nature of the Chemical Bond, 2d ed., Cornell University Press, Ithaca,

1945; J. A. A. Ketelaar, Chemical Constitution, Elsevier, New York, 1953.

26 THE CRYSTALLINE STATE [Chap. 1

bonds. Some further remarks may be found in Sec. 13-1. Valence crystals
are very hard (diamond, carborundum), are difficult to cleave, and have a
poor electrical and thermal conductivity.
\
3. Metals. In metallic crystals the outer ele~trons of the atoms have
a high degree of mobility, to which these materials owe their high electrical
and thermal conductivity. In a simplified way one may say that the
cohesive energy of metals is provided essentially by the Coulomb inter-
action between the positive ions and the negative "smeared out" charge
of the conduction electrons. The cohesive energy of metals will be
discussed briefly in Sec. 10-13. -

4. can der Waals crystals. The atoms of the rare gases such as argon
have little or no tendency to give up electrons or share them with others.
In the liquid and solid state the forces of attraction are the so-called
dispersion forces,15 which arise in the following way; The combination of
the moving negative electrons and the nucleus of an atom may be con-
sidered a system of fluctuating dipoles. The interaction between these
dipoles associated with neighboring atoms then gives rise to a relatively
weak binding (see Sec. 5-6). In organic crystals the cohesive energy is
provided by dispersion forces as well as by the interaction between
permanent dipoles (see Sec. 6-1) of neighboring molecules; the totality
of such forces is referred to as van der Waals forces. Associated with
the relative weaknes~ of these forces are Jow boiling and melting
points.
Between the extreme groups mentioned above, there are many inter-
mediate cases. An interesting intermediate group of solids are the semi-
conductors. Semiconducting elements such as Ge and Si are intermediate
between valence crystals and metals. The bonds are essentially.homopolar
and at absolute zero the elements are insulators, as diamond. However,
the electrons forming the bonds between neighboring atoms are much
less strongly bound than in diamond; thus already at room temperature
these elements exhibit a certain amount of electrical conductivity, which
increases as the temperature is raised. These elements are further dis-
cussed in Chapter 13. Ionic crystals may also become semiconducting,
by introducing impurities, or when the composition deviates from that
represented by the chemical formula ("nonstoichiometric" compounds).
These are discussed in Chapter 15.
A classification of solids given by Seitz16 is represented in Fig. 1-19
(with some slight modifications); examples of intermediate cases are
indicated. The upper row refers to elements, the lower one to solids
'" For an elementary discllssion, see, for example, M. Born, Atomic PhYSiCS, 5th ed.,
Hafner, New York, 1951.
16 F. Seitz, The Modem Theory of Solids, McGraw-Hill, New York, 1940, p. 75.
Sec. I-II] THE CR YST ALLINE STATE 27
containing more than one type of atom; the two groups meet in the van
der Waals crystals (argon as an element and CH 4 as a compound would
be examples). Between the true alloys and ionic crystals there is a group
of intermetallic compounds for which the composing metallic components
have different tendencies for giving up electrons (Mg 3 Sb 2).

,
1
Monoatomic
metals
Ge, Si Valence
crystals -_c , ~ • .... l~

(Ag,Cu) Bi (diamond) S
p
Se

Si02 van der Waals

r
crystals
SiC (A,CH4 )
"

,
FeS
Ti02
Alloys Ionic crystals !
(NiCu) (NaCl) _-
Mg 3 Sb 2 \

Fig. 1-19. Classification of solids, indicating intermediate cases.

1-12. Anisotropy of the physical properties of single crystals

The physical properties of single crystals in general depend on the

direction along which they are measured relative to the crystal axes;
this phenomenon is called anisotropy. Some examples are the following:
crystals do not grow in the form of spheres, but in polyhedra; certain
types of atomic planes dissolve more readily than others; the coefficient
of thermal expansion of Zn is 6.39 X 10-5 along the hexagonal axis and
1.41 )( 10-5 per degree C perpendicular to it; the specific resistivities of
Zn parallel to the hexagonal axis and perpendicular to it are, respectively,
PH = 6.06 X 10-6 and PJ. = 5.83 X 10-6 ohm/cm. The reason for the
a'nisotropy of the physical properties of crystals must be sought in the
regular stacking of atoms. Thus as one passes through a crystalline
arrangement of atoms or molecules along a given direction, one meets
atoms or groups of atoms at different intervals and from different angles
than one would along another direction. Single molecules are also aniso-
tropic; however, in normal liquids or gases the orientation of the molecules
is random and the physical properties become independent of the direction
along which they are measured (isotropic) as long as a large number of
molecules is involved or when a time average is taken for a single molecule.
Polycrystalline materials with a completely random distribution of the
grain orientation are also isotropic.
28 THE CR YST ALLINE STATE [Chap. I

As an example of anisotropy in a single crystal let us consider the

electrical conductivity in which an electric field E gives rise to a current 1.
In general, the current vector will not have the same direction as the
electric vector. Thus, assuming a linear relationship between cause and
effect, we may write for the current components relative to an arbitrarily
chosen Cartesian coordinate system \'

Ix = axxEx + axlI E y
+ axzE.
I" = a"xEx + oyyE" + ayzE. (1-26)
I z = azxEx + E y + azzE.
0ZlI

where the quantities aik are components of the "conductivity tensor."

It has been shown by Onsager that the tensor is symmetric, i.e., 0ik = 0kiY
Making use of this symmetry property and multiplying the expressions
(1-26) respectively by Ex, E y , and E z, one obtains upon adding

IxEx + IyEy + I.E. = a=E; + a"1IE; + a,.E; + 2ax"ExE lI

+ 2a E E. + 2azx E Ex
yz y z (1-27)

The right-hand side represents a quadratic surface; by choosing our

coordinates along the principal axes of this surface, the mixed terms
disappear and one obtains in the new coordinate system

(1-28)

where aI' a 2, and aa are the principal conductivities. Thus the electrical
properties of any crystal, whatever Jow symmetry it may possess, may be
°
characterized by three conductivities al , 2 , a3 or by three specific resis-
tivities PI' P2, P3' Note that 1 and E have the same direction only when the
applied field falls along anyone of the three principal axes of the crystal.
In cubic crystals the three quantities are equal and the specific resis-
tivity does not vary with direction. In hexagonal, rhombohedral (trigonal),
and tetragonal crystah the resistivity depends only on the angle 1> between
the direction in which P is measured and the hexagonal, trigonal, or
tetragonal axis, since in those crystals two of the three quantities PI' P2, P3
are equal. One finds
p(1)) = Pl. sin21> + PI! cos 2 1> (1-29)
where l_ and !i refer to directions perpendicular and parallel to the axis.
The effect referred to above may be called a "vector-vector" effect
"L. Onsager, Phys. Rev., 37. 405 (1931); 38, 2265 (1931); for the so-called
"reciprocity relations" derived by Onsager on the basis of the principle of microscopic
reversibility, see also C. Zwikker, Physical Properties of Solid Materials, Interscience,
New York, 1954, Chap. 5; see also Chap. 4 for anisotropy.
Sec. 1-12] THE CRYSTALLINE STATE 29
since an electric current (vector) is produced by an applied electric field
(vector). The relations obtained may also be applied to other vector-
vector effects such as thermal conductivity, where a thermal current vector
is evoked by a thermal gradient; or diffusion under influence of a con-
centration gradient.
When one considers scalar-tensor effects, similar relationships are
obtained. For example, the deformation (tensor) of a solid resulting from
a change in temperature (scalar) may be characteriled by three principal
expansion coefficients 0(1' 0(2' and O(a' Here again, in cubic crystals
iX l = iX2 = O(a and such crystals are isotropic in this respect. The angular
dependence of 0( for hexagonal, trigonal, and tetragonal crystals is given
by an expression corresponding to (1-29).
Other effects such as vector-tensor effects and tensor-tensor effects
may be treated along similar general lines. An example of a vector-tensor
effect is piezoelectricity,18 in which an electric field (vector) gives rise to a
deformation (tensor).18 The elastic deformation under influence of a
stress tensor is an example of a tensor-tensor effect. 19 These effects may
require many more constants than appeared in the relatively simple case
of a vector-vector effect outlined above.
),,'

REFERENCES :'c'

G. E. Bacon, Neutron Diffraction, Oxford, New York, 1955.

R. Beeching, Electron Diffraction, 2nd ed., Methuen, London, 1946.
M. J. Buerger, X-ray Crystallography, Wiley, New York, 1942.
C. W. Bunn, Chemical Crystallography, Oxford, New York, 1945.
A. H. Compton and S. K. Allison, X-rays in Theory and Experiment,
Van Nostrand, New York, 1935.
International Tables for X-ray Crystallography, Kynoch Press, Birmingham,
1952.
R. W. James, X-ray Crystallography, 4th ed., Methuen, London, 1950.
J. A. A. Ketelaar, Chemical Constitution, Elsevier, New York, 1953.
K. Lonsdale, Crystals and X-rays, Bell and Sons, London, 1948.
L. Pauling, Nature of the Chemical Bond, Cornell University Press,
Ithaca, 1945.
R. W. G. Wyckoff, Crystal Structures, Interscience, New York, 1948.
18 See W. G. Cady, Piezoelectricity, McGraw-Hill, New York, 1946.
19 See for further details Sec. 3-8. i" '
30 THE CRYSTALLINE STATE [Chap. J

1 i
PROBLEMS \

1-1. For the packing of spheres of radius R in a simple cubic, a

body-centered cubic and a face-centered cubic lattice show that the cube
edge and the fraction of the volume occupied by the spheres are given by
simple cubic: a = 2R; f = 7T/6
b.c.c. : a = 4R/Y3; f= (7TY3)/8

f.c.c. : a = 4R/Y2; f = (7TY2)!6

Calculate the density ratios for the three lattices.
I -2. Explain why in Fig. 1-6, the following structures are not included:
the base-centered tetragonal, the face-centered tetragonal, and the face-
centered rhombohedral.
1-3. For a b.c.c. lattice built up of spherical atoms of radius R,
calculate the number of atoms per cm 2 on the planes {IOO}, (I1O}and {III J.
Do the same for a f.c.c. and a simple cubic lattice.
1-4. Explain that the diamond structure may be considered as made
up of two interpenetrating f.c.c. lattices. Given that the cube edge for
diamond is 3.56 A, calculate the distance between nearest neighbors and
show that there are 1.77 X 1023 atoms per cm 3 . From this, calculate
the density of diamond and compare the result with the observed density.
Do the same for germanium (cube edge = 5.62 A).
1-5. For a cubic lattice show that the distance between successive
planes of Miller indices (h, k, l) is given by formula 1-3.
1-6. Explain qualitatively, and if possible quantitatively, why the
X-ray diffraction lines observed from small crystallites become broadened;
base the discussion on a one-dimensional finite array of atoms.
1-7. On the basis of the discussion of Sec. 1-7, verify the characteristic
powder patterns represented in Fig. 1-16.
1-8. Discuss in some detail how the lattice constant of a cubic crystal
may be obtained from a powder pattern. If possible, carry out the
calculations for an actual film.
1-9. Suppose the interaction energy between two a'toms is given by an
expression of the type (1-21). Given that n = 2, m = 10, and that the
two at'oms form a stable molecule with an internuclear distance of 3 A
and a dissociation energy of 4 ev, calculate a and p. Also calculate the
force required to break the molecule and the critical distance between the
nuclei for which this occurs. Furthermore, calculate the force required
Chap. I] THE CRYSTALLINE STATE 31

to reduce the internuclear distance by 10 per cent relative to the equilibrium

distance.
1-10. Consider a crystal which, in equilibrium, occupies a volume Vo;
let the total energy of interaction between the atoms in the crystal be Eo.
Assuming that the energy of interaction between the atoms may be
described by an expression of the type (1-21), show that the compressibility
I I
is given by Eo (mn/9 Vo)·
1-11. Discuss methods for growing single crystals (see, for example,
H. E. Buckley, Crystal Growth, Wiley, New York, 1951).
1-12. Discuss some physical effects which are due to anisotropy (see,
for example, C. Zwikker, Phys;cal Propert;eso.( SaUd Mate,;als, Interscience,
New York, 1954, Chapter 4).

," ,
'<[1 ;'1;.

, I

"'"

,,'1
I" <'." '."

:',j
,j .' ~

I,
Chapter 2
\\

THE SP ECIFIC HEAT OF SOLIDS AND

LA TTICE VIBRATIONS

2-1. The specific heat at con~tant volume and at constant pressure

According to the first law of thermodynamics, the amount of heat dQ

added to a system must be equal to the increase in energy dE of the system
plus the amount of work done by the system. In case the work done by
the system is of a mechanical nature only, one may thus write
dQ = dE+ pdV (2-1)
Now, E is, except for an arbitrary constant, determined uniquely by the
temperature and volume of the system. Hence

dE = G;)v dT+ G:) T dV

and (2-1) may be rewritten in the form

dQ = G;)v dT+ [(~!) + p] dV

T (2-2)

The specific heat in general is defined by dQ/dT, and unless stated other-
wise, will be assumed to refer to 1 gram molecule of the solid. However,
unless one specifies in which way the increase in temperature takes place,
the specific heat is undetermined; in particular one must specify the
corresponding change in volume, as is evident from (2-2). Thus there
exist an infinite number of specific heats, but in general one is interested
in only two: the specific heat at constant volume Cv and the specific heat
at constant pressure Cpo According to (2-2), the former is given by

(2-3)

Theoretically speaking, this is the most interesting quantity, as it is

obtained immediately from the energy of the system; most of the following
discussions will therefore refer to Cv . From the experimental point of
view, however, it is much more convenient to measure the specific heat of
32
Sec. 2-1J SPECIFIC HEAT AND LA rrICE VIBRATIONS 33
a solid at constant pressure than at constant volume. As shown in text-
books on thermodynamics, the second law leads to the following relation-
ship between Cll and CV :1 __

Cll - Cv = -T (oV)2 (op) (2-4)

, oT p oV T
This may be rewritten in terms of the volume expansion coefficient (Xv
and the compressibility K, defined by

(Xv = (1/V)(oV/oT)ll and K = -(I/V)(eV/eph (2-5)

Expression (2-4) then takes the form

8
(2-6)
7
Thus C v may be calculated from ~

Cp measurements if at the same time ~ 6

'"C

!Xv and K are known at the ~ 5

E
temperature of interest. Since both
!Xv and K are positive quantities, ~ 4 --
ep - Cv ;>- O. Q
.S 3
By way of illustration, we have
given in Fig. 2-1 Cp and Cv as
2 t
functions of temperature for cop- 1

per; note that at low temperatures

their difference becomes very small o 400 800 1200
-+- T (absolute)
and that both go to zero at T = O.
It is essentially the temperature
Fig. 2-1. The temperature variation of
variation of the specific heat at C and C for copper. [By permission
constant volume which will be from M. W.v Zemansky, Heat and Thermo-
p

discussed in the present chapter. dynamics, 2d ed., McGraw-Hill, New York,

It may be noted that ifno direct 1943, p. 237]
compressibility data are available for the temperature range of interest,
one frequently employs the relationship
(2-7)
The quantity y is called the Griineisen constant and is practically
independent of temperature. 2 Thus by calculating y at some arbitrary
temperature from available data, one may obtain an approximation for
Cv at other temperatures from a knowledge of the coefficient of volume
expansion.
1 See, for example, M. W. Zemansky, Heat and Thermodynamics, 2d ed., McGraw-

Hill, New York, 1943, p. 227.

• E. Grlineisen, Handbuch de,. Physik, 10, I-59 (1_926); see also J. C. Slater, Phys.
ReI'., 57, 744 (1940).
34 SPECIFIC HEAT AND LATTrCE VIBRA TrONS [Chap. 2

From the atomic point of view one may distinguish between various
contributions to the specific heat of solids. In the first place, there is the
contribution resulting from the atomic vibrations in the crystal; an
increase in temperature is associated with a more vigorous motion of the
atoms, which requires an input of energy. Second, in metals and in
semiconductors there is an additional contribution to the specific heat
from the electronic system. Usually this contribution is small relative to
that of the lattice vibrations, as explained in Chapter 9. As the temperature
~p
is raised from absolute zero, the
10 specific heat increases rather
rapidly from zero and finally levels
8 off to a nearly constant value. For
elements, the value at high temper~
atures is about 6 cal mole- I
t 4 degree-I. This is known as the law
of Dulong and Petit. Anomalies in
2
the specific heat curves are observed
in the ferromagnetic metals; for
o 200 400 600 800 1000 1200 example, in nickel, iron, and cobalt,
-+T
a peak is observed in the vicinity
Fig. 2-2. CD in cal mole- 1 degree- 1 for of the ferromagnetic Curie tem~
nickel as function of the absolute perature (see Fig. 2-2). The height
temperature. of the peak is of the same
order of magnitude as the normal specific heat. The peak is associated
with the transition from the ferromagnetic (ordered) to the paramagnetic
(disordered) state. Similar peaks occur in the specific heat curves of alloys
which exhibit order-disorder transitions, and in ferroelectric materials.
These anomalies are discussed in the relevant chapters; in the present
chapter the discussion is confined to the specific heat associated with
atomic vibrations.

2-2. The various theories of the lattice specific heat

In Sec. 2-10 it will be shown that the vibrational energy of a linear
chain of N atoms may be expressed as the energy of N harmonic oscillators.
Extending the arguments employed there to the three-dimensional case,
one is led to the conclusion that:
The vibrational energy of a crystal containing N atoms is
eqUivalent with the energy of a system of 3N harmonic oscillators.
This feature is common to all theories of the specific heat and the
distinction between the various theories is based on their differences in
the proposed frequency spectrum of the oscillators. The central problem
in the theory of the specific heat is therefore the calculation of the
,...
~

Sec. 2-2] SPECIFIC HEAT AND LATTICE VIBRATIONS 35

wavelengths and frequencies of the possible modes of vibration of the
crystal under consideration. The different approaches to this problem
will be outlined below.
With regard to the harmonic oscillator representation referred to
above, the following qualitative remarks may provide some clarification.
Suppose it were possible to fix the position of all the nuclei in a crystal
such that they are all in their equilibrium position. If one of the nuclei
were now displaced over a distance small compared with the shortest
interatomic distances, and then set free again, the displaced atom would
carry out harmonic vibrations about its equilibrium position, and its
energy of vibration would be the same as that of three one-dimensional
harmonic oscillators, one for each direction of motion. Applying the
same reasoning to the other atoms in the crystal, one arrives at a system
of 3N harmonic oscillators representing the vibrations of the crystal as a
whole. ~'( r (

2-3. The breakdown of the classical theory

The energy of a harmonic oscillator of natural angular frequency OJ

may be written
(2-8)
where the first term on the right represents the kinetic energy (p is the
momentum) and the second term represents the potential energy (q is the
deflection from the equilibrium position). It is well known that the average
energy of a harmonic oscillator according to classical statistical mechanics
is given by
(2-9)

where T is the absolute temperature and k is Boltzmann's constant. It is

important to note that the frequency does not enter in this result. In
other words, the vibrational energy of a crystal of N atoms is classically
always equal to
E= 3NkT (2-10)
independent of the assumed frequency distribution of the oscillators used
in the model. Now, as long as the volume of the solid is kept constant,
(2-10) is the only temperature-dependent contribution to the total energy
of the system. Thus, for a solid containing one type of atoms and putting
N equal to the number of Avogadro, one obtains for the specific heat
per gram atom,
Cv = 3Nk = 3R = 5.96 cal degree~l mole~l (2-11)
where R is the gas constant. Similarly, if the solid consists of N atoms A
and N atoms B, the specific heat per mole would be 6R, etc. The result
36 SPECIFIC HEAT AND LATTICE VlBRATIONS [Chap. 2
obtained is in quantitative agreement with experiment (if sources of the
specific heat other than lattice vibrations are subtracted) at high tempera-
tures only. In other words, it does not explain the decrease of the specific
heat at low temperatures, as observed for all solids. This discrepancy is
essentially removed when quantum theory is used, as will be seen below.
It may be noted that the classical theory led to similar difficulties in the
specific heat of molecules.

2-4. Einstein's theory of the specific heat

A great step forward toward an understanding of the specific heat

curves at low temperatures was made by Einstein in 1906. 3 Although the
physical model employed by Einstein was oversimplified, his results
definitely indicated that quantum theory contained the answer to the
difficulty encountered in the classical theory. He assumed that a solid
element, containing N atoms, could be represented by 3N harmonic
oscillators of the same frequency 'V. This model implies that the atoms
vibrate independently of each other, their frequencies being the same
because of their assumed identical surroundings. For the average energy
of an oscillator Einstein made use of a result obtained by Planck in 1900,
in connection with the theory of black-body radiation. According to
Planck, a harmonic oscillator does not have a continuous energy spectrum,
as assumed in the classical theory, but can accept only energy values equal
to an integer times hy, where h is Planck's constant. The possible energy
levels of an oscillator may thus be represented by4

n = 0, 1, 2, 3, ... (2-12)

By replacing the integrals appearing in (2-9) by summations, one thus

obtains for the average energy the expression

(e) = ~ nhve-nhv/kTj ~ e-nhv/kT (2-13)

n~O n~O

To evaluate this expression, first consider the denominator

S = ~ e-nhv/kT = (1 _ e-hv/kT)-l
n~O

Differentiating with respect to IjkT, one obtains

oS 00 hye- hv/ kT
- 2: nhve -nhv/kT -
o(ljkT) - - n=O - - (1 - e- hv/ kT )2

It is observed that the expression in the center is identical with the

3 A. Einstein, Ann. PhYSik, 22, 180, 800 (1906); 34, 170 (1911).
4 See any Introduction to Modern Physics.
Sec. 2-4] SPECIFIC HEAT AND LATTICE VIBRATIONS 37
numerator in (2-13). Substitution into (2-13) thus leads to the well-known
Planck formula for the average energy of an oscillator at a temperature T:
hv
(E) = e hv / kT _ I (2-14)

We emphasize that in contrast

with (2-9), this expression contains v'" .5
the frequency of the oscillator. The
temperature dependence of (E) is t
illustrated in Fig. 2-3, showing o 2 4
(E)jkT as function of hvjkT. Note ---+ hv/kT
that at high temperatures (E) c:::: kT, Fig. 2-3. The average energy in units of
in agreement with the classical kT of a harmonic oscillator of frequency v
theory. However, at low temper- as a function of hv/kT, according to Planck.
atures, (E) decreases exponentially
to zero. In the Einstein model, the vibrational energy of a solid element
containing N atoms is thus equal to , ':' '" L__ .'
hv
E = 3N(E) = 3N hvlkT . 1 (2-15)
e -
\
The specific heat at constant volume is therefore per mole

C = ~ E = 3R (_h_v ) 2 -,--;:--"e""hV,/k_T-----: (2-16)

V oT kT (e hv/ kT - 1)2
Before discussing this result, it may be remarked that according to
quantummechanics, the possible energy levels of a harmonic oscillator
are given by
En = (n + t)hv n = 0, 1,2, '" (2-17)

rather than by (2-12). 5 This has the effect of shifting all energy levels by
the constant amount of hv/2, and instead of (2-14), one obtains
hv hv
(E) = 2' + e hv/kT _ I (2-18) (

The first term is called the zero-point energy of the oscillator because
(E) = hv/2 for T = 0. Thus, according to quantum mechanics, the atoms
have vibrational energy even at absolute zero. The expression for the
specific heat is not altered by this result, because C v is determined by the
derivative of (E) with respect to T.
With regard to (2-16) it is observed that for kT,:?> hv, this expression
reduces in first approximation to the classical result (2-11). At low
temperatures, however, the specific heat decreases. To discuss this
5 For a proof see any introduction to wave mechanics.
38 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2
behavior, it is convenient to introduce the Einstein temperature ()E'
defined by
hv = kO R (2-19)

Expression (2-16) may then be written in the form \

(2-20)

where FE is called the Einstein function; it determines the ratio of the

1.0 De~ye
~ ..
.8 / .~ EinstelU

/V
h'
.._
~

k;

VI
.6

t .4

.2 / 1/
1;
o .2 .4 .6 .8 1.0 1.2 1.4 1.6 1.8 2.0
_Till \

Fig. 2-4. The Debye and Einstein functions as function of TlfJ.

specific heat at a temperature T and the classical (high-temperature) value

3R. The Einstein function is represented in Fig. 2-4, together with the
Debye function, which will be discussed in Sec. 2-6; We see that the curve
'Obtained has the same appearance as the observed specific heat curves.
On the other hand, the Einstein curve deviates from the experimentally
observed ones in the region of low temperatures. Experimentally, it is
found that for most solids the lattice specific heat at very low temperatures
(liquid helium) is proportional to T3. However, for T <
()E' equation
(2-20) leads to a specific heat proportional to exp (-()E/T). In other
words, the Einstein function falls off more rapidly at low temperatures
than it should. The reason for this. discrepancy must be sought in the
oversimplified model employed by Einstein. In fact, we shall see in the
next sections that rather than a single frequency v, the vibrational spectrum
of a solid covers a wide range of frequencies. This, in turn, is a result of
the fact that the atomic vibrations in a crystal are strongly coupled and
cannot be considered independent. On the other hand, because of its
simplicity, the Einstein model is frequently used in problems in which
lattice vibrations playa role.
Sec. 2-5] SPECIFIC HEAT AND LATTICE VIBRATIONS 39

2-5. The vibrational modes of a continuous medium

In the preceding section it was pointed out that the discrepancy
between the Einstein theory and experimental results in the low temperature
region was a consequence of the oversimplified model employed by
Einstein. In 1912, Debye tackled the problem from a different point of
view and, as we shall see, with great success. 6 Debye realized that it is
possible to propagate waves through solids covering a wavelength region
extending from low frequencies (sound waves) up to short waves (infrared
absorption). The essential difference between the Debye model and the
Einstein model is that Debye considers the vibrational modes of a crystal
as a whole, whereas Einstein's starting point was to consider the vibration
of a single atom, assuming the atomic vibrations to be independent of
each other.
In the present section, we shall deal with the vibrational modes of a
continuous medium, because the results are basic to the "continuum
theories" of the specific heat. Let us first consider for simplicity the

l
rational modes of a one-dimensional continuous string of length L.
ppose u(x,t) represents the deflection of the string at the point x at the
stant t. The waves may then be described by the one-dimensional wave
, equation
(2-21)

where Cs is the velocity of propagation of the waves. If it is assumed that

the end points of the string are fixed, the solutions of (2-21) are those
corresponding to standing waves:
u(x,t) = A sin (mrx/L) cos 27Tl1nt (2-22)
where n is a positive integer? 1. The wavelengths and frequencies of the
possible vibrations represented by (2-22) are given by
I An = 2L/n and Vn = cs/An = c_n/2L (2-23)
The frequency spectrum is discrete, one frequency corresponding to each
integer value n. Note that for the one-dimensional string the frequency
spectrum corresponds to an infinite number of equidistant lines, as
illustrated in Fig. 2-5a. The number of possible modes of vibration in a
frequency interval dv is, on the average, equal to
dn = (2L/c s ) dv (2-24)
In the three-dimensional case, the wave equation reads
2 2 2 2
3u 3u 3u 1 3u
-+-+-=_.-
ex2 of OZ2 c; ot 2 (2-25)

• P. Debye, Ann. Physik, 39, 789 (1912).

40 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2

Assuming a continuous medium in the shape of a cube of edge Land

assuming the faces of the cube to be fixed, the possible standing wave
solutions are, in analogy with (2-22),

u(x,y,z,t) = A sin (n x 1Tx/L) sin (n y 1Ty/L) sin (n.1Tz/L) cos 21T'Ilt (2-26)

where now nx , ny, and nz are positive integers 31. Substituting this
solution into the differential equation (2-25), one obtains the following
expression for the possible modes of vibration:

(2-27)

Thus the possible wavelengths and frequencies are determined by three

integers in this case. Let us now ask the question: What is the number

Z(I') Zip)

1 t

_v _v
(b)

Fig. 2-5. (a) Frequency spectrum for a finite continuous string,

according to (2-24). (b) Frequency spectrum for a three-dimen-
sional continuum, according to (2-30).

of possible modes of vibrations Z(v) d'll in the frequency interval between

'11 and 'Il + d'll? To anSwer this, consider a network of points, each point
being determined by three Cartesian positive integer coordinates niX' ny,
and nz • Writing
(2-28)

it is evident that the number of points in a shell between Rand R + dR

,A. is equal t0 7
(2-29)

7 Each point occupies on the average a unit volume in the integer space.
Sec. 2-5] SPECIFIC HEAT AND LATTICE VIBRATIONS 41
Now, each point corresponds to a set of three integers nx , ny, n z , and each
set of integers determines, according to (2-26), a possible mode of
vibration; hence (2-29) immediately gives the number of possible modes
of vibration in a given range. Expressing R in terms of v in (2-29) one
thus finds
(2-30)

where V is the volume of the solid. For a perfect continuum, the possible
frequencies vary between 0 and IX, the number of such possible vibrations
increasing with the square of the frequency (see Fig. 2-5b). This situation
holds, for example, in the case of electromagnetic waves in a box of
volume V. Expression (2-30) is therefore basic in the theory of black-body
radiation.
In the case of elastic waves, we may distinguish between transverse and
longitudinal waves. In general, the velocities of propagation, say C t and
c" respectively, will not be equal. To set up an expression for Z(v) dv in
this case one should keep in mind that for each frequency or wavelength
there are two transverse modes and one longitudinal mode. 8 Thus,
instead of (2-30) one obtains

Z(I') dv = 47TV (.~ + ::l) v

I I
2
dv (2-31 )

How this expression has been used in the theory of the specific heat of
solids will be discussed in the following two sections.

2-6. The Debye approximation

One may wonder what the discussion of the preceding section could
have to do with the specific heat of crystals, which are by no means
continuous but are built up of atoms, i.e., of discrete "mass points."
The reason is the following: Consider an elastic wave propagated in a
crystal of volume V. As long as the wavelength of the wave is large
compared with the interatomic distances, the crystal "looks like" a
continuum from the point 'of view of the wave. The essential assumption
of Debye is now that this continuum model may be employed for all
possible vibrational modes of the crystal. Furthermore, the fact that the
crystal actually consists of atoms is taken into account by limiting the
total number of vibrational modes to 3N (see Sec. 2-2), N being the total
number of atoms. In other words, the frequency spectrum corresponding
to a perfect continuum is cut off so as to comply with a total of 3N modes
(see Fig. 2-6a). The Debye cut-off procedure leads to a maximum
8 In the longitudinal modes, the deflection is along the direction of propagation;

in the transverse modes the deflection is perpendicular to the direction of propagation,

which gives two independent components.
42 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2

frequency VJ) (the Debye frequency) common to the transverse and

longitudinal modes; it is defined by
'I'lJ
l Z(v) dv = 417V :;
• (I C
+:;
C •0
(2 I)
II["lJ v2 dv = 3N (2-32)
t 1
or

vJj'=
.. 9N
417 V
(2 + 1)-1 \
c:; c:; (2-33) ,~~
t 1

where Z(v) as given by (2-31) has been used. It should be noted that this
procedure assumes that the velocities c t and c/ are independent of the

Z(v) Z(v)

t t
\

_p
(bl

Fig. 2-6. The Debye cut-off takes place at the Debye frequency
VlJ' common to the transverse and longitudinal modes (a), In
Born's procedure, the cut-off takes place at a common minimum
wavelength, corresponding to the maximum frequencies v, and v,
for the transverse and longitudinal modes respectively .(b). Note
that c, <: Ct.

wavelength, as in the continuum, It will be seen in Sec. 2-9 that this is not
correct for actual crystals. The order of magnitude of V]) may be obtained
by taking Nj V ~ 1022 per cm 3 and using for the velocity of sound
.--.!(}' em sec~I. This gives Vj) ~ 1013 per second. This corresponds to a
minimum wavelength of the order of one Angstrom, indicating that the
continuum theory may be at fault, especially in the high-frequency region.
Associating with each vibrational mode a harmonic oscillator of the
same frequency, one finds from (2-31) and Planck's formula (2-14) for
the vibrational energy of the crystal,

r"}) Z(v) (kT)3 3

hI' l'I m x dx
E= e''''lk1' dl' = 9N h-. kT -- (2-34)
.11 -·1 v D · o e"-l

where x = hv/kT and x", = hVlJ/kT. Here, as in the Einstein theory, it is

convenient to introduce a characteristic temperature; thus one defines the
Debye temperature as
(2-35)
Sec. 2-6] SPECIFIC HEAT AND LATTICE VIBRATIONS 43
The upper limit of integration is then equal to Xm = () niT. It is observed
that for high temperatures (T ;?> () n), x is small compared with unity for
the whole range of integration. In that case, the denominator of the
integrand in (2-34) may be replaced in first approximation by x. This
yields for the specific heat,

a result identical with the classical theory.

In the case of very low temperatures, such that T < ()[), the upper
limit of integration in (2-34) may be replaced by infinity. NOW,9

x 3 dx I 1T4

t
- 'l) CL

J (I e~ - I = 6 n4 = 15
so that
E = ~1T4 NkT(T/() ])3 for T < (j]) ( __ (2-36)

Thus the energy of vibration is proportional to T4 at low temperatures

(for the theory of black-body radiation, which may be treated in a
completely analogous way, this is the case at any temperature, because
there the upper limit to the frequency does not exist). The specific heat
at low temperatures according to Debye is thus given by

(2-37)

This is the famous Debye T3 law, which should hold for T ,;;; (}[)11O. The
genera!' expression for the specific heat as function of temperature may
be obtained by differentiating (2-34) with respect to T. For I mole of
substance one obtains in this way
(8..!.!.)
. ! ••. \

Cv = ( T):l
3R' 3.-
(}])
(0 /1'
I,
.0
D x
(e -
e X x4
I)
2 dx = 3RFD T
(2-38)

where FJ) is the Debye function. It has been represented in Fig. 2-4
together with the Einstein function. The reason that the Debye curve lies
above the Einstein curve is a result of the fact that in the Debye model,
the low-frequency modes are taken into account; at low temperatures
these have a higher average energy and temperature derivative than the
relatively high-frequency Einstein oscillators, as is evident from the
Planck formula (2-14).
To illustrate the agreement between the Debye theory and experi-
mentally observed specific heat curves, we reproduce in Fig. 2-7 measure-
ments on silver fitted to a Debye curve. From such curves it is possible
• E. T. Whittaker and G. N. Watson, Modern Ana~ysis, 4th ed., Cambridge, London,
1935, p. 265.
44 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2

to calculate the Debye temperature of the solid involved. Some t¥ical

examples are given in Table 2-1. <

6 cal/mole deg

\1
Cv
t
1 '\' ~

o 40 80 120 160 200 240 280 320 360

--T
Fig. 2-7. Comparison of the Debye specific heat curve .and
observed values (dots) for silver; the ordinate is in cal mole- 1
degree-l.

Table 2-1. Debye Temperature in Degrees Absolute for a Number of Solids

Solid OIJ Solid OIJ Solid On

I
Na 150 Fe 420 C (diam.) 1860
K 100 Co 385 NaCl 281
CII 315 Ni 375 KCI 230
Ag 215 AI 390 KBr 177
Au 170 Ge 290 AgCl 183
Be 1000 - Sn 260 AgBr 144
Mg 290 Pb 88 CaF. 474
Zn 250 PI 225
Cd 172

Notwithstanding the great success of the Debye approximation,

accurate measurements in the' low-temperature region show deviations
from the theoretical predictions. According to the Debye theory, the
T3 law should hold in the temperature region T ,,;; 0.18D' That this is not
always the case may be seen from some examples given in Table 2-2,
reproduced from Blackman's paper,lo
The () D values given in the table are calculated from (2-37) and should
be constant if the T3 law was satisfied. Similar deviations have been
found in other materials. There seems little doubt that these deviations
10 M. Blackman, Repts. Progr. Phys., 8, 11 (1941).
Sec. 2-6] SPECIFIC HEAT AND LATTICE VIBRATIONS 45
Table 2-2. Deviations from the T3 Law

NaCI KCI ./ Li
I
T On 10'C,·IT' T 10'CvlT' T O/J 10'C .. IT'
20 288 0.388 14
°D
213 0.960 30 356 0.101
IS 297 0.356 8 222 0.832 20 340 0.118
10 308 0.334 4 236 0.708 15 328 0.131
3 227 0.798

are a result of the deficiencies oftne continuum approximation, a conclusion

which is supported by the work of Blackman and Kellermann,ll the
results of which will be briefly discussed in Sec. 2-13. According to
Blackman one may expect the T3 law to hold for the temperature region

" :;..-,~
3.0 xlO- 3
'"
bI)
OJ
"0
OJ
-0
S
.... 2.0
ta
.<:
--
-a'"
OJ

.g
h
--
cS
1.0

t
15 20

Fig. 2-8. Comparison of the T'law and observed values for KCI.
[After P. H. Keesom and N. Pearlman, ref. 121

T 0(; OD/50, i.e., at considerably lower temperatures than predicted by the

Debye approximation. The P law is illustrated in Fig. 2-8 for Kel,
representing results obtained by Keesom and Pearlman. 12

2-7. The Born cut-off procedure

A modification of the Debye theory was introduced by Born, who

proposed a different cut-off procedure. In the preceding section it was
II E. W. Kellermann, Phil. Trans., A238, 513 (1940); Proc. Roy. Soc., AI7!!. 17

( 1941).
12 P. H. Keesom and N. Pearlman, Phys. Rev., 91,1354 (1953).
46 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2
noted that in the Debye theory, the maximum frequency VJ) was common
to both the longitudinal and the transverse modes. Born proposed to
cut off the spectrum in such a manner that the longitudinal and transverse
modes have a common minimum ware/ength. This, as will becpme
evident from the discussion in the following sections, is actually more
sound theoretically speaking and in line with the theory of lattice vibrations
developed by Born and von Karman. 13 Thus if one takes the common
minimum wavelength equal to
Alliin = (41TV/3N)l(3 (2-39)
one obtains two Debye frequencies, one for the longitudinal modes and
one for the transverse modes, viz.,

(2-40)

That this procedure leaves the total number of vibrational modes equal
to 3N follows immediately from (2-31) and (2-40), because

I
41TV ( ',. t"3
.0
2 v2 dv
c/
+ .0I,r" '--::lv
1 2 dv ) =
[/
3N

The frequency distribution according to this cut-off procedure is represented

in Fig. 2-6b and may be compared with that used by Debye. We leave it
up to the reader to show that Born's modification leads to the following
expression for the specific heat:

(2-41)

This expression should be compared with (2-38); ()l and ()t are the Debye
temperatures corresponding to the longitudinal and transverse modes.
Apart from the different cut-off procedure, the model is open to the same
objections as the Debye theory.

2-8. Elastic waves in an infinite one-dimensional array of identical atoms

The weakest point in the model employed in the Debye theory is the
assumption that 'the continuum representation of a crystal holds for all
possible elastic waves. In fact, we have seen that the minimum wavelength
is of the same order of magnitude as the interatomic distances and we
may thus expect that a more rigorous treatment might give different
results, especially in the high-frequency region. In the present and the
following sections we shall therefore discuss the principles of finding the
possible modes of vibration of atomic lattices. The original work is due
13 M. Born, Atomtheorie des j'esten Zustal1des, Leipzig (1923); M. Born and Th. von

Karman, Phys. Z., 13,297 (1912); 14,15 (1913).

-I ""
,Sec. 2-8J SPECIFrC HEAT AND LATTICE VIBRATIONS 47
to Born and von Karman13 and to Blackman.1° To begin with, consider
an array of equidistant mass points as represented in Fig. 2-9; the particles
all have a mass 111, and for the
moment the array will be con-
n-l n n+l sidered infinitely long. It will be
•_ a--+{• •I •I • assumed that there exists interac-
l-9 ~ ~ tion only between nearest neigh-
IXn_1 IXn I Xn +1
bors and that Hooke's law is
obeyed.14 In equilibrium let the
Fig. 2-9. Linear chain of identical mass
distance between neighboring
points. The black dots represent the
equilibrium positions, the open circles the particles be a; the deflections
displaced particles. from the equilibrium position will
be denoted by x o, Xl' X 2 , ... , X n - 1 ,
X,,, Xu cl' ...• The equation of motion- of particle n is then
111.;;" =0 -/(x" -- X,,_l) - f(x" - x,,-tl) = /(X 71 - 1 + X"+l - 2x,,) (2-42)
where / is the force constant describing the nearest neighbor interaction.
We may try to solve this equation by a running wave of the type
x,,(t) = e-i,o(l-"a1cs) = e-i(wt-qna) (2-43)
where c, is the velocity of propagation of the wave, q = wlc = 2171). is
the wave vector and na the equilibrium position of particle n relative to
the origin. Substituting this solution into the differential equation (2-42),
one obtains after dividing through by X"'

/1/(')2 = _/(e- iqa +e iqa

- 2) = ,!(sin 2 (qaI2) (2-44)
or
(,) = wmnx sin (q aI2) with w~laX = 4flm
We have thus obtained an expression for the frequency of the waves in
terms of the wave vector q, i.e., in terms of the wavelength. To each
wave vector q corresponds a frequency ('J •• The relationship has been
represented in Fig. 2-10, curve a. It is important to note that for a con-
tinuous string, the frequency v would be equal to qC,,/217, i.e., v would be
proportional to the wave vector q as illustrated by curve b in Fig. 2-10.
We are thus led to the conclusion that a continuous string and an array
of mass points give identical results only if qa 1, i.e., when the wave- <
length is large compared with the interatomic distance. This we had
expected. The difference between a continuous string and an array of
mass points may also be expressed in this way: the velocity of propagation
in a continuous string is independent of the wavelength, whereas in an
array of mass points the velocity of propagation becomes smaller as the

362 l
II For a more general treatment, see L. Brillouin, Wave Propagation in Periodic

Struc/llres, Dover, New York, 1953.

~'" I r-rc: 1"\1:' C A c l r c::rfJ:'NrJ:'C::

48 SPECIFIC HEAT AND LATTICE VJBRATIONS [Chap. 2

wavelength decreases. It is evident that this result must have a bearing

on the theory of the specific heat, because in the continuum models it
was assumed that Cs is a constant.

\
\ b
\
w
'\
bj
/\

\ I
\
\
\
\
~

-2tr/a o tria 2tr fa

I--- 2nd -+---- 1st - - - + - 2nd --l
..\ \

Fig. 2-10. Frequency of elastic waves in a mono-atomic linear

lattice as function of the wave vector q. The dashed lines corre-
spond to a continuous string. The first and second Brillouin
zones arc indicated.

Another important result which follows from the above discussion

may be obtained by comparing the solution (2-43) with another in which
q has been replaced by
qm = q + 2Trm!a with 111 = ± I, ±2, ... (2-45)

First of all, it follows from (2-44) that the frequencies corresponding to

the modes q and qm are identical. From this, and from the fact that
exp (2Trim) = I, it then follows that the solutions (2-43) with q and qlll
are identical. In other words, the state of vibration of the array of mass
points corresponding to a wave vector q is the same as that for any of
+
the wave vectors q 2Trm!a. In order to obtain a unique relationship
between the state of vibration of the lattice and the wave vector q, the
latter must be confined to a range of values 2Tr!a. Usually one chooses
the range such that
-Tr!a ~ q ~ Tr!a (2-46)

The positive q values correspond to waves propagated in one direction,

the negative q values represent waves going in the opposite direction (see
2-43). It also follows from the above discussion that the frequency is a
periodic function of q, as illustrated in Fig. 2-10. Th.; region of q values
defined by (2-46) is referred to as the first Brillouin zone. The second
zone consists of two intervals of half a period each, one on each side of
~ -;.. ..
-
r

Sec. 2-8] SPECIFIC HEAT AND LATTICE VIBRATIONS 49

the first zone as indicated in Fig. 2-10. Higher-order zones are defined in
a similar manner.
It is interesting to note that according to (2-44) there exists a maximum
frequency 1'lllilX which can be propagated through the chain, viz.,

V"",x = ~
77
(L) 1/~
171
(2-47)

The chain may thus be considered a low-pass filter which transmits only
in the frequency range between zero and V lllax ' Tn contrast with this, the
continuous string has no frequency limit. The maximum frequency of the
chain of atoms occurs when the wave vector is equal to 7T/a, i.e., for a
wavelength Alliin = 2a. Now a'_' 10- 8 cm and the velocity of sound In
solids is of the order of 105-106 cm sec-I; this gives VllIilX -::::= 1013 sec-I.

2-9. Vibrational modes of a finite one-dimensional lattice of identical atoms

In the preceding section the discussion referred to an infinite lattice;
in the present section we shall see how the boundary conditions required
for a finite lattice lead in a natural manner to an enumeration of the
possible modes of vibration. The boundary conditions may be introduced
in either of two ways, which will now be discussed:

I. Boundary conditions leading to standing waces. Consider an array

of (N + I) similar atoms, numbered from zero to N. Suppose the two
end atoms are fixed, so that (N - I) atoms are mobile. The general
solution of the equation of motion (2-42) for a single wavelength may be
written as the sum of two running waves, one propagating to the right,
the other to the left:
(2-48)
Here AI and A 2 are amplitudes, and (31' (32 are phase angles. The boundary
conditions are
xo(t) = 0 and xs(t) = 0 for all t
The first of these, when substituted in (2-48), requires Al = -A2 and
~I = (32' Since the phase angles are equal, we shall choose (31 = (32 = O.
Taking the real part of the remaining solution, one obtains
x,,(t) = 2Al sin qna sin (')t (2-49)
which represents a standing wave. These solutions lead to the same
relationship between (,) and q as the running wave solutions, viz., to
(2-44). Furthermore, q is now limited to positive values ranging from
o to 77/a. The second boundary condition imposed on (2-49) selects a
discrete set of q values, viz., those which satisfy the condition
sin qNa, = 0 or q = (7T/Na)j (2-50)
50 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2

where j is an integer. Note that j = 0 must be excluded, since this corre-

sponds to q = 0, i.e., all particles arc at rest. The maximum value of q,
viz.,' 1Tla gives jllm = N; however, this value must be excluded for t'le
same reason as j = 0. We thus conclude that

j = 1,2,3, ... ,(N - I) (2-51)

I n other words, there are just as many modes of ribration (q-values) as

there are mobile atoms.
To each value of q there corresponds a value of the frequency (lJo' •
Hence the frequency spectrum consists of (N - I) discrete lines. For
macroscopic chain lengths the spacing of the lines is so close that we may
speak of a quasi-continuous spectrum.
2. Another way of introducing the boundary conditions has been
proposed by Born and von Karman; they are called cyclic or periodic
boundary conditions and they are very convenient in the running-wave
representation of the vibrational modes. Suppose for a moment we had
a circularly shaped chain of atoms, the interatomic separation being a.
Let the length of the chain be L = No, where the number of atoms
N j;> 1. If the atoms are numbered I, 2, 3, ... ,N going around the
circle, the boundary condition that applies here is

X,,(t) = Xn+N(t) (2~52)

because the subscripts nand n +

N refer to the same particle. Applying
this to the running wave (2-43), this condition may be written

eiqna = eiq(n+N)a or q = (21TINa)g = (21TjL)g (2-53)

where g is an integer. Now, in accordance with (2-46), q is confined to

the region between -1Tla and 1Tla. In other words, the possible values
for g are
g = ±I, ±2, ±3, ... , ±N12 (2-54)

(the value g = 0 gives q = 0, corresponding to all particles at rest; this

value must therefore be omitted). The total number of different g values
(or q values) is thus equal to N. We are thus led to the same conclusion
as arrived at under (I), viz., that the number of possible vibrational
modes of a chain of atoms is equal to the number of atoms which are
free to move. In the running-wave picture, however, q can accept positive
as well as negative values; in the standing-wave representation q is always
positive. Here again, the frequency spectrum forms a discrete set of lines.
The number of possible modes in a wave vector interval dq in the case of
the running wave representation is, according to (2-53) equal to
(2-55)
Sec. 2-9] SPECIFIC HEAT AND LATTICE VIBRATIONS 51
In the standing wave representation the corresponding number is,
according to (2-50),
dj = (L/1T) dq (2-56)

In (2-55), q ranges from -1T/a to 1T/a, in (2-56), from 0 to 1TJa. This

accounts for the difference of a factor 2 in the two expressions, the total
number of vibrational modes being the same for the two representations.
Actually, one is, of course, not particularly interested in circular
chains of atoms. However, as long as N ~ I, one'can employ the boundary
condition (2-52) also in the case of a linear chain. Imagine, for example,
an infinite one-dimensional lattice divided into macroscopic sections of
length L = Na. From the physical point of view, each section should
have the same properties as a circular chain of length L, because as long
as N~ 1, each atom would "see" the same atomic (.;onfiguration, the
interaction between the atoms being confined to very small distances.

2-10. The equivalence of a vibrational mode and a harmonic oscillator

In Sec. 2-2 it was pointed out that the central problem of the specific
heat of solids is the determination of the possible modes of vibration of
the lattice under consideration. Once the answer to this question has
been obtained, the vibrational energy of the solid is calculated on the
assumption that the energy corresponding to a particular mode is the
same as that of a harmonic oscillator of the same frequency. In the present
section we shall show for the simple one-dimensional lattice of identical
atoms that this identification is justified. For a general treatment of the
three-dimensional case we refer to the literature. I5
It is well known that the energy of a harmonic oscillator of mass M
and angular frequency w may be written

where y is the deflection and p = M dyJdt is the momentum. In terms of

y alone, we may write
i
E = iM(dyJdt)2 + Mw 2y 2J2 (2-57)
We shall now show that the energy associated with a vibrational mode
can indeed be written in the form (2-57). Let us consider a mode corre-
sponding to a standing wave sin qna cos wt. The kinetic energy of the
particles in the lattice resulting from this vibrational mode is equal to

E kin =-= 2m ~ (~n) 2 = ~mw2 sin2 wt L: sin 2 {Ina (2-58)

15 M. Born and M. Goppert-Maye ANG RAU Central

d
Library
see also F.
Seitz, Modern Theory of Solids, McGra Hili. Ne Hyderaba
635
11111111111111111 \\III I111 1111
•
52 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2

where m is the mass per atom and the summation extends over aU particles
in the chain. The potential energy of the system due to the vibrational
mode q is a function of all coordinates Xn; let it be denoted by
V(xo, Xl' ... , X n , •.• ). The force exerted on patticle n is then, in accordance
with (2-42), _ - \ .
oV d 2x n - ,
xn t
+
- d- = m d 2 = !(xn - 1 x n +1 - 2x,,) (2-59)

from this one may arrive at the following expression for the potential
energy

(Note that each of the mixed terms appears twice in the summation,
providing agreement between the last two equations; this may readily
be verified by writing out the sum explicitly.) Substituting the standing
wave solution int@ (2-60), one obtains after some manipulation,

v = 21 sin 2 (qa/2) cos2 wt 2:n sin2 qna (2-61)

Making use of the relation between wand q as given by (2-44), one may
write
v = imw2 cos2 wt 2: sin2 qna
n
(2-62)

The total vibrational energy resulting from mode q is obtained by adding

(2-58) and (2-62), leading to

E = tmw2S with S = 2: sin 2 qna (2-63)

n

Note that this expression is independent of time. Suppose now we

identify (2-62) with the potential energy of a harmonic oscillator, i.e.,
with the last term in (2-57). This requires evidently

y = (mSjM)1/2 cos wt (2-64)

If the vibrational mode were indeed equivalent with a harmonic oscillator,

the kinetic energy should be, according to (2-57) and (2-64),

E kin = tM(dyjdt)2 = tmw2S sin 2 wI

This expression is identical with (2-58), which proves the sought equi-
valence. The average energy associated with a particular mode of
vibration of angular frequency Wq is thus given by Planck's formula
(2-14), i.e.,
(2-65)
Sec. 2-101 SPECIFIC HEAT AND LATTICE VrBRATIONS 53
The number of quanta no associated with the vibrational mode of wave
vector q at a temperature T is

(2-66)

The quanta are commonly referred to as phonons of frequency (Oq, in

analogy with photons in the case of electromagnetic radiation. The
concept of a phonon is convenient in the discussion of interaction of
electrons with lattice vibrations in the theory of electrical conductivity.
A phonon, like a photon, has particle aspects in the sense that one can
associate with it a certain energy hVq = liwq as well as a momentum
p = hvqlc" where C s is the velocity of propagation of the vibrational mode.
Thus the "collision" between a phonon and an electron may be treated
as a collision between two particles for which the conservation laws of
energy and momentum hold. >- i

r 2-11. The specific heat of a one-dimensional lattice of identical atoms

From the results obtained in the preceding sections it is a simple
matter to derive an expression for the specific heat of a one-dimensional
lattice of identical atoms. In the standing-wave representation the number
of modes in the wave vector interval dq is, according to (2-56), equal to
L dql7T where L is the length of the chain. The wave vector is confined
between 0 and 7Tla. The vibrational energy of the lattice at a temperature T
is thus given by
E -- ~ In-fa liwq d (2-67)
_. 7T 0 exp (liwqlkT) - I q

where the summation over the possible wave vectors defined by (2-50)
has been approximated by an integral. Employing the relation between
Wq and q as given by (2-44), one may replace dq by

dq dw = 2du) 2dw
(2-68)
dw aw llH1X cos (qaI2) a(w~lax - (1)2)1/2

Hence
E _ 2L (w max liw dw
(2-69)
- 7Ta.lo [exp (liu)lkT) - l][w;nax - (02]1/2

The specific heat as function of temperature may be obtained by dif-

ferentiating with respect to T. The result is represented by the lower
curve in Fig. 2-11 for a critical temperature e = liwmaxlk = 200oK. It is
of interest to compare this result with the continuum theory corresponding
to the Debye approximation in one dimension. According to (2-24) the
54 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap. 2

number of vibrational modes in the range dw of a continuous string of

length L is equal to L dW/1TCs ' where the velocity of propagation Cs is a
constant. Applying this model to a
2.0 cal/mole deg string of atoms by a suitable cut-off
of the frequency spectrum, one
obtains for the vibrational energy
1.5
E= _£ I' w~.x liw dw
1TC• . 0 exp (liw/kT) - 1
Cv
(2-70)
f 1.0
The upper limit W~,ax in this case is
determined by the fact that the num-
ber of modes is equal to the number
.5
of particles N in the string, i.e.,

fw~ax
(L/1TC.) Jo dw = N
o 20 40 60 80 100 120 140
or (2-71)
--+ TI'K)
w:Uax = N1TC./L
Fig. 2-11. Curve a represents the
specific heat versus Tfor a monoatomic Note that this limit is different from
linear lattice according to (2-69); curve that appearing in (2-69). The specific
b refers to the Debye theory, represent- heat calculated on the basis of (2-70)
ing Cv derived from (2-70). In both
is given by the upper curve in Fig.
cases e = 200oK. [After M. Blackman,
Proc. Roy. Soc., London, Al48, 365 2-11 again for a critical temperature
(I 935)J () = Iiw:Uax/ k = 200oK.

2-12. The vibrational modes of a diatomic linear lattice

Consider a diatomic lattice in one dimension as illustrated in Fig. 2-12;

the distance between nearest neighbors will be denoted by a. The particles
are numbered in such a way that
the even numbers have a mass M,
the odd ones m. In analogy with
o • M
2n 2n+l
o
m M
o
m
• o .
(2-42) we now have the following
equations of motion, assuming Fig. 2-12. A linear chain of equidistant
nearest neighbor interaction only: masspoints M and m.

MX 2n = !(X2n- 1 + x 2n+l - 2x2n )

mX 2n +1 = !(X2n + X 2n +2 - 2x 2n +1) (2-72)
We try to solve these equations by running waves of the type
x2n = Ae- i (wt-2nQ a l and X
2n
+1 = Be- i [w t -(2n+!lqal (2-73)
where q is the wave vector of a particular mode of vibration; A and B
Sec. 2-12] SPECIFIC HEAT AND LATTICE VIBRATIONS 55
are the amplitudes corresponding to particles of mass M and IJI, respec-
tively. Substitution of the solution into (2-72) yields the following two
equations:
(Mw 2 - 2f)A +
2Bfcos qa =- 0
(mu)2 - ~()B + 2Af cos qa = 0 (2-74)

This system flas nonvanishing solutions for A and B only if the determinant
of the coefficients of A and B vanishes, i.e.,

I (Mw
2
- 2f) 2f cos qa I
~lcos qa
(2-75)
I (/17('j2 -- 2f) = 0
This gives for the square of the frequency the following two possihilities:

(I + MI) ±f [(I;;; + M1')24Sin

2qa]1/2
(,,2 =f ;;; - Mm (2-76)

Since ('j should be positive, each value l

of (,)2 leads to a single value for ('j. '"
Thus in contrast to the monoatomic
lattice, there are now two angular (2f/mjl/2
frequencies (')+ and O)_ corresponding
to a single value of the wave vector q. (2f/M j l/2
In a plot of (') versus q (Fig. 2-13) this
leads to two "branches"; the one
corresponding to ('j_ is called the -11' /2a o 11' /2a
acoustical branch, the one associated
with w+ is the optical branch. These
two branches will now be discussed on Fig. 2-13. The optical (upper
the assumption that M > m. For curve) and acoustical (lower
q ~= 0 we obtain curve) branches corresponding to
a diatomic linear lattice.

£0+= [2f(~+ ~)]1/2 and (')_=O for q=O (2-77)

From the form of (2-76) it is observed that here, as in the monatomic case,
the frequency is a periodic function of the wave vector. The first zone
thus limits the values of q to the range between -1TJ2a and +1TJ2a as
shown in Fig. 2-13. For q = ±1Tj2a, the two angular frequencies are
evidently
w+ = (2fJm)1/2 and w_ = (2fJM)1/2 for q = ±1TJ2a (2-78)
The complete curves for £0+ and (O_ versus q are illustrated in Fig. 2-13.
The larger the mass ratio MJm, the wider the frequency gap between the
two branches. The existence of a "f.k)rbidden" f~~~l'-JWl:""IWWJ-.__
, " " l ) eEl>! d{AL LIBRAR Y
56 SPECIFIC HEAT AND LATTICE VIBRATIONS (Chap. 2 ,
region will also be encountered in the electron theory of solids. Note
also that the optical band becomes narrower with increasing Mlm ratio.
It is of interest to investigate the physical difference between the two
branches. This may be done by calculating the ratio of the amplitudes
A and B in the two cases. Let us first consider the situation for q = 0,
i.e., for infinite wavelength. From (2-77) and (2-74) it fo~Iows that
for the acoustical branch: A=B
for q = 0 (2-79)
for the optical branch: -MA =mB
In other words, in the acoustical branch all
AlB
I
particles move in the same direction. In the
I optical branch, on the other hand, the two
I types of particles move in opposite directions
I
I in such a manner that the center of gravity
I in each cell remains at rest. For other values
1 I
I of q the ratio AlB may be calculated from
I (2-76) and (2-74). The results are shown in
I
1r 12a Fig. 2-14. It is observed that at the edge of
I the zone, i.e., for q = ±7T12a, the following
conclusion can be drawn: in the acoustical
" -m/MI
branch the light particles of mass m are aU'
at rest (B = 0), whereas in the optical branch
Fig. 2-14. The amplitude the heavy particles of mass M are at rest
ratio AlB as function of the (A = 0). For a more detailed discussion we
wave vector q for the acousti- refer to Brillouin, op. cit., Sec. 15.
cal branch (upper curve) and
A few remarks may be made here in
the optical branch (lower
curve). A corresponds to M, connection with the absorption of electro-
E to m and M > m. magnetic radiation by ionic crystals. It is well
known that these crystals absorb strongly in
the infrared region of the spectrum, corresponding to a frequency
v ~ 1013 sec-l and a wavelength A ~ 3 X 10-3 cm. Evidently the wave
vector of these waves is of the order q = 27T/A ~ 103 cm- I • Now the
limit of the zone of the lattice vibrations corresponds to 7T/2a ~ lOS
em-1 . In other words, in the (() versus q plot, these vibrations are
practically those corresponding to the maximum of the upper branch.
The infrared absorption frequency should thus be approximately given by
1
Wopticai ~ [ 2/ ( ;;; + M1 )] 1/2
in accordance with (2-77). It is for this reason that the upper branch is
called the optical branch. The infrared absorption thus corresponds to a
vibration of the positive ion lattice relative to the negative ion lattice such
that the center of gravity in each cell remains at rest.
)ec. 2-13] SPECIFIC HEAT AND LATTICE VIBRATIONS 57

2-13. Vibrational spectra and specific heat of three-dimensional lattices

The calculations of the vibrational modes of a one-dimensional lattice

may be extended to two and three dimensions. For the general theory
we refer to the literature, and it may suffice here to mention some of the
results obtained. I6 The vibrational spectrum of a two-dimensional lattice
was first calculated by Blackman, who also computed the spectrum for a

140

r-.-----,_..-_ _ ~

8D

t 120

10 20 30 40 50 60 70 80
-T('K)

Fig. 2-15. The Debye temperature as function of T for a simple

cubic lattice. [After Blackman, ref. 17]

simple cubic latticeY From these results he was able to calculate the
specific heat in the manner outlined for the one-dimensional case in
Sec. 2-11. In the low temperature region the specific heat thus obtained
may be equated to the Debye formula (2-37) and the Debye temperature
On can be computed for different temperatures. The results obtained by

Z(wl

t
260
o 1.2 2.4 3.6 4.8 6.0 o 20 40 60 80 100
_ wXlO-13 - T('K)
(a) (b)

Fig. 2-16. The vibrational spectrum of NaCI is given in (a). The

circles in (b) represent () D calculated on the basis of (a); the curve in
(b) is obtained from experiment. [After Kellerman, ref. 18]

Blackman for the simple cubic lattice are represented in Fig. 2-15. It is
observed that ()n is by no means constant, indicating the possibility of
appreciable deviations from the Debye theory in actual crystals.
16 See M. Born and M. Goppert-Mayer, op. cit.; F. Seitz, op. cit.; L. Brillouin,
op. cit.
17 M. Blackman, Proc. Roy. Soc. (London), A148, 384 (1935); A159, 416 (1937);

PrOf. Cambridge Phil. Soc., 33, 94 (1937).

58 SPECIFIC HEAT AND LATTICE VIBRATIONS [Chap.2-'

An investigation of NaCl has been made by Kellermann,I8 using ionic

and repulsive forces between the particles. Figure 2-16a gives the vibra-
tional spectrum of NaCl obtained by Kellermann, and the difference with
a continuum spectrum as used in the Debye theory is obvious. The
Debye temperature ()D as function of T calculated by Kellermann is
given by the circles in Fig. 2-16b. It is observed that the theory is in
remarkably good agreement with the curve obtained experimentally.

REFERENCES
M. Born and M. Goppert-Mayer, Handbuch der PhYSik, 24 (2) (1933).
M. Born and K. Huang, Dynamical Theory of Crystal Lattices, Oxford,
New York, 1954.
M. Blackman, Reports on Progress in Physics, 8, 11 (1941).
L. Brillouin, Wave Propagation in Periodic Structures, Dover, New
York, 1953. •
A. Eucken, Handbuch der Experimental Physik, 8 (1) (1929).
P. H. Keesom and N. Pearlman, Encyclopedia of Physics, 14, Springer,
Berlin, 1956.
J. de Launay, in F. Seitz and D. Turnbull (eds.), Solid State PhysiCS,
Vol. 2, Academic Press, New York, 1956.
E. Schrodinger, Handbuch der Physik, 10 (1933).
F. Seitz, Modern Theory of Solids, McGraw Hill, New York, 1940,
Chap. 3.
PROBLEMS
2-1. (a) Give a derivation of expression (2-4) for the difference
between C p and C v . (b) Calculate C p - C v per mole of sodium at room
temperature if at this temperature the compressibility of sodium is
12.3 X 10- 12 cm 2 dyne- I and the linear coefficient of expansion is
6.22 X 10 -5; compare the result with Cp - C v for a monatomic gas.
Also calculate the Griineisen constant for Na.
2-2. The possible energy levels of a rigid rotator according to quantum
mechanics are given by En = (fj2/2J)n(n +
I) where J is the moment of
inertia and n = 0, 1,2, .... For the molecules H2 and Cl 2 calculate the
energy difference between the ground state and the first excited state for
rotation about an axis perpendicular to the line joining the nuclei.
(Answers. Resp., 14.7 X 10-3 and 0.06 X 10- 3 ev.) Also estimate the
value of E1 - Eo for rotation about the line joining the nuclei and show
18 E. W. Kellermann, Phil. Trans., A238, 513 (1940); Proc. Roy. Soc. (London),A178,
17 (1941).
1('
Chap. 2] SPECIFIC HEAT AND LATTICE VIBRATIONS 59

that this rotation does not in general contribute to the rotational specific
heat. At which temperatures for H2 and Cl 2 do quantum effects enter in
the rotational specific heat? If it is given that the number of possible
states corresponding to an energy level En for a rotator is equal to
2n(n + 1), show on the basis of statistical mechanics that the rotational
specific heat for a molecule such as Cl z at room temperature is R cal per
mole. (Hint: According to statistical mechanics the average energy at T
is given by
(E) = [~EnZn exp (-En/kT)]/[~ Z" exp (-E"/kT)]
n It

where Zn is the number of possible states associated with En- For the
problem under consideration one can replace the summations by
integrals. )
2-3. Discuss in SOBle detail the specific heat of a diatomic molecule
(including translation, rotation, and vibration). What is the value of
Cp/Cv in various temperature regions? L__.:_
2-4. Consider an array of N similar atoms, the separation between
nearest neighbors being a. Discuss the specific heat of the system on the
basis of the Debye approximation and show that at low temperatures the
specific heat is proportional to T.
2-5. Discuss the specific heat of a two-dimensional square lattice
with a nearest neighbor separation a on the basis of the Debye approxi-
mation. Show that at low temperatures the specific heat is proportional
to 1'2.
2-6. Consider a cavity filled with black-body radiation in equilibrium
with a temperature bath T. As is well known, the energy of radiation per
unit volume u is a function only of T; also, the radiation pressure
p = uJ3. In a p- V diagram, carry out a Carnot cycle with this "gas":
first expand isothermally from VI to V 2 , then expand adiabatically such
that the temperature drops slightly from T - tl T; finally, return to the
starting point by isothermal and adiabatic compression. By making use
of a well-known theorem about the efficiency of transforming heat into
work, show that the energy density u is proportional to T4. Explain why
the specific heat of the radiation gas is always proportional to T3, whereas
for a solid in the Debye approximation this is true only at low temperatures.
2-7. Discuss in some detail the analogy between the mechanical
properties of an array of equidistant similar atoms and a low-pass electric
filter. (See, for example, Brillouin, op. cit.)
2-8. Discuss the specific heat of a solid on the basis of the cut-off
procedure suggested by Born (Sec. 2-7) and show that one arrives at an
expression of the type (2-41).
Chapter 3

SOME PROPERTIES OF METALLIC LATTICES

3-1. The structure of metals _.

Most metals crystallize in one of the following three structures:

the body-centered cubic lattice (b.c.c.) in which each atom is surrounded
by eight nearest neighbors, the face-centered cubic lattice (f.c.c.) in which
a given atom has twelve nearest neighbors, and the hexagonal close
packed lattice (h.c.p.), also with a coordination number of twelve.
From the dimensions of the elementary cell, as obtained from X-ray
diffraction or otherwise, one may define a radius for the atoms on the
assumption that they are spherical in shape; the radius so defined is then
given by half the distance between nearest neighbors. That this procedure
has a physical meaning follows from the fact that for those metals which
crystallize in more than one structure, each structure being stable over
a certain range of temperatures, the radii so obtained are very nearly the
same. Table 3-1 gives the distances of closest approach (twice the atomic
Table 3-1. Structure and Distance of Closest Approach (at 20'C) (or Metals
which Crystallize in Any o( the Three Simple Metallic Structures. The
asterisks indicate the normal form.
I
Body-centered Face-centered I Hexagonal
cubic cubic close packed

Metal d(A) Metal d(A) Metal d(A)

Li 3.039 Cu 2.556 C( Be" 2.225
Na 3.715 Ag 2.888 Mg 3.196
K 4.627 Au 2.884 Zn 2.6E4
V 2.632 Al 2.862 Cd 2.979
Ta 2.860 Th 3.60 at TI* 3.407
Cr 2.498 Pb 3.499 C( Ti* 2.89
Mo 2.725 y Fe (extra-
polated) 2.525 Ot Zr* 3.17
ex W* 2.739 fJ Co 2.511 Hf 3.1 )
at Fe" 2.481 Ni 2.491 oc Co" 2.506
r5 Fe (1425 C) 2.54 P Rh* 2.689 Ru 2.649
Pd 2.750 Os 2.675
Ir 2.714
Pt 2.775

60
Sec. 3-1) SOME PROPERTIES OF METALLIC LATTICES 61
radii) for metals which crystallize in one of the three structures mentioned
above. 1
The b.c.c. and f.c.c. lattices have been represented in Fig. 1-4. The
h.c.p. structure represented in Fig. 3-1 is closely related to the f.c.c.
structure, as may be illustrated with reference to Fig. 3-2. Let the dots in
Fig. 3-2 represent a layer of spheres in close packing. On top of this we
place another layer, represented by the crosses. The atoms of a third
layer may now be placed on top of the second one in either of two ways:
(1) they can be placed in positions corresponding to the open circles in
Fig. 3-2, or (2) they can be placed in positions identical in projection with

• First layer
, ,'; 'h' ".~" " )( Second layer

• or 0 Third layer

Fig. 3-1. The hexagonal close Fig. 3-2. Illustrating the relation-
packed structure. ship between the h.c.p. (. x. x
etc.) and the f.c.c. (.xO.xO.,
etc.) structures.

those of layer I (dots). Thus the two possible arrangements may be

represented symbolically by the sequences 1, 2, 1, 2, ... and 1, 2, 3, I,
2, 3, .... The former corresponds to the h.c. p. structure; the latter is
equivalent to the f.c.c. structure as may readily be seen by identifying
the layers of Fig. 3-2 with atomic planes perpendicular to a body diagonal
in the f.c.c. structure. Hence, both the h.c. p. and f.c.c. structures correspond
to a close packing of spheres; the b.c.c. structure does not. The fraction
of volume occupied by spheres in closest packing is 21/2( TT/6) :::::: 0.74, as
shown in Problem I-I. The density ratio for a f.c.c. (or h.c.p.) lattice and
a b.c.c.lattice built up of spheres of the same radii is 1.09 (see Problem I-I)'
The reason for a particular metal to crystallize in a particular structure
must be sought in the fact that the free energy E - TS of the system for
this structure is lower than that for any other structure. 2 The same remark
1 For a complete list of lattice parameters, see, for example, C. S. Barrett, Structure

of Metals, 2d ed., McGraw-Hill, New York, 1952. p. 646.

2 For the thermodynamic conditions for equilibrium, see Appendix A.
62 SOME PROPERTIES OF METALLIC LATTfCES [Chap. 3

may be made with reference to those metals which have different structures
in different temperature regions (allotropy). This phenomenon is exhibited
especially by the three- and four-valent metals and by the transition
metals. 3 For example, IX Fe (b.c.c.) is stable up to 910 o e; between 910 0 e
and l400 e the stable structure is y Fe (f.c.c.); between l400 e and the
0 0

melting point (l530°C) the structure is again b.c.c. (a Fe). Here again, the
transformation from one structure to another is dictated by the requirement
of minimum free energy. This does not mean that such transformations
take place as soon as the existing structure becomes unstable. ]n fact, a
transformation of structure involves a rearrangement of atoms, and such a
process may take a long time. The reason is that even though the free
energy after the transformation is lower than in the initial state, the two
states are usually separated by an energy barrier or activation energy
(see Sec. 3-5). Thermodynamics specifies only the equilibrium condition
but does not give any information about the velocity of the reaction or
processes involved in establishing equilibrium. From the atomic point of
view, the stability of crystal structures is a problem of cohesive energy,
involving the interaction between the atoms. A brief discussion of the
cohesive energy of metals is presented in Sec. 10-13 based on the electron
theory of metals.

3-2. Lattice defects and configurational entropy

According to thermodynamics, the equilibrium of a solid (under low

external pressure) at a temperature T is determined by the minimum value
of the free energy F = E - TS (see Appendix A). We shall see below that
this condition leads necessarily to the existence of a certain amount of
disorder in the lattice at all temperatures T> OaK. We emphasize from
the beginning that the lattice disorder or lattice defects discussed in this
section do not include accidental faults in tlu: crystal resulting from non-
ideal growing conditions; the defects under consideration are present
as a result of the thermodynamic equilibrium conditions. Frenkel 4 was the
first to recognize that lattice defects play an important role in a number
of physical properties of solids, and Schottky5 has contributed a great deal
by expanding these ideas. The simplest examples of lattice disorder are
vacant lattice sites and interstitial atoms (see Fig. 3-3); the latter are
3 Elements with incompletely filled inner electron shells are called transition elements.

For example, Fe, Ni, and Co have an incompletely filled 3d shell, while the 4s shell
is occupied; these metals thus belong to the transition metals. For the notation of s, p,_
d,.r g, ... electrons, see textbooks on atomic theory; see also Sec. 18-2.
'J. Frenkel, Z. Physik, 35,652 (1926); also J. Frenkel, Kinetic Theory of LiqUids,
Oxford, New York, 1946, an extremely clear book, which, notwithstanding its title,
contains a great deal of information about solids.
;, See, for example, C. Wagner and W. Schottky, Z. physik. Chern., Btl 163 (1931);
W. Schottky, Z. physik. Chern., B29, 353 (1935).
Sec. 3-2) SOME PROPERTIES OF METALLIC LATTICES 63
atoms occupying positions in the lattice which in the perfect lattice would
be unoccupied. In discussions of this kind it is necessary to point out the
distinction between what we shall refer to
as thermal and configurational (or mixing) • • • • • •
entropy; these quantities will be denoted,
respectively, by Stll and Scf' The thermal
• • • • • •
entropy Slh is determined by the number v
• D • • • •
of different ways Wtl , in which the
total vibrational energy of the crystal • • • • • •
may be distributed over the possible
Fig. 3-3. A vacancy (V) and
vibrational modes; according {Q the well-
an interstitial atom (I) in
known Boltzmann relation (see Appendix a two-dimensional square
E),6 lattice.

(3-1)

For example, in the Einstein model of a solid (see Sec. 2-4), W tI , stands
for the number of different ways in which the energy of vibration may be
distributed over the 3N harmonic oscillators representing the solid
consisting of N atoms. When v is the Einstein frequency, and hv <{ kT, we
have, according to Problem 3-3,

Stll = 3Nkfl + log (kT/hv)] (3-2)

The configurational entropy of a crystal has nothing to do with the
distribution of energy; it is determined solely by the number of different
ways W('fin which the atoms may be arranged over the available number of
lattice sites. Consider for example a lattice containing N" atoms of type
A and Nb atoms of type B and assume that the lattice sites are all equivalent
in the sense that a given lattice site may be occupied by A or B. It is left
to the reader to show in Problem 3-2 that

W('f = (N" + Nt')! ':-'

(3-3)
N,,!Nb!

represents the number of different arrangements of N" A atoms and Nb

B atoms over a total of (Na + N b ) lattice points. The configurational
entropy associated with Wd is again given by the Boltzmann relation,

(3-4)

• For an elementary treatment of statistical thermodynamics and a number of

applications to solid state physics, see R. W. Gurney, Introductioll !o Statistical
Mechanics, McGraw-Hili, New York, 1949; also M. Born, Atomic Physics, 5th cd.,
Hafner, New York, 1951.
64 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

Fo~ a perfect crystal containing identical atoms and in the absence of any
lattice defects, w,.[ = 1 and Se[ = 0 because there is only one possible
arrangement of the atoms. The total entropy occurring in the usual
thermodynamic formulas is equal to the sum of the thermal and
configurational entropies, i.e., \
\
(3-5)

The results obtained above may be used to explain qualitatively the

reason for the existence of lattice defects at any temperature T > o.
Suppose, for example, that in a perfect metallic crystal we produce a
certain number of vacant lattice sites by transferring atoms from the
interior of the crystal to the surface. This will require a certain amount of
energy, i.e., E increases. Consequently F
increases and this by itself is thus unfa vor-
able in the thermodynamic sense. On the
other hand, the creation of the vacancies
increases the disorder in the crystal and
thus increases the configurational entropy
from zero to a certain value determined
by the number of vacancies n produced.
In fact, according to (3-4) the con-
figurational entropy associated with the
-TScf
possible arrangements of N atoms and n
Fig. 3-4. Schematic representa- vacancies over a total of (N + 11) latrice
tion of the energy and the con- sites is
figurational entropy term as
function of the fraction of vacant Sef = k log [
(N
"
+ n)!] (3-6)
lattice sites nlN. The minimum N.n.
of the free energy F determines
the equilibrium value of nlN.Now, because the entropy enters in the
free energy expression in the form- TS,
an increase in entropy reduces F and is thus favorable thermo-
dynamically. As a result of the above described competition between
energy on the one hand and entropy on the other, the stable configuration
is one in which a certain fraction of the lattice sites is unoccupied. A
schematic representation of F as function of the fraction nlN has been
given in Fig. 3-4.; it has been assumed for simplicity that the thermal
entropy is independent of nlN. The equilibrium corresponds to the
minimum value of F at the temperature T. Any further increase in the
disorder of the lattice would require an energy larger than the associated
reduction due to the increase in entropy. Similar arguments may be
applied to other types of lattice defects. In the next section we shall
discuss the number of lattice defects as function of temperature
quantitatively.
Sec. 3-3] SOME PROPERTIES OF METALLIC LATTICES 65

3-3. The number of vacancies and interstitials as function of temperature

Consider a perfect lattice containing N similar atoms at a temperature

T; the free energy of this (unstable) crystal will be denoted by FpPl'fect(T).
Suppose we create n vacant lattice sites; let the energy required to create
one vacancy be cp,oO We shall assume that CPv is independent of n, which is
justified as long as n <{ N; also, we assume that no two vacancies are
nearest neighbors of each other. The energy of the imperfect crystal is
then increased by ncp" relative to that of the perfect crystal. Also there
is associated with the imperfect crystal a configurational entropy S(.f
given by (3-6). Furthermore, let us assume that the thermal entropy
increases per vacancy by an amount LlS th ; the physical reason for this
change will be discussed below. We may then write for the free energy of
the imperfect crystal

F(n, T) = F;)erfect(T) + ncpv - nT!J.Sth - kTlog

(N + n)!
N! n! (3-7)

In order to find the equilibrium value of n, we make use of the fact that in
equilibrium (o}/dn},p = O. Employing Stirling's formula m the form
log x! ,..._, x log x for x ~ 1, we find from (3-7),
(3-8)

Thus, apart from a constant determined by !J.Su., the probability for a

given lattice site to be unoccupied is given by a Boltzmann factor containing
the energy offormation of a vacancy CPv' We shall see in Sec. 3-4 that for
metals CPv is of the order of one electron volt. The type of disorder discussed
above is usually called Schottky disorder; vacancies are frequently
referred to as Schottky defects.
So far, our treatment has been essentially a thermodynamic one. In
order to get an insight into the physical meaning of the thermal entropy
change !J.Sth per vacancy, we shall consider a simple Einstein model of a
solid. The thermal entropy of the perfect crystal is then equivalent to
the thermal entropy of a system of 3N harmonic oscillators with the
Einstein frequency v and is given by (3-2) as long as kT~ hv.
In the imperfect crystal, the atoms neighboring a vacancy will have a
vibrational frequency smaller than v because the restoring forces are
reduced, particularly along the direction of the line joining the atom and the
vacancy. In order to simplify the discussion, we shall assume that in the
imperfect crystal each atom neighboring a vacancy is, in the Einstein
model, equivalent to 3 harmonic oscillators of a frequency v' < v. Thus
when x is the number of atoms surrounding a vacancy, the Einstein model
as used here leads to
3nx oscillators of frequency v'
(3N - 3nx) oscillators of frequency l'
66 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

The thermal entropy of the imperfect crystal is then, in analogy with (3-2)
Sth = 3nxk (I + log (kT/hv')] + (3N ~ 3nx)k [I + log (kT/hl')] (3-9)
Subtracting (3-2) from (3-9) and dividing the result by n, one finds for the
increase in thermal entropy per produced vacancy,
~Stll = 3xk log (vly') (3-10)
Although the model employed here is a simple one, it deafly demonstrates
the fact that ~Sth is a consequence of the change in the frequency spectrum
of the lattice vibrations. For this model, substitution of (3-10) into (3-8)
leads to
n/N = (vjjJ')~.r e-<$,/kT (3-11 )
Because v > v', we see that the change in thermal entropy favors the
formation of vacancies, because the pre-exponential factor is > 1. This
factor may be large because 3x is a rather large number (24 for b.c.c. and
36 for f.c.c.).
A remark may be made here about the temperature dependence of <Pv.
It is evident that as T increases, the lattice expands, the binding forces
are reduced, and thus <Pt' decreases with temperature. In first approxi-
mation one may write a linear relationship between <Pt. and T, i.e.,
<Pv = <Pvo (1 - ocT) (3-12)
where oc is a temperature coefficient and <Pvo the energy of formation
of a vacancy at T = O. In the literature 7 one frequently encounters the
following argument in connection with expressions of the type (3-8) or
(3-II): when one substitutes (3-12) into (3-8), one obtains

and one argues that if it were possible to measure nlN, a plot of log (nIN)
versus 1jkT would give <Pvo rather than CPv; furthermore, it is argued that
the pre-exponential factor is multiplied by exp (cxCPvo/k]. These arguments
are, however, incorrect since they neglect the temperature variation of ~S
accompanying the change in <Pv. 8 In fact, for zero pressure we have
d(~S)/dT = (lIT) dcpJdT

and measurements of nj N as function of T actually measure <P" (See also

Sec. 7-1.)
, See, for example, N. F. Mott and R. W. Gurney, Electronic Processes ill Ionic
Crystals, Oxford, New York, 1946, p. 30; W. Jost, Diffusion in Solids, LiqUids, Gases,
Academic Press, New York, 1952, p. 116.
• This has been pointed out bJ C. Zener in W. Shockley (ed.), Imperfections in Near~v
Perfect Crystals, Wiley, New York, 1952, p. 296. Similar objections in connection with
the theory of diffusion in ionic crystals have been raised by Y. Haven and J. H. van
Santen, Philips Research Repts., 7, 474 (1952).
Sec. 3-3) SOME PROPERTIES OF METALLIC LATTICES 67

Other types of lattice defects may be treated in a similar way as

vacancies. Consider, for example, Frenkel defects, which are formed when
atoms which initially occupy a normal lattice position migrate into
interstitial lattice positions. A Frenkel defect thus consists of two com-
ponents: a vacancy plus an interstitial atom. We leave it up to the reader
to show in Problem 3-7 that the number of Frenkel defects in equilibrium
at a temperature T is given by
for n <{ N (3-13)
where N is the number of atoms, Ni is the number of possible interstitial
positions, ~Sth is the change in thermal entropy per Frenkel defect, and
4>F is the energy of formation of a Frenkel defect. The factors 2 appear in
the exponentials because a Frenkel defect has two components. In chemical
language the formation of a Frenkel defect may be written in the form of
an equilibrium reaction: .:'- , 1fI' _
_,/ I , 7 i

occupied lattice site I .. . I

+ .
unoccuple d Interstitia
. . I ~ vacancy
. . I site + Interstitia (3-14)

From this, readers familiar with the law of mass action will readily
recognize that n should be proportional to (NNi )1/2 and that the
exponentials in (3-13) are correct.

3-4. The formation of lattice defects in metals

There are a large number of different types of lattice disorder in

metals. However, usually only a few of these will predominate, viz., those
for which the energy of formation is smallest; this is evident from the
results obtained in the preceding section. A few words may be said here
about the processes and the energy involved in the creation of simple lattice
defects such as vacancies and interstitials. A vacant lattice site may be
formed, for example, by a process such as indicated in Fig. 3-5a. Suppose
an atom such as B jumps into position A on the surface; the vacant site it
leaves behind may then become occupied by an atom such as C when the
latter jumps into the vacancy. Successive jumps of this kind thus lead to
the diffusion of a vacant lattice site from the surface into the interior of the
crystal. The external surface is not necessarily the only source of supply of
vacancies; internal cracks, pores, and dislocations (see Sec. 3-12) serve a
similar purpose in this respect. The sources mentioned may also act as
sinks for the disposal of vacancies ; for example, when the temperature of a
crystal is lowered and the density of vacancies must be reduced.
The energy of formation of a vacancy by a process of the kind described
above is determined essentially by the energy expended during the first
few jumps. Once the vacancy is separated from the source by several
lattice distances, the energy of the crystal becomes essentially independent
68 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

of the lattice site "occupied" by the vacancy (at least as long as it does not
become a nearest ncighbor of another vacancy or lattice defect). This is
represented schematically in Fig. 3-5b. It should be kept in mind, however, .
that although the energy before and after a jump may be the same, a
certain "activation cnergy" is always required to make the jump. In other
words, two possible neighboring lattice sites for a vacancy are separated by
a barrier, as indicated by E j in Fig. 3-5b. It is for this reason that the

•
•
A~
• • • ·B •
2(.c _}
• • D. •
4(Y
• • E· • •
--+ Position
• • • • •
(al (bl

Fig. 3-5. Sequence of jumps producing a vacancy which migrates

into the interior of the crystal (a). In (b) the potential energy of the
vacancy is shown schematically as it diffuses in; the limiting value
rp,. is the energy of formation, Cj is the jump activation energy of the
vacancy.

establishment of thermal equilibrium may require a long time, especially

at low temperatures where the m'obility of the vacancies, or rather of the
atoms neighboring a vacancy, becomes smaIL It is thus possible, by
quenching a crystal from a relatively high to a low temperature, to "freeze
in" a high-temperature configuration of the atoms.
A Frenkel defect may arise as a result of the migration of a "normal"
atom into a nearby interstitial position. When the interstitial does not
fall back into the vacancy so produced, either the interstitial or the vacancy,
or both, may migrate further away from the point of creation and ultimately
one is left with a free interstitial and a free vacancy. Thus there are
various degrees of dissociation before the two components of the Frenkel
defect are free from each others' influence. The schematic representation
of Fig. 3-5b is' therefore also valid for the formation of a Frenkel defect.
A theoretical calculation of the energy r?v required to create a vacancy is
quite complicated. This may be appreciated from the following arguments:
Consider a macroscopic piece of metal containing N atoms. Suppose that
it requires a total energy E to separate all atoms from each other. When
Es is the average energy r~quired to take an atom from the surface of the

metal to infinity, then C s = EjN; Es is the sublimation energy. For copper,

for example, Es = 3.52 ev. Consider now an atom in the interior of the
crystal; let the potenti/al energy of this atom due to the presence of all other
Sec. 3-4] SOME PROPERTIES OF METALLIC LATTICES 69
atoms in the crystal be --€O i . The total dissociation energy of the crystal E
is then equal to N€OJ2, the factor 2 arising from the fact that the interaction
. energy between any two atoms should be counted only once; thus,
( i = 2€O", which means that an atom at the surface is, on the average,

bound half as strongly as an atom in the interior. The physical meaning

of €Oi may also be expressed in this way: it represents the energy required
to remove an interior atom to infinity if the position and the charge distri-
bution of the other at0111s remain unchanged. The energy required to form a
vacancy, i.e., the energy required to transfer an atom from the interior to
the surface, may then be written in the form

cPv == Ei - Er - €s == Es - Er (3-15)

where €Or is the energy gained as a result of the rearrangement of the

electrons and atoms after the vacancy is formed. Huntington and Seitz
have calculated cPv for copper and find cPu = 1.4 ev. 9 This is in good
agreement with an experimental value of 1.39 ev derived by Overhauser
from annealing experiments of copper samples bombarded with 12 Mev
deuterons. lO With the value of €O" = 3.52 ev quoted above, it follows from
(3-15) that €Or = 1.7 ev. Note that the rearrangement of the atoms and
electrons around the vacancy contri butes an energy term of the same order
as cP,. itself; if €Or were zero, cP" would be equal to the sublimation energy.
In connection with the fact that establishment of thermal equilibrium
of vacancies requires the migration of vacant lattice sites, we may mention
that the activation energy for jumping (€Oj in Fig. 3-5b) of a single vacancy
in copper is approximately 0.68 ev according to Overhauser.lO .
Vacancies may also occur in pairs, i.e., in the form of two neighboring
vacant lattice sites. According to an estimate by Bartlett and Dienes it
requires an energy between 0.23 and 0.59 ev to dissociate a pair of vacancies
in copper; the actual value is probably closer to 0.59 ev than to the lower
limit.ll A pair of vacancies probably has a much higher mobility in the
lattice than a single vacancy, since one expects smaller repulsive interactions
for a pair. Experimental evidence for the presence of pairs of vacancies
in copper has been obtained by studying the annealing out of lattice
imperfections produced by cold working and high-energy particle bombard-
ment. It turns out that at rather low temperatures, the annealing proceeds
at a much faster rate than can be explained by the diffusion of single
vacancies. Larger aggregates of vacancies may also be present.
9 H. B. Huntington and F. Seitz, Phys. Rev., 61, 315 (1942); 76,1728 (1949); H. B.

Huntington, Phys. Rev., 61, 325 (1942).

HI A. W. Overhauser, Pilys. Rev., 90,393 (1953).

lJ J. H. Bartlett and G. J. Dienes, Pllys. Rev., 89, 848 (1953). For further information

about \acancies in metals and alloys, see F. Seitz, Acta Cryst., 3, 335 (1950); c. Zener,
Acta Crvst., 3,346 (1950); J. Bardcen, Phys. Rev., 76,1403 (1949); R. Smoluchowski
and H. Burgess, Pllys. Rev., 76,309 (1949); H. R. Paneth, Pllys. Rev., 80, 708 (1950).
70 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

3-5. Interstitial diffusion in metals ""!\

The simplest mathematical formulation of the diffusion of atoms in
solids is based on the assumption that the net flow of atoms is proportional
to the gradient of the concentration, i.e.,
\
1= -D grad n ( 3-16)

where I is the flux of atoms in cm- 2 sec-I, n is the number of atoms per cm3 ,
and D is the diffusion coefficient. In general, D is itself a function of the
concentration n. 12 Expression (3-16) is known as Fick's first law; the
minus sign indicates that the current flows from regions of high concen-
tration to regions oflow concentration. Applying the continuity equation,
one obtains Fick's second law:

"[njct = --div 1= div (D grad n) = DV 2n (3-17)

where the last equality is correct only if D is independent of the spatial

coordinates, which implies in general that D is also independent of n.
We should mention that (3-16) may be generalized in a number of
ways. For example, D is a scalar quantity only in cubic crystals or in an
isotropic medium; in general, D is a tensor. A discussion of the properties
of this tensor has been given by Onsager (see Sec. 1_12).13 Also, the actual
driving force of the diffusion process is not the concentration gradient but
the gradient of the chemical potential. For a discussion of these and other
generalizations we refer the reader to a review by Ie Claire. 14
From measurements of diffusion coefficients at various temperatures
it has been found that the temperature dependence of D is well described by
the formula
(3-18)

where Do is a constant and E is the activation energy of diffusion. An

analysis of the experimental data by Dienes indicates that Do is mainly
determined by the quantity EjTm' where Tm is the melting point of the
solid; in fact, he concludes that Do is proportional to exp (EfTmV~ A
. theoretical interpretation of this proportionality has been proposed by
Zener.16
12 See for example D. E. Thomas and C. E. Birchenall, J. Metals, August 1952,
p,867,
13 L. Onsager, Ann. N. Y. A cad. Sci., 46, 241 (1945),

HA, D, Ie Claire, Progress ill Metal PhYSiCS, Interscience. New York, Vol. I (1949),
Vol. 5 (1954).
J" G. 1. Dienes, 1. Appl. Phys., 21,1189 (1950).

Jij C. Zener in W. Shockley (ed.), Imperfections ill Nearly Perfect Crystals, Wiley,

New York, p. 299.

Sec. 3-5] SOME PROPERTrES OF METALLIC LATTICES 71

From the atomic point of view, the simplest type of diffusion in solids is
the diffusion of interstitial atoms. The reason is that in this case there
exists no doubt as to the actual atomic mechanism involved; the inter-
stitial atoms presumably jump from one interstitial position to a neighboring
one. The diffusion of hydrogen, oxygen, nitrogen, and carbon in iron and
other metals are examples of this mechanism. In order to discuss this
type of diffusion from an atomic point of view, consider a set of parallel
atomic planes of interplanar distance A. We shall assume that there exists
a concentration gradient of the diffusing particles along the x-axis which is
perpendicular to the atomic planes. An atom in an interstitial position may
jump in the positive x-direction (forward) in the negative x-direction
(backward) or it may jump in a direction perpendicular to the x-axis.
We shall denote the probability for a given interstitial atom to make any
jump per second by p. Actually, the probability for a jump depends on the
probability that the neighboring interstitial site will be empty. We shall
assume, however, that the fraction of interstitial positions which is
occupied is <{I, so that p may be considered independent of the concen-
tration of interstitials. 17 The probability for a jump per second in the
forward direction will be denoted by fp; furthermore, we shall assume that
the probabilities for a forward and backward jump are equal. The diffusion
problem is then reduced to a simple random-walk problem.
Denoting the number of diffusing particles per cm2 on the plane
located at x at the instant t by n(x) we have
, ~) , ,

n(x + ?.) = n(x) + (en/ex)?. + t,(2;2n/ax2)?.2 + .. .

(3-19)
n(x - ?.) = n(x) - (an/ax»). + ! (2Pn/ex 2)?.2 + .. .
Thus, when we consider the situation at the instant t + bt where bt <{ lip,
the increase bn of the number of particles on the plane located at x is
given by the number of particles jumping from (x - ?.) into x, plus the
number of particles jumping from (x + ?.) into x, minus the number of
particles jumping away from plane x. Since we have assumed bt <{ lip, it is
not necessary to consider other planes besides the three employed. Hence
e2n en e2n
bn(x) = fp bt eX2?.2 or at = fp?.2 ex2 (3-20)

It is observed that this result is identical with the "macroscopic" equation

(3-17) with
D =fp?.2 (3-21)

Since f is determined solely by the geometry of the lattice and since;' is

nearly independent of T, the temperature dependence of the diffusion
" This assumption is equivalent to the assumption of a diffusion constant inde-
pendent of concentration in the "macroscopic" theory.
72 SOME PROPERTIES OF METALLIC LATTICES

coefficient must enter via the jump probability p. The simplest model that
-_
[Chap. 3 'lp..

can be set up to determine the temperature dependence of p is to consider a

particle moving in a fixed potential energy curve of the type illustrated in
Fig. 3-6. Let the potential minimum A correspond to the interstitial
position in which the particle finds
itself, and let B correspond to a
neighboring interstitial position. The
barrier of height Ei is a result of the
fact that as the particle moves from one
interstitial position to another it is
A B squeezed between the atoms con-
Fig. 3-6. The energy barrier be- stituting the host lattice. Assuming
tween two interstitial positions. the potential to be parabolic, the atom
will vibrate as a harmonic oscillator.
The frequency of vibration Vi may be considered as the number of
attempts per second made by the particle to cross the barrier. However,
any attempt can succeed only if the energy of the particle is ?Ei' As
shown in Problem 3-6, the fraction of time spent by the particle in energy
states ;?:Ei is simply given by exp (-EJkT). Hence, for the probability of a
jump from A to B we find per second,
(3.22)
When the jumping problem is considered more rigorously than has been
done above, one obtains a formula of the same form ls as (3-22), but Ei is
then replaced by a free energy I1Fi = ( i - TI1Si , i.e.,
i (3-23)
where I1Si is the entropy difference between the state in which the particle
is halfway between A and B, and the state in which the particle is in A.
Since an interstitial atom may jump into more than one neighboring
position, p is obtained by summation of (3-23) over all Pi' From (3-21) and
(3-23) we thus obtain
(3-24)

Let us now apply the results obtained above to a specific case. In Fig. 3-7
we have represented the diffusion coefficient of carbon in oc iron (b.c.c.)
as function of temperature according to WertJ8 Note that equation (3-18)
is satisfied for D-values covering 14 cycles of 10, with .
E = 0.874 ev z
and Do = 0.020 cm sec- 1 (3-25)
The interstitial positions in a b.c.c. lattice are indicated in Fig. 3-8;
they correspond to the centers of the faces and edges of the elementary cube.
18 For details, see C. Wert and C. Zener, Phys. Rev., 76, 1169 (1949); C. Wert, Phys.
Ref' .• 79, 601 (1950).
..
.,.
Sec. 3-5]
\
SOME PROPERTIES OF METALLIC LATTICES 73
It is observed that only from two-thirds of these positions is it possible to
jump forward or backward; from positions in which this is possible, the
relative probability for a forward jump is t. Hence, in this case
Temp 'C
~ o
.....
I I 8.....
-2

/
;::;-
-6 /
I
U
0>
,/
""S
Q
'"
E. -10
v
/
/
bIl
..s
0
.....
-14
t v
-18 /
V 3.8 3.0 2.2 1.4 .6 o
10 3 fT

Fig. 3-7. The diffusion coefficient of carbon in Cl iron (b.c.c.).

[After C. Wert, Phys. Rev., 79, 601 (1950)J

f =i X t = -!. Since the four possible jumps from any interstitial position
are equivalent, we obtain from (3-24) with A = a12, where ais the cube edge,

(3-26)

Comparison of (3-18) and (3-26) shows that for interstitial diffusion of

the type under consideration, the activation energy for diffusion is identical
with the activation energy for the atomic jumps. The value of exp (tl.Sjk)
may be estimated as follows: for (X iron a = 2.86 A; putting y ~ k(}jh
where () = 420 K is the Debye temperature of iron, one obtains y ~ 1013
0

sec-I. From the known value Do = 0.020 cm 2 sec-lone then obtains

exp (tl.Sjk) ~ 7.
We may mention here that Zener has derived the following approximate
relationship :19
(3-27)
19 C. Zener, J. Appl. Phys., 22, 372 (1951).
74 SOME PROPERTlES OF METALLIC LATTICES [Chap. 3

where Tm is the melting point, Ei is the activation energy employed above,

and fJ is a constant which for most metals lies between 0.25 and 0.45.
According to (3-27) and (3-26), Do should depend exponentially on
(EJTm), in agreement with the empirical
relationship obtained by Dienes. I5 Also,
• for ex iron Zener finds fJ = 0.43, leading
to exp (D.Slk) r:::::: 12 as compared with the
I \ //
.. \ 1 \
value
/
/' of 7 estimated above.
• I }:( •
I • / \ 3-6. Self-diffusion in metals
1// \

~D----~- When a thin layer of copper con-

,/
.- ,/

• \
taining the radioactive isotope C U64 is
\
,/ \
deposited on the surface of a "normal"
piece of copper, it is observed that the
Fig. 3-8. Interstitial positions radioactive isotopes gradually migrate into
(dots) in a h.c.c. lattice; these the interior of the specimen. This type of
sites are located at the centers of
the faces and the edges of the
diffusion is referred to as self-diffu!,ion,
cube. since the electronic structures of the various
isotopes of a given element are identical
and since it is the electronic structure which essentially determines the rate
of migration. The above-mentioned experiment indicates that there is a
continuous reshuffling of the copper atoms in the lattice. In other words,
one may associate a finite lifetime with the occupation of a given lattice site
by a particular atom. The coefficient of self-diffusion in metals depends
exponentially on the temperature in accordance with equation (3-18).
For example, for the self-diffusion of copper one finds (3-18) satisfied with20
D = 0.20 cm 2 sec-I, E = 2.05 ev (Cu)
Similarly, for the self-diffusion coefficient of sodium it has been found
that 21
Do = 0.242 cm 2 sec-I, E = 0.454 ev (Na)
Several mechanisms have been proposed for the self-diffusion process:
(I) the L'acancy mechanism, (2) the direct interchange between neighboring
atoms, (3) interstitial diffusion. In a particular case, the mechanism
requiring the smallest activation energy will dominate; it is therefore well
possible that in different types of metals different diffusion mechanisms
occur.
20 A. Kuper, H. Letaw, L. Slifkin, E. Sonder, and C. T. Tomizuka, Phys. Rev., 96,

1224 (1954); according to a private communication of Dr. Slifkin, the numerical values
in the original paper were in error; the correct ones have been given above.
21 N. H. Nachtrieb, E. Catalano, and J. A. Weil, J. Chem. Phys., 20,1185 (1952);

see also 20, 1189 (1957) for a discussion of the pressure dependence of the self-diffusion
coefficient of Na. •
Sec. 3-6J SOME PROPERTIES OF METALLIC LATTICES 75
In the vacancy mechanism it is assumed that the self-diffusion is
essentially determined by the diffusion of vacancies. Thus it is assumed
that a given atom can jump to a neighboring site only when the latter is
vacant. It is evident that the self-diffusion coefficient in this case will be
proportional to the fraction of lattice sites which is vacant and to the jump
probability for a vacancy per second. For a metal in thermal equilibrium,
the probability for a given site to be vacant is given by (3-8).
n/ N = e!!.S,./ke -.pjkl'

where ~SV refers to the thermal entropy change associated with the
creation of a vacancy. The probability for a jump of a vacancy to a
nearest neighbor site is given by a formula of the form (3-23). Hence the
self-diffusion coefficient for the vacancy mechanism may be written as
(compare 3-26):
(3-28)
where the subscripts j refer to jumps; y is a numerical factor determined
by the geometry of the lattice. Note that the
activation energy for diffusion is in this case
given by the sum of the energy of formation
of a vacancy and the jump activation energy,
i.e.,
(3-29)

We may recall that Overhauser lO found for

copper CPv = 1.39 ev and E; = 0.68 ev, the
sum of which is 2.07 ev. This is in good
agreement with the experimental value of E
quoted above. Huntington and Seitz 9 calcu- Fig. 3-9. Illustrating the two-
lated the activation energy for the direct inter- ring (direct interchange be-
change (see Fig. 3-9) between two neighboring tween two atoms) and the four-
atoms in copper and found a value four times ring diffusion mechanisms.
larger than the observed value. These authors
also found that the energy required to transfer a surface atom to an in-
terstitial position requires an energy of nearly 13 ev. It thus seems that
the interstitial and direct exchange mechanism are very unlikely in eu;
the vacancy mechanism is evidently operating in this case. Nachtrieb 21
et al. believe that the vacancy mechanism is also responsible for the self-
diffusion in sodium.
We should mention that besides the two-ring direct interchange referred
to above, there are other possibilities of direct interchange involving more
than two atoms. In Fig. 3-9, for example, we have indicated a four-ring
mechanism investigated by Zener. 22 Zener has shown that the activation
22 C. Zener, Acta Cryst., 3, 346 (1950).
76 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

energy associated with the four-ring mechanism in copper requires only 40

per cent of that associated with the simple interchange of two neighbors.
He concludes from his analysis that the ring mechanism might operate in
b.c.c. metals and that the vacancy mechanism dominates in the f.c.c. metals,
such as copper.
\.
3-7. Chemical diffusion in metals; the Kirkendall effect

The diffusion of foreign atoms in a lattice is usually referred to as

chemical or impurity diffusion. An example of this type of diffusion has
already been discussed in Sec. 3-5, in which the impurities were assumed
to move interstitially. Presently we shall be concerned with the diffusion
of impurities which occupy normal lattice sites, i.e., the impurities have
simply replaced a certain number of atoms of the host lattice. For the
discussion of this type of diffusion it is convenient to distinguish between
very low and high impurity concentrations.

Very low solute concentration. This is the simplest case since the
interaction between the impurity atoms may be neglected; furthermore,
complications arising from lattice defects associated with high-impurity
densities are avoided (see below). In order to illustrate the type of problems
encountered in this case, consider a certain metal A which is known to have
a self-diffusion governed by the vacancy mechanism. Suppose a very small
fraction of A atoms is replaced by B atoms and let us inquire about the
diffusion coefficient DBA of the B atoms in the A lattice. When PBv
represents the probability for a B atom to have a vacant lattice site as a
nearest neighbor and PBi represents the probability per second for a B
atom neighboring a vacancy to jump into the vacancy, then DBA will be
proportional to the product P BvP Bj' In a similar notation, the coefficient of
self-diffusion D.1A of the A lattice is proportional to PAvP Ai' Hence
DEA/ D AA = (PBv/P.1v)(PBi/PAj) (3-30)
It is of interest to point out that if the vacancies were distributed at random,
P Bv = PAv; when P.1v "# P Bv the vacancies evidently have a preference for
A or B neighbors.
Experimentally one finds that in general the activation energies and the
Do values associated with DBA and D AA may differ appreciably. This
indicates that PAv "# PEv and (or) that PAl "# PBi' A very accurate and
systematic study in this respect has in recent years been carried out by
Slifkin, Tomizuka, et al. 23 They measured, besides the self-diffusion of
23 For Sb in Ag, see E. Sonder, L. Slifkin, and C. T. Tomizuka, Phys. Rev., 93, 970

(1954); for Cd, In, and Sn in Ag, see C. T. Tomizuka and L. Slifkin, Phys. Rev., 96,610
(1954); for self-diffusion of Ag, see L. Slifkin, D. Lazarus, and C. T. Tomizuka,J. Appl.
Phys.,23, 1032 (1952); R. E. Hoffman and D. Turnbull, J. Appl. Phys., 22, 634 (1951);
E. S. Wadja, Acta Metallurgica, 2, 184 (1954).
Sec. 3-7] SOME PROPERTIES OF METALLIC LATTICES 77

silver, the diffusion in silver of elements following it in the periodic table,

viz., Cd, In, Sn, and Sb. Since radioactive tracer techniques were employed,
the concentration of the diffusing impurities could be kept very low
(10- 4-10-5). The activation energies and the Do values are given below.

I Ag Cd In Sn Sb
I
£ 45.50 II 41.70 40.63 39.30 38.32 keal/mole
Do 0.724 0.454 0.416 I 0.255 0.179 em' /see
I
It is interesting to note that both £ and Do vary in a systematic manner
as the number of extra valence electrons relative to silver increases from
one (Cd) to four (Sb). A theory of impurity diffusion for low concen-
trations in which the excess nuclear charge and excess number of valence
electrons of the impurity atoms relative to the host atoms play an essential
role has been developed by Lazarus. 24 The results mentioned above have
been discussed in the light of Lazarus' and Zener's25 theories by Tomizuka
and Slifkin.

High solute concentrations. The analysis and interpretation of chemical

diffusion data for high concentrations of the diffusing impurities is much
more complicated than for very low concentrations. First of all, the
diffusion coefficient is itself a function of concentration, which makes the
analysis more difficult; methods of analysis and a compilation of diffusion
data may be found in Jost, op. cit. Furthermore, the high concentration
gradients induce large gradients of the lattice parameters, and consequently,
imperfections which may act as short-circuiting paths for the diffusion.
It is suspected that in many of the chemical diffusion data nonhomogeneous
diffusion of this kind, or along grain boundaries, is involved. For an
extensive analysis of this subject we refer the reader to Nowick. 26

The Kirkendall effect. An interesting effect associated with the diffusion

of zinc and copper in brass (CuZn) was discovered by Kirkenda1l 27 . He
observed a mass flow relative to the initial interface of a copper-brass
diffusion couple which indicated that the zinc diffuses out of the brass more
rapidly than copper diffuses in. Confirmation of this observation was
obtained from an experiment by Smigelskas and Kirkendall in which inert
wires (markers) were embedded at the two interfaces of a Cu-brass-Cu

,. D. Lazarus, Phys. Rev., 93, 373 (1954).

2, C. Zener, J. App!. Phys., 22, 372 (1951).
26 A. S. Nowiek, J. App!. Phys., 22, 1185 (1951).

" E. O. Kirkendall, Trans. A/ME, 147, 104 (1942).

78 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

system. 28 They found that as the diffusion progressed, the markers moved
towards each other. The fact that the displacement of the m2.rkers was
proportional to the square root of the time indicated strongly that the
marker movements were related to the diffusion process itself.29 The
Kirkendall effect has since been found in many other systems; for example,
da Silva and Mehl have observed the effect in eu-Zn, Cu-Sn, Cu-Ni, Cu-Au,
Ag-Au. 30
Assuming that the markers are fixed relative to the system of lattice
sites, and assuming that the diffusion is governed by a vacancy mechanism,
a mass flow of atoms in a given direction must be compensated by a flow of
vacancies in the opposite direction. Thus in the copper-brass system, the
net flow of atoms out of the brass is balanced by a flow of vacancies from
the copper into the brass. For an excellent treatment of the theory of the
Kirkendall effect, the reader is referred to a papcr by Bardeen and Herring
in W. Shockley (ed.), Imperfections in Nearly Perfect Crystals, Wiley,
New York, 1952. Dislocations play an essential role in the atomic theory
of the effect as sources and sinks for vacancies (see Sec. 3-12).

3-8. The elastic constants of metals

For further reference and as an introduction to the following sections

of this chapter we may review very briefly some of the fundamental
principles of elastic stress-strain relations in crystals. 31 Let us first consider
an isotropic elastic medium under uniform stress along an arbitrarily
chosen x-direction. Let x' represent the distance of a given atom in the
material under stress relative to a fixed plane perpendicular to the x-axis.
When x represents the distance of the same atom in the unstressed material,
the strain Ex is defined by
EX = (x' - x)/x (3-31)
Thus Ex is a dimensionless quantity which may be positive or negative
depending on whether the stress is tensional or compressional. For small
values of the strain, Hooke's law is satisfied, i.e., the strain Ex is then
proportional to the stress along the x-direction ax (a force per unit area)

(3-32)

28A. D. Smigelskas and E. O. Kirkendall, Trails. A/ME, 171, 130 (1947).

29For a simple random-walk diffusion, the mean square displacement of the
particles is given hy (X2) = 2Dt, so that the root mean square displacement is propor-
tional to t 1/ 2• See, for example, lost, op. cit., pp. 25 ff.
30 da Silva, Atomic Flow ill Diffusion Phenomena, Thesis, Carnegie Institute of

Technology, 1951.
31 See for a detailed treatment, A. E. H. Love, A Treatise 011 the Mathematical Theory
of Elasticity, Dover, New York, 1944; or S. Timoshenko, Theory of Elasticity, McGraw-
Hill, New York, 1934.
Sec. 3-81 SOME PROPERTIES OF METALLIC LATTICES 79
The proportionality factor E is called Young's modulus. When ax repre-
sents a tensile stress, there will be a contraction of the material perpen-
dicular to the x-axis such that

(3-33)

where 'I' is called the Poisson ratio.

Besides the compressional and tensile strains mentioned above, there
are shear strains, as illustrated in Fig. 3- 10; shear strains are represented
by the symbol y. Consider two parallel planes separated by a distance d
and let the planes be displaced relative __ T
to each other in some direction parallel
to the planes by the amount dx; the shear
strain is then defined by

y = dx/d = tan IX (3-34) )

For small shear strain y is approximately \
equal to the angle IX. The shear strain is
produced by a shear stress T, which is a Fig. 3-10. The shear stress T
force per cm 2 ; for small strains Hooke's produces a displacement ~x of
the upper plane as indicated;
law may be applied and the shear strain is defined as
y = ~x/d = tan IX.
y =T/G (3-35)
where G is called the elastic shear modulus. It can be shown that, for
isotropic bodies, the three quantities E, l', and G satisfy the relation

G = E/2(y + 1) (3-36)

Isotropic bodies therefore are characterized by two independent elastic

constants. Crystals, on the other hand, require more than two elastic
constants, the number increasing with decreasing symmetry. Cubic
crystals (b.c.c., f.c.c.), for example, require 3 elastic constants, hexagonal
crystals require 5, and materials without symmetry elements require 21.
In discussing the stress-strain relations in crystals it is convenient to
start by considering the forces acting on a small cube dx dy dz which forms
part of a strained crystal. The force exerted on the cube by the surround-
ing material may be represented by three components on each of the six
faces of the cube. However, when the cube is in equilibrium, the forces on
opposite faces must be equal in magnitude and of opposite sign. Thus the
stress condition of the cube may be described by nine couples. Three such
couples have been indicated in Fig. 3-11, viz., those for which the forces
are parallel to the x-axis. One of these corresponds to a compressional or
tensile stress ax" (force per cm2); the other two are the shearing stresses
Txz and TXY which respectively tend to rotate the cube about the y- and
80 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

z-direction. Extending this reasoning to the forces parallel to the y- and

z-axis one thus ends up with the stress tensor

.L _ _ _ _ ~----
axx

.;.~

'1'e
TXY

(1"ff

'1'.11
Tx.

1',..
°u
\
However, the reaqer will readily convince himself that if rotation is absent,
y

\
U xx --i---

z
Fig. 3-11. Illustrating the three couples of forces acting along the
x-direction; an is a tensile stress, Tx. and Txz are shear stresses;
'Tx. represents a force acting along the x-axis in a plane perpendicular
to the y-axis, etc. Similar forces act along the y- and z-directions.

the tensor must be symmetrical, i.e., TyX = TXY etc. The stress condition
may thus be specified by six independent stresses,

(3-37)

As a result of the stresses, the crystal is strained, i.e., an atom which in the
unstrained crystal occupied the position x, y, z will in the strained crystal
occupy the position x', y', z'. When the distortion is homogeneous, the
displacements are proportional to x, y, z and we have in analogy with
(3-31) the more general expressions

x' - x = + YXyy + yx. Z

ExxX

y' - y = YyXx + + YyZz

EY?lY (3-38)
z' - Z = YzxX + YZyy + EzzZ
where the E'S and Y's refer to normal strains and shearing strains, respec-
tively. The strain tensor is again symmetrical if rotation is absent and the
~ .
Sec. 3-81 SOME PROPERTIES OF METALLIC LATTICES 81

strain condition of the cube may be specified by the six strain components

(3-39)

When Hooke's law is satisfied the strain and stress components (3-39) and
(3-37) are linearly related. Thus in analogy with (3-32) we have, for
example,
axx = Cll €xx + C12 €YY + C13 €zz +
C14Yvz +
C15Yzx +
c1SYxv (3-40)

There are six such equations, and hence 36 moduli of elasticity or elastic
stiffness constants Ci ;.32 The relations, which are the inverse of type (3-40),
express the strains in terms of the stresses; for example,

(3-41)

The six equations of this type define 36 constants Si) which are called the
elastic constants. It can be shown that the matrices cij and Sij are sym-
metrical; hence a material without symmetry elements has 21 independent
elastic constants or moduli. Due to the symmetry of crystals, several of
these may vanish. In cubic crystals, as mentioned above already, there are
three independent elastic moduli which are usually chosen as Cn , C12 ' and
Cw Some representative values for cubic metals are given in Table 3-2.
The atomic theory of elasticity is based on the forces acting between the
atoms; we refer the reader to the books quoted at the end of this chapter
for a discussion of this subject.

Table 3-2. Elastic Moduli for Some Cubic Metals

in 10 1 • dyne/cm'

Metal Structure C l1 C 12 ";1.1

---"

AI f.c.c. 1.08 0.62 0.28

Cu f.c.c. 1.70 1.23 0.75
Pb f.c.c. 0.48 0.41 0.14
K b.c.c. 0.046 0.037 0.026
Fe b.c.c. 2.37 1.41 1.16

3-9. Plastic deformation of metals

When a crystal is deformed elastically under influence of applied

stresses, it returns to its original state upon removal of the stresses.
However, if the applied stresses are sufficiently large, a certain amount of
deformation remains after removal of the stresses: the crystal has been
32 Other names for these quantities are in use.
82 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

plastically deformed. We shall see below that the atomic interpretation of

plastic flow of crystals requires the introduction of a new type of lattice
defects, viz., dislocations. The remainder of this chapter will be devoted
to a discussion of the most essential properties of such defects; the
approach to the problem given here follows rather closely the exposition
found in Cottrell's book Dislocations and Plastic Flow in Crystals cited at
the end of this chapter. To begin with, a few pertinent experimental facts
concerning the plastic flow of single crystals will be reviewed.
In many crystals plastic flow results from the sliding of one part of a
crystal relative to another. In Fig. 3-12 we have illustrated schematically
how such a process may lead to an increase in the length of a crystal
under influence of tension. The
. Slip direction
' I .: sliding process is referred to as slip;

P"'I~LLZ:Jl-Pull
the plane and direction in which
the slip occurs define, respectively,
the slip plane and the slip direction.
This type of mechanism evidently
Fig. 3-12. Illustrating the slip process deforms the outer surface of the
due to a tensile stress. The dashed line crystal and leads to so-called slip
shows the original cross section of the bands, as indicated in Fig. 3-12. The
material; note the increase in length
resulting from thi" slip. amount of slip associated with a slip
band may be several thousand Ang-
stroms. From what has been said so far, one can draw an important
conclusion: plastic deformation is inhomogeneous in the sense that
only a relatively small number of atoms actually take part in the slip
process, viz., only those atoms which form layers on either side of a slip
plane. Elastic deformation, on the other hand, affects all atoms in a
crystal. This difference between plastic and elastic deformation indicates
that the atomic interpretation of plastic flow must be based on an entirely
different model than that of elastic deformation. In fact, the elastic
properties of solids can be understood quite well in terms of interatomic
forces acting in a perfect lattice; plastic deformation, however, cannot be
discussed properly on the basis of a perfect lattice, i.e., it cannot be dis-
cussed by simply extending the theory of elasticity to the case of large
stresses and strains. It will be shown below that if plastic flow were to
occur in a perfectly periodic lattice, much larger shear stresses would be
required than those for which plastic flow is observed.
Besides being characterized by inhomogeneity, plastic flow is also
anisotropic. Slip usually takes place preferentially in planes of high atomic
density, e.g. along {Ill} planes in a f.c.c. lattice. Also, the direction of slip
commonly coincides with a direction along which the number of atoms per
unit length is high.
We shall now mention another important result obtained from experi-
ment, viz., the existence of a critical resolved shear stress TC' In Fig. 3-13
Sec. 3-9) SOME PROPERTIES OF METALLIC LATTICES 83
consider a cylindrical crystal of cross section A under influence of a tensile
force F. Let the normal to the active slip plane make an angle rx with F,
and let the angle between the slip
direction and F be 13. The resolved F
shear stress, i.e., the force acting per
unit area of the slip plane in the slip
direction, is then given by

'T = (F/A) cos rx cos 13 (3-42) Slip

direction
since the area of the slip plane is
A/cos rx. Similarly, the tensile stress
per unit area normal to the slip
plane is

a = (F/ A) cos 2 rx (3-43)

')
Suppose now that for given values F
of rx and 13 the force F is gradually in- Fig. 3-13. Geometry of slip plane, slip
creased from zero. Even for relatively direction, and tensile force F.
small stresses a certain amount of
plastic flow occurs, but the rate of flow is small and one speaks of creep.
It turns out, however, that the rate of flow increases very rapidly whenever
the resolved shear stress T reaches a critical value Te' At the same time, the
results indicate that the tensile stress normal to the slip plane is of little or
no influence on the mechanism of slip. For pure crystals, the critical shear
stress lies in the range between 10 6 _10 7 dynes per cm 2 . In general, Tc
decreases with increasing temperature. Also, Tc increases as a result of
alloying or cold working.

3-10. The interpretation of slip; dislocations

One of the central facts which a theory of slip must explain is that in a
pure crystal certain atomic planes start gliding across each other under
influence of a shear stress of the order of 106 _10 7 dynes per cm 2 • We shall
first show that the theoretical critical shear stress based on a perfect lattice
is much larger than the observed values for pure crystals. For this purpose,
we resort to a simplified model suggested by Frenkel. 33 With reference to
Fig. 3-14a, consider a cross section through two neighboring atomic planes
separated by a distance d. Without external forces, let the fully drawn
circles represent the equilibrium positions of the atoms. Suppose now
that a shear stress T is applied, and that as a result, all atoms in the upper
plane are displaced by an amount x relative to their original position.
33 J Frenkel, Z. Physik, 37, 572 (1926).
84 SOME PROPERTIES OF METALUC LATTICES [Chap. 3

Interchanging the role of dependent and independent variables, we may

also say that for a displacement x, a shear stress T(X) is required. Suppose
now that we want to plot T as a function of x. First we note that as a result
of the periodic nature of the system, T will vanish for x = 0, a/2, a, etc.,
where a is the distance between neighboring atoms within the planes (see
\
x T
---~T

,al (b)

Fig. 3-14. Under influence of the shear stress T the upper plane of
atoms in (a) is displaced over a distance x (dashed circles). The
periodic behaviour of T, according to Frenkel, is indicated in (b).

Fig. 3-14b). Oversimplifying the problem, we shall assume with Frenkel

that this periodic function is given by

T(X) = Tc sin (21Tx/a) (3-44)

The "amplitude" Tc is evidently the critical shear stress in this model and
it is this quantity that we wish to estimate. This may be done by realizing
that for x ~ a the usual theory of elasticity should apply; under these
circumstances
T(X) c::: (21Tx/a)Tc for x~a

On the other hand, the elastic strain, in accordance with (3-34) and (3-35)
is given by
y = x/d = TIG

where G is the shear modulus. From the last two equations it follows that
in this model
Tc c::: (G/21T)(a/d) c::: G/21T (3-46)

where the last approximation is justified because a c::: d. Since G c::: 1011
dynes per cm 2 (see C44 in Table 3-2), one obtains in this model a theoretical
shear stress Tc c::: 10 10 dynes per cm 2, which is several orders of magnitude
larger than the observed ones. Although it must be admitted that Frenkel's
model is open to objections, more refined calculations confirm the con-
clusion that it is impossible to obtain agreement between theory and
Sec. 3-10) SOME PROPERTIES OF METALLIC LATTICES 85

experiment on the basis of a model where atomic planes glide past each
other in the manner assumed above (see also Problem 3-12). In Fig. 3-14
it was assumed that the atoms of the upper atomic plane move simul-
taneously relative to the lower plane; this assumption is tied up with the
assumption of a perfect lattice and here we are at the root of the difficulty.
In an attempt to remove this difficulty, let us assume that the crystal
contains an imperfection of such a nature that the slip process is governed,
not by the simultaneous motion of the atoms of one plane relative to
another, but by the consecutive motion of these atoms. Before specifying
this model further, it may be useful to remind the reader of the fact that a
worm moves forward by displacing its segments one after the other rather
than by a simultaneous displacement of all the segments. The atomic
model for the progression of slip, based on the dislocation model, is
analogous to a wormlike motion.
The dislocation model for slip may be introduced with reference to the
crystal of Fig. 3-15a; let the plane PQR be a slip plane. This plane has
been redrawn in Fig. 3- I 5b. In the slip plane consider an arbitrary closed
curve ABC; the n:gion inside this curve is hatched in Fig. 3-15b. Suppose
now that in some way or other the material located over the hatched area
in the upper half of the crystal is displaced by an amoum b relative to
the lower half of the crystal; at the same time, the material in the upper
half lying over the area outside ABC is left undisplaced. In this manner we
have obtained a situation in which only a fraction of the upper half of the
crystal has slipped relative to the lower half. The ratio / of the area ABC
and the total area of the slip plane will be referred to as the fraction of
slip that has occurred in this plane. Thus, if in some way or other the
area ABC could be made to grow, / would increase and for / = I the
whole upper half of the crystal would be displaced by an amount b
relative to the lower half. For / < ], the average displacement of the upper
half relative to the lower half is/b.
The line ABC introduced above marks the boundary in the slip plane
between slipped and unslipped material; this line is called a dislocation
line. The vector b which defines the magnitude and direction of the slip
is called the Burgers vector. 34 Since the atoms always seek positions of
minimum energy, it will be evident that b must connect two atomic
equilibrium positions, i.e., the possible vectors b are determined by the
crystal structure. When the displacement equals one lattice spacing, the
dislocation is said to have unit strength. From calculations of the strain
energy associated with dislocations, Frank has shown that dislocations of
strength larger than unity are in general unstable; they dissociate into
dislocations of unit strength. 35
So far, we hav~ only given a definition of a dislocation. In order to see
3. J. M. Burgers, Proc. Koninkl. Ned. Akad. Wetenschap., 42, 293, 378 (1939).
35 F. C. Frank, Physica, 15, 131 (1949). ' , .'
86 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

how this model may account for a number of observations on plastic flow,
various questions must be raised; for example:
I. Assuming that a slip plane
such as PQR in Fig. 3-15 contains
a dislocation as indicated, one should
be able to show that under influence
of a shear stress, applied in the
proper direction to the crystal, the
dislocation tends to grow; under
la) Ib) these circumstances the slipped region
Fig. 3-15. Schematic representation of
would increase in size and slip would
a ring dislocation ABC in a slip plane proceed. Moreover, the calculated
PQR. Slip has occurred only across the critical shear stress should agree
hatched area. quantitatively with the observed
values. \
2. We have seen above that slip in a single slip plane may correspond
to displacements of the order of 1000 A; on the other hand, once a dis-
location such as ABC in Fig. 3-15 has swept through the whole slip plane,
the slip produced is only b c:::: 2 A, and moreover, the dislocation has then
disappeared. It will thus be necessary to account for large numbers of
dislocations taking part in the slip process and for sources which supply
such dislocations.
3. Are other physical properties, besides plastic flow, determined to at
least a measurable degree by the presence of dislocations so that indepen-
dent information regarding the properties of dislocations can be obtained?
Some of these questions will be discussed below; of course, many
more can be asked.

3-11. Motion of dislocations under influence of a uniform shear stress;

dislocation density

With reference to Fig. 3-15, suppose a uniform shear stress T is applied

to the crystal along the direction of the Burgers vector. Mott and Nabarro
have shown that this leads to a force on the dislocation line such that the
slipped area tends to groW. 36 Consider an element ds of the dislocation
line; suppose this element is displaced outwardly (Fig. 3-15b) by an
amount dt along a direction perpendicular to ds. The area swept out by
the line element is then ds dl. According to what has been said in the pre-
ceding section, this corresponds to an average displacement of the upper
part of the crystal relative to the lower part by an amount ds dt bfA, where
A is the area of the slip plane. The work done by the shear stress is equal
36 N. F. Mott and F. R. N. Nabarro, "Report on Strength of Solids," Phys. Soc.
(LOlldol1). 1948, p. I. • .•
't')~
,,.
...: I
Sec. 3-11] SOME PROPERTIES OF METALLIC LATTICES 87

to the total shear force TA times the average shear displacement, i.e., equal
to Tb ds dl = dW. This corresponds to a force -dWjdl acting on the
element ds in the direction of the normal. Hence the force per unit length
is equal to
F=Tb (3-47)

Thus the applied shear stress produces a force per unit length everywhere
along the dislocation line equal to Tb and perpendicular to the line element.
If the force is large enough to make the dislocation line move in the direc-
tion of F, the slipped area in Fig. 3-15 will grow and slip will occur under
influence of the shear stress.
On very general grounds one can show that the critical shear stress for
slip should be very small for the dislocation model. In order to see this,
let us consider the regions near the dislocation line somewhat more
closely. Because of the nature of interatomic forces, the boundary
between the slipped and unslipped regions is not sharp, but rather vague,
extending over several atomic distances. The atoms near the dislocation
line of Fig. 3-15, at the inside, have nearly completed the slip process;
those near the dislocation line on the outside are just beginning to slip. As
a result of the periodic nature of the potential for the atoms, those at the
outside of the dislocation line and close to it tend to push the dislocation
line inward, since this would allow them to occuPY their initial equilibrium
positions. On the other hand, the atoms inside the dislocation line and
situated close to it tend to push the line outward, since this would make it
possible for them to occupy their new equilibrium positions associated
with completed slip. Far away on either side of the dislocation line, the
atoms occupy normal lattice positions and are not affected by the dis-
location. Thus to a first approximation, the forces on the dislocation line
balance and it should start moving under the smallest of shear forces.
It thus looks as if this model is too successful in explaining the relatively
low observed critical shear stress; however, when one goes to a second
approximation, one finds that the critical shear stress calculated for this
model is not zero, but in fact of the same order of magnitude as observed
values. 37
Density o/dislocations. It was mentioned above that a single dislocation
line sweeping across a slip plane gives rise to a displacement of the order of
a few Angstroms; thus any appreciable plastic deformation must be the
result of a large number of dislocations sweeping across many slip planes.
It will be evident that the rate of pla~tic flow will be determined by the rate
at which dislocation lines sweep through the slip planes, i.e., the rate of
flow may be expected to be proportional to the total length of all active
dislocation lines and the average velocity with which the elements of these
lines move. One has therefore introduced the concept of "dislocation
37 See Cottrell, op. cit., p, 62.
88 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3
density," p = S/V, where Sis the total length of the dislocation lines and V
is the volume of the crystal. Note that p has the dimension length-2•
More specifically, one arrives at this concept by the following reasoning:
Consider an element ds of a dislocation line such as ABC in Fig. 3-15.
Let v be the velocity of the element along the direction of the normal to ds
in the slip plane. When H is the height of the crystal and A is the area of
the slip plane, the increase in strain per second due to the motion of the
element ds is equal to
dyldt = v ds blAH (3-48)

Considering the rate of flow resulting from all dislocations in planes

parallel to the plane PQR in Fig. 3-15, we have to sum expression (3-48) in
a suitable fashion, i.e., we must replace ds by the total length S of all these
dislocations and v by some average velocity (v). Hence
> ,

'.

dyjdt = (v) SbjV = pb(v) (3-49)

where p is the dislocation density. Methods to determine the dislocation

density in crystals will be mentioned in Sec. 3-15.

3-12. Edge and screw dislocations

The elements of a ring dislocation such as ABC in Fig. 3-15 may be

considered as composed of two basic types of dislocations: edge disloca-
tions and screw dislocations. A pure edge or Taylor-Orowan dislocation
is defined as a dislocation for which the Burgers vector b is everywhere
perpendicular to the dislocation line. 3s A screw or Burgers dislocation is
defined as a dislocation for which the Burgers vector b is everywhere
parallel to the dislocation line. Thus in Fig. 3-15b the vertical elements are
of the edge type, the horizontal elements are of the screw type; the
remainder is mixed edge and screw. We shall now consider the physical
structure of these basic dislocations.

Edge dislocations. The simplest edge dislocation is one for which the
dislocation line is straight. Its formation may be vizualized in terms of a
slip process with reference to Fig. 3-16a. Suppose the block of material ~
cut across the area ABEF so that across this area the upper and lower
parts are disconnected.
The upper half is then pushed sideways such that the line AlB' which
initially coincided with AB is shifted by an amount b as indicated. If in
this position the two halves were glued together, we would have produced
an edge dislocation. The upper half of the block will clearly be under
38 G. 1. Taylor, Proc. Roy. Soc., A145, 362 (1934); E. Orowan, Z. Physik, 89, 605,

614,634 (1934).
Sec. 3-12] SOME PROPERTIES OF METALLIC LATTICES 89

compression, the lower half under tension. A square network of lines

drawn on the front face BCD before the operation, would, after the
operation, look as indicated in Fig. 3-16b. This strain pattern suggests
immediately an altecnative method by which an edge dislocation may be
produced. Consider the intersections of the network of lines of Fig. 3-16b
as representinOg rows of atoms perpendicular to the plane of the paper.

D
(al Ibl

Fig. 3-16. In (a), EF represents an edge dislocation line; (b) gives

the strain pattern. [After A. H. Cottrell, Dislocations and Plastic
Flow in Crystals, Oxford, New York, 1953, p. 22]

The edge dislocation may then be obtained by cutting the block along the
plane EFGH, and putting the half plane of atoms initially above AB,
inside the cut. This gives rise to the "extra" half plane of atoms corre-
sponding to HE in Fig. 3-16b, which is typical of an edge dislocation.
Note that if the extra half plane HE were displaced to the right, slip would
progress, and when HE has finally reached the right-hand side of the
block, the upper half of the block has completed slip by the amount b.
The slip process resulting from a
moving edge dislocation has been
illustrated in Fig. 3-17. Edge dis-
locations for which the extra half
·ClJ· Gi····
. ... . . ....
.... .. .. .. .. ...
••• J... • ••••
... ..
plane lies above the slip plane are
--
called positive. If the extra half Fig. 3-17. Motion of a positive edge
plane lies below the slip plane, one dislocation to the right, leading to slip.
speaks of a negative edge dislocation. [After Taylor]
We leave it to the reader to show
for himself that the slip process of Fig. 3-17 resulting from a positive
edge dislocation moving to the right can also be achieved by motion of a
negative edge dislocation of the same strength to the left.
The definition of an edge dislocation does not necessarily imply that
the dislocation line is straight. In fact, any curved line will do as long as it
90 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

is perpendicular to the Burgers vector b. Thus by inserting in a block of

material an extra half plane with an irregular boundary, we can produce
what is known as an irregular edge dislocation. An edge dislocation may
therefore contain jogs as indicated in Fig. 3-18. If
an atom such as Q diffuses into the lattice, interstitial
atoms may be produced or vacancies annihilated at
the expense of the extra half plane. Similarly, if an
atom occupying a normal lattice position were to move
into the position directly on the left of Q, the extra
Fig. 3-18. Extra
half plane would grow and a vacancy would be pro-
half-plane of atoms duced or an interstitial annihilated in the lattice
which jogs at Q. itself. Thus edge dislocations may act as sources or
sinks for vacancies and interstitials. 39 The reader
will realize that these properties are directly associated with the extra
half plane which characterizes an edge dislocation. Interstitials or
vacancies may also be generated as a by-product of the recombination
of a positive and a negative edge dislocation. Consider, for example, the
case where the slip plane of a positive edge dislocation is parallel to that
of a negative edge dislocation, the former lying two interatomic distances
above the latter. When these dislocations meet, one arrives at a situation
represented in Fig. 3-19 in which a row of vacancies is left after recombina-
tion; similarly, if the half planes overlap, one or more rows of interstitials
become available.
The presence of an extra half plane
of atoms in an edge dislocation restricts
the motion of an edge dislocation mainly
to the slip plane. The reason is that any - - - - []- - - - - }Slip planes
motion perpendicular to the slip plane - - - - -- -- - -
requires either a growth or a reduction of 1
the half plane. Thus the easy direction of
motion of an edge dislocation is in the
slip plane since the number of atoms in Fig. 3-19. Indicating the forma-
the extra half plane is conserved in this tion of a row of vacancies (repre-
case. Any motion of an edge dislocation sented by square) upon recom-
bination of a positive and a
perpendicular to the slip plane is termed negative edge dislocation; the
nonconservative because it involves either dislocation Jines are perpen-
rejecting or accepting "extra" atoms. dicular to the plane of the paper.
Nonconservative motion is, of course, not
excluded, but its occurrence depends on whether the diffusion of atoms
is rapid enough to sustain it.

Screw dislocations. In Fig. 3-20 we have represented the atomic

configuration in the vicinity of a screw dislocation piercing the surface of a
3. See, for example, F. Seitz, Admnces in Physics, 1,43 (1952),
Sec. 3-12] SOME PROPERTIES OF METALLIC LATTICES 91

simple cubic lattice. This configuration may be obtained by cutting the

block across the area BF H M and then pushing the upper part backward in
the direction of the Burgers vector b, as indicated. The dislocation line
BM is parallel to b; note that a screw dislocation line is necessarily
straight, in contrast with an edge dislocation line. As one moves around
the dislocation line along a circuit such as AKLCDE, one advances in the
direction of BM by an amount equal to b for every turn; hence the term
"screw" dislocation. Since no extra
half plane is involved in a screw dis-
location, one cannot speak in this
case of nonconservative motion. Thus H
the motion of a screw dislocation is
less restricted than that for an edge;
the screw dislocation can in fact move
along any cylindrical surface with the
Burgers vector as its axis. If in Fig. Fig. 3-20. Schematic representation
3-20 the dislocation line moves to the of a screw dislocation in a simple
cubic lattice; the dislocation line
left, slip proceeds; thus screw dis- BM is parallel to the Burgers
locations, like edge dislocations, can vector b.
produce plastic flow.
An interesting feature of screw dislocations in connection with crystals
grown from vapors or solutions may be mentioned here. 40 In these cases
the crystal growth is a result of supersaturation and of the conditions on the
surface of the growing crystals. In order for the atoms deposited on the
surface to be firmly bound, the surface must contain steps, since at the
corners of these steps they can be bound by two or more atoms. Suppose
now that a crystal without dislocations has such steps on its faces.
Gradually these steps become filled up and ultimately the surface becomes
flat and unsuitable for further growth. However, if the crystal has a screw
dislocation, such as in Fig. 3-20, continuous growth becomes possible,
since as new material is deposited at the step, the step simply rotates but
never disappears. Experimental evidence strongly supports these
considerations.

3-13. Stress fields around dislocations

Many of the properties of dislocations are determined by the stress

fields they produce in the surrounding material. Calculations of the stress
fields are usually carried out on the assumption that the medium is isotropic
and characterized by a shear modulus G and a Poisson ratio v. We shall
not give the details of such calculations here, but only mention the results
40 W. K. Burton, N. Cabrera, and F. C. Frank, Nature, 163, 398 (1949); see also,

on crystal growth, Discussions Faraday Soc., 5 (1949); L. J. Griffin, Phil. Mag., 41,196
(1950).
92 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

for edge and screw dislocations. 41 In Fig 3-21 consider the cross section of
a cylindrical piece of material; the axis of the cylinder will be taken as the
z-axis of a Cartesian coordinate system. Suppose we produce a cut in the
plane y = 0, which extends between the axis and the outer surface as
indicated. We now let the material above the cut slip to the left by an
amount b, leading to the configuration
Y indicated by the dotted line. We have
then produced a positive edge dislocation
along the z-axis with a Burgers vector
along the x-axis; the plane y = 0 is the
slip plane. In terms of the coordinates r
and e, the stress field of the dislocation
x line may then be shown to be given by the
following tensile and shear stresses:

Gb . ()
(Jrr = (Joo = - 217r(1 _ v) SIll (3-50)

Fig. 3-21. An edge dislocation

Gb
along the z-axis in a cylindrical piece
of material.
T r6 = TOr =
217r( 1 - ~)
COS e (3-51)

Here positive values of a refer to tension, negative values of a refer to

compression; (Jrr is a radical compression or tension, while a ee is a
compression or tension acting in a plane perpendicular to r. The shear
stress Tro acts in a radial direction. It is observed that the stresses vary as
l/r. In the region above the slip plane arr is negative, corresponding to a
compression, in agreement with our previous qualitative discussion;
below the slip plane arr corresponds to a tensile stress. It must be
emphasized that the stresses become infinite for r = 0 and therefore a small
cylindrical region of radius ro around the dislocation must be excluded. In
an actual crystal this difficulty does not arise, since the material consists of
atoms; on the other hand, the stresses in the immediate vicinity of an
actual dislocation will also be large, and Hooke's law is probably not
valid in that region. For example, for r = b the strains are of the order of
-~17(1 - v) c::: 25 per cent.
On the basis of these results, let us now estimate the energy of formation
of an edge dislocation of unit length. The final shear stress in the plane of
the cut is given by (3-51) with e = O. For a cut extending over unit
length along the z-direction, the energy required to form the dislocation
is evidently equal to the integral over the cut surface of half the product of

41 For further details and references, see A. H. Cottrell, Di,'locations and Plastic Flow
ill Crystals, Oxford, New York, 1953; W. T. Read, Dislocations in Crystals, McGraw-
Hill, New York, 1953.
Sec. 3-131 SOME PROPERTIES OF METALLIC LATTICES 93
stress and strain, i.e., equal to

-f
1
2
R

To
Gb 2
27Tr(1 - '1')
dr =
Gb 2
47T(l - '1')
log (R/ro) (3-52)

where R is the radius of the piece of material. Note that as R becomes

infinite the energy of formation goes to infinity. By way of an estimate, let
us take R = 1 cm, ro = 10- 7 cm, G = 5 X 1011 dynes cm- 2 , b = 2.5 X
10-8 cm, and v = k. One then obtains an energy of 6 X 10-4 erg cm-I,
which corresponds to approximately 10 ev per atom along the dislocation
line.
The configurational entropy of an edge dislocation is very small indeed;
in fact, according to Problem 3-14, the configurational entropy per atom
along the dislocation line for the dimensions assumed above contributes to
the free energy a term of the order of 10-6 kT. This result, combined with
the energy of formation estimated above, leads to the important con-
clusion that the density of dislocations in thermal equilibrium with a
crystal essentially vanishes. In this respect dislocations behave altogether
differently from "atomic" lattice defects such as vacancies and interstitials.
The configurational entropy associated with the latter is so large that the
density of such defects in thermal equilibrium may be appreciable. The
essential reason for this difference is the fact that a dislocation is a "line"
defect rather than a collection of independent "point" defects; since
the dislocated atoms must keep in line with each other, the number of
possible configurations is strongly limited. The reason why relatively high
dislocation densities are preserved in a crystal will be explained in Sec. 3-14.
For a screw dislocation along the z-axis in a cylindrical piece of material,
the stress field is completely given by a shear stress:

. TzO = TO.? = Gb/27Tr (3-53)

The absence of tensile and compressional stresses in this case is associated

with the absence of an extra half plane of atoms. Note that the stresses do
not contain e, i.e., the stress field is cylindrically symmetric as one might
have expected. The energy of formation of a screw dislocation is approxi-
mately two-thirds that of an edge dislocation of the same length in the
same material, as shown in Problem 3-15.

3-14. Interaction between dislocations

Since any dislocation is surrounded by a stress field, the energy required

to form a dislocation in a piece of material which contains already another
dislocation will be different from that required to form the dislocation in
the absence of the other. In other words, there will be an energy of
interaction between two dislocations; the gradient of the interaction
94 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

energy determines the force between them. This can most easily be
demonstrated for two parallel screw dislocations; in this case the stress
fields have cylindrical symmetry and one expects the force between them
to depend only on their distance apart, i e., the force should be a central
force. To illustrate this, suppose a piece of material contains a screw
dislocation along the z-axis (Fig. 3-22) and let us produce a second screw
dislocation parallel to the first one, at a
distance r. As before, we produce a cut
extending from A to B in Fig. 3-22 and
displace the material on one side of the cut
relative to that on the other side over a dis-
tance b along the z-direction. Since at the
moment we are interested only in the in-
x teraction energy of the two dislocations, we
shall calculate only the work required to pro-
Fig. 3-22. Referring to the
duce the second dislocation in so far as this
calculation of the interaction work is determined by the presence of the
energy of two screw dis- first dislocation. Thus, if E; represents the in-
locations running along the teraction energy per unit length of dislocation,
z-axis; one is located at the We may write
origin, the other in A. [After
Cottrell, op. cit., p. 50]
(3-54)

where Gb/21Tr is the shear stress produced along the z-direction in the cut by
the dislocation at the origin. The force between the two dislocations is
then
F(r) = -dEJdr = Gb 2/21Tr (3-55),
Note that the force varies as l/r. For dislocations of opposite sign the
force is attractive; for equal signs the force is repulsive.
Similar considerations may be held for the interaction between edge
dislocations. In this case the force has a radial as well as a tangential
component. Thus for two-edge dislocations of equal sign, along the z-axis
and with a Burgers vector along the x-axis, one obtains 42

Gb 2
Eo = 21T(1 _ v)r sin 20 (3-56)

where 0 is the angle between r and the x-axis (see Fig. 3-23). Here again,
the radial force is repulsive or attractive depending on whether the
dislocations have equal or unequal signs. In the latter case the signs of
both Fr and Fo must be reversed in (3-56). We have mentioned earlier that
the motion of an edge dislocation is mainly confined to the slip plane
(conservative motion). For this reason, the force component along the
.. See Cottrell, op. cit., p. 47. 'l,'
Sec. 3-14) SOME PROPERTJES OF METALLIC LATTICES 95

x-direction is the most important; for two-edge dislocation of the same

sign this component may be obtained from the relation (see Fig. 3-23)
Fx = FT cos (j - Fo sin (j (3-57)
Substituting Fr and Fo from (3-56), one finds readily
F = Gb 2x(X2 - y2)
(3-58)
x 27T(l - v)r 4
It is observed that this component vanishes for x = 0 and for. x = y.
Furthermore, when x > y, or (j < 45°, two
parallel edge dislocations of the same sign y
repel each other in the direction of the slip
plane; for x < y, or (j > 45°, they attract
each other along the x-axis. The stable
configuration for the two dislocations
occurs when they lie vertically above each
other. This conclusion is also true when
a large number of edge dislocations of the
same sign are involved. In fact, such an
array of dislocations has been suggested
by Burgers as a model for a grain bound- Fig. 3-23. Radial and tangential
ary between two crystallites of different components of the force exerted
by an edge dislocation at the
orientation. 43 origin on an edge dislocation at
Dislocations also interact with a free A. Both dislocations lie along
surface. In fact, any dislocation will be the z-axis and have a Burgers
attracted by a free surface, since a motion vector along the x-axis. The
towards the surface would reduce the strain calculation in this case involves a
cut along AB.
energy. According to Koehler the force of
attraction is approximately given by an
image force, i.e., approximately equal to the force of attraction produced
by a dislocation of opposite sign located at the image position of the first
one relative to the surface. 44
While on the subject of· stress fields around dislocations, we may
mention that impurities are in general attracted by edge dislocations. If
the impurity atoms are "larger" than those of the host lattice, they will
tend to move toward the region of tension, since in this way the tension will
be somewhat released in this region. On the other hand, if the impurity
atoms are "smaller" than the host atoms, they tend to be deposited in the
region of compression.
In the preceding section we mentioned that dislocations are not in
thermal equilibrium with the lattice and the question was raised as to why
.3 J. M. Burgers, Proc. Koninkl. Ned. Akad. Wefenschap., 42, 293 (1939); Proc. Phys.
Soc. (London), 52, 23 (1940). For experimental evidence, see next section.
H J. S. Koehler, Phys. Rev., 60, 397 (1941).
96 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

it is not possible to remove almost all dislocations in a solid by annealing.

The reason for this is the following: The density of dislocations in a solid
is determined essentially by its history, i.e., by conditions under which the
crystal was grown, cold working, etc. Certain parts of the dislocations may
be mobile; for other parts the motion may be hindered or completely
inhibited by interaction with impurities or other dislocations. Consider, for
example, a point at which three dislocation lines meet. In general, such a
point is essentially immobile, since it involves nonconservative motion of
one or two of the dislocations involved. Ultimately, therefore, the dis-
locations probably arrange themselves in a sort of three-dimensional
network or superstructure in the solid. 45 Although such a situation is not
thermodynamically stable, it may be very stable in the mechanical sense
for reasons just explained. We shall return to this point in the
discussion of mosaic structures in Sec. 3-15.

3-15. Estimates of dislocation densities

Tn this section we shall discuss briefly some methods by which the

density of dislocations in solids may be estimated.

1. Plastically bent crystals. Plastic bending of crystals takes place in a

manner similar to the bending of a deck of playing cards. As illustrated in
Fig. 3-24a, this process can be understood in terms of a slip process of thin
layers of the crystal, the slip direction at one end being opposite to that
at the other end. Since the bent state is stable, it seems reasonable to

la) Ib)

Fig. 3-24. Plastically bent crystal (a) and the corresponding

dislocation model (b). [After Cottrell, op. cit., p. 29J

assume that the crystal in this state contains a number of edge dislocations
in a pattern such as the one illustrated in Fig. 3-24b. In order to calculate
the density of dislocations required to bend a certain specimen to a certain
radius of curvature, consider a single glide packet. When L is the length of
the outer arc and t is the thickness of the packet, the length of the inner arc
is evidenly L(l - tfR) where R is the radius of curvature. Suppose now
that the packet contains n positive edge dislocations; we must then have
'1b = tLfR, where b is the absolute value of the Burgers vector. Since the
iensity of dislocations in this case is simply given by the number of
•• F. C. Frank, Report of Pi((sbu~r:h Conference on Plastic Deformation of Crystals,
950, p. 100. .. ,.. ' ,<M
~, ;
.: t
Sec. 3-15] SOME PROPERTIES OF METALLIC LATTICES 97

dislocation lines piercing through a unit area of the plane of the paper,
we..obtain
p = niL! = llRb (3-59)
For example, to bend a crystal to a radius of 3 cm one requires, with
b c::::: 3 X 10- 8 cm, a dislocation density pc::::: 107 cm- 2•

2. Estimates from X-ray diffraction measurements. In Chapter 1 we

discussed. the conditions for X-ray diffraction from crystals and found that
reflection occurs only if the Bragg condition is fulfilled. Now, if a crystal
had perfect periodicity, the angular spread about the Bragg angle should be
not more than about 5 seconds. However, most crystals show an angular
spread of the order of several minutes. In order to explain discrepancies of
this kind, Darwin 46 and Ewald 47 introduced, many years ago, the notion of
a mosaic crystal, i.e., they assumed that an actual crystal is made up of a
number of small blocks which themselves are perfect but which are slightly
misoriented relative to each other. It is presently believed that this mosaic
structu. e may be the result of the three-dimensional network of dis-
locations mentioned in the preceding section. Assuming that this is the
case,48 an estimate of the dislocation density in terms of the observed. total
angular spread () of the X-ray pattern may be made in the following manner:
Suppose the surface area of the crystal involved in the X-ray measurements
has a side L. Let the density of dislocations in the crystal be p, so that p
dislocation lines pierce through a unit area of the surface of the crystal.
Let us now define the edge A of each block in the mosaic structure in such a
way that A2 = lip, i.e., we associate one block with each dislocation line
coming out of the surface. The average angular misfit between blocks is
then ex = blA radians; these misfits may be positive or negative. Thus as
we pass across the crystal over a distance L, we pass LI A blocks, and the
probable angle of misfit between the first and the last block is ex (LIA)1/2.
Identifying this angle with the total observed spread of 0 radians, we find
() = ex(LIA)1/2 or {j = bV/2p3/4 (3-60)
For a typic~l case of a pure crystal let us take L = 0.1 cm; () = 10-2
radian, and b = 3 X 10-8 cm. We then obtain p c::::: 108 cm- 2 . Note that in
this case A c::::: 10-4 em, in agreement with other estimates.
3. In heavily cold-worked metals the density of dislocations is
sufficiently high to produce an increase of a few per cent in the electrical
resistivity. According to calculations by Dexter, densities of dislocations
of the order of 1012 cm- 2 are required to explain measurements made on
cold-worked copper. 49 Similar estimates have been obtained from
.6 C. G. Darwin, Phil. Mas'" 27, 325" 675 (1914),
"p, p, Ewald, Ann. Physik, 54, 519, 577 (1917).
48 R. D. Heidenreich and W. Shockley, "Report on Strength of Solids," Phys. Soc.
(London), 1948, p. 57. ,- .,.,_
.. D. L. Dexter, Phys. Ret'., 86, 770 (1952).
98 SOME PROPERTIES OF METALLIC LATTlCES [Chap. 3

measurements of other physical properties, such as the magnetic

saturation of cold-worked ferromagnetic materials. 50
4. In the preceding section we mentioned that Burgers suggested that the
boundary between two crystals differing in orientation by a small rotation
oc may consist of a set of edge dislocations as indicated in Fig. 3-25. If D
is the average distance between the dis-
locations, the angle should presumably be
equal to IX = bl D, where b is the magnitude
of the Burgers vector. This model' has been
verified for germanium single crystals in the
following manner :51 A germanium crystal
was grown from a seeded melt along the <l00)
direction. Grain boundaries were then re-
vealed by etching with an acid. When the
Fig. 3-25. Burgers disloca-
boundaries were examined under high mag- ,
tion model of a symmetrical nification, they were fouad to consist of
grain boundary. regularly spaced conical pits, as shown in
the micrograph of Fig. 3-26. It is believed
that each etch pit corresponds to a single dislocation piercing through the
surface. Because of the strain in the vicinity of a dislocation line, the

-.'.....
iii:
. . ...
.....
.

/O,M

Fig. 3-26. Optical micrograph of lineage boundary in germanium

single crystal, viewed in face transverse to growth direction.
Lighting oblique. (Reproduced with permission from F. L. Vogel,
W. G. Pfann, H. E. Corey, and E. E. Thomas, Phys. Rev., 90, 489
(1953))
;;0 W. F. Brown, Php,. Rev., 60, 139 (1941).

51 F. L. Vogel, W. G. Pfann, H. E. Corey, and E. E. Thomas, Phys. Rev., 90, 489

(1953 ).
Sec. 3-15) SOME PROPERTIES OF METALLIC LATTICES 99
material around it presumably dissolves preferentially. The distance
between the pits may be obtained by counting, and the angle IX may
be determined from X-ray diffraction experiments. For three specimens,
the calculated distance between dislocations and the observed distance
between etch pits are given below.

rx (seconds) Deale. (cm) DubS. (cm)

17.5±2.5 (4.7 ::1: 0.7) X 10~' (5.3 ± 0.3) X IO~'

65.0:': 2.5 (1.3 ± 0.1) X 10~' I
I
(1.3 ± 0.1) X 10~'
85.0::": 2.5 (0.97 :+: 0.2) ;: 10~' (0.99 ::I- 0.2) X IO~'
I ~
It is observed that the agreement is remarkably good. One might probably
conclude that the etch pit method is presently the most direct method for
determining the dislocation density.

3-16. The ~rank-Read mechanism of dislocation multipJication

We have mentioned before that the amount of slip occurring in a slip

plane requires a large number of dislocation lines sweeping across it in
succession. One possible mechanism by which dislocations may multiply
has been suggested by Frank and Read ;52 this mechanism is illustrated
schematically in Fig. 3-27 with the slip plane coinciding with the plane of
the paper. Suppose the line AD is
part of the three-dimensional dis-
location network in a crystal and
that points A and D themselves are
immobile. Under influence of a suit-
ably applied shear stress the line will
be deformed successively to the stages
I, 2, 3, 4, and 5. The latter stage
results when finally the two points P
and Q meet; when this happens the
bent structure breaks up into a new
straight part AD and a ring dis-
location. In this manner, the line AD Fig. 3-27. Illustrating the Frank-Read
may produce an unlimited amount mechanism of dislocation multiplication.
of slip. It can be shown that the stress
required for this process is of the order of CbIL, where L is the length of
the line. For further details concerning this subject we refer the reader
to the literature.

'2 F. C. Frank and W. T. Read, Phi's. Rev., 79, 722 (1950).

100 SOME PROPERTIES OF METALLIC LATTICES [Chap. 3

REFERENCES
c. S. Barrett, Structure of Metals, 2d ed., McGraw-Hili, New York, 1952.
A. H. Cottrell, Theoretical and Structural Metallurgy, Arnold, London,
1953.
A. H. Cottrell, Dislocations and Plastic Flow in Crystals, Oxford, New
York, 1953.
W. Hume-Rothery, The Structure of Metals and Alloys, Institute of
Metals, London, 1936.
W. Hume-Rothery, Electrons, Atoms, Metals and Alloys, Institute of
Metals, London, 1948.
W. Jost, DiffUSion in Solids, Liquids, Gases, Academic Press, New York,
1952.
N. F. Mott and H. Jones, Theory of the Properties of Metals and Alloys,
Oxford, New York, 1936.
W. T. Read, Dislocations in Crystals, McGraw-Hill, New York, 1953.
F. Seitz, The Physics of Metals, McGraw-Hill, New York, 1943.
W. Shockley (ed.), Imperfections in Nearly Perfect Crystals, Wiley, New
York, 1952.
A. R. Verma, Crystal Growth and Dislocations, Academic Press, New York,
1953. '
C. Zener, Elasticity and Anelasticity of Metals, University of Chicago
Press, Chicago, 1948.
Report of a Conference on Strength of Solids, Physical Society, London,
1948.
SympOSium on Plastic Deformation of Crystalline Solids, Carnegie Institute
of Technology and Office of Naval Research, 1950.
Report of the Bristol Conference on Defects in Crystalline Solids, Physical
Society, London, 1954.
For review papers see also:
Progress in Metal Physics, Interscience, New York, beginning with
Vol. 1, 1949.
Advances in PhYSiCS, Quarterly Supplement to the Philosophical Magazine,
beginning with Vol. 1, 1952:
Chap. 3) SOME PROPERTIES OF METALLIC LATTICES 101

PROBLEMS

3-1. When N is an integer ~ 1, one may approximate the expression

log (N!) = log 1 + log 2 + ... + log N
by an integral. From this, prove Stirling's formula log (N!) ~ N log N.
3-2. Suppose one has N boxes and n balls, where both Nand n are
~ I; the balls are all of the same color and indistinguishable.
(a) If there is no restriction on the total number of balls in any given
box, show that the number of ways in which the balls can be distributed
over the boxes is equal to (N + n)!/N!n!
(b) Suppose each box can contain either one ball or no ball; with this
restriction, show that the number of ways in which the balls can be distri-
buted over the boxes is equal to N!/(N - n)!n!
3-3. Consider a system of N one-dimensional harmonic oscillators, all
of the same frequency v. According to Sec. 2-4 the vibrational energy of
this system for a temperature T;> hv/k is approximately equal to NkT =
nhv, where n is the total number of vibrational quanta associated with
the N oscillators. Making use of the answer of Problem 3-2a, show that
the thermal entropy of the system is equal to
SIll ""' Nk [1 + log (kT/hv)] for hv <{ kT
This proves expression (3-2). Also find an expression for Stll for
temperatures which are not high compared with hv/k. Furthermore,
derive an expression for the free energy F of the system for both temperature
ranges.
3-4. Consider a system of N one-dimensional harmonic oscillators in
contact with a temperature bath T; all oscillators have the same frequency
v. Assume thai in equilibrium the oscillators have a total of n vibrational
quanta hv; consider n for the moment as a variable and find an expression
for the free energy F. From the equilibrium condition (3F/onh = 0,
derive Planck's formula for the average energy of an oscillator at a
temperature T. (Note; In the preceding problem one makes explicit use of
Planck's formula, in contrast with the present problem.)
3-5. Estimate the number of vacancies per atom in thermal equilibrium
for a crystal at T = 300° and T = 600°, assuming that the energy required
to form a vacancy is lev.
3-6. Show that for a quantized as well as for a classical harmonic
oscillator the average fraction of time spent in energy states ;;:?E is given
by exp (-E/kT).
3.7. Show that the number of Frenkel defects in a solid element in
thermal equilibrium at a temperature T is given by expression (3-13).
102 ... SOME PROPERTIES OF METALLIC LATTICES (Chap. 3

3-8. Consider a low-temperature modification A and a high-tempera-

ture modification B of a certain element. I n order to discuss the equilibrium
between these modifications, assume for simplicity that the lattice vibrations
may be represented by Einstein models of frequencies v" and VO' Suppose l

that the binding energies per atom in the two modifications are given by
- E " and -E/). Explain why E" > Eli' Set up an expression for the free

energy per atom in each of the modifications. Then write an expression for
the change in the free energy t::.F if one atom is transferred at constant T
from A to B. In equilibrium, t::.F = O. Show that there is only one tempera-
ture for which the two modifications are in equilibrium, viz., Tee( =
• (Eb - Ea)/[k log (vu/vJ. What can one conclude about the ratio vb/Va, and
explain why the answer is reasonable.
3-9. Consider a b.c.c. lattice built up of atoms which may be assumed
to be hard spheres of radius R. Calculate the maximum radius of a hard
spherical atom that would fit in an interstitial position. Do the same for a
f.c.c. lattice (in this case there are two types of interstitial positions !).
How many interstitial positions are there in both types oflattices per normal
lattice site?
3-10. Consider a particle restricted to motion in one dimension.
Suppose the particle undergoes consecutive displacements with equal
probability to the left or to the right, the absolute magnitude of the
displacements being A. Show that the mean square displacement for N
steps is equal to NA2. Also show that the probability for the particle to be
found at a distance nA relative to the origin, after N steps, is given by
1)"" N!
pen)~ = ( :2 l(N + n)/2] ![(N -- n)J2]!
From this, show that for N'}:> 1 the probability to find the particle after a
time interval t at a distance x relative to the origin is given by
2T)1/2
P(x,t) c:::: ( TTt exp (-X 2T/2A 2t)

where T is the time required for a single step.

3-11. An infinite medium contains at t = 0 a quantity Q of a diffusing
substance per cm 2 concentrated in the plane x = O. Show that the concen-
tration c(x,t) is given by

c(x,t) = 2(TT~t)I/:!. exp (-x 2J4Dt)

From this and the results obtained in the previous problem, show that the
diffusion coefficient in terms of the random walk problem is given by
D = }.2j2T. Also show that the mean square displacement for a time t
is given by (2Dt)1/ 2•
Chap. 3] SOME PROPERTIES OF METALLIC LATTICES 103
3-12. Express the theoretical shear strength of a perfect lattice in
terms of the shear modulus G on the assumption that slip will start when
the shear strain is 10 per cent, compare the result with that obtained in
Sec. 3-10 on the basis of Frenkel's model.
3-13. Show that the elastic strain energy in a crystal under the stress at
which slip begins is of the order of 103 ergs cm- 3 . Assuming that the strain
energy were converted into heat, what would be the rise in temperature of
the material?
3-14. Consider a solid in the form of a cube of 1 cm3 containing a
dislocation line perpendicular to one of the faces. Show that the configura-
tional entropy is ,.._,1O- 6 k per atom along the dislocation line. For the
importance of this result see Sec. 3-13.
3-15. Show that the energy of formation for a screw dislocation per
unit length is equal to (Gb 2 (47T) log (R(ro) where the symbols used are
those of Sec. 3-13. For a Poisson ratio l' "::::' L this is about two-thirds
that of an edge dislocation (see 3-52).
3-16. Show that the force between two positive edge dislocations is
given by expression (3-56); follow the same procedure as that employed in
the text to calculate the force between two screw dislocations. Make use of
the cut indicated in Fig. 3-23.

')"

.. '~ .
"
J ; •• _ , ',t ,~:);:

\ '
Chapter 4 \ \
\
SOME PROPERTIES OF SIMPLE ALLOYS

4-1. Interstitial and substitutional solid solutions

When an element B is dissolved in a metal A and the B atoms occupy

interstitial positions in the A lattice, one speaks of an interstitial solid
solution. An example of this type is austenite, which is an interstitial
alloy of carbon in y iron (f.c.c.). Since the interstitial positions provide
room only for relatively small atoms, interstitial solid solutions are likely
to be formed with the elements H, B, C, N, and 0; the approximate
radii of these atoms are, respectively, 0.5, 1.0, 0.8, 0.7, and 0.6 A.
When a metal A is alloyed with a metal B and the B atoms occupy
positions which are normally occupied by A atoms, a substitutional solid
solution is formed. It is only with these alloys that we shall concern
ourselves. Substitutional solid solutions of two metals may occur only
over limited ranges of composition, the structure varying from one range
to anbther. A solid solution at either end of a binary phase diagram is
called a terminai soijd solution; the other ranges of solid solutions are
referred to as intermediate solid solutions. 1
Certain binary systems, such as the Cu-Ni and Au-Ag systems, exhibit
a continuum of solid solutions for all compositions without change in
structure. This requires first of all that both metals have the same structure;
furthermore, the radii of the two types of atoms must be approximately
the same (within about 15 per cent). Gold and silver, for example, both
have an f.c.c. structure with lattice constants of, respectively, 4.0783 A
and 4.0856 A (at room temperature). Besides these geometrical factors,
other factors such as valence, chemical properties, etc. enter into the
conditions for solubility. That geometrical factors and the number of
valence electrons do not alone determine the formation and properties of
an alloy may be illustrated by the observation that the lattice constant in
the Au-Ag system exhibits a minimum, as shown in Fig. 4-1. The straight
line which is dotted in the figure represents what is known as Vegard's
law; negative as well as positive deviations from Vegard's law are
)bserved in alloys.
When like atoms attract each other more strongly than unlike ones,
1 For a discussion of phase diagrams, see, for example, G. Tamman, The States of

Iggregation, Van Nostrand, New York, 1925; or J. S. Marsh, Principles of Phase

)jagrams, McGraw-Hili, New York, 1935.
104
Sec. 4-1] SOME PROPERTIES OF SIMPLE ALLOYS 105
one may expect a low solubility, at least at relatively low temperatures,
since there will be a tendency for a second phase to precipitate out. In
the opposite case, with a dominant
attraction between unlike atoms, A 4.080 alA)
atoms will tend to have B atoms as t !

nearest neighbors; in that case ordered 4.076

structures or superlattices may occur
(see Sec: 4-4). 4.072

4-2. Mutual solubility as function of 4.068

temperature
4.064 '---'--'---L--'-_'_-'---L.--1~--'
o 20 40 60 80 100
In a simplified model of a metal or - - Atomic per cent Ag
alloy one may describe the cohesive Fig. 4-1. The lattice constant (A)
energy in terms of the sum of the in- for the gold-silver system as function
teractions between pairs of neighb9fing of composition; the dashed line
atoms. On the basis of this model we represents Vegard's law. (After
shall consider the solubility of a metal Barrett, Structure of Metals,
McGraw-Hili, 2d ed., p. 222, 1952]
A in a metal B as function of tem-
perature. 2 Suppose that from a piece
of metal A and from a piece of metal B we remove, respectively, an
interior A and B atom; then we put the A atom in the vacancy of the
B lattice and the B atom in the vacancy of the A lattice. The work required
for this process, assuming the two metals have identical structures, may
be written
(4-1)

Here epAA' epnn, and epAB represent, respectively, the dissociation energy of
an AA, BB, and AB pair of nearest neighbors; z is the coordination
number, i.e., the number of nearest neighbors of a given atom. Whether
or not the two metals will have a wide or narrow solubility range depends
on the quantity ep defined by (4-1). When ep > 0, like atoms attract each
other more strongly than unlike atoms, and hence we expect a limited
solubility. On the other hand, when ep < 0, there is a preferential attraction
between unlike atoms, and the solubility may cover the whole range of
compositions, as in the Ag-Au system.
°
We shall consider the case ep > (limited solubility), inquiring about
the variation of the solubility with temperature. Suppose an alloy of the
substitutional type contains Na A atoms and Nb B atoms. For convenience
we shall introduce the atomic concentrations c = Nal Nand 1 - c = Nbl N,
where N = Na + N b • We shall now express the free energy F = E - TS
of the alloy in terms of c; in order to find the equilibrium concentration
2 See also A. H. Cottrell, Theoretical and Structural Metallurgy, Arnold, London,

1953.
106 SOME PROPERTIES OF SIMPLE ALLOYS [Chap. 4

at the temperature T we may then make use of the thermodynamic

condition (2Fj2eh = O. We may write
F = Ebinding +E vibr - TSth - TS"f \ (4-2)
The terms here are, respectively, the binding energy of the alloy relative
to the system of infinitely separated atoms, the vibrational energy of the
lattice, the thermal entropy term, and the configurational entropy term.
The binding energy of the alloy may be found from the following
arguments, assuming nearest neighbor interaction only: The total number
of pairs of nearest neighbors is Nz/2 (the factor i arises since otherwise
each pair is counted twice). If we assume a completely random distribution
of A and B atoms over the lattice (which is probably never exact in
practice), the probability for a pair chosen at random to,be
of the AA type is e2
of the BB type is (l - c)~
of the AB type is 2e(l - e)
The factor 2 in the last case enters because we count AB as well as BA
pairs; the sum of the probabiliti/ _equals unity, as it ought to. Employing
the dissociation energies introd'uced above, we may write

Eb = -tNZ[C24>AA + (l - e)24>BB + 2c(~ - C)4>AB]

or, in terms of 4> defined by (4-1)
Eb = -tNz[C4>AA + (1 - C)4>lHl - cCl - c)4>J (4-3)

The minus sign arises from the fact that the mutual potential energy of
two atoms equals minus the dissociation energy. In order to simplify
matters we shall assume that the thermal entropy is independent of c, i.e.,
we assume that when an A atom is substituted for a B atom, the vibrational
spectrum of the lattice does not change; this assumption does not impair
the general conclusions.
The configurational entropy is determined by the number of different
ways in which Na atoms of kind A and N b atoms of type B may be distributed
over Na + Nb lattice sites (vacancies are neglected). Hence, according to
the Boltzmann relation,
N!
-TScf = -kTlog N IN I
a' b'

Applying Stirling's formula log N! ~ N log N and expressing the result

in terms of e, we obtain
-TScf = NkT[c log c + (1 - c) log (1 - c)] (4-4)
Substituting (4-3) and (4-4) into (4-2) and applying (oFjoch = 0, one
Sec. 4-2] SOME PROPERTIES OF SIMPLE ALLOYS 107
arrives at the following result for the equilibrium concentration c of the
A atoms;

kTlog CJ e = tz[<p.u. - <PBB - <p(1 - 2e)] (4-5)

For given values of <p, <P AA' and <PBB' this equation can be solved numerically
for c. If we consider the special case <PAA = <PilE we obtain
e/(l - c) = exp [-z<p(l - 2c)/2kT] (4-6)
which for small concentrations reduces to the simple Boltzmann expression
e = exp (-z<p/2kT), .. - f - - : · (4-7)
In Fig. 4-2 we have plotted 2kT/z<p as function of c. The region above the
curNe corresponds to a homogeneous solid solution; the region below the
curve corresponds to temperatures that are Homogeneous solution
too low to give a true solid solution. The .5
symmetry of the curve is, of course, due to
our assumption <PAA = <PHIl' In practical
cases, a great part of the solubility curve
may lie above the melting point so that
in the phase diagram only those parts will t Phase mixture
enter that are close to either of the pure
metals. When the reader takes a look
at phase diagrams of binary alloys he
will readily recognize the occurrence o .5 1.0
_c
of the ·domelike shapes similar to that Fig. 4-2. The solubility curve
of Fig. 4-2. To give a numerical example, for a binary alloy, according to
suppose that the maximum solubility of equation (4-6).
a certain metal in another is I per cent
at 300°C. In that case, kT,-...J 0.05 ev and from (4-7) one finds
z<p ~ 0.46 ev. Treatment similar to that given here for substitl,ltional alloys
may be given for interstitial ones. , I

4-3. The Hume-Rothery electron compounds

When zinc is added to copper (f.c.c.) up to atomic concentrations of

approximately 35 per cent, a solid solution is obtained with an f.c.c.
structure in which copper atoms are replaced by zinc atoms; this phase is
called the IX phase. For higher zinc concentrations there is a fJ phase with
a b.c.c. structure which is stable over a narrow concentration range in
the vicinity of 50 per cent Zn; a y phase with a complicated cubic structure
containing 52 atoms per unit cell which is stable in the vicinity of 70 per
cent Zn; and an € phase (h.c.p.) in the neighborhood of 80 per cent Zn.
These regions are separated by regions corresponding to a mixture of the
two neighboring phases. If one writes the approximate concentrations for
108 SOME PROPERTIES OF SIMPLE ALLOYS [Chap. 4

which the phases of narrow composition range occur in terms of a chemical

formula, one obtains:
{J phase (b.c.c.) CuZn
r phase (complex cubic) CUsZns
€ phase (h.c.p.) CuZn 3
Similar sequences of phases with the same structures are found in many
\
alloys, but the compositions at which they occur may be quite different
from those given for the brass system above. It is obvious that the alloy
compositions corresponding to the various phases cannot be explained in
terms of the usual chemical valence rules. It was pointed out by Hume-
Rothery, however, that the electron to atom ratio. is approximately the
same for a given phase of different alloys.3 A few examples are given in
Table 4-1 to illustrate this.
Table 4-1. Compositions and 'Electron-to-Atom Ratio for Structurally Analogous Phases

Electron-atom ratio 3:2 Electron-atom ratio 21 :13 Electron-atom ratio 7:4

fJ structure (b.c.c.)
If
y structure (compl. cub.) E structure (h.c.p.)

CuZn • Cu.Zns CuZn 3

CuBe
Cu.AI
Cu.Sn
Cu.AI.
Cu.Cd.
Au.Cd.
. CuCd.
Cu 3 Ge
AgZn 3
AgCd Ag.Cd. Ag.Sn
AgMg CU31Si. AuZn.

Since the phases have a certain range of compositions over which they
are stable, the chemical formulas and the electron-to-atom ratios given in
the table are approximate. However, there is a striking regularity when
these "compounds" are considered from this point of view. For the alloys
given in the table the electron-to-atom ratios are calculated on the basis of
the normal number of \ ..1ence electrons associated with the atoms involved.
In order to fit alloys containing transition metals such as Fe, Co, Ni into
this scheme, one must assume that these atoms contribute zero valence
electrons. For example, FeAI has the {J structure corresponding to an
electron-to-atom ratio 3 : 2.
An interpretation of the change in structure associated with an increase
in the electron-to-atom ratio has been given by Jones in terms of the band
theory of metals. 4 Essentially, the picture is the following: In the
expression for the total energy of an alldy there occurs a term associated
3 W. Hume-Rothery, J. Inst. Metals, 35, 295, 307 (1926); see also by the same author

Atomic Theory for Students of Metallurgy, Institute of Metals, London, 1946.

• H. Jones, Proc. Roy. Soc. (London), AI44, 225 (1934); A147, 396 (1934). See also
N. F. Mott and H. Jones, Theory of the Properties of Metals and Alloys, Oxford, New
York, 1936; and C. Zener, Phys. Rev., 71, 846 (1~47); also references in footnote 3.
Sec. 4-3] SOME PROPERTIES OF SIMPLE ALLOYS 109
with the kinetic energy of the conduction electrons; since this is a positive
term, it is unfavorable for the cohesive energy. As one increases the
electron-to-atom ratio it may be advantageous for the lattice to change
its structure if this permits a reduction of the total energy of the system.
We may give here the results obtained by Jones from calculations of the
band structure for the electron-to-atom ratios for which a new phase
should appear in the alloys.
Phase ............................. {3 y e
Hume-Rothery ratio ................ 1.5 1.615 1.75
Jones ratio ........................ 1.480 1.538 1.7
The agreement between theory and experiment is quite good in view of
the approximate nature of the calculations.

4-4. Superlattices

In the discussion of hlttice defects in metals in the preceding chapter

we saw that the number of defects increases with increasing temperature.
Thus the crystals are in a state of higher order at lower temperature. We
shall now discuss briefly another type of order, viz., that occurring in
many alloys. Although in some of our previous discussions we assumed
that the various types of atoms in a solid solution are distributed at

, I \ I I
'-...J, ' I I __.
f ','. , .-f.--;;:""--- -.
I , " 1·"- I

,./
/
I
0---'<
\
\
,. 0-+-
,./
I
.
I

OZn atoms OAu atoms

• Cu atoms • Cu atoms

./
Fig. 4-3. Ordered structures ofCuZn (fJ brass) (a), and of AuCua (b).

random over the available lattice sites, there is a great deal of experimental
evidence which shows that this is frequently not the case. For example,
the structure of {3 brass (CuZn) at low temperatures approaches an ordered
structure in which corner points of a cubic unit cell are occupied by Zn
atoms and the center by Cu atoms (see Fig. 4-3a). Thus, in the completely
ordered state, brass may be vizualized as two interpenetrating simple
cubic lattices of Cu and Zn. As the temperature is raised the degree of
order decreases, as will be further discussed below; at a critical tempera-
ture Tc the degree of order drops rapidly. Another example of an ordered
110 SOME PROPERTIES OF SIMPLE ALLOYS [Chap. 4

structure or superlattice is given in Fig. 4-3b for AuCu 3 ; the corners of

the cubic cell are occupied by Au atoms, the centers of the faces by Cu
atoms. This distribution is in agreement with the ratio of the numbers of
Cu and Au atoms given by the formula AuCu 3 . The same structure has
been observed for PtCu 3 , FeNi 3 , and MnNi 3 .
Part of the experimental evidence for the existence of ordered structures
in alloys is provided by the observation of "extra" X-ray diffraction lines
which gradually disappear as the temperature is increased. 5 The reason for
the extra lines lies in the fact that in the ordered structures, certain planes
of atoms may have a different scattering power than parallel planes

.275

~ .250
S
co
...
~ .225

.s'..,"
'-'

.200
co
.a'"
ci. .175
rf.l

t .150

.125
440 480 500'C

f'ig. 4-4. The specific heat of fJ brass (CuZn) as function of

temperature. [After Sykes and Wilkinson. ref. 6)

containing different atoms; in the random distribution these differences

in scattering power do not occur. Further experimental evidence is derived
from anomalous peaks observed in the specific heat of these alloys; an
example is presented in Fig. 4-4. 6 The integral of the "extra" specific heat
over the temperature corresponds to the total eneI gy required to go from
a completely ordered to a random distribution. Note the sharp drop
which defines a critical temperature. The electrical resistivity of these
alloys also drops quite sharply at Tc as one goes from high to low tempera-
tures. 7 Since the resistivity decreases as the periodicity of the potential
seen by the electrons becomes more perfect, this again indicates a transition
from a disordered to an ordered state (see Chapter 11).
In attempting to introduce a quantity which describes the degree of
ordt;r associated with a given distribution of atoms in an alloy, one may
• See, for example, C. Sykes and H. Evans, J. Inst. Metals, 58, 255 (1936) for powder
diffraction patterns of AuCu a•
• C. Sykes and H. Wilkinson, J. Inst. Metals, 61, 223 (1937).
7 See, for example, N. S. Kurnakow and N. W. Ageew,J.lnst. Metals, 46, 481 (1931).
Sec. 4-4) SOME PROPERTIES OF SIMPLE ALLOYS 111

take different points of view. In one of these one is concerned about

the degree of long-distance order; in another one is interested in the
degree of short-distance order. These two viewpoints will be discussed
briefly below.

4-5. The long-distance order theory of Bragg and Williams8

We shall consider an alloy of the simple composition AB which in the

completely ordered structure may be represented by two interpenetrating
lattices of A and B atoms. If these lattices run through the whole crystal
without discontinuities, one may define the sites corresponding to one
lattice as ot sites and those of the other lattice as f3 sites. In the completely
ordered structure all ot sites are occupied by A atoms, and all f3 sites by
B atoms. In an incompletely ordered alloy one may then define right
(A on ot, B on f3) and wrong atoms (A on f3, B on ot). When Rand W
represent, respectively, the number of right and wrong atoms, the long-
distance order parameter is defined by

Y = (R - W)/N= (2R - N)/N (4-8)

where N = R + W is the total number of atoms. When R = N there is

complete order and Sf' = 1. When W = N, Y = -1; this situation also
describes a state of complete order, since by interchanging the ot and f3
sites, this case becomes physically identical with R = N. Complete dis-
order exists when R = N/2, corresponding to Y = 0; therefore only the
range between 0 and 1 for the order parameter is of physical interest.
Let us now investigate on the basis of a simple model how Y should
vary with temperature. First of all it will be evident that disorder in the
alloy may be produced only by interchanging the positions of a right A
and a right B atom; thus, if in a certain alloy there are R right atoms in
all, R/2 of these occur on the IX sites and an equal number occur on f3 sites.
Since the alloy at absolute zero tends to be completely ordered, the energy
required to produce disorder must be positive. Now suppose that the
alloy in thermal equilibrium contains R right atoms and W wrong atoms.
If in this state we were to interchange the positions of a right A and a
right B atom, the change in W would be Ll W = -LlR = 2. Since in
thermal equilibrium the change LlF in the free energy associated with Ll W
must vanish (Ll W ~ W), one can readily find the equilibrium values for
Rand W in the following manner: Suppose that the energy required to
produce a pair of wrong atoms in the state R, W is 4>(R, W). The con-
figurational entropy associated with the state R, W is

Scf = k(Nlog N - R log R - Wlog W) (4-9)

8 W. L. Bragg and E. J. Williams. Proc. Roy. Soc. (London), A145, 699 (1934).
112 SOME PROPERTIES OF SIMPLE ALLOYS [Chap. 4

Thus the change L\Scf associated with L\ W is

\
L\Scf = -k(L\R log R + L\Wlog W) = 2k log (R/W) (4-10)
Neglecting thermal entropy changes for simplicity, we may write
L\F = 0 = 4>(R, W) - 2kTlog (R/ W) . \.

or R/ W = exp [4>(R, W)/2kT] (4-11)

Let us now inquire about the nature of the function 4>(R, W). Consider
a given right A atom; the probability for an arbitrarily chosen nearest
neighbor of this atom to be a B atom (right) is R/ N; the probability that
a nearest neighbor atom is an A atom is WIN. The potential energy of the
A atom in the field of its nearest neighbors is then

where we use the same symbols as in Sec. 4-2. Similarly, the potential
energy of a right B atom in the field of its nearest neighbors is

We leave it as Problem 4-6 for the reader to show that this model of
nearest neighbor interactions leads, for the energy required to interchange
the positions of the right A and B atoms, to the expression

4>(R,W) = 4>o(R - W)/N = 4>0[1' (4-12)

where 4>0 = z(24)AB - 4>AA - 4>BB) is a positive quantity since the dissocia-
tion energy 4>AB for an unlike pair is larger than that for a pair of similar
atoms. The physical meaning of 4>0 is that it represents the energy required
to produce 2 wrong atoms in the completely ordered lattice ([I' = 1). It
is observed that according to (4-12) the energy required to produce 2
wrong atoms decreases as the amount of order decreases. Qualitatively,
this can readily be understood; for example, if two atoms in the completely
disordered state ([I' = 0) are interchanged, the energy is, on the average,
zero because in the long-distance theory the distribution of A and B atoms
around a given A or B atom is then random. Actually the simple linear
relationship (4-12) between 4>(R, W) and [I' was introduced by Bragg and
Williams as an assumption; we see that this assumption is equivalent to
the model employed above in which the interaction between the atoms is
simplified to nearest neighbor interactions with constant 4> AA, 4> AB, and
CPBn values.
When (4-11) and (4-12) are substituted into (4-8) we obtain the
following implicit equation for the long-distance order parameter.
[I' = tanh (4)o[l'/4kT) (4-13)
Sec. 4-5J SOME PROPERTIES OF SIMPLE ALLOYS 113
This equation may be solved graphically by introducing the variable
x = %Y/4kT or Y = 4kTx/% (4-14)
where Y must satisfy the equation Y = tanh x as well as (4-14). The
function tanh x is represented in Fig. 4-5. TheY(x) curves corresponding

i
tanh x

3
_x

Fig. 4-5. Graphical solution of equation (4-13) as explained in text.

to (4-14) produce a set of straight lines, of slope equal to 4kT/cfo, i.e.,

proportional to T. The intersection of the tanh x curve with one of the
straight lines then gives the value of Y for the corresponding temperature.
Since the slope of the tanh x curve for very small values of x is equal to
unity, there exists.a critical tem-
perature Te above whichY = 0, viz., 1.0t--_ _

.8
Thus in this theory the order dis- !I
appears altogether at Te' The tem- .6 t
perature dependence of Y according .4
to the Bragg-Williams theory is given
.2
in Fig. 4-6. Note the rapid drop in the
vicinity of Te. The reason for this
lies in the fact that once a certain o .1 .2 .3
amount of disorder is present, it - kT/<Po
becomes easier for the thermal Fig. 4-6. The long distance order
motions to produce more disorder parameter as function of temperature,
(see 4-12). One therefore speaks of according to the Bragg-Williams theory.
a cooperative phenomenon. Other
cooperative phenomena are ferromagnetism and ferroelectricity; it is
instructive to compare the theoretical treatment of those phenomena
with the order-disorder treatment given above.
114 SOME PROPERTIES OF SIMPLE ALLOYS [Chap. 4
For fJ brass, Tc 740oK, so that according to (4-15) the quantity CPo
,-...J

is approximately 0.25 ev in this case.

A few words may be said here about the "extra" specific heat associated
with the order-disorder transition. The energy required to increase R by
dR is, according to the definition of cp, equal to -CPo.9"d R/2. Making use
of (4-8) one may thus write
dE = -(Ncpo/4).9" d.9" ; (4-16)
The specific heat per atom associated with the order-disorder transfor-
mation if thus given by
!
llcv = (l/N)(dE/dT) = -(CPo.9"/4)(d.9"/dT) (4-17)
This function has been plotted in
&:vlk Fig. 4-7; we see that the theoretical
1.5
t curve drops to zero at T e , whereas
1.0 the experimental curves show tails
extending to higher temperatures (see
.6 Fig. 4-4). Apart from this, the two
curves have the same general shape.
o When one calculates the area under
-TITe the extra specific heat curve, one
Fig. 4-7. The specific heat associated
obtains from (4-17),
with rile order-disorder transition, roo C v dT = kTe/2 (4-18)
according to Bragg and Williams. .10
in fair agreement with experiment.

4-6. Short-distance order theories

The essential difference between the long-distance and short-distance

theories of order may be illustrated with reference to Fig. 4-8. From the
long-distance order point of view, this lattice would be highly disordered
and yet we observe that nearly all atoms have unlike atoms as nearest
neighbors. In other words, if one were to employ the relative number of
unlike nearest neighbors as a criterion for order, the lattice of Fig. 4-8
has a high degree of order. Theories based on this concept have been
worked out by many investigators. 9 Short-range order may be defined in
terms of the number of right pairs (AB) and the number of wrong pairs
(AA, BB). Thus consider an A atom and let the probability for a
given nearest neighbor to be a B atom be (l + (1)/2 and to be an A atom
• H. A. Bethe, Proc. Roy. Soc. (London), AlSO, 552 (1935); E. J. Williams, Proc.
Roy. Soc. (London), A152, 231 (1935); R. Peierls, Proc. Roy. Soc. (London), A154, 207
(1936); J. G. Kirkwood, J. Chern. Phys., 6, 70 (1938); c. N. Yang, J. Chern. Phys., 13,
66 (1949); Y. Y. Li, J. Chern. Phys., 17,447 (1949); H. A. Kramers and G. H. Wannier,
Phys. Rev., 60, 252, 263 (1941); L. Onsager, Phys. Rev., 65,117 (1944); F Zernicke
Physica, 7, 565 (1940).
Sec. 4-6] SOME PROPERTIES OF SIMPLE ALLOYS 115
(I - a)/2; a is then the short-distance order parameter. For complete
order, a = I, for a random distribution of atoms, a = O. Suppose that
the dissociation energies CP.I.l and cP 1m are equal, and, of course, smaller
than cP .lB. In that case we should have, according to the Boltzmann
distribution,
(I + a)/(I - a) = exp [(cp.\1\ - CPA.,,)/kTJ = exp (cp/kT) (4-19)
Thus if cP were a constant independent of the degree of order, a would
decrease slowly to zero at high temperatures and there would be no
critical temperature. In Bethe's theory cP is calculated in terms of the
long-range order which exists in the crystal; since cP decreases with
decreasing long-range order, a decreases more rapidly to zero in the

o 0 0 • •
• • 0 o 0
o o o • • •
• .00 0
c5
- __
0 0 • • •
<7

·A; OB; ~) A or B o -T

Fig. 4-8. lllustrating the difference Fig. 4-9. The temperature dependence
betwecnlong distance and short distance of the long-range and short-range order
order; from the former point of view parameters for an AB3 super-lattice.
the lattice is very disordered, from the [According to Bethe, ref. 9]
latter point of view it is well or~ered.

vicinity of the critical point than for constant cp. As an example we give
in Fig. 4-9 the long-range and short-range order parameters Y' and a for
a superlattice of the AB3 structure. For the details of short-distance order
theory we refer the reader to the literature. We may mention here an
approximate theory developed by Cowley in which the order parameter is
expressed in terms of the coefficients of the Fourier series, which determines
the intensity of X-ray scattering. 10 This makes a direct comparison
between theory and experiment possible; the agreement is very good.

REFERENCES

Besides the references given at the end of Chapter 3, see also:

J. Lumsden, Thermodynamics of A 1I0ys, Institute of Metals, London, 1952.
J. S. Marsh, Principles 0.( Phase Diagrams, McGraw- Hill, New York, 1935.
For reviews of the theory of order-disorder, see:
F. C. Nix, J. Appl. Phys., 8, 783 (1937).
10 J. M. Cowley, Phys. Rev., 77, 669 (1950); J. Appl. Pltys., 21, 25 (1950).
116 SOME PROPERTIES OF SIMPLE ALLOYS [Chap. 4

F. C. Nix and W. Shockley, Revs. Mod. Phys., 10, 1 (1938).

T. Muto and Y. Takagi, "The Theory of Order-Disorder Transitions in
Alloys," in Solid State Physics, Vol. 1, edited by F. Seitz and
D. Turnbull, Academic Press, New York, 1955.

PROBLEMS
4-1. Write an essay on the phase diagrams of binary alloys, showing
that you are familiar with the meaning of such diagrams. (See, for
example, J. S. Marsh, Principles of Phase Diagrams, McGraw-Hill, New
York, 1935).
4-2. For the Bragg-Williams theory of long range order show that
-Cd !/'/dT) for T = Tc is infinite.
4-3. For the Bragg-Williams theory show that the specific heat
associated with the order-disorder transition is given by c = -(CPo/8)
(d !/,2/dT) per atom. Also show that for T= Tc the order-disorder specific
heat is equal to 3k/2 per atom.
4-4. Discuss the theory of Bethe for order-disorder and compare the
results with those of the Bragg-Williams theory, in particular with reference
to the value of the critical temperature and the specific heat versus
temperature curve. (See H. A. Bethe, Proc. Roy. Soc. (London), A150,
552 (1935), or N. F. Mott and H. Jones, Theory of Metals and Alloys,
. Oxford, New Ycrk, 1936).
4-5. Discuss the work of Cowley on the order-disorder problem (see
footnote 10).
4-6. Consider an alloy AB with R right atoms and W wrong atoms in
the sense of the Bragg-Williams theory. Assuming only nearest neighbor
interaction, show that the energy required to produce two more wrong
atoms is given by cp = CPo(R - W)/(R + W), where 4>0 corresponds to cP
for W = o. This proves equation (4-12).
',j
~''' .. ,

~ r "

Chapter 5 {
LATTICE ENERGY OF IONIC CRYSTALS
, I
.i
5-1. Introductory remarks
One of the fundamental problems in the theory of solids is the
calculation of the binding energy of a crystal. This evidently requires a
knowledge of the forces acting between the composing particles. The
simplest group of crystals to deal with in this respect are the ionic crystals,
for which calculations of the cohesive energy were made in 1910 by Born l
and Madelung. 2 The basic assumption in the theory of the cohesive
energy of ionic crystals is that the solid may be considered as a system of
positive and negative ions. This is a good example of the simplification
of a problem resulting from considering certain groups of elementary
particles as units, the calculations being carried out for these units rather
than for the elementary particles themselves. For example, in sodium
chloride it is assumed that these units are the Na'l- ion, with an electron
configuration ls2, 2s2, 2p 6 and the CI- ion, with an electron configuration
Is2, 2s 2, 2p6, 3s2, 3p 6. In the theory one works with these ions as "charged
particles," forgetting to a large extent about their internal constitution.
The influence of the latter may then be introduced in the form of refinements
of the theory.
We shall begin with a discussic.n of perfect crystals, assuming that all
ions occupy the proper lattice points. However, perfect crystals do not
exist, and even if a crystal is "perfectly grown" and chemically pure there
are always a (relatively small) number of lattice defects present, as discussed
in Chapter 3. The changes in lattice energy resulting from a few simple
types of lattice defects will be discussed in Chapter 7.

5-2. The fundamental assumptions of Born's theory

Born's theory of the lattice energy is based on the assumption that

the crystals under consideration are built up of positive and negative ions.
If we assume that the charge distribution in these ions is spherically
symmetric, the force between two such ions depends only on their distance
apart and is independent of direction. As an example, consider a lattice
of the NaCI structure, represented in Fig. 5-1. We shall denote the
1 See, for example, M. Born, Atomtheorie des festen Zustandes, Teubner, Leipzig,

1923; also, Handbllch der PhYSik, Vol. 24/2, Springer, Berlin, 1933.
2 E. Madeiung, Physik. z., 11,898 (1910).

117
118 LATTICE ENERGY OF IONIC CRYSTALS [Chap. 5

shortest interionic distance by r and consider this quantity a variable for

the moment. A given sodium ion is surrounded by 6 Cl- ions at a distance
r, 12 Na+ ions,at a distance rV2, 8 Cl- ions at a distance rV3, etc. The
Coulomb energy of this ion in the field of all other ions is therefore

Ec = - :2 (:1- ~~ :3 -:4
+ + ~; - ... ) (5-1)

where e is the charge per ion. Note that because Coulomb forces decrease
relatively slowly with distance, it is not sufficient to consider only a few
shells of ions around the central ion.
Evidently, the coefficient of e2 /r is a pure number, determined only
by the crystal structure. Series of this type have been calculated
by Madelung,3 Ewald,4 and Evjen. 5 For the
_C./'F--+-'_-+/-;.-'--a/ NaCl structure the result is
f'/~I--1I~/'-i-I-,-1~/
I,
I,
I
,I
Ec = -Ae2 /r with A = 1.747558 ... (5-2)
lo-_1-L- The constant A is called the Madelung
77
!~:J_ ',,/1
/' , ..."/9-1- constant. For other crystal structures composed
~-r---r-~;--+-<1
of positive and negative ions of the same
valency, the Madelung constants are6
Cesium chloride A = 1.762670
NaCI Zincblende (ZnS) A = 1.6381
Wurtzite (ZnS) A = 1.641
Fig. 5-1. The sodium
chloride structure. Note that e in (5-2) represents in general the
electronic charge times the valence of the ions
under consideration. The minus sign in (5-2) indicates that the
average influence of all other ions on the one under consideration
is of an attractive nature. To prevent the lattice from collapsing, there
must also be repulsive forces between the ions. These repulsive forces
become noticeable when the electron shells of neighboring ions begin to
overlap, and they increase strongly in this region with decreasing values
of r. These forces, as other overlap forces, can best be discussed on the
basis of wave mechanics, because they are of a nonclassical nature. Born
in his early work made the simple assumption that the repulsive energy
between two ions as function of their separation could be expressed by a
power law of the type B'jrn, where B' and n are as yet undetermined
constants characteristic of the ions in the solid under consideration. 7
E. Madelung, Physik. z., \9, 524 (1918).
3

P. P. Ewald, Ann. Physik, 64, 253 (1921).

4

5 H. M. Evjen, Phys. Rev., 39, 675 (1932). .

• J. Sherman, Chern. Revs., 11, 93 (1932); for other struCtures containing ions of
different valency, see; for example, F. Seitz, Modern Theory of Solids, McGraw-Hill,
New York, 1940, p. 78.
? See also Sec. 1-11.
Sec. 5-2] LATTICE ENERGY OF IONIC CRYSTALS 119

Focusing our attention again on one particular ion, we may thus write
for the repulsive energy of this ion due to the presence of all other ions,

(5-3)

where B is related to B' by a numerical factor. In view of the fact that

repulsive forces depend so strongly on the distance between the particles,
the repulsive energy (5-3) is mainly determined by the nearest neighbors
of the central ion. The total energy of one ion due to the presence of all
others is then obtained by adding (5-2) and (5-3):

(5-4)

Assuming that the two types of forces just discussed are the only ones
we have to take into account and neglecting surface effects, we thus find
for the total binding energy of a crystal containing N positive and N
negative ions, E

E(r)=N(-A~+~)=N€(r)
, r rn
(5-5)

We multiplied by N rather than by

2N because otherwise the energy
between each pair of ions in the
crystal would have been counted
twice. The two contributions to E(r)
are represented schematically in Fig.
5-2. If we consider the crystal at /
/ '"
absolute zero, the equilibrium con- la
I
ditions require E to be a minimum, I
which wi1I be the case for the equi-
Fig. 5-2. Schematic representation of
librium value r = ao, where ao rep-
the energy of attraction (a) and of
resents the smallest interionic distance repulsion (b) as function of the lattice
in the crystal at T = O. For this parameter. The resultant (c) exhibits a
minimum minimum for a lattice constant ao.
corresponding to equilibrium.
(dE/dr) r~ao = 0 (5-6)
From the last two expressions one thus obtains the following relation
between the two unknown parameters Band n: ., "'".

B = (Ae 2 /n)ag- 1 (5-7)

Substitution into (5-5) yields for the lattice energy EL ,

(5-8)
120 LATTICE ENERGY OF IONIC CRYSTALS [Chap. 5

where EL = ,,(ao). The interionic distance can be obtained from X~ray

diffraction data; the charge per ion is also known, and thus the lattice
energy can be calculated if the repulsive exponent n is known. How
information regarding n may be obtained is discussed in the next two
sections.

5-3. Calculation of the repUlsive exponent from compressibility data

Born obtained the unknown repulsive exponent n from measurements

of the compressibility of the crystals as follows: The compressibility Ko
at absolute zero is given by
(5-9)
where Vo is the volume of the crystal corresponding to an interionic
distance a o ; V corresponds to the variable r. The relation between
volume and interionic distance must of course be of the form
V= cNr3 (5~10)

where c is a constant determined only by the type of lattice. For NaCI,

for example, c = 2. Hence
dE dE d 2E 1 d ( 1 dE)
dV = 3cNr2' dr and dV2 = 9c2N2r2' dr ~. dr
(5-11 )

From (5-5) we thus obtain

1 (ddV2E) a = 9cWag
2
1 [-4Ae 2
n(n + 3)B] (5-12)
KocNa~ = o ~+ a~H
Substituting B from (5-7), we find
n = 1 + 9cao 1Koe A
4 2
(5-13)
from which the parameter n can be calculated if Ko is known. Some
experimental values for alkali halides according to Slater, and obtained
by extrapolation of compressibility measurements to T = 0, are given
below. s
LiF 11 = 5.9 NaCl II = 9.1
Liel 11 ~ 8.0 NaBr 11 = 9.5
LiBr 11 - 8.7
We note that there is a marked variation' from one crystal to another.
However, even an appreciable error in n leads to a relatively small error
in the lattice energy, which is proportional to (1 - lin). If we change n
by unity, EL changes by only 1 or 2 per cent. According to (5-8) and in
view of the relatively large values of n, most of the lattice energy is due to
8 J. C. Slater, Phys. Rev., 23, 488 (1924).
Sec. 5-3] LATTICE ENERGY OF IONIC CR YST ALS 121
the Coulomb interaction, and the repulsion contributes only a relatively
small fraction. On the other hand, the repulsive and attractive forces
acting on anyone ion just balance for r = 00 and thus are equal in
magnitude. 1"111'1. ,";, ,if,""; , 'I'

5-4. The repulsive exponent as function of electron configuration

It will be obvious that the repulsive forces acting between two ions
will depend on the distribution of the electronic charges in the ions and
especially on the number of electrcns in the outer shells. For example,
we would expect n to be larger for NaCl than for LiCl, because the Na+
ion has eight outer electrons, the Li I- ion has only two. From an approxi-
mate treatment of the interaction between closed-shell electronic con-
figurations, Pauling arrived at the following values of n as a function of
the occupation of electronic shells. 9 ) , .,

Table 5-1. Repulsive Exponent as Function of Electron Configuration

Electron configuration'

Ion type
K L M N 0 n

He 2 ..... . . ..... ..... . •••• o • 5

Ne 2 8 ..... . ..... . ...... 7
Ar (eu) 2 8 8(18) ...... . ..... 9
Kr (Ag) 2 8 18 8(18) . , . , .. 10
Xe (Au) 2 8 18 18 8(18) 12

This table should be used by taking the average value of n for the two
ion types occurring in the crystal. For NaCl, for example, one takes the
average of 7 and 9; for NaF the average of 7 and 7, etc. Note that this
table is in qualitative agreement with the experimental values of Slater
referred to above.

5-5. Calculated and experimental lattice energies

The lattice energy €L may now be calculated from (5-8) by substituting

the proper values for the charge of the ions, the interatomic distance and
the Born exponent n. Values for €L so obtained are given in Table 5-2
for alkali halides and the alkaline earths oxides. The charge per ion in
the latter group is assumed to be 2e; it is not quite certain that these
• L. Pauling, Proc. Roy. Soc. (London), 114, 181 (1927); J. Am. Chern. Soc., 49, 765
(1927); Z. Krist., 67, 377 (1928).
122 LATTICE ENERGY OF IONIC CRYSTALS [Chap. 5

oxides can be considered ionic compounds. It may be remarked that

CsCI, CsBr, and CsI crystallize in the cesium chloride structure (see
Fig. 5-3), whereas all other compounds in the table have the NaCl structure.
The expansion of the lattice, entering through the interionic distance a o,
can usually be neglected; the coefficient of expansion of ionic crystals at
room temperature is of the order of 10-4 per degree.

Table 5-2. Lattice Energies for Alkali Halides and Alkaline Earth Oxides.
The cakulated values are based on (5-8). The experimental values are
obtained in a manner to be described below.

a o in ('L in ev ('L illev

Compound
Angstroms " calc. expo

LiF 2.07 6.0 10.5 ......

NaF 2.31 7.0 9.3 ......
KF 2.66 8.0 8.3 ......
RbF 2.82 8.5 7.9 ......
CsF 3.00 9.5 7.5 ......
LiCI 2.57 7.0 8.4 8.6
NaCl 2.81 8.0 8.0 7.9
KCl 3.14 9.0 7.1 7.1
RbCI 3.27 9.5 6.9 7.0
CsCI 3.56 10.5 6.5 6.7
LiBr 2.74 7.5 7.9 8.2
NaBr 2.97 8.5 7.5 7.5
KBr 3.29 9.5 6.8 6.8
RbBr 3.42 10.0 6.6 6.6
CsBr 3.71 11.0 6.2 6.4
LiI 3.03 8.5 7.4 7.8
NaI 3.23 9.5 7.0 7.2
KI 3.53 10.5 6.5 6.6
Rbi 3.66 11.0 6.2 6.S
CsI 3.95 12.0 5.9 6.3

MgO 2.10 7.0 41.0 ......

CaO 2.40 8.0 36.5 ......
SrO 2.57 8.5 34.5 ......
BaO 2.75 9.5 32.5 ......

An experimental check on the calculated values of the lattice energies

may be obtained from what is known as a Born-Haber cycle. Consider,
for example, 1 gram atom of solid sodium reacting with t gram molecule
of Cl 2 gas. As a result of the reaction, solid NaCl is formed and a certain
amount of heat Q (the "heat of formation") is given off. The change in
Sec. 5-5] LATTICE ENERGY OF IONIC CRYSTALS 123
energy due to such a reaction may be calculated by considering the
following steps
Nasolid + SNa --+ Navapor l(il:j

Navapor + INa -+ Na+ + electron

iC1 2 + iDcl, --+ Cl
CI + electron --+ Cl- + ECl
(Na+ + Cl-)gas -+ NaCl solid + €L
Nasolid + iCl2 + SNa + INa + iDcl, --+ NaCl solid + ECI + €L
The quantities introduced all refer to the formation of one ion pair of
solid NaCl. Here SNa represents the sublimation energy of sodium per
atom. Sublimation energies in general can be determined experimentally

IJ'

CsCl
Fig. 5-3. The CsCI and the ZnS (sphalerite or zincblende) struc-
tures. The open circles in the ZnS structure are located at points
obtained by displacements of 1/4 along three cube edges of the
corresponding corner point. For one of the open circles we have
indicated how it is surrounded by four black dots occupying the
corner points of a regular tetrahedron, with the open circle at the
center.
by direct caloric measurements or from measurements of the vapor
pressure as function of temperature. The ionization energy INa represents
the energy required to take away the outer electron of the sodium atom,
and can be obtained experimentally either from optical measurements or
by bombardment of atoms with electrons and measuring the minimum
energy of the latter required to produce ions. The dissociation energy
D CI • required to separate the two Cl atoms in a Cl 2 molecule can be
obtained by determining the dissociation constant as function of tempera-
ture. The electron affinity ECI is the energy gained by combining an
electron and a Cl-atom. Electron affinities can be determined by measuring
the ionization energy of the negative ions, or by measuring the density of
halide ions in alkali halide vapor.1 o Now, we also know that
Nasolid + iCl 2 --+ NaClsolid + q
10 J. E. Mayer, Z. Physik, 61, 798 (1930); L. Helmholz and J. E. Mayer, J. Chern.

Phys., 2, 245 (1934); P. P. Sutton and J. E. Mayer, J. Chern. Phys., 2,146 (1934); 3,20
(1935); J. E. Mayer and M. McC. Maltbie, Z. Phys., 75, 748 (1932).
124 LATTICE ENERGY OF IONIC CRYSTALS (Chap. 5
where q refers again to the heat of formation per "molecule" NaCI formed.
Subtracting this equation from the one obtained above, we find for the
lattice energy per ion pair,
ELexp. = SNa + INa + iDcI, - ECI + q (5-14)
For NaCl, all quantities on the right-hand side are known from experiments
and thus we are able to give an experimental value for E]. which may be
compared with the one calculated with the Born theory. For NaCl we
find, for example, from (5-14),
ELexp. = 1.1 + 5.1 + 1.2 - 3.8 + 4.3 = 7.9 ev
whereas Born's theory yields 8.0 ev. The experimental values obtained in
this way are listed in Table 5-2, and we see that theory and experiment
agree within a few per cent, indicating that the relatively simple approach
is essentially correct.
For the fluorides and oxides, the electron affinities are not known
from experiment, and they are usually calculated by replacing EL expo by
ELcalc. in (5-14). We note that for oxygen the electron affinity is negative,
i.e., it requires energy to add 2 electrons to the atom. This is not surprising,
because after the first electron has been added, we have a negative 0- ion
and we would expect addition of a second electron to require appreciable
energy. An experimental determination of the affinity of a neutral oxygen
atom for the first electron added gave 2.2 ev according to Lozier. l l Now
the total electron affinity for the addition of 2 electrons is -7.3 ev when
calculated from the lattice energy of oxides in the manner indicated above.
Thus addition of the second electron requires about 9.5 ev. The usually
accepted values of the electron affinities are given in Table 5-3 together
with the dissociation energies of the diatomic molecules (in electron volts).
Table 5-3. Electron Affinities and Dissociation Energies

Electron affinity Dissociation energy

F 4.25 ev 2.75 ev
CI 4.0 2.50
Br 3.8 2.01
1 3.45 1.58
0 -7.3 1.52
S -3.5 2.75
Se -4.2 2.50

5-6. Stability of structures and ionic radii

Ionic compounds of the composition A+B- occur in the sodium

chloride structure, the cesium chloride structure, and the zinchlende
11 w. W. Lozier, Phys. Rev., 46, 268 (1934).
Sec. 5-6] LATTICE ENERGY OF IONIC CRYSTALS 125
structure (ZnS). The latter two are represented in Fig. 5-3. In the CsCI
structure each ion is surrounded by 8 nearest neighbors of opposite sign;
in NaCl by 6, and in zincblende by 4. One may thus ask why a certain
compound crystallizes in a particular structure.
The answer must obviously be sought in the fact that the energy should
be a minimum, and the problem is thus reduced to explaining why for a
given compound its natural structure has a lower energy than any other
structure. We shall see that some insight into this problem may be
obtained from considerations of the size of the ions.
For metals one defines the atomic radius as half the distance between
nearest neighbors, although it is recognized that the meaning of the size
of an atom is necessarily vague. For ionic crystals one could try a similar
approach, but one is immediately faced with the difficulty that these
compounds consist of at least 2 types of ions, so that the lattice constant
provides information only about the sum of two radii. A little considera-
tion of the interionic distances as given in the preceding section shows
that to a fair approximation ionic radii are additive quantities. For
example, if one calculates the difference (r K + - r Na +) from the values
given in Table 5-2 for the halides of these metals, one finds from the
fluorides, f
q '!
rK+ - r x ,,+ = aKF - ax"", = 0.35 Angstrom .' 4." ·1
and from the chlorides, bromides, and iodides in the same manner 0.33 A,
0.32 A, and 0.30 A, respectively. We see that the difference is roughly
constant and that it has meaning to associate a rather definite radius
with each ion. It is also obvious that a table of ionic radii can be obtained
only if the radius of one ion is known. Goldschmidt in 1927 has tabulated
ionic radii based on a radius of the F- ion of 1.33 A, a value which he
decided upon on the basis of work by Wasastjerna on the relation between
polarizability and ion size. 12 Pauling, in the same year, independently
published ionic radii based on theoretical calculations of the radii of some
ions_I2 The two sets are not equal, which is not surprising because of the
inaccuracies involved. One commonly refers to the Goldschmidt and the
Pauling radius of a given ion. In Table 5-4 the Goldschmidt radii (G) do
not refer to the original set but include many recent X-ray diffraction
data, especially those of Zachariasen. 13 Contrary to the tables by Gold-
schmidt, the radius for 0 2- is 1.45 A rather than 1.35 A. The radii
according to Pauling are also given in Table 5-4.
Returning now to the question of stability, we would expect at first
sight that the CsCI structure should always be more stable than the other
'" V. M. Goldschmidt, Chefll. Berichte, 60, 1263 (1927); L. Pauling, J. Am. Chell/.
Soc., 49, 765 (1927).
13 W. H. Zachariasen, Acta Crystal/., 1,265 (1948); Ph),s. Rev., 73,1104 (1948);

Chefll. Ph),s., 16,254 (1948).

126 LATTICE ENERGY OF IONIC CRYSTALS [Chap. 5
structures, because it has the highest coordination number. Now, although
it is true that a high coordination number will lead to strong binding and
thus high stability, there is another requirement to be fulfilled, viz., that
ions of opposite sign should be separated by as small a distance as possible.
In other words, positive and negative ions should "touch," because any
increase in their separation would give a higher energy (less binding)
according to equation (5-8). It is at this point that a consideration of the
relative radii of the ions can provide at least a guiding principle. To
illustrate this, let us consider an ionic crystal of the type A+B- with ionic
radii 'I
and '2' where we assume 'I
< '2' Suppose we build a CsCI
structure with these ions, assuming that positive and negative ions touch
each other. The cube edge, corresponding to the ·separation of ions of
equal sign, is then
a = (2/V3)(,1 '2) +
Table 5-4. Goldschmidt (G) and Pauling (P) Ionic Radii in A

Ion G P Ion G P Ion G P

.'_

H 1.54 2.08 BeH 0.30 0.31 B3+ 0.2 0.20

F 1.33 1.36 Mg2+ 0.65 0.65 AP' 0.45 0.50
Cl 1.81 1.81 CaH 0.94 0.99 Sea. 0.68 0.81
Br 1.96 1.95 Sr 2 + 1.10 1.13 y3+ 0.90 0.93
I 2.19 2.16 BaH 1.29 1.35 La 3+ 1.04 1.15
Zn2+ 0.69 0.74 Ga 3+ 0.60 0.62
0' 1.45 1.40 Cd 2+ 0.92 0.97 In3+ 0.81 0.81
S'- 1.90 1.84 Hg2+ 0.93 1.10 TI3+ 0.91 0.95
Se 2 2.02 1.98 Pb 2+ 1.17 1.21
Te' 2.22 2.21 Fe3+ 0.53 ......
Mn 2+ 0.80 0.80 Cr 3+ 0.55 ......
Li' 0.68 0.60 Fe" 0.76 0.75
Na" 0:98 0.95 Co2+ 0.70 0.72 CH 0.15 0.15
K+ 1.33 1.33 Ni'+ 0.68 0.69 Si H 0.38 0.41
I
Rb' 1.48 1.48 1:1
Cu2+ 0.92 ...... TiH 0.60 0.68
Cs" 1.67 1.69 ZrH 0.77 0.80
Cu+ 0.95 0.96 Ce H 0.87 1.01
AgT 1.13 1.26 Ge H 0.54 0.53
Au+ ...... 1.37 Sn4+ 0.71 0.71
TP 1.51 1.44 Pb H 0.81 0.84

Suppose the ion of radius 'I is the ion in the center of the cube. If we
now increase the radius '2 gradually, leaving 'I constant, we reach a value
of /"2 such that further increase makes it impossible for the central ion to
touch the ones at the corners. This critical value is clearly reached when
Sec. 5-6] LATTICE ENERGY OF IONIC CRYSTALS 127
Thus '2> 1.37'1 would lead to an increase in the distance between
positive and negative ions and consequently to an increase in energy.
The competition between coordination number on the one hand and
separation between positive and negative ions on the other will thus set
in as soon as the ratio of the radii becomes larger than 1.37 and a more
favorable structure may result, viz., the NaCl structure. The stability
limits of the latter may be investigated in the same way. In this case the
critical ratio of the radii is determined by - r? ,- -'-,t'o'--, , .'
'.' I· , '-/'
2'2 = ('1 + '2)V2 or '2 = 2.44'1
Again, if the ratio becomes larger than 2.44, positive and negative ions
cannot touch each other, leading to an increase of the energy and conse-
quently to the formation of the more stable zincblende structure (Fig.
5-3). For this structure, positive and negative ions cannot touch each
other if '2> 4.55r1 . The stability limits as derived from the above
simplified billiard ball model for the ions are therefore
cesium chloride .. , ... ".1 < ,.11'1 < 1.37
sodium chloride." .. ",,1.37 < r2/'1 < 2.44
zincblende .. """ ....... 2.44 < r2/r, < 4.55

It must be emphasized that these results can be looked upon only as a

rough rule. In general, however, one may say that the esCI structure is
found in those compounds for which the ionic radii are nearly equal,
whereas the zincblende structure occurs only when the ratio of the radii is
about two or more. This may be illustrated by a few examples in Table 5-5.

Table 5-5. Ratio of Negative and Positive Ion Radii for Salts with the
Cesium Chloride and Zincblende Structure

Cesium chloride Zincblende

, _Ir, r_lr
structure structure

CsC! 1.1 ZnS 2.1

CsBr 1.2 ZnSe 2,3
Csl 1.3 BeS 5.1
n~1 1.2 BeSe 5.6
'.• I";2':J,; ~( 1.3 CuCl 1.9
1) L5 CuBr 2.0
CuI 2,3
"
A detailed discussion of the stability of the cesium chloride and sodium
chloride structures has been given by May.14 It is finally of interest
to note that structure transformations have been observed under
H A. May, Phys, Rev., 52,339 (1937).
128 LATTICE ENERGY OF IONIC CRYSTALS [Chap. 5
high pressures. A review of this subject may be found in a book by
Bridgman. 15

5-7. Refinements of the Born theory

The development of wave mechanics provided a better understanding

of the chemical bond and interatomic forces in general. As a result,
several refinements of the Born theory have been made, in particular by
Born and Mayer and their collaborators. 16 The essential refinements were
the following:
1. Quantum mechanical calculations of the forces between ions
indicate that a simple power law for the repulsive forces (5-3) cannot be
rigorous. One therefore replaced this law by an exponential one of the
form
rp
EreI' (r) = ce- / \ (5-15)
where c and p are constants.
2. One added an attractive term to the lattice energy corresponding
to the van der Waals forces which act between ions or atoms with a rare
gas electron configuration.
3. One took into account the "zero-point energy" of the crystal.
We shall not go through the calculation of the lattice energy which
includes the modifications just mentioned, because the method is in
principle the same as the one followed above. Also, the differences in
the results obtained are slight. However, a few remarks about the modi-
fications themselves, in particular about those mentioned under (2) and
(3) may be in order.
The van der Waals forces are responsible for the cohesion in the
liquid and solid states of rare gases as well as for most organic crystals.
These forces have been treated by London17 and Margenau 18 on a quantum
mechanical basis. An approximate expression for the interaction energy
of two atoms or ions with filled shell electron configuration is
3 1)(11)(2
E(r) = - - . _ . _ _
1112
(5-16)
2 ,6 II + 12
where II and 12 refer to the ionization energies of the particles involved
and 1)(1' 1)(2 refer to the polarizabilities. The nature of these forces is
essentially a quantum effect, although the fact that they vary with the
sixth power of the distance may easily be shown from classical
considerations.
'" P. W. Bridgman, Physics of H(f{h Pressure, 2d ed., Macmillan, New York, 1950.
16 M. Born and J. E. Mayer, Z. Physik, 75, I (1932); J. E. Mayer, J. Chern. Phys., 1.
270 (1933); J. E. Mayer and M. G. Mayer, Phys. Rev., 43, 605 (1933).
17 F. London, Z. Physik, 63, 245 (1930).

18 H. Margenau, Phys. Rev., 38, 747 (1931); Revs. Mod. Phys., 11, I (1939).
Sec. 5-7] LATTICE ENERGY OF IONIC CRYSTALS 129
A homogeneous electric field E induces in an atom a dipole (see
Sec. 6r2):
ft =qx =ex.E (5-17)
where q and x are, respectively, the effective charge and displacement;
is the polarizability of the atom. The energy of the atom in the field is
ex.
then
E = - (:r qEdx = _ (E qE': dE = -iex.E2 (5-18)
Jo Jo q
For a field strength varying with time, one would have for the average
energy,
E = -(rx/2)(E2) (5-19)

Now, suppose the atom is under influence of another atom at a distance r.

The latter may be considered a system of oscillating dipoles formed by
the nucleus and the electrons. The electric field strength of a dipole
varies as r- 3 and hence, according to (5-18), the energy of one atom in
the field of another may be written
" . : ,', ')

E = -constant/Ii (5-20)

The mutual energy of two atoms would then be given by the sum of two
terms of the type (5-20). From the classical point of view, therefore, these
forces are a consequence of the dipole-dipole interaction between the
atoms.
Actually, the energy corresponding to (5-16) is only part of the van
der Waals energy and there is an infinite series of rapidly converging
terms. The next one corresponds to dipole-quadrupole interaction and
varies as ,8.
For the alkali halides, the attractive energy corresponding to (5-16) is
of the order of a few per cent of the total lattice energy. For the silver
halides it is appreciably more; e.g., for AgBr it is about 14 per cent.
This is a consequence of the relatively high polarizability of the silver ion.
We should note that the van der Waals energy sometimes plays an
important role in the discussion of the stability of different lattice
structures. 19
The zero-point energy of the crystal is also a consequence of quantum
mechanics. The possible energy levels of a harmonic oscillator are given
by
E = (n + l)hJl (5-21)
where n is an integer and JI is the frequency. Thus, even at absolute zero
an oscillator has a zero point energy of hJl/2. Now, in the Debye theory
19 J. E. Mayer, J. Chem. Phys., 1,270 (1933); 1,327 (1933); J. E. Mayer and R. B.

Levy, J. Chem. Phys., 1,647 (1933).

130 LATTICE ENERGY OF IONIC CRYSTALS [Chap. 5
of the specific heat of solids, a crystal is represented formally by a system
of harmonic oscillators with a frequency spectrum given by (see Sec. 2-6)

~ ~ ~~ (2
F(lI) dll = 47TV 3
Ct
+ 3c,1 ) 112 dll
\ (5-22)

where V is the volume of the crystal and C t and c! are, respectively, the
velocities of propagation of transverse and of longitudinal elastic waves•
. Making use of the definition of the Debye frequency Y D , one may write
(5-23)

where N stands for the total number of atoms or ions in the crystal.
Hence, at absolute zero, the contribution of the zero-point energy is .\

t Jo(Vn F(Y)hv dy = 9
sNhllD (5-24)

Per ion pair this corresponds to 9hv D /4. With a Debye frequency of the
order of 1012_1013 sec-1 this gives about 0.1 ev. As a correction to the
lattice energy the zero point energy thus contributes about 1 per cent.
Note that this correction reduces the values given in Table 5-2, wherea~
the van der Waals correction raises them. In general, the van der Waals
correction is more important for heavy elements (large polarizabilities),
and the zero-point energy for light elements (high Debye frequency). As
an example, we give here the various contributions to the lattice energy
for the two extreme cases LiF and CsI (all energies in ev).
LiF CsI
Coulomb ............... -12.4 -6.4
Repulsive ............... + 1.9 +0.63
Dipole-dipole ......... - 0.17 -0.48
Dipole-quadrupole ... - 0.03 -0.04 " j' }{:t

Zero-point .............. + 0.17 +0.3 f~',;t:.r{t$i

REFERENCES
M. Born, Atomtheorie des festen Zustandes, Teubner, Leipzig, 1923.
M. Born and M. Gappert-Mayer, Handbuch der Physik, Vol. 24/2,
Springer, Berlin, 1933, pp. 723-794.
1. A. A. Ketelaar, Chemical Constitution, Elsevier, New York, 1953.
N. F. Mott and R. W. Gurney, Electronic Processes in Ionic Crystals,
2d ed., Oxford, New York, 1948, Chap. 1.
F. Seitz, The Modern Theory of Solids, McGraw-Hill, New York, 1940,
Chap. 2.
Chap. 5] LATTICE ENERGY OF IONIC CRYSTALS 131

PROBLEMS

5-1. Show that the Madelung constant for a one-dimensional array of

ions of alternating sign with a distance a between successive ions is equal
to 2 log 2.
5-2. Calculate the compressibilities at absolute zero from (5-13) for
LiF and BaO, assuming the values of n given in Table 5-1.
5-3. A molecule of the vapor of an alkali halide is presumably built
up of a positive and a negative ion. Assuming the quantities B' and n in
the repulsive energy to be the same as in the solid state, show that

€g/€s = 's/Arg and (rs/rg)n-l = 6/A

where €g and €s represent, respectively, the binding energy per molecule

in the gaseous and solid state; r g and rs are the equilibrium distances in
the gaseous and solid state. Show further that for this model €g is
approximately two-thirds of € .••
5-4. Set up the simple Born theory in a more general fashion than is
done in the text, so as to include cases of ions of different valency, such
as CaF 2, Fe 20 3 , etc.
5-5. Discuss the experimental methods by which the quantities on the
right-hand side of equation (5-14) may be determined.
5-6. Derive the expression for the lattice energy, replacing the power
law describing the repulsive energy by an exponential law of the type
(5-15). Calculate the constants c and p occurring in that expression for KBr.
5-7. Verify the values for the dipole-dipole contribution and for the
zero-point energy to the total lattice energy for LiF and CsI, given on
page 130.
5-8. Show that the polarizability of a metal sphere of radius R is
equal to R3.
5-9. Consider two ions of charges +e and -e. Assume that one of
them has a polarizability <X. and that the other has zero polarizability.
Show that the Coulomb interaction between the two ions as function of
their separation r is given by cp = -(e2/r)(l <X./2r). +
5-10. Consider two ions of charges +e and -e; the polarizabilities
of the ions are <X.l and 0(2' Show that the dipole moment induced in one
of them is given by
#1 = (rte<X. l + 2re<x' <x'2)/(,s -
1 4oc l 0(2)
with a similar expression for #2; r denotes the separation between the
132 LATTICE ENERGY OF IONIC CRYSTALS [Chap. 5
nuclei. (See, for example, P. Debye, Polar Molecules, Dover, New York,
1945, p. 60.)
5-11. Discuss the binding energy and dipole moment of alkali halide
molecules on the basis of an ionic picture and compare the results with
experiment (see E. S. Rittner, J. Chern. Phys., 19, 1030, 1951).
5-12. Give a simplified discussion of van der Waals forces (see, for
example, S. Glasstone, Theoretical Chemistry, Van Nostrand, New York,
1944, p. 423).

" ~.,

•. 1, l',( ,,<
Chapter 6

DIELECTRIC AND OPTICAL PROPERTIES

OF INSULATORS

In the present chapter a brief survey will be given of the atomic

interpretation of the dielectric and optical properties of insulators. The
theory given here is essentially classical; for the quantum theory of
dielectrics we refer to the literature (see, for example, J. H. van Vleck,
Theory of Electric and Magnetic Susceptibilities, Oxford, New York, 1932).
This chapter is divided into two parts: in part A we shall essentially be
concerned with the static dielectric constant, in part B, the frequency
dependence of the dielectric properties, including optical absorption and
dielectric losses, will be discussed. It may be emphasized that only isotropic
substances, for which E, D, and P are parallel vectors, will be considered.
,. f
j

Part A. Static Fields ~.

6-]. Macroscopic description of the static dielectric constant

As an introduction to the concept of the static dielectric constant of a

substance, consider the following well-known experimental result: Two
plane parallel plates of area A and separation d are charged with a surface
charge density q, one plate being positive, the other negative. If the space
between the plates is evacuated and if d is small compared with the
dimensions of the plates, there will result a homogeneous electric field
between the plates, the field strength being given by
Evac = 47Tq = D (6-1)

in esu; D is called the electric displacement or flux density. The potential

, difference between the plates is equal to
flh
4>vac = Evac . d
and the capacitance of the system is defined by

evac = Aq/4>vac = Q/4>vac (6-3)

Suppose now that the space between the plates is filled with an insulating
substance, the charge on the plates being kept constant. It is then observed
that the new potential difference 4> is lower than 4>vac' and similarly, the
133
134 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6
capacitance C of the system is increased. The static dielectric constant
\"
Es is then defined by
(6-4)

Thus, as a result of introducing the substance, the field strength is reduced

from the value Eyac to the value E, where
Evac = D = EsE (6-5)
In other words, the effective surface charge density on the plates is now
q' = E/47T rather than q = Evac/47T, and one may say that introducing the
dielectric is equivalent to reducing the surface charge
density by an amount
P = q -q' = (Evae/47T)(1 - liEs) = (E., - 1)E/47T (6-6)
+
Thus, under influence of the external field, the dielectric
facing the positive plate acquires a negative induced
surface charge density P and vice versa. This is
+ illustrated in Fig. 6-1. We shall see later that this
conclusion is in accord with the atomic interpretation
+ of the dielectric constant; in fact, it will be shown
that P is equal to the electric dipole moment induced
Fig. 6-1. Schematic in the substance per unit volume by the external
illustration of
charges induced at
field; P is called the polarization of the substance.
the surface of a From (6-5) and (6-6) it follows that one may write
dielectric.
D = E + 47TP = EsE (6-7)

The link between the macroscopic quantity Es and the atomic theory of
the dielectric constant is provided by the relation (6-6). In fact, it will be
shown below that P may be expressed in terms of the properties of the
atoms and molecules composing the dielectric.
i
6-2. The static electronic and ionic polarizabilities of molecules

Although we are mainly interested in the dielectric properties of

solids, it will be useful to consider first the much simpler problem of the
behavior of free atoms and molecules in an external electric field. The
term "free" refers to a system in which to a good degree of approximation
the mutual interaction between the particles may be neglected, as in a
gas of low density. A basic concept in the discussions to follow is that
of the electric dipole moment of a system. For a system of elementary
charges e i located at the end points of a set of vectors T i , drawn from a
common origin, the dipole moment is defined as
(6-8)
Sec. 6-2] DIELECTRIC PROPERTIES OF INSULATORS 135
For systems which, as a whole, are neutral, i.e., when Liei = 0, one can
show readily that M is independent of the origin chosen (see Problem
6-1); it is with such neutral systems that we shall concern ourselves. As
an example, the dipole moment corresponding to two charges +e and -e,
separated by a distance d, is ed.
In a free atom, the charge distribution is such that the dipole moment
in the absence of an external field vanishes; the center of gravity of the
electron distribution coincides with the nucleus. Consider now an atom
in a static homogeneous external field E. The force exerted on the positive
nucleus will then be oppositely directed to the forces exerted on the
electrons. As a result, the external field tends to draw the center of gravity
of the electrons away from the nucleus. On the other hand, the attractive
forces between the electrons and the nucleus tend to preserve a vanishing
---+E E

/'

"\ \
/
/
/

'.
I
I +e \
J d Ze-
\
\ /
\ /
"- '-

Fig. 6-2. Schematic illustration of Fig. 6-3. Simplified model for esti-
the displacement of the electron mating the magnitude of the elec-
orbit relative to the nucleus for a tronic polariz.ability of an atom, as
hydrogen atom under influence of an described in the text.
external field E.

dipole moment in the atom. Consequently, an equilibrium situation is

reached in which the atom bears a finite dipole moment. This has been
represented schematically in Fig. 6-2. The resulting dipole moment is
thus induced by the field as a result of an elastic displacement of the
electronic charge distribution relative to the nucleus. The induced moment
may be represented by
fJ.ind = rx.E (6-9)
where IX. is called the electronic polarizability of the atom. It should be
noted that (6-9) is actually only the first term of a power series in the
field strength. For the usual fields employed in dielectric measurements,
however, (6-9) is a very good approximation.
To obtain an idea of the magnitude of rx e , consider the following
simplified model; Suppose the atom is represented by a nucleus of charge
Ze and a homogeneous negative charge distribution inside a sphere of
radius r. If the nucleus is displaced over a distance d, as shown in Fig. 6-3,
136 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6

the restoring force is equal to the force exerted on the nucleus by a

negative charge Zed3 jr3. The equilibrium condition is then

ZeE = (Ze)2djr3
f \
\ (6-10)

This gives for the induced dipole moment, ,,\z

(6-11)

For this simple model, therefore, the polarizability IXe is equal to r3.l Note
that IX. has the dimensions of a volume. For r::: 10-8 cm, we see that IXe
is of the order of 10- 24 cm 3 • Hence, for an external field of 300 volts per
cm one finds d::: 10-15 cm, which shows that for most practical field
strengths the condition d <r is satisfied. It is for this reason that in (6-9)
one usually retains only the first term. For atoms with more than one
electron, similar considerations are valid, and with each atom or ion one
may associate a certain electronic polarizability IX •• It will be evident that
in general atoms with many electrons tend to have a larger polarizability
than those with few electrons. Electrons in the outer electronic shells will
contribute more to !Xc than do electrons in the inner shells, because the
former are not so strongly bound to the nucleus as the latter. Positive
ions therefore will have relatively small polarizabilities compared with
the corresponding neutral atoms; for negative ions the reverse is true.
We give a few examples in Table 6-1; more complete tables are available
elsewhere. 2 I

Table 6-1. Some Electronic Polarizabilities ill 10- 24 cm 3• The values for
the alkali and halide ions are those given by Bottcher; the others are due
to Pauling
IX, 1)(, 01.

He 0.20 Li+ 0.02

Ne 0.39 Na+ 0.22 F- 0.85
Ar 1.62 K+ 0.97 CI- 3.00 lIFn
Kr 2.46 Rb+ 1.50 Br- 4.13
Xe 3.99 Cs+ 2.42 1- 6.16 ~- -~--------

The polarizability as function of the frequency of the applied field will

be discussed in Sec. 6-9. It will be shown there that !X e may be considered
a constant up to frequencies corresponding to the ultraviolet spectrum.
1 A wave-mechanical treatment of the polarizability of the hydrogen atom may be

found in N. F. Mott and S. N. Sneddon, Wave Mechanics and its Applications, Oxford,
New York, 1948, p. 166. See also H. R. Hasse, Proc. Cambriqf{c Phil. Soc., 26, 542
(1930). Second-order perturbation theory gives the value rY., = 9a~/2 = 0.667 X 10- 24
cm 3 (ao is the radius of the H atom).
2 C. J. F. Bottcher, Rec. trav. chim., 62, 325, 503 (1943); L. Pauling, Proc. Roy. Soc.

:London), A1l4, 181 (1927); N. F. Mott and R. W. Gurney, Electronic Processes ill
Ionic Crystals, 2d ed., Oxford, New York, 1948, p. 14.
Sec. 6-2] DIELECTRIC PROPERTIES OF INSULATORS 137
So far, we have considered only simple atoms and ions. For molecules
one is faced with two more possible influences of an external field:

I. Molecules may have permanent dipole moments which may be

aligned in an external field.
2. The distances between ions or atoms may be influenced by an
external field.

For exaJ'!1ple, a molecule such as HCI may in first approximation be

considered to consist of two ions; the permanent dipole moment is thus
equal to the effective charge per ion times the separation of the ions.
Symmetric molecules like H 2' CO 2 , CCI 4 , etc. evidently have no permanent
dipole moment. An external electric field will tend to orient permanent
dipoles along the field direction, and one speaks of orientational polariza-
tion. This contribution to the total polarizability of a molecule will be
discussed in Sec. 6-3.
In molecules as well as in atoms an external field will displace the
electrons with respect to the corresponding nuclei. Over and above this,
however, a displacement of atoms or ions within the molecule may be
caused by an external field. For example, in an HCI molecule an external
field will change the interionic distance to some extent, leading to a change
in the dipole moment. Similarly, in a molecule like CCl 4 (which has no
permanent dipole moment) a change in the bond angles between the CCI
groups will produce a dipole moment because each of these groups by
itself does have a dipole moment. This kind of induced polarization is
called atomic or ionic polarization because it is a consequence of the
displacement of atoms within the molecule. The induced electric dipole
moment resulting from elastic displacements of ions within the molecule
may again be represented by an expression of the type (6-9), by replacing
7.,. by the atomic polarizability OCa' It should be noted that OC n refers to
an average over all possible orientations of the molecule with respect to
the field. In Sec. 6-9 it will be shown that OC a may be considered a constant
up to frequencies in the infrared spectrum. For most molecules, oc" is of
the order of I 0 per cent of (Xc'
Summarizing, one may conclude that the electric properties of a
molecule may be characterized by the following three quantities:

(a) (X"representing the polarizability due to electronic displacements

within the composing atoms or ions.
(b) (Xa' representing the polarizability due to atomic or ionic displace-

ments within the molecule (changes in bond angles and interatomic

distances).
(c) a permanent dipole moment fL.
138 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6

6-3. Orientational polarization

In this section we shall consider the polarizability of a molecule in a

static field, resulting from its permanent dipole moment. Consider, for
example, a gas containing a large number of identical molecules, each
with a permanent dipole moment lL. Without an external field, the dipoles
will be oriented at random and the gas as a whole will have no resulting
dipole moment. An external field E will exert a torque on each dipole
and will tend to orient the dipoles in the direction of the field (see Fig.
6-4). On the other hand, this ordering influence of the external field will
be counteracted by the thermal
+e motion of the particles. The problem
/.~--... eE therefore may be stated as follows:
What is the average component of
'E the dipole moment per molecule in
the direction of the applied field at a
eE--_ /
-e temperature T? To answer this ques-
tion it will be assumed that the dipoles
Fig. 6-4. Illustrating the torque exerted may rotate freely. We then have
on a dipole by an external field. before us a simple problem in statis-
tical mechanics.
Let us define the potential energy of a dipole making a 90° angle with
the external field as zero. The potential energy corresponding to an angle
() between lL and E is then equal to

-f-lEcos (j = -lL' E (6-12)

According to statistical mechanics, the probability- for a dipole to

+
make an angle between () and 0 d() with the electric field is then
proportional to
27T sin () d() exp [(f-lE cos ()/kTj

where 27T sin () dO is the solid angle between 0 and 0 d(). Hence the +
average component of the dipole moment along the field direction is equal
to
"
J
f-l cos () sin 0 dO exp [(f-lE cos ()/kT]
D=O :',-,r:"}i
f-l(cos (j) (6-13)
"
Jsin 0 dO exp [(f-lE cos ()/kT]
B~O

To evaluate the integrals, let

(f-lE/kT) cos () = x and (f-lE/kT) = a 'cf'"'W' (6-14)

Sec. 6-3] DIELECTRIC PROPERTIES OF INSULATORS 139

We then obtain
+a
f xex dx = e
1
(cos 0) = - f-+
a
a
Q

a
+ e- Q

a
1
- -a = L(a) (6-15)
a ex dx e - e-
-a

The function L(a) is called the Langevin function, since this formula was
first derived by Langevin in 1905 in connection with the theory of para-
magnetism. 3 In Fig. 6-5,L(a) has been
L(a)
plotted as a function of a = p,E/kT.
," 1

)1/3)a
Note that for very large values of t /

a, i.e., for high field strengths, the 1.0

.8
function approaches the saturation .6
value unity. This situation would .4
correspond to complete alignment .2
of the dipoles in the field direction, o 2 3 4 5 6
because then p(cos 0) = p. _. a=/JoE/kT
As long as the field strength is
not too high and the temperature is Fig. 6-5. The Langevin function L(a).
not too low, the situation may be For a <
1, the slope is 1/3.
strongly simplified by making the
approximation a ~ 1 or pE ~ kT. Under these circumstances the
Langevin function L(a) = a/3, so that then

p(cos 8) = (P2/3kT)E for pE ~ kT , (6-16)

As an example of the condition implied in (6-16), consider a field of

3000 volts per cm. The dipole moment p of a molecule is of the order of
10-to esu of charge times 10-8 cm, i.e., about 10- 18 cgs units,4 so that
pE-::::. 10-17 in cgs units. On the other hand, kT at room temperature is of
the order of 10-14 erg and for this example the condition is certainly satis-
fied. In this example saturation would be approached only in the vicinity
of 1°K. It may be noted that the quantum mechanical treatment of this
problem leads essentially to the same results as obtained here.~'
The existence of electric dipoles in molecules was first postulated
by Debye in 1912;6 this concept has contributed a great deal to the
present understanding of dielectrics as well as to our knowledge of
molecular structure. We shall now see how the molecular quantities
Ct., Ct a , and p enter in the description of the macroscopic dielectric

3 P. Langevin, J. Physique, 4, 678 (1905). ,o'¢ ,

• 10- 18 esu cm is caJJed a "Debye unil." ni ;1;".

• See, for example, P. Debye, Polar Molecules, Dover, New York, 1945.
• P. Debye, Phys. Z., 13,97 (1912).
140 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6

6-4. The static dielectric constant of gases

We are now in a position to give an atomic interpretation of the static

dielectric constant of a gas. It will be assumed that the number of mole-
cules per unit volume is small enough so that the interaction between
them may be neglected. In that case, the field acting at the location of a
particular molecule is to a good approximation equal to the applied field
E. Suppose the gas contains N molecules per unit volume; the properties
of the molecules will be characterized by an electronic polarizability OCe>
an atomic polarizability ()(a' and a permanent dipole moment fl. From the
discussions in the preceding two sections it follows. that, as a result of the
external field E, there will exist a resulting dipole moment per unit volume:

(6-17)

Note that only the permanent dipole moment gives a temperature-

dependent contribution, because ()(e and ()(a are essentially independent of T.
If the gas fills the space between two capacitor plates of area A and
separation d, the total dipole moment between the plates will be equal to

M=PAd

This simple relation shows immediately that the same total dipole moment
would be obtained by assuming that the dielectric acquires an induced
surface charge density P at the boundaries facing the capacitor plates, as
discussed in Sec. 6-1. Hence the quantity P introduced here as the dipole
moment per unit volume is identical with the quantity P introduced in
Sec. 6-1, where it represented the induced surface charge density at the
dielectric-plate interface. Therefore, combination of (6-17) and (6-6) leads
immediately to the Debye formula for the static dielectric constant of a gas. 6

€s - 1 = 47TP/E = 47TN(iJ. e + iJ. + f-l2/3kT)

a (6-18)

As an example of an application of this formula, we show in Fig. 6-6 the

temperature dependence of some organic substances in the gaseous state.'
Note that (€s - 1) has been plotted versus the reciprocal of the absolute
temperature, leading to straight lines, in agreement with formula (6-18).
From the slope of the lines and a knowledge of the number of molecules
per unit volume, the dipole moment f-l may be obtained. Also, from the
extrapolated intercept of the lines with the ordinate, one can calculate
(oc e + iJ. a ). The determination of dipole moments has contributed a great
1:leal to our knowledge of molecular structure. For example, CCI 4 and
7 R. Sanger, Phys. z., 27, 556 (1926).
Sec. 6-4) DIELECTRIC PROPERTIES OF INSULATORS 141
CH 4 , according to Fig. 6-6, do not possess permanent dipole moments,
in agreement with the symmetric structure of these molecules. Similarly,
the fact that H 2 0has a dipole moment
of 1.84 Debye units, whereas CO 2
has no dipole moment, indicates
that the CO 2 molecule has a linear 8
structure, whereas in HllO the two
OH bonds must make an angle ;::<
different from 1800 with each other. 8 \"'~ 6
;;-
o..... ~CH2CI2
6-5. The internal field according to
Lorentz
t 4 _ _ _ CHCI 3
CC14
2
The theory of the dielectric con-
stant of solids and liquids is much - - - - - - C H4
more complicated than that for OL-__- L____J -____L -___J
gases. In gases one may, to a good 2.5 3.0 3.5
~ lOOOjT
approximation, assume that the field
acting on the particles is equal to Fig. 6-6. Temperature variation of the
the externally applied field E. In static dielectric constant of some vapors.
[After Sanger, ref. 7]
solids and liquids, however, a given
molecule or atom "sees" not only
the external field, but the fields produced by the dipoles on other
particles as well. As a result of the long range of Coulomb forces, the
latler contribution can no longer be neglected. The central problem in
the theory of the dielectric constant of liquids and solids is therefore
the calculation of the field at the position of a given atom. This field
is called the internal or local field and is different from the externally
applied field E.
To calculate the internal field, the following method was suggested
by Lorentz: 9 Select a small spherical region from the dielectric with the
atom for which the local field must be calculated at the center (see Fig.
6-7). The radius of the sphere is chosen large enough to consider the
region outside the sphere as a continuum of dielectric constant "s' For
the region inside the sphere, however, the actual structure of the substance
must be taken into account. The following contributions to the internal
field at the location of the atom then arise:
(i) The contribution from the charge density on the plates, giving
47Tq = D.

8 For a table of dipole moments of a large number of molecules, see, for example,

the article on diele:tric polarization by O. Fuchs and K. L. Wolf, Hand- und

Jahrbuch der chemischen Physik, Vol. 6, Leipzig, 1935.
9 H. A. Lorentz, The Theory of Electrons, Teubner, Leipzig, 1909, Sec. 117.
142 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6
(ii) The contribution from the induced charges at the plate-dielectric
interface. According to Sec. 6-1, this contributes -47TP to the
field strength.
(iii) The contribution from the charges induced at the spherical surface.
(iv) The contribution from the atomic dipoles of all atoms inside the
spherical region.
To calculate the contribution (iii)
we first note that as a consequence of
the symmetry of the problem, only field
components parallel to E have to be
taken into account. Thus, consider a
ring of area 27TR2 sin e de on the inner
surface of the sphere. The surface
charge density depends on the angle
e and is equal to -P cos (). Hence
the charge on this ring is - P cos () 27T R2
sin e de, leading to a Coulomb field
at the center in the direction of E
Fig. 6-7. lllustrating the calculation equal to
of the internal field as described in
the tex t. ;::>l U" l P cos2 e . 27T R2 sin ede
(6-19)
R2
Thus th61contribution (iii) is equal to

-27TP r-1cos2 ed(cos e) = (47T/3)P (6-20)

.+1

For the moment let contribution (iv) be represented by E 4 • When

certain conditions of symmetry are fulfilled, this contribution may vanish
and in that case the internal field would be given by
Ei = D - 47TP + 47TP/3 = E + 47TP/3
or
Es
E., = -3- E
+2 for E4 = 0 (6-21)

This field is frequently referred to as the Lorentz field; it is always larger

than the applied field E. To investigate whether or not E4 = 0, we may
proceed as follows. Let the atoms inside the sphere have coordinates X k ,
Yk' Zk and dipole moment components Ilk"" Ilky, Ilkz' One may then write
for the contribution E4 in the direction of E,

_ " ( 3x~ - ,~
E4 - L
k
Ilk'"
'k
5 + Ilky 3X'kkYk + Ilkz 3X'kkZk)
5 5 (6-22)

As an example, consider a simple cubic lattice of like atoms, the

external field direction coinciding with a cube edge. In view of the
Sec. 6-5] DIELECTRIC PROPERTIES OF INSULATORS 143
symmetry of the problem, Ph = Pkz = 0, and Pka; will be the same for
all atoms. Furthermore, for the atoms inside a spherical region,
(6-23)

Obviously, (6-22) vanishes for a simple cubic lattice and (6-21) should
hold if the assumption of point like dipoles is accepted. We leave it up
to the reader to show that (6-22) also vanishes for b.c.c. and f.c.c. lattices
and for crystals such as NaCI. It must be emphasized that (6-21) does
not hold for all cubic crystals. For example, in barium titanate, which
has cubic symmetry, the oxygen ions are surrounded by TiH ions in such
a way that their contribution to (6-22) does not vanish.lO One must
therefore be careful in applying (6-21); one should start. from (6-22) in
order to evaluate £4 for the particular problem encountered. ll It will also
be evident from the above discussion that each type of atom in a given
crystal has, in general, its own internal field because the environment of
the different atoms is generally different. Thus the internal field at the
location of atoms of type 1,2, etc. may be written in the form

(6-24)

where the y's are the internal field constants. Only if £4 = 0 do we have
y = 41T/3. The internal field for tetragonal and simple hexagonal lattices
has been calculated by Mueller. 12
Even if the crystal symmetry is such that (6-21) applies, it does not
mean that the Lorentz field gives results in agreement with experiments.
This may be due to an overlapping of atoms as well as to the fact that
the dipolar fields produced by atoms which are only a few Angstroms
away are far from homogeneousP The latter makes it doubtful whether
one may employ the relation
}' " Pinuucctl = r:x£i (6-25)

to calculate the dipole moment induced in the central atom, as is done

in the theory outlined in the next section.
As a side line, it may be of interest to remark that the application of
(6-21) to polar liquid dielectrics has led to a great deal of confusion in
the literature. It was not until 1936 that Onsager realized that the internal
field cannot be used as the field which tends to orient the dipoles. 14 The
'I)For a discussion of the dielectric properties of this material, see Chapter 8.
11 For a generalized expression for E. and an application to BaTi0 3 see J. H. van
Santen and W. Opechowski, Physica, 14, 545 (1948).
12 H. Mueller, Phys. Rev., 47, 947 (1935); 50,547 (1936).

11 See N. F. Mott and R. W. Gurney, op. cit., p. 16.

H L. Onsager, J. Am. Chern. Soc., 58, 1486 (1936); see also C. J. F. Bottcher,

Physica, 9, 937 (1942); A. J. Dekker, Physica, 12, 209 (1946); D. G. Frood and A. J.
Dekker, J. Chern. Phys., 20, 1030 (1952). f Q' n .,H: ..,
144 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6
reason is that part of the internal field is contributed by the "reaction
field" of the dipole, which has the same direction as the dipole itself and
hence is ineffective in orienting the dipole. (See Problem 6-6.)

6-6. The static dielectric constant of solids \ )

From the discussions in the preceding sections it is evident that in

general the dielectric polarization P may be considered the sum of three
contributions,
(6-26)
where the subscripts e, a, and d refer, respectively, to electronic, atomic,
and dipolar polarization. This provides a basis for the classification of
dielectrics into three classes:
(i) Substances for which P a = P d = 0, so that P = Pc
(ii) Substances for which P d = °and P = P e + P a
(iii) Substances for which all three contributions are different from
zero.
Although the calculation of the internal field is usually complicated
by the fact that the Lorentz expression (6-21) does not apply, some remarks
may be made about each of these classes in so far as they apply to solids.
(i) Su~stances for which the static polarization is entirely due to
electronic displacements are necessarily elements, such as diamond. If
we assume for the internal field an expression of the type (6-24), one
obtains from the relation
Pc = NoceEi = (€s - I)E/47T (6-27)
the following expression for the dielectric constant:
€s - 1 = 47TNoc)O - Nyoc e) (6-28)
where N represents the number of atoms per unit volume. In the particular
case for which the Lorentz expression for the internal field (6-21) is valid,
y = 47T/3. The resulting expression is then usually written in the form
of the Clausius-Mosotti formula, which may be obtained by substitution
of (6-24) into (6-27):
(6-29)
The main experimental test of the correctness of either (6-28) or (6-29) is
provided by measurements of the dielectric constant as function of the
number of atoms per unit volume. It has therefore been applied mainly
to gases. For solid elements one would have to vary the temperature in
order to vary N and the possible range of N values is of course very
limited. We do not know of any such measurements on, say, diamond or
other possible solids which may fall in this class of dielectrics.
Sec. 6-6] DIELECTRIC PROPERTIES OF INSULATORS 145
It may be noted that for the class of substances under consideration,
the dielectric constant is equal to the square of the index of refraction,
E. = n 2 • The reason is, that OC e is constant even for frequencies in the
visible spectrum, as will be explained in Sec. 6-9. This relationship has
been confirmed experimentally for diamond by Whitehead and Hackett. I5
The dielectric constant of diamond is 5.68 ± 0.03.
(ii) In general, solids containing more than one type of atom, but no
permanent dipoles, exhibit electronic as well as atomic or ionic polarization.
Of particular interest in this respect are the ionic crystals, such as the
alkali halides. Consider, for example, a NaCl crystal in an external static
field E. Apart from the electronic displacements in the ions relative to
the nuclei, the positive ion lattice will tend to move as a whole relative
to the negative ion lattice. Consequently, a considerable contribution to
the total polarization may be expected to arise from the ionic displacements
(Pa ). That this is indeed the case, becomes apparent from a comparison
of the values of the static dielectric constant defined by
Pe +P a = (Es - 1)E/47T (6-30)
and the "high-frequency dielectric constant" EO, defined by
Pe = (EO - 1)E/47T (6-31)
(The high-frequency dielectric constant is equal to the square of the index
of refraction for visible light; at such frequencies the ionic displacements
cannot follow the field variations and consequently EO = n2 is a measure
only of P e .) By way of illustration, we give in Table 6-2 values for Es and
EO for the alkali halides. I6

Table 6-2. Static and High-Frequency Dielectric Constant for Alkali Halides

i
£, £0 = n2 I
'. ". Eo = /I?

LiF 9.27 1.92 KF 6.05 1.85

LiCI 11.05 2.75 KCI 4.68 2.13
LiBr 12.1 3.16 KBr 4.78 2.33
Lir 11.03 3.80 KI 4.94 2.69
NaF 6.0 1.74 RbF 5.91 1.93
NaCI 5.62 2.25 RbCI 5.0 2.19
NaBr 5.99 2.62 RbBr 5.0 2.33
Nal 6.60 2.91 Rbi 5.0 2.63
I
Hence P a is about two or three times P e in these compounds. In non-
ionic compounds, on the other hand, Pais usually a relatively small
fraction of P e•
15S. Whitehead and W. Hackett, Proc. Phys. Soc. (London), 51, 173 (1939).
16For a number of other ionic solids, see for example N. F. Mott and R. W.
Gurney, op. cit., p. 12.
146 DlELECTRlC PROPERTIES OF INSULATORS [Chap. 6

Let us now investigate if a simple theory can account for the observed
difference between the static and high-frequency dielectric constants.
Suppose the positive and negative ions acquire induced dipole moments
of, respectively, p+ and p_, under influence of a static field E. Furthermore,
suppose the positive ion lattice is displaced over a distance x relative to
the negative ion lattice. The atomic polarization may then be represented
by a point dipole ex at the location of each positive ion, because x is very
small compared with the lattice constant. The total electric dipole moment
per unit volume is then
P = N(p+ + p_ + ex) = (Es - I)Ej41T (6-32)
where N represents the number of ion pairs per unit volume. For the
moment let us assume that the internal field at the location of a positive
ion is the same as that at a negative ion site and let it be represented by
E;. We may then write : J\
x ; , ;J
Xu-33)
where CX e+ and CX e_ represent the electronic polarizabilities of the positive
and negative ions. To find the ionic displacement x, it should be remem-
bered that the equilibrium situation is determined by the equality of the
force on a positive ion resulting from the field and the restoring force
produced by the deformation of the lattice. Let the latter be represented
by lx, w~ere I is the restoring force constant. Then

eEi = Ix or x = eEilf (6-34)

From the last three equations it then follows that I

}'

(6-35)

If it were assumed that E; is given by the Lorentz expression (6-21), the

last expression could be rewritten as
(6-36)

This expression is analogous to the Clausius-Mosotti equation (6-29),

with the additional term e 2lfassociated with the elastic ionic displacements.
To investigate whether or not (6-36) describes the alkali halides satis-
factorily, it is convenient to set up an equation relating Es and the high-
frequency dielectric constant EO' determined by (6-31). Thus, if there were
only electronic polarization, which is the case if one measures the index
of refraction for visible light (EO = n 2 ), and if again the validity of the
Lorentz expression were assumed, one would have

Pe =
EO -
~ E
I
= N(cx e+
EO +2 E
+ cx e_) - 3 - (6-37)
Sec. 6-6] DIELECTRIC PROPERTIES OF INSULATORS 147
Substitution of the factor N(r:t.e+ + O(e-) from this equation into (6-36)
yields the following relation between lOs and EO:

(6-38)

This relation may be checked by inserting the value for f as obtained

from compressibility data and the Born lattice theory. It turns out,
however, that the measured values of lOs and EO do not satisfy (6-38) too
well. This indicates that the Lorentz expression for the internal field does
not describe the situation correctly. In fact, it seems that the formula
47TNe 21f
lOS - EO = 1 -4:--7T--:N-'e=-:2--:j3=-1j
-
-C- (6-39)

gives much better agreement with the experiments. This formula was first
derived by Hojendahl,I7 who introduced rather special assumptions about
the internal field at the location of positive and negative ion sites. From
the above discussion it is evident that the theory of the static dielectric
constant of simple crystals such as the alkali halides is not in a completely
satisfactory state, mainly because of the difficulties involved in calculating
quantitatively the internal field.
It may be noted here that the force constant f and the masses of the
positive and negative ions determine the infrared frequency associated
with the lattice vibrations. It is therefore possible to express the difference
(lOs __'_ EO) in terms of the infrared absorption frequency of the lattice. IS

A discussion of recent work on this topic may be found in H. Frohlich,

Theory of Dielectrics, Oxford, New York, 1949, Sec. 18.
(iii) In substances composed of molecules which bear permanent
electric dipole moments, the total polarization is· made up of three
contributions,
(6-40)

where P d corresponds to the dipolar contribution. There exists no general

quantitative theory for dipolar solids because first of all the same
difficulties arise in evaluating the internal fields as in class (ii), and further-
more, the dipoles in such solids may not be able to rotate at all or only
to some extent. The discussion must therefore be limited to some
qualitative remarks. As an example of a dipolar solid which behaves in a
relatively simple manner, we show in Fig. 6-8 the dielectric constant
measured as function of temperature for CsH5N02 (nitrobenzene).19 It is
observed that at the melting point there is a large increase in the dielectric
constant. This is interpreted as an indication that in the solid the dipoles
17 K. HojendahI, Kgl. Danske Videnskab. Selskab, 16, No.2 (1938).
,. B. Szigeti, Trans. Faraday Soc., 45, 155 (1949); Proc. Roy. Soc. (London), A204,
51 (1950).
19 C. P. Smyth and C. S. Hitchcock, J. Am. Chern. Soc., 55, 1830 (1933).
148 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6

cannot rotate freely and P a is essentially zero; in the liquid, alignment

of the dipoles in the field direction is possible, so that the increase in € is
determined by the now freely rotating dipoles. The subsequent slow
decrease in € is a consequence of the thermal motion of the particles, as
may be understood from equation (6-16). In other cases, the behavior
may be more complicated, as illustrated by Fig. 6-9, in which € versus T
24
40
20

30
16
fs
12
t
8
10
4 • <-,' ;·(r~'ft·

0
290 300 80 120 160 200
-T('K} _T('K)

Fig. 6-8. The static dielectric con- Fig. 6-9. Dielectric constant of
stant of nitrobenzene as a function hydrogen sulfide as function of
of tempera~re. [After Smyth and temperature. [After Smyth and
Hitchcock, ref. 20] Hitchcock, ref. 20]

has been plotted for H 2S.20 The melting point of H 2S is 187.7°K. In this
case, the dipoles are apparently "frozen in" at temperatures below !03.5 D K;
at this temperature the structure changes in such a manner that the dipolar
groups become mobile; as the temperature is further increased, the
dielectric constant decreases as a result of increased thermal motion.
The other changes evidently affect essentially the density of the material,
i.e., N is reduced at these transition points.

Part B. Alternating Fields

6-7. The complex dielectric constant and dielectric losses

When a dielectric is subjected to an alternating field, the polarization

P also varies periodically with time and so does the displacement D. In
general, however, P and D may lag behind in phase relative to E, sO that,
for example, if
E = Eo cos wI (6-41)
2. C. P. Smyth and C. S. Hitchcock, J. Am. Chel11. Soc., 55, 1296 (1933); 56, 1084
(1934).
Sec. 6-7] DIELECTRIC PROPERTIES OF .INSULATORS 149
we have
D = Do cos (0)/ - b) = DI cos ('It + D2 sin 0)/ (6-42)
where b is the phase angle. Clearly,
(6-43)
For most dielectrics Do is proportional to Eo, but the ratio Do/Eo is
generally frequency-dependent. To describe this situation, one may thus
introduce two frequency dependent dielectric constants: ._
,,'(w) = DI/Eo :- (Do/Eo) cos b
(6-44)
,,"«(I) = D2/Eo = (Do/Eo) sin 0

It is frequently convenient to lump these two constants into a single

complex dielectric constant,
E* == e' - iE" (6-45)
because the relation between D and E, both expressed as complex
quantities, is then simply
(6-46)
as may readily be verified.
,J It is noted that according to (6-44) there exists the relation
(6-47)
and because both ,,' and €" are frequency-dependent, the phase angle 0 is
frequency-dependent. We shall now show that the energy dissipated in
the dielectric in the form of heat is proportional to ,,". The current
density in the capacitor is equal to ,\

1= dq = _!_ . dD =.:.:!_ (-D1 sin

dt 477 dt 477
cut + D2 cos wt) (6-48)

where use has been made of (6-1) and (6-42); q is the surface charge
density on the capacitor plates. The energy dissipated per second in the
dielectric per unit volume is I
W 2fT!," .
W=-
277 .
JEd! I (6-49)
o
By substitution of (6-48) and (6-41) into (6-49) one readily finds that the
integral containing D1 vanishes and one is left with
(6-50)
The energy losses are thus proportional to sin 0; for this reason sin 0 is
called the loss factor and 0 is the loss angle. 21
21 One frequently calls tan (j the loss factor; this is correct only for small values of <5,

because then tan D ~ sin /) = D.

150 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6

6-8. Dielectric losses and relaxation time

Let us consider a dielectric for which the total polarization P s in a

static field is determined by three contributions,

(6-51)

In general, when such a substance is suddenly exposed to an external

static field, a certain length of time is required for P to be built up to its
final value. In the present section it will be assumed that the values of
P,. and P" are attained instantaneously, i.e., we shall be concerned with
frequencies appreciably smaller than infrared frequencies. The time
required for P" to reach its static value may vary between days and lO-la
second, depending on temperature, chemical constitution of the material,
and its physical state.
To begin with we shall give a phenomenological description of the
transient effects based on the assumption that a relaxation time can be
defined; we can then proceed to consider the case of an alternating field.
Let P d , denote the saturation value of P d obtained after a static field E
has been applied for a long time. It will be assumed that the value of P a
as function of the time after the field has been switched on is given by

(6-52)
Hence,
(6-53)

For the decay occurring after the field has been switched off, this leads to
a well-known proportionality with e- f / In the case of an alternating
T
•

field E =, Eoe;"", equation (6-53) may be employed if we make the following

change: p,/s must be replaced by a function of time Pds(t) representing
the saturation value which would be obtained in a static field equal to
the instantaneous value E(t). Hence for alternating fields we shall employ
the differential equation 22

(6-54)

Now, our final goal is to express the real and imaginary parts of the
dielectric constant in terms of the frequency wand the relaxation time T.
For this purpose we shall define the "instantaneous" dielectric constant
E,,, by
1
P
e
+ Pa = E -
_e_a_ _
417
E (6-55)

"" For a proof that this procedure is correct, see, for example, M. Gevers, Philips
Research Rep/s., 1, 279, 298 (1946); M. Gevers and F. K. Du Pre, Trans. Faraday Soc.,
42.-\, 47 (l946).
Sec. 6-8) DIELECTRIC PROPERTIES OF INSULATORS 151
We may then write
(6-56)

where Es is the static dielectric constant. Substitution of Pd. into (6-54)

yields
dPd=~(E8-E'IlE iwt_ p ) (6-57)
dt T 41T oe d
. \:
. \

Solving this equation, we obtain

(6-58)

The first term represents a transient in which we are not interested here.
The total polarization is now also a function of time and is given by
p. + +
P" Pit). Hence, for the displacement one obtains

D(t) = E*E(t) = E(t) + 41TP(t) (6-59)

where E* is the complex dielectric constant. From the last two equations
and from the definition E* = E' - iE" the following expressions result:

(6-60)

(6-61)

These equations are frequently referred to as the Debye equations. In

Fig. 6-10 the quantities E' and E" are represented as functions of WT. It is
observed that the dielectric loss, which is proportional to E" according to
(6-50), exhibits a maximum for (r)T = I, i.e., for an angular frequency
equal to liT. Also, for frequencies appreciably less than l/T, the real part
of the dielectric constant E' becomes equal to the static dielectric constant.
In this frequency range, therefore, the losses vanish and the dipoles
contribute their full share to the polarization. On the other hand, for
frequencies larger than liT, the dipoles are no longer able to follow the
field variations and the- dielectric constant E' approaches E.".
The question may now be raised as to which physical models actually
satisfy the above phenomenological theory. We shall discuss here a
particular one as an example, viz., the case in which certain positive ions
in a solid may have two equilibrium positions separated by a distance 2a.
For simplicity it will be assumed that the line joining the two positions
A and B is parallel to the external field direction, as indicated in Fig. 6-11.
152 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6
As long as there is no external field, we shall assume that the energy in
sites A and B are equal, so that without field there are just as many ions
in A sites as in B sites. If we assume that, without field, the potential

L--- E \

, ....
__ 2a--
-logw

Fig.6-10. Debye curves for E' and E" Fig. 6-11. The full curve represents
as function of frequency for a di- the potential energy for a positive
electric with a single relaxation time. ion in the absence of an external
field; with a field E, the dashed
curve results.

energy barrier separating the two types of sites is cp, the probability per
second for an ion in an A site to jump into a B site is, according to
statistical mechanics, of the form

Po = 'P exp (-cp/kT) (6-62)

•
where 'P is a frequency factor of the order of 1012 per second. Thus, without
external field, the ions will continuously change over from A and B sites,
but on the average there are per unit volume NI2 in A sites and Nf2 in
B sites if N is the total number of such ions per unit volume.
Suppose now that suddenly a static field E is applied in the direction
as indicated in Fig. 6-11. Particles in A sites will then see a potential
barrier (cp - eaE) and particles in B sites see a barrier (cp +
eaE); hence
the ions will prefer B sites over A sites. In equilibrium we must evidently
have just as many particles making transitions A -+ Bas B -+ A, so that

Naoo Po exp (eaE/kT) = NbooPo exp (-eaE/kT) (6-63)

or

where Naao and Nboo represent the equilibrium values for the number of
particles in A and B sites with an external field E. Let us now consider
the transient phenomenon as we go from the initial state NaO = Nbo = NI2
to the final state Naoo and N boc ' Particularly, we are interested in the time
dependence of (Nb - N a ) because the dipole moment per unit volume
resulting from this effect is
(6-64)
•
Sec. 6-8] DIELECTRIC PROPERTIES OF INSULATORS 153
At a particular instant we have

dNa/dt = -NaPab + NbPba

(6-65)
dNb/dt = NaPab - NbPba

Subtracting these equations, keeping in mind that Na + Nb = N, one may

write

Now, one may assume for not too high field strengths that eaE <{ kT,
so that

Pab =Po exp(eaE/kT)c:::'. Po(l + eaE/kT) _---t'

t £}rt! .,
and similarly,

Pba c:::'. Po(1 - eaE/kT)

Hence (6-66) reduces to

-T
(dfdt)(Nb - N a) = -2Po(Nb -- N a)
+ 2poNeaE/kT (6-67) Fig. 6-12. The dielectric constant
as a function of temperature at a
The solution of this equation, for the given frequency, as predicted from
initial condition specified above, is the model discussed in the text.

NeaE _ t
N - N = - - (1 - e 2Po) (6-68)
b a 2kT
and the polarization due to this mechanism is, according to (6-64) and
(6-68), given by 'i.n~:h
Ne 2a2 E 1
Ptl(t) = - k - (1 - e- t / with T = - T
(6-69)
)

2 T 2po
'i ,,' \.
Note that this equation has the same form as (6-52), which was the basis
on which the Debye equations were derived. The relaxation time is thus
equal to the reciprocal of the jumping probability per unit time in the
absence of an external field. Note also, that for this type of mechanism
the relaxatioq time decreases with increasing temperature and so does the
saturation polarization. It is of interest to observe that if the quantities
t:' and t:" are measured at a constant frequency but at different temperatures,
the curves as indicated in Fig. 6-12 may be expected to result.
For other possible models which lead to the Debye equations, see
Frohlich, op. cit., Sec. 11. It should be pointed out that the interpretation
of experimental results on dielectric losses frequently requires a distri-
bution of relaxation times rather than a single one as assumed in the above
154 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6

discussions. One then employs the following equations instead of (6-60)

and (6-61)

\ (6-70)
E" = (E - E ) foo F(T)wTdr j
s ea 0 1 + w2r
where F(T) is the distribution function of the relaxation times, such that

fooo F(T) dT = 1 (6-71)

For further details we refer to the literature. 23 ,24

6-9. The classical theory of electronic polarization and optical absorption

In Sec. 6-2 the concept of the static polarizability due to elastic dis-
placements of electrons and ions was introduced. In the present section
the classical theory of this phenomenon in alternating fields will be dis-
cussed. From formula (6-10) it is evident that the restoring force deter-
mining the displacement is in first approximation proportional to the
displacement itself. The discussion is therefore based on the model of an
harmonic oscillator. The differential equation governing the motion of an
elastically bound particle of charge e and mass m in an alternating field
Eoe iwt may be written
'
<;l I
(6-72)

where W o is the natural angular frequency of the particle; W o = (/jm)1/2

where / is the restoring force constant; the second term on the left-hand
side is a damping term, which results from the fact that the particle emits
radiation as a consequence of its acceleration. 25 The solution for this
forced damped vibration is
e -,;-__
X(/) = _. eiwt _
E 0".--_
m w~ - w2 iyw +
We first of all note that in a static field, i.e., for W = 0, this reduces simply
to
x = eEo/mw~ or as = ex/Eo = e2jmw5 for w = 0 (6-74)
23 For a review, see M. Gevers, Philips Research Repts., 1,279,298 (1946); see also

M. Gevers and F. K. Du Pre, Trans. Faraday Soc., 42A, 47 (1946).

2' For dielectric losses in alkali halides resulting from Schottky defects and divalent
impurities, see R. G. Breckenridge, J. Chern. Phys., 16, 959 (1948); 18, 913 (1950);
also his article in W. Shockley (ed.), Imperfections in Nearly Perleet Crystals, Wiley,
New York, 1952 .
.. A proof that this leads to a term proportional to dx/dt may be found in R. Becker,
Theorie der Elektrizitiit, 6th ed., Teubner, Leipzig, 1933.
Sec. 6-9] DIELECTRIC PROPERTIES OF INSULATORS 155
where IXs is static polarizability associated with the elastically bound
particle. If we take for e and m the electronic charge and mass, this
expression would correspond to the contribution of a particlar electron to
the electron polarizability. Now we have seen in Sec. 6-2 that the electronic
polarizabilities are of the order of 10-24 cm 3 ; this gives a natural frequency
Yo = WO/27T c::: 1015 per second. Thus, even for frequencies corresponding
to the visible spectrum, the electronic polarizability may be considered
constant. If e and m refer to an ion, the natural frequencies are of the
order of 1013 per second, corresponding to the infrared part of the
spectrum. <0 -1
Let us now consider the frequency t
dependence of the polarization re-
sulting from the elastic displacements.
It must be emphasized that the field
strength appearing in equation (6-73)
for the displacement x(t) is the in-
ternal field and not the externally
applied field; only in the case of gases
of low density may these two fields
be considered equal. Let us first
consider the case of a gas, for which
one may write Fig. 6-13. Behaviour of €& and €ii as
E*-I. . . function of frequency in the vicinity of
p*=_o--E e,u·t=Noc*E e,wl (6-75) the resonance frequency Woo
" 47T 0 e °
where the asterisks indicate complex functions. The polarizability is
immediately obtained from (6-73) by multiplying by e and dividing by the
field strength. Hence
e2 I
E* = I + 47TN - ' --,------ (6-76)
o m «)t - U)2 + iyw
Now, writing again E6 = E~ - iE~, one finds
e2 «)2 _. 0)2
E~ = 1 + 47T N - . -2C;---O-::---~'
m «(1)0 - (1)2)2 + y 2w 2
(6-77)

Ii e2 Y(l)
= 47TN - . ) (6-78)
EO
m (w6 - ( 2
)2 +y 2w 2

The energy absorbed per unit volume is proportional to E~, according to

(6-50). In Fig. 6-13 we have represented (E~ I) and -
as functions of E;;
the frequency w. Note that E;; contains the damping factor y, which has
the dimensions of a frequency; if there were no damping, there would be
no absorption. This type of absorption is called resonance absorption,
for obvious reasons. In the absorption region, the dielectric constant E~
depends on frequency and one speaks in this connection of dispersion.
156 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6
<)
The region for which decreases with increasing frequency is referred to
as the region of anomalous dispersion.
For solids, assuming the internal field to be given by the Lorentz
expression (6-21), we should write instead of (6-75),
\
p*
e
= €6 -
417
1E
0
eiwt = NIJ,.*
e
(€6 +
3
2) E 0
eiwt (6-79)
which leads to ,.
47TN
or €* = 1 + ----- (6-80)
o 1/1J,.: - 417N/3
Substituting IJ,.: obtained from (6-73) in the same way as above, this gives
2
€*
o
= 1 + 417N -me . w~
---:;-----:------,,-,--
,_ w 2 + iyw - 417Ne 2 /3m
(6-81)

Comparing this with (6-76) for a gas, we see that by defining a new
frequency
(6-82)
the same behavior is obtained as above; in the formulas obtained for a
gas, one only has to replace w~ by wi,
i.e., the absorption frequency is
displaced.
In optical work it is usual to introduce instead of the quantity €6 the
complex index of refraction. A few remarks in this connection may there-
fore be in order. It is well known that Maxwell's equations for a non-
magnetic insulator give for the velocity of propagation of light the expres-
sion v = ely'; On the other hand, the index of refraction is defined as
n = e/v. This leads to the Maxwell relation € = n 2• Now, when there is
absorption, the electric component of a light wave polarized in the y-
direction and propagated in the x-direction may be represented by
(6-83)
where exp (-wkx/e) takes care of the absorption. The coefficient k is
called the extinction coefficient. Its physical meaning is the following:
when the wave has propagated over a distance equal to the wavelength in
vacuum Ao = 217C/W, the amplitude is reduced by a factor e- 2rrk Now
instead of (6-83) we may also write
E"ix,t) = Aeiw(t-n'x/c) (6-84)
where n* is the complex index of refraction and where evidently
n* = n - ik (6-85)
From this relation, together with (n*)2 = €6 = €~ - i€~, it then follows
that
€~ = n2 - k 2 and €~ = 2nk (6-86)
Sec. 6-9] DIELECTRIC PROPERTIES OF INSULATORS 157
and the formulas (6-77) and (6-78) are thus also valid for and (n 2 - k 2)
2nk, respectively. Note that the absorption per unit volume is proportional
to nk. -. .
~. . i'i.:~~ ~ _;_.~,'

t P (real part) : ,"

I,
J -_

Pe - - - - - - - - - - - - --

Micro- Infrared
waves

~>;" ~>,/
Fig. 6-14. The real part of the total polarization P as function of
frequency for a dipolar substance with a single atomic and "_
electronic resonance frequency.

The above considerations may be applied equally well to ionic dis-

placements. To summarize the frequency-dependence of the polarization
we have represented, fn Fig. 6-14, pew) for a dipOlar substance with a
single atomic and electronic absorption line. ,
;

REFERENCES

R. Becker, Theorie der Elektrizitiit, 6th ed., especially volume II, Teubner,
Leipzig, 1933.
C. J. F. Bottcher, Theory of Electric Polarization, Elsevier, Amsterdam,
1952.
W. Fuller Brown jr., Encyclopedia of PhYSiCS, 27, Springer, Berlin, 1956,
pp. 1-154.
P. Debye, Polar Molecules, Dover, New York, 1945.
Dielectrics discussion, Trans. Faraday Soc., 42A, (1946).
H. Frohlich, Theory of Dielectrics, Oxford, New York, 1949.
R. J. W. LeFevre, Dipole Moments, 2d ed., Methuen, London, 1948.
O. Fuchs and K. L. Wolf, "Dielektrische Polarisation," Hand- und
lahrbuch der chemischen Physik, Vol. 6, Leipzig, 1935.
E. J. Murphy and S. O. Morgan, "Dielectric Properties of Insulating
Materials," Bell System Tech. I., 16, 493 (1937); 17, 640 (1938);
18, 502 (1939). J :'H)~~;;~ Lil"J~t. ')d; Lcd; ,1 t,
158 DIELECTRIC PROPERTIES OF INSULATORS [Chap. 6
C. P. Smyth, Dielectric Constant and Molecular Structure, Chem. Catalog,
New York, 1931.
J. H. van Vleck, Theory of Electric and Magnetic Susceptibilities, Oxford,
New York, 1932.
A. von Hippel, Dielectric Materials and Applications, Technology Press,
Cambridge, Mass. and Wiley, New York, 1954. (This volume con-
tains papers by 22 contributors and has been edited by A. von
Hippe!.)
A. von Hippel, Dielectrics and Wares, Technology Press, Cambridge,
Mass. and Wiley, New York, 1954. I'
PROBLEMS

6-1. Consider a system of positive and negative charges, the system

being neutral as a whole. Show that the dipole moment of the system as
defined by (6-8) is independent of the location of the origin of the co-
ordinate system.
6-2. Show that the potential energy of a dipole fJ. in an external field
E may be written -fJ. • E. Also show that if IX is the polarizability of an
atom, the energy of the atom in an electric field E is given by -(1X/2)£2.
6-3. From the electronic polarizabilities for the alkali and halide ions
given in Table 6-1 and from the lattice constants for the alkali halides as
obtained from X-ray diffraction data, calculate the high-frequency
dielectric constant for some of these salts on the assumption that the
internal field is given by the Lorentz expression; compare the results with
the experimental values given in Table 6-2.
6-4. Calculate the field strength required to reach 0.1 per cent of the
saturation value of the orientational polarization of a dipolar gas at room
temperature if the dipoles have a strength of 1 Debye unit.
6-5. Consider a system of noninteracting dipoles which are confined
to two possible orientations relative to an applied field E: either parallel
or antiparallel. Show that at a temperature T the average dipole moment
along the field direction is equal to ft2/kT (which differs by a factor 3 from
formula (6-16).
6-6. (a) A sphere of dielectric constant Ei and radius R is brought in a
homogeneous field E; the sphere is surrounded by vacuum. Show that
the field inside the sphere is homogeneous and given by 3E/(E i + 2).
(b) A substance of dielectric constant EO contains a spherical cavity of
radius R. If the field at large distances from the sphere is homogeneous
and equal to E, show that the field inside the cavity is homogeneous and
Chap. 6] DIELECTRIC PROPERTIES OF INSULATORS 159

equal to 3EoE/(2Eo + I). (This field is called the cavity field; note that it
is independent of R.)
(c) Consider a homogeneously polarized sphere of radius R in vacuum;
there is no applied field. If P is the polarization of the sphere show that the
field inside the sphere (the self-field) is given by Es = -(47T/3)P = -M/R3,
where M is the total dipole moment of the sphere .
•
(d) A spherical cavity of radius R inside a homogeneous dielectric E
contains a rigid dipole fl. at its center. There is no applied field. Show that
the field inside the cavity is homogeneous and given by ffl., where

f= ~ (E-l) 2 R3

This field is called the reaction field of the dipole.

Hint: For all these problems the general solution of Laplace's equation
V'2V= 0 is of the form
V = -(A/r2 + Br) cos 0
The constants A and B must be found from the boundary conditions.
6-7. Discuss the theory of Bottcher of the refraction of electrolytes
and explain how he arrived at the polarizabilities of the alkali and halide
ions given in Table 6-1. (See C. 1. F. Bottcher, Theory of Electric Polariza-
tion, Elsevier, New York, 1953, p. 273; also footnote 2.)
6-8. Readers familiar with the variation method in wave mechanics
may show that if one employs a variation function 'Pdt + Az) for a
hydrogen atom in an external field along the z-direction, one obtains for
the polarizability 4aZ = 0.59 X 10-24 cm 3 (a o = radius of first Bohr orbit;
the correct answer is 9aU2).
6-9. Explain the shapes of the e' and e" curves represented in Fig. 6-12.
6-10. Discuss the dielectric losses in alkali halide crystals resulting
from pairs of vacancies and from divalent positive impurities (see footnote
24; also, Y. Haven, Report of the Conference on Defects in Crystalline
Solids, Bristol, 1954, p. 261).
6-11. Consider the parallel arrangement of the following two circuit
branches: one branch consists of a capacitor C 1 , the other of a capacitor
C 2 plus a series resistor R. Show that this circuit is the equivalent of a
capacitor filled with a dielectric satisfying the Debye equations.
6- I 2. Discuss the theory of the dielectric constant of alkali halides of
Roberts; this theory is based on a simplified model involving rigid and
weightless ionic boundaries. See S. Roberts, Phys. Rev., 77, 258 {I 950).
'<\..,

.. Chapter 7·
-,-

IONIC CONDUCTIVITY AND DIFFUSION

l "\
\
7-1. I,attice defects in ionic crystals

We have seen in Sec. 3-3 that a metallic lattice in thermal equilibrium

contains a certain number of lattice defects. Examples of such defects are
vacant lattice sites, interstitial atoms, pairs of vacancies, etc. The formation
of a particular type of lattice defect requires a certain energy cP and because
the equilibrium number of defects depends on a Boltzmann factor con-
taining cP, those defects with the lowest cP value will predominate.
Ionic crystals should, according to thermodynamics, also contain
defects in thermal equiJibrium with the lattice. Here again, the most
common types are vacancies and interstitial ions. Other defects are, of
course, possible in principle; for example, some positive ions may occupy
lattice positions that are normally occupied by negative ions. It would
seem, however, that the production of such disorderly arrangements
would require very high energies and thus their relative numbers would be
very smalLl In other words, ionic crystals may be looked upon as com-
pletely ordered "alloys" (apart from vacant sites and possible interstitial
ions) of a metal and a metalloid.
Let us consider an ionic crystal of the composition A +B-. Positive ion
vacancies may. then be produced in a similar way as in metals, viz., by a
number of successive jumps of positive ions (Fig. 7-1). The result would be
equivalent to taking a positive ion somewhere from the interior of the crystal
and placing it at the surface. 2 Suppose now that a number of positive ion
vacancies would have been produced in this manner while the negative ion
lattice remained perfect. The surface of the crystal would then contain an
excess of positive charge, the interior an excess of negative charge. Thus
space charges would be set up. It is obvious that such space charges would
counteract the formation of more positive ion vacancies. On the other
hand, the field set up by the space charges would favor the formation of
negative ion vacancies. We thus conclude that as a consequence of the
tendency to prevent the build-up of space charges, an ionic crystal should
contain nearly equal numbers of positive and negative ion vacancies. 3
1 J. ~ van Santen, Philips Research Repts., 5, 282 (1950), discusses order-disorder

for Coulomb fo,:ces.

2 Vacancies may also originaie at dislocation jogs inside the crystal; see Sec. 3-12.

3 A treatment of the space charge problem may be found in J. Frenkel, Kinetic

Theory afLiquids, Oxford, New York, 1946.

160
Sec. 7-1] JONIC CONDUCTIVITY AND DIFFUSION 161
Thus even if the energy 1>+ required to produce a single positive ion
vacancy were appreciably different from the energy 1>- to produce a
single negative ion vacancy, they would occur in approximately equal
numbers in the interior of the crystal. It is obvious from this that their
number will be determined only by the sum of the formation energies
(7-1)
As in Chapter 3, it will again be assumed that the external pressure may be
taken as zero, so that the equilibrium condition requires the free energy
E - TS to be a minimum. The free energy of the fictitious perfect crystal
will be represented by
" _.J_
\ <
(7-2)

where the energy Ep incorporates the binding energy as well as the

vibrational energy. The entropy is thermal entropy only, because for a
perfect crystal the configurational entropy vanishes. Let the actual crystal
contain n positive and n negative ion vacancies. Its configurational
entropy is then
S"f = k log [(N +
n)!/N!n!J2 (7-3)

The term in square brackets represents the number of ways in which N

positive ions and n positive ion vacancies may be distributed over a total
of (N +
n) sites. The same holds for the negative ion sites, hence the
square. The free energy of the actual crystal may thus be represented by
F" = Fp + n1> - T(S" - Sp) _. 2kT log [(N + n)!/ N!n!] (7-4)

where Sa is the thermal entropy of the actual crystal. Let us define the
increase in thermal entropy LlSth resulting from the production of a
positive plus a negative ion vacancy by
(7-5)
Applying the equilibrium condition (oF/ onh = 0 to (7-4) we obtain
for n~N,
",
n = N exp (LlS tl J2k -1>/2kT) (7-6)
Note that the essential factor is the Boltzmann factor containing 1>/2, i.e.,
half the energy required to produce a positive plus a negative ion vacancy.
The exponential term containing the change in thermal entropy per vacancy
LlStl J2 may be calculated on the basis of a particular model, for example,
an Einstein model. In that case the calculation is similar to that given in
Sec. 3-3 for metals. Thus let us assume that the Einstein frequency
associated with the ions in the perfect lattice is 1'.4 In the actual lattice,
• It would be more realistic to introduce two Einstein frequencies, one for the positive
and one for the negative ions; the essential conclusions, however, would remain the
same. "', 1(";;'.
162 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7
let the Einstein frequency of an ion neighboring a vacancy be v' « v).
The actual crystal then corresponds to 6zn linear oscillators of frequency v'
and (6N - 6zn) oscillators of frequency v, where z is the number of
nearest neighbors surrounding a vacancy. The thermal entropies of the
perfect and actual crystals are then given, respectively, by (see equation 3-2)

Sv = 6Nk log (kT/hv) + 6Nk

Sa = 6znk log (kT/hv') + (6N - 6zn)k log (kT/hv) + 6Nk
where we assumed kT ~ hv. Hence

Sa = Sv + 6znk log (v/v') (7-7)

According to (7-7) and (7-5), we may then write for the increase in thermal
entropy per vacancy formed,

b..Sth /2 = 3kz log (v/v') (7-8)

For this model, the expression for the density of vacancies may then be
be obtained by substituting (7-8) into (7-6), giving

n/N = C exp (-4>/2kT) with C = (v/v')3Z (7-9)

Note that the frequency ratio is larger than unity, so that the thermal
entropy changes favor the formation of vacancies.
Here, as in the case of metals, one frequently finds the argument in the
literature that if 4> depends on temperature in accordance with a relation
of the type
4>(T) = 4>0 + T (d4>/dT) = 4>0 - yT (7-10)

the actual expression for the density of vacancies should be

- (7-11)

However, the objections raised in connection with this argument in

Sec. 3-3 are also valid in this case: 5 it does not take into account the
temperature variation of the thermal entropy change b..S tll . In fact, for
zero pressure we have
d4>/dT = Td(b..Sth)/dT (7-12)

Suppose now that n/N could be measured in some way and that over a
limited range of temperatures the result could be expressed by ,
d
n/N = A exp (-€/kT) or € = -k d(l/T) log (n/N) (7-13)

• Y. Haven and J. H. van Santen, Philips Research Repts., 7, 474 (1952).

Sec. 7-1] IONIC CONDUCTIVITY AND DIFFUSION 163
where If is the "experimental" slope of log (n/ N) plotted versus 1/kT.
Substituting the general expression (7-6) into (7-13) and making use of
(7-12), one finds
" =4>/2 (7-14)

Hence, one actually measures 4> in this manner. Also, the pre-exponential
factor A as determined experimentally is always equal to exp (6.s/2k).
Approximate methods to calculate the energy 4> required to create a
positive plus a negative ion vacancy will be discussed in Sec. 7-3 and we
shall therefore postpone giving numerical values for the quantities
involved. +
It will be evident that a positive and a y+
negative ion vacancy will attract each other as + + +

a result of the Coulomb field between them. + +

For large distances, the energy of attraction is
equal to -e2 /a, where If is the dielectric con- + +
stant of the medium. They may therefore com-
+' +
bine to form pairs of vacancies (Fig. 7-1). At
a given temperature there will exist a certain + + +
tatio between the number of single vacancies _ I c I +
+
and the number of pairs, the ratio depending
on the dissociation energy required to separate + + +
a pair into two singlets. There are evidently Fig. 7-1. The sequence
certain degrees of dissociation depending on of jumps I, 2, 3 may lead
whether the distance between the single vacancies to the formation of a
is small or large; in a sense one may therefore positive ion vacancy A;
speak of a thermally excited state of a pair if tile B represents a negative ion
vacancy; C an associated
distance between the vacancies is only a few pair of vacancies formed
atomic diameters. Reference to the importance as a result of Coulomb
of pairs of vacancies for diffusion in ionic attraction.
crystal will be made later.
Interstitial ions in combination with vacancies may also occur: for
example, a positive ion may jump into an interstitial position, leaving a
vacancy behind. If the vacancy and interstitial ion are far enough apart to
prevent an immediate recombination, one speaks of Frenkel defects.
In this case it is not necessary to have equal numbers of positive and
negative Frenkel defects, because their formation does not require the
setting up of space charges over macroscopic distances. In general,
\ depending essentially on the energy required to form them, either the
positive or negative Frenkel defects will predominate. Also, they may occur
in combination with Schottky defects. The calculation of their density as
function of the energy 4> required to produce a Frenkel defect is essentially
the same as that given above for Schottky defects, i.e., one finds an
expression for the free energy of a crystal containing n defects and
Sec. 7·2) IONIC CONDUCTIVITY AND DIFFUSION 165
If (7-17) refers to an ion taken from vacuum to water, H is called the
hydration energy of the ion.
It is probably useful to look at this electrostatic problem from a
somewhat different angle: an ion inside a dielectric material produces a
polarization in the dielectric as a consequence of its Coulomb field. In
turn, the polarized surroundings will produce a field at the location of the
ion. To find the reaction potential at the center of the ion we proceed as
follows. Referring to Fig. 7-3 the field strength in the dielectric is given by

E = e/€f 2 = D - 47TP = EE - 47TP (7-18)

all vectors having radial direction. Hence the dipole moment induced in a
volume clement dT located at a distance r from the center is equal to
,
(7 -19)
This dipole moment produces a potential at the center of the sphere of
P dT/r 2 , and thus the reaction potential in the center is

V = I( DO P
- dT = rcf)
- e ( 1 - -1)' . -I ' 47Tr2 dr = -e ( 1 - -1) (7-20)
. I'=R r2 • R 47Tr2 E r2 R €

Thus we conclude from (7-17) and (7-20) that the energy of the ion in the
reaction field is

~2 eV= ~
2R
(1 -~)€ (7-21)

We note the appearance of the factor L which always occurs whenever we

are concerned with the energy of a charge in a reaction potential.
Returning to our original problem, we see that according to (7-16) and
(7-17) the energy required to dissolve the crystal is, per ion pair,

A e
2

ao
(1 _~)n _~2 (I __ ~') ('_I
e2
R+
+ _1 )
R_ E
(7-22)

where R+ and R_, respectively, represent the radii of a positIve and a

negative ion. For the NaCl lattice A = 1.746, and if for simplicity we
assume R+ +
R_ = a o and R+ = R_, then (7-22) becomes
2 2

1. '
1. 746 -e ( 1 - -1) - -2e ( 1 - -1) (7-23)
ao , n ao " E

We see that, for sufficiently high values of E, expression (7-23) may

become negative, in which case one would expect appreciable solubility
because energy is liberated by dissolving the crystal. This is frequently
the case for water (€ = 81), whereas for most organic solvents E is too
small to make (7-23) negative. Although the above reasoning is strongly
simplified, it is obvious that the dielectric constant, and thus the hydration
166 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7
energy of the ions, plays a major role in the theory of solubility of ionic
solids. The simple electrostatic problem mentioned above will also enter
in the discussion of the next section. '

7-3. The activation energy for the formation of defects in ionic crystals

In Sec. 7-1 we derived an expression for the number of vacancies in an

ionic crystal in thermal equilibrium at a temperature T. According to
(7-6) or (7-9) this number is essentially determined by the formation energy
-+
1> = cp+ cp_. Let us first consider the energy 1>+ involved in the formation
+ + +
t
+ ~+
"0
+-_

+
;t , +
--+

~
+ + +

Fig. 7-2. Showing the polarizing effect Fig. 7-3. Jost model to calculate the
of a positive ion vacancy on its sur- polarization energy resulting from the
roundings. The surrounding negative presence of a vacancy. The vacancy is
ions are displaced slightly outward; the represented by a spherical cavity of
positive ions assume positions slightly radius R inside a homogeneous di-
displaced toward the vacancy. In electric €; the charge e at the center
addition to the ionic displacements, the represents the effective charge of the
effective negative charge of the vacancy vacancy.
induces dipoles in the surrounding ions.

of a positive ion vacancy. Suppose a positive ion is removed from the

interior of the crystal to infinity, while the charge. distribution in the
crystal is kept the same as it was. The energy required for this step is
obviously given by
EL =
2
e ( 1 --
A-
ao n
1) . "-
(7-24)

if we use the simple Born lattice theory. Putting the ion from infinity on
the surface of the crystal leads to a gain in energy of
------
~2 EL = ~A
2 a
~.
o
(1 -~)n (7-25)

Thus if nothing else would happen, cp+ would be equal to the difference of
(7-24) and (7-25). However, the removal of a positive ion will affect the
neighboring ions in such a way that an adjustment takes place by which
energy is gained, thereby lowering cp+. Referring to Fig. 7-2, we note that
from the point of view of the surroundings of a positive ion vacancy, it looks
IONIC CONDUCTIVITY AND DIFFUSION 167
egative charge has been added at this lattice site. In other words,
an excess of negative charge in the vicinity of the missing positive
IS
Consequently the surrounding material will become polarized.
polarization consists first of the formation of dipoles induced in the
ions by the Coulomb field of the missing ion, second of a slight ionic
displacement as indicated in Fig. 7-2. Because of the long range of
Coulomb forces, it is not sufficient to take into account only nearest
neighbors; the effect will spread over distances many times the lattice
constant. The calculation of this polarization energy P+ is very complicated
although it may be understood in principle on the basis of a simplified
model, first introduced by Jost. 8 If we consider the vacancy as a spherical
hole inside a homogeneous dielectric constant € the hole bearing a charge e
at its center, we obtain the situation given in Fig. 7-3. The charge e, due
to the missing ion, polarizes the dielectric and thus in turn will create a
reaction potential Vat the location of the charge. We see that this problem
is identical with the one treated in the preceding section. Thus the polari-
zation energy is given by
p+ = ~ eV = ~. ~(I ~. ~.) (7-26)
2 2 R+ €

From (7-24), (7-25), and (7-26), one obtains

(7-27)

For negative ion vacancies the same reasoning applies, so that the energy
required to produce a positive and a negative ion vacancy is equal to

cp =cp+ + cp_ = A e
ao
2
(I -~)n _~e2
2
(1 _ ~) (_1 +.!_ )=
€ R+ R_
€L- P+ _ P_

(7-28)
The first term, of course, can be calculated with good accuracy, but as far
as the remainder is concerned the problem arises as to what values one
should assign to R+ and R_ in this idealized model. These values can be
found with good approximation only by comparison with more accurate
calculations of P+ and P_ based on an actual ionic picture rather than on a
continuum. Calculations of this kind have been made by Mott and
Littleton 9 and more recently to a higher approximation by Rittner,
Hutner, and Du Pre.lO As an example of the results of the former authors,
we cite those for NaCl and KCI below (all energies in electron volts).
*' L P., P- cp R ,. R
NaCL........ 7.94 3.32 2.76 1.86 0.58a o 0.95a.
KCI.......... 7.18 2.71 2.39 2.08 0.61a o 0.8Sa o
8 W. lost, J. Chem. Phys., 1,466 (1933); Trans. Faraday Soc., 3", 860 (1938); W.

Jost and G. Nehlep, Z. Physik. Chem., 832, I (1936); 834, 348 (1938).
• N. F. Mott and M. J. Littleton, Trans. Faraday Soc., 34, 485 (1938).
10 E. S. Rittner, R. A. Hutner, and F. K. Du Pre, J. Chem. Phys., 17, 198 (1949).
[Chap. 7
]68 IONIC CONDUCTIVITY AND DIFFUSION
')f ionic
The values of R+ and R_ are obtained by substituting the valut enter
and P_ given by Mott and Littleton into (7-26). We note that the nun.
vacancies depends on 4>0/2, according to (7-6). Also, we see how impor.
the polarization energy is for the formation of vacancies in ionic crystals.
In fact, for NaCl it reduces the value of 4> for NaCI from 7.94 to only
1.86 ev. Because of the relatively small value of 4>, vacancies in alkali
halides close to the melting point may occur in concentrations of the order
of 10-4 per ion.
From the results quoted above it follows that for alkali halides
Rc :::::: 0.6a o and R_ :::::: 0.9a o. We shall see in Sec. 7-5 that the calculated
values of 1> are in fairly good agreement with experiments.
Similar estimates have been made of the activation energies required
for the formation of Frenkel defects in ionic crystals. It turns out that in
alkali halides, defects of the vacancy type are much more likely to occur
than interstitial ions. However, for silver halides there is theoretical and
experimental evidence for the occurrence of Frenkel defectsY
We have seen above that the "effective" charge of a positive ion
vacancy is negative, of a negative ion vacancy is positive. Thus there will
be attraction between vacancies of opposite sign and one may expect them
to form pairs. The binding energy of a pair of vacancies is about 0.9 ev in
the alkali halides_12 A pair of vacancies is neutral and thus will not lead to
ionic conductivity. On the other hand, they correspond to dipoles and
consequently may give rise to dielectric losses at relatively low frequencies;
for a review of recent work on this subject we refer to the literatureP
Also, pairs of vacancies of opposite sign appear to be very mobile in the
alkali halides and are therefore important for diffusion in these crystals. a
Besides single vacancies and pairs of vacancies, higher aggregates of
course are possible, as triplets, quadruplets, etc.

7-4. Example of self-diffusion in alkaJi haJides

As an example of diffusion in ionic crystals, some measurements by

Mapother, Crooks, and Maurer will be discussed briefly.1 5 These investi-
gators measured the self-diffusion of radioactive sodium in NaCI and
NaBr in the following manner: A thin layer of about 5 X 10-4 cm of
radioactive saIt containing the isotope Na 24 was deposited on one face of a
cubic crystal, approximately 1 cm on edge. The crystal was then held at a
11 J. Tetlow, Ann. Physik, 5, 63, 71 (1949); Z. physik. Chem., 195, 197,213 (1950);

for further references see the article by F. Seitz in W. Shockley (ed.), Imperfections in
Nearly Perfect Crystals, Wiley, New York, 1952.
12 J. R. Reitz and J. L. Gammel, J. Chelll. Pllys., 19,894 (1951).

13 See, for example, the paper by R. G. Breckenridge in W. Shockley (ed.), Imperf<!c-

tiolls in Nearly Perfect Crystals, Wiley, New York, 1952.

It J. G. Dienes, J. Chem. Phys., 16, 620 (1948); F. Seitz. Phys. Rev., 79,529 (1950).

1> D. Mapother, H. N. Crooks and R. Maurer, J. Chem. Phys., 18, 1231 (1950).
Sec. 7-4] IONIC CONDUCTIVITY AND DIFFUSION 169
constant temperature for a certain length 'of time. After this diffusion
anneal, the distribution of radioactive sodium was determined by means of
a sectioning technique, employing a microtome. In a similar fashion,
Schamp has investigated the diffusion of bromine in NaBr. 16 • What one
measures in this way is the self-diffusion of the radioactive ions in the salt.
It must be emphasized that this type of experiment is altogether different
from one in which one heats the salt in the vapor of one of the constituents;
in such experiments one obtains information about the diffusion of color
centers in the lattice (see Sec. 15-6).
According to Fick's first law, the net flux of ions is proportional to the
concentration gradient (see Sec. 3-5), i.e.,

J = -D grad n* (7-29)

where J is the number of radioactive atoms crossing 1 cm 2 per sec., D

is the diffusion coefficient, and n* is the number of radioactive ions per cm3 .
Applying the continuity condition - en*/ot = drv J, (7-29) becomes
on*
Tt = div (D grad n*) (7-30)

Assuming the diffusion coefficient D to be independent of the concen-

tration of radioactive ions, one obtains for the one-dimensional problem
under consideration,
on* o2n*',
-=D-- ., '. (7~31)
at ox 2

The solution of this equation for the boundary conditions in the experiment
mentioned above iS17
r n*
n*(x,t) = (7TD~)112 exp 4Dt
(_X2) (7-32)

Here n*(x,t) is the density of radioactive ions at x after an annealing

period t; no * is the initial density at the surface. This solution is based on
the assumption that the migration of radioactive sodium is a result of a
single diffusion process, because only one diffusion constant D has been
introduced. That this assumption is correct may be seen from Fig. 7-4
where the logarithm of the counting rate has been plotted versus the
square of the distance from the surface. It may be pointed out that the
situation is not always so clearcut as in these experiments. For example,
results of similar measurements made by Redington18 on the self-diffusion
of Ba in BaO crystals, when plotted in analogy with Fig. 7-4, give a curve
16H. W. Scharr.p, Thesis, University of Michigan, 1951.
17See, for example, W. Jost, Diffusion in Solids, Liquids, Gases, Academic Press,
New York, 1952, p. 19.
18 R. W. Redington, Phys. Rev., 87, 1066 (1952).
170 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7

consisting of two straight parts separated by a knee. Redington has

interpreted his results in terms of two diffusion processes, each having its
own diffusion constant.

700 600 500 400 350°C

-9 \
'"I
S
x 5
'i:
]_ Q0 -10
,£
"'<=
,,
~
.Q
;>

~
0
t -11
" ".,
t ,,
,,
",
-12

"
o 100 200 300 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7
-+- IDepth)2 II unit=2.34XlO- 7 cm 2) _lOOO/T

Fig. 7·4. Distribution of radioactive Fig. 7·5. The fully drawn curve repre-
Na in NaCl. T = 603°C; t = 5.92 h; sents the directly measured self-diffusion
D = 1.52 X 10 10 cm 2 /sec. [After coefficient of Na in NaCl as function of
Mapother, Crooks, and Maurer, ref. 15] temperature. The dashed curve is cal-
culated from the measured conductivity
by means of equation (7-45). [After
Mapother, Crooks, and Maurer, ref. 15]

The diffusion constant of Na in NaCt as a function of temperature is

represented by the fully drawn curve in Fig. 7-5. Evidently the diffusion
constant satisfies the relation

:,._ (7-33)
'-----._---
where E is an activation energy. It must be noted, however, that the high-
and low-temperature regions have different activation energies of,
respectively, 1.80 ev and 0.77 ev. This point will be taken up below;
it is believed that the low activation energy results from the presence of
divalent positive impurities. For diffusion measurements on crystals
containing intentionally added divalent positive ions, see the work by
Witt and Aschner. 19 In the next section, the diffusion measurements will be
interpreted in terms of the migration of lattice defects.

19 H. Witt, Z. Physik, 134, 117 (1953); J. F. Aschner, Thesis, University of

Illinois, 1954.
Sec. 7-5] IONIC CONDUCTIVITY AND DIFFUSION 171

7-5. Interpretation of diffusion in alkali halides

It is evident that diffusion of ions in a perfect lattice, i.e., in a lattice

in which all lattice sites are occupied by the proper ions, is impossible
because a given ion has no place to go. Diffusion is therefore possible only
by the migration of interstitial ions or by the migration of vacant lattice
sites. We have seen before that in the alkali halides lattice vacancies are
the predominant type of defects. Thus the positive ions surrounding a
positive ion vacancy may jump into the latter; consequently, the vacancy
moves through the crystal by virtue of positive ions jumping into it and
diffusion becomes possible.
Consider then in Fig. 7-6 the A C B
sodium chloride structure, assuming
for simplicity that the x-axis along
which the diffusion of radioactive
sodium takes place coincides with
one of the cube edges. A particular
positive ion vacancy, such as the one
in Fig. 7-6 indicated by the square
may then in time carry out a jump ---.x
to any of 12 equivalent positions,
assuming the latter are occupied by
positive ions. Of these possible A C B
jumps, tltere are 4 in the positive
x-direction, 4 in the negative x-direc- Fig. 7-6. The positive ion vacancy at
tion, and the remaining 4 leave the the center may jump to any of the
twelve surrounding positive ion sites
vacancy in the original plane. Thus
at a distance aY2. The planes A, B,
if p is the probability per second and C are perpendicular to the x-axis,
for the vacancy to make any jump, along which the diffusion takes place.
p/3 is the probability per second for
a displacement +a, -a, and 0, respectively, if a is the shortest inter-
ionic distance. Let us represent the number of radioactive positive ions
crossing 1 cm 2 of the plane C in Fig. 7-6 per second, going from plane
A to B, by N!. Similarly, let N!- represent the same number crossing plane
C by going from plane B to A. Then if N is the density of positive ions per
cm3 , n is the density of vacancies, and n* is the density of radioactive
positive ions,
N * =-._._.
I n p _ n*
_,. 2a 2 N 3 N

N_ = _1_ . !!.. .
2a2 N 3 N
e.
_!_ (n* + dn* a)
dx

Here 1/2a2 represents the total number of positive lattice sites per cm 2
c •

172 IONIC CONDUCTIVITY ANn DIFFUSION [Chap. 7

on plane A or B; nlN represents the probability that such a site is vacant,
and n* I N represents the probability that a positive ion in plane A is radio-
active. Consequently the net number of radioactive positive iOIlS passing
1 cm 2 of plane C per second from left to right is \

* * np dn* (7-34)
J=N...... -N..... =-6N2a · dx

Comparing (7-34) with (7-29) and remembering that N = 1/2a3 , one

obtains for the diffusion constant associated with the migration of singl~
positive ion vacancies
1 n
D = _a2 _p (7-35)
3 N
The reader may compare this result with expression (3-21). As expected,
the self-diffusion coefficient is proportional to the number of vacancies
per unit volume n and to the jump probability of a vacancy per second p.
As in Sec. 3-5, p may be written in the form
(7-36)
where ')I is a frequency and Ej is the activation energy associated with a
jump. Finally then, the coefficient of self-diffusion based on the assumption
of the migration of single positive ion vacancies may be obtained by
substituting (7-9) and (7-36) into (7-35), yielding

(7-37)

The constant C arises from the thermal entropy change associated with the
production of vacancies, as discussed in Sec. 7-1. We note that in a plot of
log D versus II kT, the slope of the line according to the above interpretation
is determined by the sum (Ej + rf/2), i.e., by the energy required. for the
formation of vacancies plus the activation energy for jumping. Thus, from
the diffusion measurements of Na in NaCl, represented in Fig. 7-5, it
follows from the slope in the high-temperature region that E j + rf/2 =
1.80 ev.
The break in the log D versus liT curve leading to a smaller slope in
the low-temperature region may in principle be a result of either or both
of the following two causes: (1) the presence of divalent positive impurities,
(2) the freezing-in of positive ion vacancies. The explanation is as follows:
Suppose that a salt like NaCl contains in solid solution a small amount of
SrCI 2 or of the chloride of another divalent metal, the divalent positive
ions occupying sites which are normally occupied by the singly charged
Na+ ions. The condition of electric neutrality then requires that for each
divalent positive ion present, there must be a positive ion vacancy. Such
crystals then may contain at lower temperatures more positive ion
Sec. 7-5] IONIC CONDUCTIVITY AND DIFFUSION 173
vacancies than would be expected on the basis of thermal equilibrium
alone. In fact, below a critical temperature, the number of vacancies per
unit volume would then remain constant, the critical temperature being
higher the larger the density of divalent impurities. At high temperatures,
however, the number of thermally produced vacancies would predominate
over the number required by the presence of the divalent ions and the
crystal would behave in a normal fashion. Now, if the number of vacancies
per unit volume is independent of temperature, the temperature dependence
of the diffusion coefficient is according to (7-35) and (7-36) determined by
t"'2 fador exp (-E;/kT). Thus if the presence of divalent metallic ions is
accepted as the cause of the break in the log D versus l/T curve, the
activation energy for jumping may be obtained separately from the slope
of the curve in the low-temperature region. In view of the fact that
(€ + cp/2) is known from the high-temperature slope (the "intrinsic"
region), both €; and cp may be obtained. Because of strong experimental
evidence, to be further discussed in the next sections, the above explanation
seems now generally favored over the freezing-in hypothesis. The latter
hypothesis is based on the following reasoning: Suppose a crystal contains
a certain number of lattice defects in thermal equilibrium at a high tempera-
ture. If the temperature is suddenly lowered, it will take a certain amount
of time for the new equilibrium to be established because this requires a
migration of vacancies. At lower temperatures such time intervals may be
very long and consequently, the crystals may contain many more defects
than would be permitted by the equilibrium conditions.
For the diffusion of positive ion vacancies in NaCl, it follows from the
slope in the low-temperature region of Fig. 7-5 that €; = 0.77 ev. Hence,
because (€; + cp/2) = 1.80 ev, the experimental value for cp is 2.06 ev.
This is in reasonable agreement with the theoretical value of 1.86 ev
given on page 167.
For a vibrational frequency of the ions in the lattice of the order of
1013 per sec, one finds for the probability of a jump of a positive ion
vacancy per second in the alkali halides,

p = ve-';lkT '::: 1 sec-1 at room temp. (7-38)

From (7-37) it follows that the pre-exponential factor in the expression for
the diffusion coefficient is equal to

when v'::: 1013, a'::: 3 . 10-8 cm and C,::: 100. The experimental value
of Do for the intrinsic region in NaCl, according to the work of Mapother,
Crooks, and Maurer, is 3.1 cm 2 sec-I, and 0.67 cm 2 sec-1 for NaBr.
Diffusion of positive ions does not necessarily take place as a result of
174 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7
migration of single positive ion vacancies only. In fact, at least two other
possible diffusion mechanisms must be considered in the alkali halides:
(i) Diffusion resulting from migration of pairs.
(ii) Diffusion resulting from migration of divalent positive 'impurities
\
together with associated vacancies.
These two mechanisms are illustrated
+ + + in Fig. 7-7. A pair of vacancies may
r-, diffuse as a result of positive or negative
+ - ,+ I - + +
:c I ions jumping into the corresponding
- IA :B I + vacant site of the pair. The resulting
diffusion coefficient is given by an ex-
+ +
pression of the type
+ +

+ + + + D pair = const. exp (

cf> - €11
kT
+ €j1»
(7-39)

Fig. 7-7. The pair AB may dif-

fuse by the positive ion C jumping
where cf> is the energy required to produce
into the vacancy A, or by a a positive plus a negative ion vacancy, €11
negative ion jumping into B. is the binding energy of a positive and
The associated complex divalent negative ion vacancy and €jp is the activa-
positive ion-positive ion vacancy tion energy for the jumping of a pair.
may migrate as a result of inter-
change between the divalent ion
Theoretical estimates give €11 ~ 1 ev
and the vacancy D, combined and €jp""'" 0.4 ev for NaCl.20 It may be
with singly charged positive ions expected, therefore, that pairs diffuse much
jumping into the vacancy. more rapidly than single vacancies, because
their activation energy for jumping is only
about half that for a single positive ion vacancy. That this must be so
may be seen qualitatively because the jumping ions are allowed more free
space in the former case.
The influence of the presence of divalent positive ions on the diffusion
may be understood as follows: For each divalent positive ion, there must
be a positive ion vacancy to satisfy the neutrality condition. A certain
fraction of these vacancies are free and contribute to the diffusion as
discussed above. However, not all these vacancies are free, because they
are attracted by the divalent positive ions as a result of Coulomb inter-
action. Thus there will be a certain number of associated complexes,
consisting of a divalent positive ion and a neighboring vacant positive ion
site. This unit may migrate through the crystal as a result of other positive
ions jumping into the vacancy and as a result of possible jumps of the
divalent ion into the vacancy. It may be of interest at this point to give
2. G. J. Dienes, J. Chem. Phys., 16, 620 (1948); N. F. Mott and R. W. Gurney

Electronic Processes in Ionic Crystals, Oxford, New York, 1940, Chap. 2.

,f 'i
Sec. 7-5] IONIC CONDUCTIVITY AND DIFFUSION 175
values of the binding energy between divalent positive iQns and positive ion
vacancies as calculated by Bassani and Fumi :21
Cd2+ Ca2+ Sr2+
NaCl ........ . 0.38 ev 0.38 ev 0.45 ev
KCI ......... . 0.32 0.32 0.39
Thus these binding energies are roughly half as large as those for pairs
of vacancies in the alkali halides. The study of the influence of divalent
impurities on the physical properties of alkali halides receives a good deal
of attention at present.
Although we have limited ourselves to the discussion of a rather
restricted area of the field of diffusion in ionic crystals, the same general
ideas apply to other cases. For further study we therefore refer the reader
to the literature. 22
+
7-6. Ionic conductivity in "pure" alkali halides M

When a potential difference is applied between

two opposite faces of an ionic crystal, an electric
current may be detected. For the alkali halides these
currents are too large to be explained in terms of
the motion of electrons because the number of M
electrons in the conduction band for the tempera-
tures involved would be much too small. Thus
Fig. 7-8. Essential ex-
the currents must be a result of the migration of perimental arrange-
ions under influence of the electric field, similar ment for measuring
to the electrolytic conduction of aqueous solu- transport numbers.
tions of salts. That the currents are indeed of
an ionic nature is also indicated by the fact that decomposition occurs
at the electrodes.
The first problem which arises is to determine which constituent carries
the current. Although the actual experiments are usually more involved,
this question may be answered in principle by employing an experiJnental
arrangement 22 such as indicated in Fig. 7-8. Two slabs of a salt M+X- are
pressed together between two electrodes of the metal M. For the polarity
as indicated, the two following extreme possibilities exist:
(i) Only positive ions move; in that case the cathode will grow at the
expense of the anode, the thickness of the two salt slabs remaining
the same.
(ii) Only the negative ions move; the X- ions are then neutralized at
the anode and form new layers of salt. Hence the anode decreases
21F. Bassani and F. G. Fumi, quoted by F. Seitz, Revs. Mod. Phys., 26, 7 (1954).
22See W. lost, Diffusion in Solids, Liquids, Gases, Academic Press, New York, 1952,
Chap. 4.
176 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7
in thickness, the cathode increases. Furthermore, slab I will grow
at the expense of slab 2.
If both types of ions contribute to the current, the result will be
intermediate between (i) and (ii). By weighing, the relative contri-
butions to the ionic' current by the positive and negative ions may be
determined.
The ionic conductivity of an isotropic crystal is defined by the scalar
equation , ".
1= aE

where I is the current density, E is the field strength, and a is the con-
ductivity. If the conductivity of the positive ions alone is a+, the transport
number of these ions is defined by

(7-40)

Similarly, t_ = a_la, and of course t+ + t_ = l.

In the alkali halides the experi-
,r" External field ments show that the positive ions are
...... _ C
f __ much more mobile than the negative
ones. In the older literature one will
find for KCl, for example, values f.or
t+ of about 0.9 over a wide tempera-
ture range. Recent measurements on
crystals of high purity indicate, how-
ever, that the presence of small
Fig. 7-9. The fully drawn curve amounts of divalent positive ions has
represents the resultant of the field-free a marked influence on the measured
potential curve (dashed) and the linear transport numbers. For very pure
potential (dashed) resulting from the
external field E. A, B, and C may be
KCl, Kerkhoff finds t+ = 0.88 at
associated with positions of a positive 525°C and t+ = 0.70 at 600°C. 23
ion in the planes A, B, C of Fig. 7-6. We shall return to this point in Sec.
7-7 and first discuss the interpre-
tation of ionic conductivity in terms of lattice defects.
In the alkali halides ionic conductivity, like diffusion, is explained in
terms of the motion of vacant lattice sites. The positive ion vacancies
have an effective negative charge and will therefore move toward the
anode; similarly, the negative ion vacancies will move towards the
cathode. As mentioned above, the mobility of the positive ion vacancies
is appreciably larger than that of the negative ones, and for the moment it
will therefore be assumed that the conductivity is entirely due to the
motion of the former. For simplicity we shall use the geometry of Fig. 7-6,
assuming an electric field along the x-axis. Let us denote the number of
23 F. Kerkhoff, Z. Physik, 130,449 (1950).

i J
Sec. 7-6] IONIC CONDUCTIVITY AND DIFFUSION 177
positive ion sites per cm3 by N, the number of positive ion vacancies per cm3
by n. If the electric field in Fig. 7-6 is directed to the right, a positive ion
vacancy will jump with a higher probability to the left than to the right,
because it is negatively charged. The potential energy along the line of
motion may therefore be represented by the full curve in Fig. 7-9 which is
the resultant of the dashed field-free curve and the linear potential due to the
external potential difference. Clearly then, the probabilities per second for
a jump to the left and to the right are, respectively,

p_ = iv exp [--(€j - t aeE)jkTJ

(7-41)
p_ = tv exp [-(€j + t aeE)jkTJ
where the notation used is identical with that of Sec. 7-5; E represents
the field strength. The current density, i.e., the net flux of charge passing
per second through 1 cm2, is then equal to

(7-42)

because Ij2a 2 is the number of positive ion sites in a plane perpendicular

to the x-axis of an area of 1 cm 2 and njN is the probability for such a site
to be vacant. Now, for nearly all practical cases, aeE ~ kT, so that in first
approximation
n e2vEe-';lkT
1= - . - - = aE (7-43)
N 6akT

Now the number of vacancies n is given by (7-9), so that the conductivity

is equal to
Ce 2v ~,
a = 6akTexp [-(€j +
t~)jkT] , (7-44)

We note that the current density is proportional to E only as long as

aeE ~ kT, i.e., Ohms law is valid only under this particular condition.
For very high electric fields such that aeE is not small compared with kT,
the current increases exponentially with the field strength. According
to (7-44), the conductivity associated with the positive ion vacancies
depends on the two activation energies €j and ~, as does the coefficient
of self-diffusion. In fact, the conductivity a is related in a simple manner
to the diffusion coefficient, as was first pointed out by Einstein. From
(7-37) and (7-44) it follows that :;,; '''i:

ajD = Ne 2 jkT (7-45)

It must be emphasized that the Einstein relation is valid only if the

conductivity and self-diffusi<;>n are due to the same mechanism; in the
178 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7
present case the assumption implicit in the derivation of (7-45) is that
both phenomena are a result of the migration of single positive ion
vacancies. In Fig. 7-5 the diffusion coefficient calculated from the con-
ductivity by means of (7-45) is represented by the dashed curve. That the
Einstein relation is not exactly satisfied is of interest for the interpretation
of the diffusion mechanism. First of all, in the high-temperature region
the slope of the diffusion coefficient curve as calculated from (7-45)
appears to be slightly larger than the directly measured one. This may
be explained as a result of the fact that a small fraction of the ionic
current is carried by the negative ion vacancies; these, of course, do not
contribute to the self-diffusion of Na. In the low-temperature region,
the calculated diffusion coefficient is somewhat smaller than the directly
measured one. This implies that besides the diffusion of positive ion
vacancies, there is some diffusion associated with the migration of neutral
carriers. For example, pairs of vacancies and positive divalent ions
associated with vacancies (see Fig. 7-7) may contribute to the diffusion
but will not contribute to the ionic conductivity.
We have seen above that in the alkali halides the ionic current is
carried for the greater part by the positive ions. This is not always the
case, however. In the halides of barium and lead, for example, the
negative ions are mainly responsible for the ionic conductivity. In the
silver halides, the positive ions are the mobile constituent.

7-7. Ionic conductivity in alkali halides with added divalent impurities

We have mentioned several times the influence of the presence of

divalent metallic ions on the properties of alkali halides. Although the
study of such solid solutions was initiated in 1938 by Koch and Wagner
on silver halides, the subject has received a great deal of attention lately,
and a few remarks may therefore be in order.
It is possible to grow crystals of alkali halides or silver halides with
intentionally added small amounts of the halides of divalent metals,
such as Sr, Ba, or Ca. The density of crystals of KCI containing small
amounts of CaC1 2 and SrCl 2 has been measured by Pick and Weber.24
The results demonstrate that the divalent ions are incorporated sub-
stitutionally, i.e., they occupy lattice sites which are normally occupied
by the monovalent alkali ions.
In Fig. 7-10 we give as an example of the influence of the divalent ions
on the conductivity some results obtained by Kelting and Witt.25 The
logarithm of a has been plotted versus liT for a "pure" crystal of KCI
(curves 7 and 8) and for KCl with different amounts of SrC1 2 • We note

M H. Pick and H. Weber, Z. Physik, 128,409 (1950) .

•• H. Kelting and H. Witt, Z. Physik, 126, 697 (1949).

Sec. 7-7] IONIC CONDUCTIVITY AND DIFFUSION 179
that all curves come together to a single straight line, the intrinsic region.
In that region, the conductivity is determined essentially by the density
of vacancies produced thermally. Thus the slope of the intrinsic curve
is determined by the sum of the activation energies €j and cfo/2 in accordance
with (7-44). Now for each divalent ion there is one positive ion vacancy.

400 500 600 700·C

s:: I '

]' -6

t
-7

1.8 1.6 1.4 1.2 1.0

_lOOO/T

Fig. 7-10. The ionic conductivity ofKCI crystals containing various

amounts of SrCt.. In units of 10- 5 the numbers refer to the
following mole fractions: M, = 19; M. = 8.7; Ma = 6.1;
M. = 3.5; M5 = 1.9; M. = 1.2; M 7 ,s = O. [After Kelting
and Witt, ref. 25]

Consequently, at low temperatures the number of vacancies per unit

volume remains constant and is equal to the density of divalent metal
ions. At a given temperature, the experiments show that the "induced"
conductivity is nearly proportional to the concentration of the divalent
metal. This justifies the above interpretation and indicates that the
vacancies are almost completely dissociated from the divalent ions.
The importance of measurements of this kind lies in the fact that they
permit us to determine:
(i) The mobility of the positive ion vacancies. ," H" \"

(ii) The density of Schottky defects in the intrinsic range.

(iii) The binding energy of a divalent impurity and a positive ion
vacancy.
This follows from the following considerations: when the conductivity
180 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7
a and the concentration of charge carriers n are known, the mobility !.t
(i.e., the velocity per unit field) may be calculated from the relation

a = ne!.t \ (7-46)
\
Comparison of this expression with (7-43) shows that this in turn allows
one to calculate the jump probability. As mentioned before, the
probability for a jump of a positive ion vacancy at room temperature is
about I per second for the alkali halides. Once the mobilities are known,
the density of Schottky defects in the intrinsic range may be determined
from the measured conductivity. In this fashion Etzel and Maurer find
for the density of Schottky defects in the intrinsic range for NaCI,26

n = l.2 X 1023 exp (-1>12kT) per cm3 (7-47)

where 1> = 2.02 ev is the energy required for the formation of a positive
and a negative ion vacancy. Close to the melting point, this gives a
density of Schottky defects of about 1018 per cm3, i.e., about 1 vacancy
per 1()4 ions. At room temperature n c:::: 106 per cm3 • It is of interest to
compare (7-47) with the theoretical expression (7-9). With N c:::: 1022
it follows that the constant Cc::::I O.
Information about the binding energy of a divalent positive ion and a
positive ion vacancy may be obtained from the fact that the "induc~d"
conductivity is not exactly proportional to the concentration of the added
divalent salt. In this way, Etzel and Maurer conclude that a fraction of
the vacancies is associated With the divalent impurities, the binding energy
being about 0.3 ev for NaCl containing CaC1 2 .26 However, this topic
is still in a state of flow and will not be discussed here any further. We
may refer to page 175, where calculated binding energies are given.
We mentioned in Secs. 7-5 and 7-6 that the break in the log D and log (]
versus liT curves is now generally interpreted as resulting from the
presence of divalent impurities rather than as a freezing-in of vacancies.
As experimental evidence we reproduce in Fig. 7-11 measurements by
Kerkhoff 27 of the conductivity and positive ion transport number for three
KCI crystals. It is important to compare the position of the knees in the
three cases; as the materials become purer, the knee shifts to lower
temperatures, in agreement with the above interpretation. It is also of
interest to note the influence of the divalent ions on the measured positive
ion transport numbers, mentioned in Sec. 7-6. Evidently most of the trans-
port numbers quoted in the literature are unreliable as a consequence of the
presence of impurities. The recrystallization of the "analytically pure"
KCI carried out by Kerkhoff corresponds to a tenfold increase in purity.
26 H. W. Etzel and R. J. Maurer, J. Chern. Phys., 18, 1003 (1950).
2, F. Kerkhoff, Z. Physik, 130,449 (1951).
Sec. 7-7] IONIC CONDUCTIVITY AND DIFFUSION 181

C) ;::;
C)

§
8
"Cl

~
<lI

'2
.~

8
/ VI ""
...;
" /: \":;

'"
<Il

i:- '" "'"

...;
t)
<lI

8.... 5'"
:.::
8.... It:l

"" I
.... 0;0
' - - - ' - - - ' - - - - 0 ; 0 - '• ...;
0
...; OC!
I ',I,'j'

C) r-r---.------,;::;
~
~ 8

(
0;0

8
'"

,.,:;j'

..t
'"
oS
<lI
bI)
t:l
f
1 ]
....
o ::s
gj
X <lI
""+ 0;0
...;
;:!l .~

~
"" .... 0;0
I I I
(l-m I_m 'l0) ,() 018o[ _

We may finally mention the influence of divalent positive ions on the

dielectric losses of alkali halides. The associated complex of a divalent
ion and a vacancy corresponds to a dipole. The direction of this dipole
may change as a result of the jumping of the vacancy as well as by the
interchange of the divalent ion and the vacancy. When the dielectric
losses are measured as function of frequency (or temperature), a peak
182 IONIC CONDUCTIVITY AND DIFFUSION [Chap. 7

at the jumping frequency (which depends on temperature through

a Boltzmann factor) may be expected. For experimental work on this
topic we refer to Breckenridge and Haven. 28

REFERENCES \
W. Jost, Diffusion in Solids, Liquids, Gases, Academic Press, New York,
1952.
N. F. Mott and R. W. Gurney, 2d ed., Electronic Processes in Ionic
Crystals, Oxford, New York, 1950.
F. Seitz, "Color Centers in Alkali Halides I, "Ras. Mod. Phys., 18, 384
(1946); II, ReDs. Mod. Phys., 26, 7 (1954).
W. Shockley (ed.), Imperfections in Nearly Pe~rect Crystals, Wiley, New
York, 1952.
PROBLEMS
7-1. From equation (7-9) calculate the number of vacancies per unit
volume, assuming N = 1022 cm-3 , 1> = 2 eV, and Vo = vv'2.
7-2. Assuming a simple Coulomb interaction between positive and
negative ion vacancies, estimate the binding energy of a pair of vacancies
in LiF, NaCI, and KI.
7-3. Neglecting ionic displacements, set up a general expression for
the energy required to produce a Frenkel defect in a crystal of the sodium
chloride structure, employing the simple Born theory. Calculate the
energy required to form a Frenkel defect in NaCi and compare the result
with that required to form a positive and a negative ion vacancy. (To
check your results, see, for example, W. Jost, Diffusion in Solids, Liquids,
Gases, Academic Press, New York, 1952, p. 108.)
7-4. Assuming only a Coulomb interaction between a divalent
positive ion and a positive ion vacancy, employing the static dielectric
constant of the medium, calculate the association energy of the complex
for NaCi. Compare the result with the more detailed calculations of
Reitz and Gammel, J. Chem. Phys., 19, 894 (1951) and of Bassini and
Fumi (footnote 21). . I'
7-5. Neglecting thermal entropy changes, set up an expression for
the free energy of a crystal with the NaCi structure containing n 1 single
positive ion vacancies, n 1 single negative ion vacancies, and n 2 pairs of
28 R. G. Breckenridge, J. Chern. Phys., 16,959 (1948); 18,913 (1950); ~ee also his

article in W. Shockley (ed.), Imperfections in Nearly Perfect Crystals, Wiley, New York,
1952, p. 219; Y. Haven, J. Chern. Phys., 21,171 (1953) .

. .
Chap. 7] IONIC CONDUCTIVITY AND DIFFUSION 183
vacancies. From the minimum conditions OF/anI =0 and of/2n 2 = 0,
show that

where € represents the binding energy of a pair and 4> is the energy re-
quired to produce a single positive and negative ion vacancy.
7-6. On the basis of the simple Born lattice theory calculate the energy
required to create a positive and negative ion vacancy in MgO. Assume
that in. the Jost model R+ = 0.6a and R_ = 0.9a and use for the dielectric
constant the value 9.8 (Answer: The lattice energy is 41 ev per ion pair;
the total polarization energy in 34 ev; 4> = 7 ev).
7-7. Consider a crystal of monovalent ions of the NaCl structure.
Let N represent the number of positive ion sites per cm3 , nd the number of
added divalent positive ions per cm3 . Furthermore, let nc be the number
of associated complexes per cm3, so that (nd - nc) equals the density of
free positive ion vacancies and free divalent ions. Show that in thermal
equilibrium ::'!"",

ncno ' = I2e·/kT .

(n d - n c)2

where € is the association energy of the complex. (See A. B. Lidiard,

Phys. Rev., 94, 29 (1954).)
7-8. Consider a solution of n molecules of NaCI per cm3 of water.
Suppose the concentration is small enough for the interaction between
the ions to be negligible. Consider the ions as spheres of radii R+ and R_
and show that the electrical conductivity is given by a = (ne 2 /67T'f})
+
(1/ R+ 1/ R_) where 'f} is the viscosity of water ('f} c::: 10-2 cgs units at
20°C). Find an expression for the "effective viscosity" in the case of
ionic conductivity in solid NaCI. Calculate the mobilities of Na+ and CI-
ions in solution on the assumption that R+ and R_ are equal to the ionic
radii; compare the results with the experimental values at 20°C
(fl+ = 4.5 X 10-4 and fl- = 6.8 X 10-4 cm seci volt- I cm- I ).

7-9. Discuss the determination of the concentration and association

of lattice defects in NaCl from measurements of the ionic conductivity
and dielectric losses. (See Y. Haven, Report of the Conference on Defects
in Crystalline Solids (Bristol 1954), Physical Society (London), 1955,
p. 261. { , ' :,

",
\
Chapter 8

FERROELECTRICS

8-1. General properties of ferroelectric materials

The dielectrics discussed in the preceding chapter show a linear relation-

ship between polarization and applied electric field. In the present chapter
we shall deal with dielectrics for which this relationship exhibits hysteresis
effects. Since the dielectric behavior of these materials is in many respects
analogous to the magnetic behavior of ferromagnetic materials, they are
called ferroelectric solids, or simply ferroelectrics. A ferroelectric is
spontaneously polarized, i.e., it is
p
polarized in the absence of an external
field; the direction of the spontaneous
polarization may be altered under
""",.. )',.'" influence of an applied electric field.
In general, the direction of spon-
-----r..;---;,.t£---.f----~ E taneous polarization is not the same
throughout a macroscopic crystal.
Rather, the crystal consists of a
number of domains; within each
domain the polarization has a specific
direction, but this direction varies
Fig. 8-1. Schematic representation of from one domain to another. On the
hysteresis in the polarization versus basis of the domain concept, the
applied field relationship. occurrence of hysteresis in the P
versus E relationship can be explained
as follows: With reference to Fig. 8-1, consider a crystal which initially has
an over-all pOlarization equal to zero, i.e., the sum of the vectors represent-
ing the dipole moments of the individual domains vanishes. When an
electric field is applied to the crystal, the domains with polarization com-
ponents along the applied field direction grow at the expense of the
"antiparallel" domains; thus the polarization increases (0 A). When all
domains are aligned in the direction of the applied field (BC), the polariza-
tion saturates and the crystal has become a single domain. A further
increase in the polarization with increasing applied field results from "nor-
mal" polarization effects discussed in the preceding chapter; rotation of
domain vectors may also be involved if the external field does not coincide
184
Sec. 8-11 FERROELECTRICS 185
with one of the possible directions of spontaneous polarization. The extra-
polation of the linear part BC to zero external field gives the spontaneous
polarization Ps • The value of P" so obtained is evidently the same as the
polarization which existed already within each of the domains in the virgin
state corresponding to 0 in Fig. 8-1. Thus, when we speak of "spontaneous
polarization" we have in mind the polarization within a single domain and
not the over-all polarization of a crystal. We note here that the spon-
taneous polarization and its dependence on temperature, or on other
external conditions that might be imposed, can be measured by displaying
the hysteresis loop on an oscilloscope screen. When the applied field for a
crystal corresponding to point B in Fig. 8-1 is reduced, the polarization
of the crystal decreases, but for zero applied field there remains the
remanent polarization Pr where Pr refers to the crystal as a whole. In order
to remove the remanent polarization, the polarization of approximately
half the crystal must be reversed and this occurs only when a field in the
opposite direction is applied. The field required to make the polarization
zero again is called the coercive field Ec. It is evident that if the coercive
field is larger than the breakdown field of the crystal, no change in the
direction of spontaneous polarization can be achieved, i.e., under those
circumstances we cannot speak of the solid as a ferroelectric.
In connection with the last remark a few words may be said here about
the crystal structure of ferroelectrics. A necessary, but not sufficient,
condition for a solid to be ferroelectric is the absence of a center of
symmetry. ]n total there are 21 classes of crystals which lack a center of
symmetry; the classes are based on the rotational symmetry of crystals.
Of these 21 classes, 20 are piezoelectric, i.e., these crystals become polarized
under influence of external stresses. As soon as the crystal structure of a
particular solid falls within this group, it can be predicted to be piezo-
electric; piezoelectricity is thus determined solely by the symmetry
properties of a crystal. Ten out of the 20 pieozelectric classes exhibit
pyroelectric effects. These pyroelectric crystals are spontaneously polarized.
However, the polarization is usually masked by .urface charges which
collect on the surface from the atmosphere; when the temperature of such
a crystal is altered, the polarization changes and this change can be
observed, hence the name pyroelectricity. As in the case of piezoelectricity,
pyroelectric properties can be predicted as soon as the crystal structure of
the solid has been determined. The ferroelectric materials discussed below
are part of the group of spontaneously polarized pyroelectrics. However,
they have the additional property that the polarization can be reversed by an
applied field. This additional feature cannot be predicted from the crystal
structure; it can be established only on the basis of a dielectric experiment.
The ferroelectric properties of a ferroelectric disappear above a
critical temperature Tc; this temperature is called the ferroelectric Curie
temperature. Associated with the transition from the ferroelectric to the
186 FERROELECTRlCS " [Chap. 8
nonferroelectric phase are anomalies in other physical properties. Thus
for a first-order transition, there will be a latent heat; for a second-order
transition the specific heat will exhibit a discontinuity (see Sec. 8-7).
We should also mention that the spontaneous polat:ization in the ferro-
electric state is associated with spontaneous electrostrictive strains in the
crystal; thus the ferroelectric structure has a lower symmetry than the
non polarized state. At the transition temperature a change in crystal
structure is theref'Jre observed.
The dielectric constant of a ,ferroelectric is, of course, not a constant,
but depends on the field strength at which it is measured; this is a con-
sequence of the nonlinear relationship between P and E. When one speaks
of "the dielectric constant," one refers to the slope of the curve OA in
Fig. 8-1 at the origin, i.e., E is measured for small applied fields so that no
motion of domain boundaries occurs. The dielectric constant E so defined
is very large in the vicinity of the transition temperature, of the order of
J04_I05. Above the transition temperature E obeys the Curie-Weiss law,

€ = C' j(T - 8) + EO (8-1)

where C' is a constant and 8 is a characteristic temperature which is

usually some degrees smaller than the transition temperature Tc; EO is a
constant contributed by the electronic polarization. In the vicinity of the
transitic,n temperature EO may be neglected, since it is of the order of unity
and €',;> EO' Likewise, the susceptibility X = (00: - l)j41T c::: Ej41T is given
by X =, C/(T - 8) in this region, where C = C' j41T is called the Curie
constant.
Tre interpretation of ferroelectric properties is based on the one hand
on thermodynamic considerations, which are independent of any particular
modd; on the other hand, theories have been advanced on the basis of
atomic models. The latter require for their verification detailed
studies of the structure of the crystals as function of temperature. An
excellent description of structure studies on ferroelectrics can be found in
G. Shirane, F. lona, and R. Pepinsky, "Some Aspects of Ferroelectricity,"
Proc. JRE, December 1955, p. 1738. This paper also contains a large
number of references to the literature on the subject.

8-2. Classification and properties of representative ferroelectrics

We shall now give some experimental data concerning the properties of

representative ferroelectrics. The presently known ferroelectrics can be
conveniently classified into four groups, the classification being based on
their chemistry and structure.
1. The first solid which was recognized to exhibit ferroelectric properties
is Rochelle salt, the sodium-potassium salt of tartaric acid; it has the
Sec. 8-2] FERROELECTRICS 187
chemical formula NaKC1H 4 0S·4H 2 0.1 The salt was tlrst prepared in
1672 by a pharmacist Seignette, living in Rochelle; it is therefore also
Jknown under the name Seignette salt. It is representative of the "tartrate
group." Other members of this group are those in which a fraction of the
potassium in Rochelle salt is replaced by NH 4 , Rb, or TI. Lithium
ammonium tartrate and lithium tantalum tartrate also belong to this
group.
Rochelle salt has the peculiar property of being ferroelectric only in the
temperature region between -18°C and 23°C, i.e., it has two transition
temperatures. In the region above 23°C and below -18°C it crystallizes
in the orthorhombic structure (three mutually perpendicular axes a, b, c).
In thc ferroelectric phase the crystal is monoclinic and the angle bctween
the a- and c- axes differs from 90°. The spontaneous polarization
occurs along the direction of the original orthorhombic a-axis. Thus
Rochelle salt has only one polar axis and two possible polarization
directions (+ and -- along the a-axis). The domain pattern of this salt is
therefore rather simple.
The dielectric constants for Rochelle salt along the three axes are
given in Fig. 8-2, according to Halbliitzel. 2 Note that Ea reaches values as
high as 4000 near the transition temperatures. In the region above 23°C the
susceptibility along the a-axis can be represented by the Curie-Weiss law,

In th..: region below - 18°C the susceptibility is de scribed ';,y

The spontaneous polarization of Rochelle salt as function of temperature is

represented by the lower curve in Fig. 8-3; the upper curve corresponds
to the deuterated salt. Note that the replacement of hydrogen by deuterium
has a marked influence on the magnitude of the spontaneous polarization
and on the temperature range over which the material is ferroelectric.
In this connection we may mention that some theories of the ferroelectric
properties of Rochelle salt have been based on the idea that certain hydrogen
bonds are essential in the polarization mechanism;3 the effect associated
with the replacement of H by D would seem to support this idea. Recent
investigations of the structure of Rochelle salt with X-ray and neutron
diffraction techniques are believed to show, however, that the hydrogen
bonds may not at all be involved in the mechanism of the transition. 4
1 J. Valasek, Phys. Rev., 17, 475 (l92I); 19, 478 (1922); 20, 644 (1922); 24, 560

(1924).
2 J. Halbliitzel, He!v. Phys. Acta, 12,489 (1939).

3 W. P. Mason, Phys. Rev., 72, 854 (1947).

, B. C. Frazer, M. McKeown, and R. Pepinsky, Phys. ReI'., 94, 1435 (1954).

FER ROELECTRICS "
[Chap. 8

!l
255'K 296'K
4 I
I
I
I
I \
:l

~
..s"" 2
t E"

100 150 200

--TI'K)

Fig. 8-2. The logarithm of the dielectric constants of Rochelle salt

along the a, band c axes as function of the absolute temperature.
[After HalblUtzel, ref. 2]

-T('K)

Fig. 8-3. The lower curve represents the spontaneous polarization

" for Rochelle salt as function of temperature. The upper curve
corresponds to the deuterated salt. [After Halbliitzel, ref. 2]

I ',.L
Sec. 8-2] FERROELECTRICS 189

~. In 1935 Busch and Scherrer discovered ferroelectric properties in

potassium dihydrophosphate, KH 2P0 4 .5 This is a typical example of the
second group of ferroelectrics, consisting of dihydrogen phosphates and
arsenates of the alkalimetals.
In cOJltrast with Rochelle salt, KH 2 P0 4 has one Curie temperature,
Tc = 12jOK. Above the transition temperature it has a tetragonal
structure (3 mutually perpendicular axes a, a, c); below To it is ortho-
rhombic (3 mutually perpendicular axes a, b, c). The c-axis is the direction

Me/em'!.
5 5
4 4
P. 3 i "bD
..Q 3
t 2
--~-'->.-
~
2
1 t 1
OL_~~~~~~~~~ 0
100 105 110 115 120 125 50 100 150 200 250 300
-TtOK) -TtOK)

Fig. 11-4.The spontaneous polari- Fig. 8-5. The logarithm of the di-
zation of KH 2 PO. as function of electric constants of KH 2 PO. along
temperature. [After A. von Arx and the c- and a-axes. [After Busch,
W. Bantle, Helv. Phys. Acta, 16,211 ref. 5]
(I 943)J

along which the spontaneous polarization occurs and here, as in Rochelle

salt, there is only one polar axis. The spontaneous polarization and the
dielectric constant as function of temperature are given in Fig. 8-4 and
Fig. 8-5. The dielectric constant above the Curie temperature follows the
Curie-Weiss law (8-1) with the numerical values

to = 4.5 + 3100/(T - 121)

From an analysis of the structure of KH 2P0 4 it appears that the P04
groups form tetrahedrons with the four oxygens at the corners and the
phosphorus at the center. 6 These phosphate groups are bound together
by what is known as a hydrogen bond. 7 In these bonds, the proton may
occupy a number of possible positions, each of which corresponds to a
certain polarization of the unit cell. Recent experiments employing
neutron diffraction confirm the important role played by these ions.
S G. Busch and P. Scherrer, Naturwiss., 23, 737 (1935); G. Busch, Helv. Phys. Acta,
11,269 (1938).
6 B. C. Frazer and R. Pepinsky, Acta Cryst., 6, 273 (1953); S. W. Peterson, H. A.

Levy, and S. H. Simonsen, J. Chem. Phys., 21, 2084 (1953); Pllys. Rev., 93, 1120 (1954);
G. E. Bacon and R. S. Pease, Proc. Roy. Soc. (London), A220, 397 (1953).
, See L. Pauling, Nature olthe Chemical Bond, Cornell University Press, Ithaca, 1945.
"
190 FERROELECTRICS [Chap. 8
Replacement of hydrogen by deuterium in KH2PO~raises its Curie tempera-
ture from 123 0 to 213°K, an increase of 90°C. 8 It thus seems fairly certain
that the hydrogen bonds are essential in the polarization of this group of
ferroelectrics.
3. Wainer and Salomon in 1942 \ )served a number of anomalous
dielectric properties of barium titanate (BaTi0 3 ). It was recognized in this
country as a ferroelectric material by von Hippel and coworkers 9 and
independently, by investigators in England, Holland, and Switzerland.
This brings us to the third group of ferroelectrics, viz., the so-called
oxygen octahedron group. This group
i. can be subdivided into others, one of
which is the subgroup of the perovskites
®P Ba2+ with the general chemical formula A B0 3 ,
o ()2- where A is a di- or monovalent metal
• Ti4+ and B is a tetra- or pentavalent metal.
BaTi03 is the most important and most
thoroughly studied representative of the
perovskites. In the nonpolarized phase
Fig. 8-6. The structure of BaTi0 3 it has cubic symmetry; the Ba2t ions
in the cubic phase. occupy the corners of a cube, the
oxygen ions are located at the centers
of the faces, and the Ti4+ ion is at the center (see Fig. 8-6). Typical for the
BaTiO;j structure and for the other members of this group is the arrange-
. ment of the highi) j'olarizable oxygen ions in the form of an octahedron
with a small metallic ion at the center.
Barium titanate has an upper transition temperature of 120°C; above
this temperature it is non ferroelectric and has the cubic structure of
Fig. 8-6. In this region the dielectric constaD t is well described by the
Curie-Weiss law, .. L.
€ = 1. 7 X 105 j(T - 393) I

Below the Curie temperature, the direction of the spontaneous polarization

and the crystal structure vary in the following fashion: ~
~.-
Temp. region CK) Dir. ofpo/. S/ruc/lire
278-393 [001) tetragonal
193-278 [011] orthorhombic
<193 [III] rhombohedral

The transition points are evident from Fig. 8-7 and Fig. 8-8, representing,
respectively, the dielectric constant and spontaneous polarization as
8 B. T. Matthias, Science, 113,591 (1951); see also Phase Trans/ormations ill Solids,

National Research Council, Wiley, New YOlk, 1951.

" For a review, see A. von Hif'lpc1 R, us. Mod. Pllys., 22, 221 (1950).
Sec. 8-2] FERROELECTRICS 191

• function of temperature. IO Thus BaTi0 3 has three ferroelectric phases.

As the spontaneous polarization sets in at 393°K, the crystal expands in the
direction of polarization (c-axis) and contracts perpendicular to it (a-axis) .
... 10,000 j '"

8000

i
4000

2000

o~==~~~=c~~~~~~ __~
90 130 170 210 250 290 330 370 410
-+T('K)

Fig. 8-7. The dielectric constant of BaTi0 3 as function of

"u. temperature. [After Merz, ref. 101

In connection with Fig. 8-8 it should be mentioned that the spontaneous

polarization was measured along the [001} direction, so that actually
the values obtained in the regions 193° < T < 278° and T < 193°K should

16
'"S
-...
u" 12
:j", :
: . <0
.....
0
X 8 I
I
o..~

.
\ ,. j
,
t 4 ; .'. ~
1

o ---'--
120 180 240 300 360
-T('K)

Fig. 8-8. The spontaneous polarization of BaTi0 3 • [After Merz,

ref. 10]

be multiplied, respectively, by and v2 vi

Thus the "Spontaneous polari-
0
zation is nearly constant in the region below say 300 K.
It is interesting to note that the Curie temperature of barium-strontium
titanate mixtures varies linearly with the lattice constant of the mixed
,. W. J. Merz, Phys. Rev., 76, 1221 (1949).
FERROELECTRICS [Chap. 8
;tals. n In this way Curie temperatures between 83°K and 393°K can •.
obtained.
Other compounds of the perovskite structure which are known to be
'oelectric are KTa0 3 , NaTa0 3 , KNb0 3 (Tc = 708°K) and NaNb0 3
= 913°K). ,
4. Recently a fourth group of ferroelectrics has been found which is
related to the groups mentioned above. Th's group is exemplified, by
lllidine aluminium sulfate hexahydrate, Nfl ':NH 2)zAIH(S04h·6H 20.12
e structure of these compounds is present] unknown; they apparently
compose before a Curie temperature is reached.

3. The dipole theory of ferroelectricity

In order to obtain some appreciation of the problems encountered in

e interpretation of ferroelectiicity, we shall first discuss the dipole theory
. ferroelectricity in its simplest form. The existence of spontaneous
)Iarization in general requires a physical model in which the dipole
.oments of the different unit cells are oriented along a common direction.
his brings ferroelectrics in the class of cooperative phenomena, the
)operation between the different unit cells in this case consisting of a
mdency for a given unit cell to have its dipole direction parallel to that of
s neighbors. The dipole moment per unit cell may result partly from
lectronic and ionic displacements and partly from permanent dipoles. The
arly theories aimed at explaining the properties of Rochelle salt were
lased on the assumption that the permanent dipole moments of the H 20
;roups were responsible for the spontaneous polarizationP These dipoles
vere assumed to be freely rotating, and a theory analogous to the Langevin-
Neiss theory of ferromagnetism was developed. The essential point in the
lipole theory is that the internal field E; which tends to orient a given
:lipole is assumed to be of the form,

Ei= E+ yP (8-2)

where E is the externally applied field, P is the polarization, and y is the

internal field constant. This expresses the cooperation between the dipoles,
because the larger P, the larger Ei and the stronger the tendency for the
dipole under consideration to align itself in the direction of the polarization
of its surroundings. For the high temperature region, an internal field of
the form (8-2) indeed leads to the Curie-Weiss law (8-1), as may be seen in
11 D. F. Rushman and M. A. Strivens, Trans. Faraday Soc., 42A, 231 (1946).
12 G. Shirane, F. Jona, and R. Pepinsky, lac. cit.
13 P. Kobeko and J. Kurchatov, Z. PhYSik, 66,192 (1930); R. H. Fowler, Proc. Roy.
Soc. (London), 149, I (1935). It is illustrative to compare the dipole theory of ferro-
electricity with the Bragg-Williams theory for order-disorder transitions in alloys (see
Chapter 4).

t ..t
Sec. 8-3] FERROELECTRICS 193
the following manner. As long as one is far away from saturation of the
polarization, one may write in accordance with (6-16)
P = Nfl (cos e) = N ((l2j3kT)Ei (8-3)
where N is fhe number of dipoles fl per unit volume. l4 From (8-2) and (8-3)
it then follows that
Nfl2j3kT ejy
X = PjE = 1 _ NYfl2j3kT = T_ e (8-4)

where the "extrapolated" Curie temperature e = yNfl2j3k and the Curie

constant is ely.
To show that (8-2) also leads to
T>(J (J
spontaneous polarization, we make I I
use of the Langevin expression (6-15), I I /71< 9
~~ 1.0 I I /
which allows for saturation effects. I I
_,..;-/--L!xl
Applied to the case under consider- Q:; 1/
ation, this gives t .5 I / , /
I ,/~

P = Nfl (cos () = NflL (:~) o

/

2 4 6 8 10

= N flL [:T (E + yP) ] (8-5)

Fig. 8-9. The fully drawn curve repre-
sents the Langevin function; the dashed
where L(x) is the Langevin function. lines are those given by expression (8-7)
We may now ask, Does this equation for various temperatures. The slope of
provide a nonvanishing solution for L(x) at the origin is 1/3.
P in the absence of an external field?
We shall see that the answer is positive, so that (8-2) indeed leads to the
possibility of spontaneous polarization. Putting E = 0 in (8-5), we may
write
P/Nfl = PjPsat = L(x) (8-6)
where
x = flyP/kT or P/Nfl = (kT/Nfl2y )X (8-7)
Nfl = Psat represents evidently the saturation polarization corresponding
to complete alignment of the dipoles. In Fig. 8-9 we have represented
P/Ps"t as function of x according to (8-6), leading to L(x). However,
P/PKat should also satisfy (8-7), which corresponds to a set of straight lines
passing through the origin, the slope of the lines being given by kT/ N fl2 y.
A few of these lines have been represented in Fig. 8-9. Thus the solution
for PjPsat corresponding to the temperature Tl is determined by the inter-
section of L(x) and the line of slope kTl /Nfl2y .l5 It is observed that as T
14 For simplicity, the contributions to P resulting from electronic and ionic displace-

ments will be neglected in this section, because it does not impair the essential arguments.
15 It can be shown that the origin, which is also a common point of the straight line
and the Langevin function, corresponds to an unstable physical state; PI> however,
corresponds to a stable physical state. '. ,
194 FERROELECTRICS [Chap. 8

decreases, the slope of the straight line (8-7) decreases and the solution
P/Poat approaches unity. Also, when the temperature is higher than a
critical value determined by \
kTc/Np2y =! or Tc = N p 2y /3k = e , (8-8) "
it is observed that (8-6) and (8-7) intersect only at the origin. (Note that
in this model Tc = 0.) In other words, there is no spontaneous polarization
for T > e. By means of the method outlined above, it is thus possible,
to find PIP,at as function of Tie and the
result is represented in Fig. 8-10. It is
observed that just below the Curie tem-
perature, the spontaneous polarization
increases rapidly, in agreement with ex-
periment. (Compare, for example, Fig.
o _. TIB 8-4.)
One mav thus conclude that the
Fig. 8-10. Schematic representa- assumption ~u-2) for a model of freely
tion of the spontaneous polari- rotating dipoles accounts for: (a) lhe
zation as function of temperature,
as derived from the procedure
Curie-Weiss law above the Curie tem-
given in Fig. 8-9. perature; (b) the possibility of spon-
taneous polarization below the Curie
temperature; (c) qualitatively the correct temperature behavior of
PIPsat versus temperature in the ferroelectric region. It does not explain
the existence of two Curie temperatures, observed in the case of Rochelle
salt.
It may be of interest to point out the relation between the internal field
constant y appearing in the above theory and the anomalous peak in the
specific heat as function of temperature observed for ferroelectrics in the
vicinity of the Curie temperature. In the completely ordered state, when all
dipoles are aligned in parallel, the energy of a given dipole in the field of
all others is equal to -PyPsat because in general the energy of a dipole !J.
in a field E is given by -!J. . E. Thus the energy of polarization in the
ordered state is per unit volume equal to -NpyPsat/2, where the factor of
t is introduced because otherwise the energy of each pair of dipoles
would be counted twice. Now, as the temperature is increased to above the
Curie temperature, the spontaneous polarization decreases to zero.
It is evident that an "extra" amount of heat must be supplied to the
crystal to bring about the transition from the completely ordered to the
completely disordered state. Let Ce represent the extra specific heat per
unit volume; we may then write
(8-9)
Thus, if Ce(T) and P sat are known from experiment, (8-9) allows one to
calculate the internal field constant y. However, y may also be obtained
Sec. 8-3] FERROELECTRlCS 195

from (8-4) if the Curie constant and the Curie temperature are known.
According to Blattner and Merz one obtains the following results :16
y from (8-9) y /rolll (8-4)

Rochelle salt......... 2.1 2.2

BaTiO a .............. . 0.044 0.049
KH 2 PO •........ : .... . 0.37 0.48

It is observed that the agreement is rather good, especially because ?'

differs appreciably for the three substances. Blattner and Merz take this as
• an argument in favor of the internal field theory outlined above. It seems,
however, that the agreement between (8-4) and (8-9) follows from much
more general considerations than given here and the conclusion drawn is
probably unjustified. 1?

8-4. Objections against the dipole theory

In connection with Rochelle salt, the following objections may be

, raised against the theory outlined in the preceding section: in the vapor,
H 20 has a dipole moment of 1.85 Oebye units; if we assume this to be the
same in Rochelle salt, one calculates for the maximum spontaneous
polarization

P sat = Nfl = 1.52 X 1022 X 1.85 X 10-18 = 28120 esu

The experimental value is about 750 esu which is smaller by a factor of

nearly 40. Furthermore, the dipole theory does not predict the existence of
two Curie points, as observed for Rochelle salt.
A much more serious objection against the dipole theory is of a
theoretical nature and refers to the use of the internal field given by
equation (8-2). In fact, if the dipole theory based on (8-2) were correct, a
large number of polar liquids should also be ferroelectric; we know, on the
other hand, that ferroelectric materials are rare. The incorrectness of
(8-2) was first pointed out by Onsager in 1936 and may be understood in
the following way:18 Consider a spherical cavity of molecular radius
inside a dielectric in the absence of an external field. Suppose a dipole fl
is located at the center of the cavity. The dipole will polarize the
surrounding material and this in turn will produce a "reaction field" inside
the cavity. If the dielectric is homogeneous, it can be shown that the reac-
tion field Er is homogeneous and parallel to the dipole f.L.19 It is evident
16 H. Blattner and W. Merz, Helv. Phys. Acta, 21, 210 (1948).
17 For a discussion of this point see E. T. Jaynes, Ferroelectricity, Princeton
University Press, Princeton, 1953, Chaps. 1,3.
18 L. Onsager, J. Am. Chern. Soc., 58, 1486 (1936); see also C. J. F. Bottcher,

I.
Theory of Electric Polarization, Elsevier, New York, 1952, pp. 63 If.
See, for example, C. J. F. Bottcher, op. cit., Chap. 3; see also Problem 6-6.
- .
buted by the timeaverage of the reaction field; this part is equal to Er(cos 0)
where 0 is the angle between !L and E and, as emphasized above, does
not produce a torque on the dipole. To find the actual field strength tend-
ing to orient the dipole, one must subtract the reaction field component in
the external field direction. This may be done simply by first taking away
the dipole and calculating the field inside the cavity. The field so obtained
is called the cavity field and is equal to _ ._ \
t ~ Ec = [31:/(21: + 1)]£ \ _ (8-10)
(Note that this is always smaller than the Lorentz field.)
t Making use of the formula PIE = (I: - 1)/417, we may
write (8-10) in the form

t Ec = E + ~P/(21: + 1) = E + Y(I:)P
Comparing this expression with (8-2), one sees that y
(8-11) -
.t ~ is not a constant but that it depends on the dielectric
constant in such a manner that as I: increases, Y decreases.
Fig. 8-11. Anti-
ferroelectric ar- Now, if instead of (8-2) one werp to employ (8-10) as the
rangement of di- field producing the torque on t ~ dipoles, the possibility
poles. for spontaneous polarization jsappears (see Problem
8-5). Although the above model is admittedly over-
simplified and needs refinement, the arguments shed doubt on the validity
of the dipole theory based on the internal field (8-2). In fact, calculations
by Luttinger and Tisza on a model consisting of dipoles occupying the
lattice points in a simple cubic structure indicate that the stable con-
figuration for such a system contains alternate arrays of dipoles oriented
in opposite directions (see Fig. 8-11).20 Such arrangements of course, have
no resultant polarization; they correspond to a so-called antiferroelectric
arrangement. 21 Substances which appear to be antiferroelectrics are
tungsten trioxide (W0 3 ) and lead zirconate (PbZr0 3 ).22

8-5. Ionic displacements and the behavior of BaTi03 above the Curie
temperature

In Sec. 8-3 we have seen that the dipole theory, with an expression of
the type (8-2) for the internal field, led to a Curie-Weiss law for the suscepti-
bility above the Curie temperature. However, in Sec. 8-4 it was pointed
20J. M. Luttinger and L. Tisza. Phys. Rev., 70, 954 (1946); 72,257 (1947).
21C. Kittel, Phys. Rev., 82, 313, 729 (1951).
22 S. Roberts, Phys. Rev., 83, 1078 (1951); E. Sawaguchi, H. Mariwa, and S. Hoshino,

Phys. Rev., 83, 1078 (1951) .

.)oc. ~L.onaO~), 14,}, 1 (1<J35): !t is illustrative to compare the dipole theory of ferr~­
electriCIty wIth the Bragg-Wllhams theory for order-disorder transitions in alloys (see
Chapter 4).
Sec. 8-5] FERROELECTRlCS 197
out that the internal field (8-2) could not be considered the field producing a
torque on the dipoles. On the other hand, the objection of Onsager raised
there does not refer to electronic and ionic displacements, and for these an
internal field of type ~-2) may stilI be applied. In this section it will be
shown that in case the dielectric constant of a material is large compared
with unity, a Curie-Weiss law may be obtained which is solely due to
electronic and ionic displacements. 23 At first sight this may seem somewhat
surprising because one generally connects a strong temperature de-
pendence of € with the existence of permanent dipoles. .. .. ::;" .~ ..... J
For the sake of argument, let us _ -_
assume that for a particular nondipolar " t - - ~.--- ,--

solid the Clausius-Mosotti expression 4 _.' . _. '--r

holds (which is based on the Lorentz '"
• internal field formula): ;:: 3
~
(£-I)J(£+2)=(47TJ3)NIX=fJN (8-12) t 2
Here N represents the number of unit

_-
1
.cells per cm3 and IX represents the total
polarizability per unit cell; it will be
assumed that IX is independent of tem- o .5 1.0
.-1
• perature. As long as £ is of the order of . +2
10 or smaller, any changes in N resulting Fig. 8-12. The logarithm of the
from thermal expansion do not affect the dielectric constant 10 as function of
value of £ to any great extent. On the the quantity (10 - 1)/(10 + 2).
other hand, if £ ~ I, the left-hand side
of (8-12) approaches unity and it is observed from Fig. 8-12 that small
variations in fJN may lead to large changes in the dielectric constant. In
order to determine the temperature coefficient of £, differentiate (8-12)
with respect to T; this yields, after dividing through by N,
3 d€ 1 dN
(£ + 2)( € - I) dT = N . dT = - 3A. (8-13)

where A is the linear coefficient of expansion of the solid. Making use of

the fact that £ ~ I, so that (£ +
2)(£ - I) c:::'. £2, one obtains

Jd£ = - JA dT
£2
or £ = T__!_f!__
_ () (8-14)

The last expression has indeed the form of the Curie-Weiss law; the
Curie temperature () enters as a constant of integration. It is of interest to
note that the Curie constant is equal to the reciprocal of the linear coeffi-
cient of expansion. For BaTi03 , ;. ~ 10-5 per degree, which gives fair
agreement with the experimental value for the Curie constant quoted in
23 G. H. Jonker and J. H. van Santen, Science, 109,632 (1949).
198 FERROELECTRICS [Chap. 8
Sec. ~-2. Although the assumption of the validity of the Clausius-Mosotti
relation (8-12) for BaTi0 3 is doubtful, the simple arguments given here
definitely indicate the importance of lattice expansion for the temperature
dependence of the dielectric constant in case E ~ 1.

8-6. The theory of spontaneous polarization of BaTi0 3 \

Since ferroelectricity occurs in relatively few substances, it seems that
the crystal structure of ferroelectrics is of paramount importance in any
explanation of this phenomenon. It was first pointed out by Megaw that if
one employs the Goldschmidt radii for the different ions in BaTi0 3 it is
found that the space available for the TiH ion inside the oxygen octahedron
is somewhat larger than the size of this ion requires. 24 This observation
has induced a number of theoretical attempts to explain the ferroelectricity
of BaTi0 3 on the assumption that the TiH ion plays an essential role.
If one were to explain the spontaneous polarization of 50,000 esu solely
on the basis of a displacement ofTiH ion, one would require a displacement
d such that
4Ned=50,OOO or dc::::_O.15 X 1O-8 cm
~

which seems not unreasonable. Actually, the required displacement would

be less than this, because BaTiOahas a large index of refraction (n = 2.4 or
EO = 5.76). In fact, if one assumes the Lorentz-Lorenz relation one

obtains

where (Xri and (X((i are the polarizabilities of the ions assr Jated with
electronic and ionic displacements, respectively.23 Now, if t:lt: right-hand
side of this expression becomes unity, E becomes infinite, and spontaneous
polarization will occur. Thus the TiH displacement would have to account
for less than 38 per cent of the total polarization.
One theory based on the assumption that the Ti4+ ions are mainly
responsible for the ferroelectric properties of BaTiO a has been developed
by Mason and Matthias. 25 These authors assume that the stable position
for the Ti 4+ is not in the center of the unit cell (Fig. 8-6) but that there
exist six stable positions corresponding to slight displacements from the
center toward the six surrounding oxygen ions. In each of these positions,
the unit cell would thus bear a dipole moment. They furthermore assumed
an internal field of the type (8-2) and essentially their theory is similar
to the dipole theory discussed in Sec. 8-3. With this theory it is not
2t H. D. Megaw, TrailS. Faradav Soc., 42A, 224, 244 (1946).
l'iP. Mason and B. T. Matthias, Phys. Rev., 74, 1622 (1948); also W. P. Mason,
Piezoelecfric Crystals and Their Applications in Ultrasonics, Van Nostrand, New York,
1950. • ''"' "i""~'"".· '
..
• I .
Sec. 8-6] FERROELECTRICS 199
possible, however, to obtain consistent agreement with experiment. 26
That a dipole theory for BaTi0 3 is hardly acceptable follows from the
fact that the observed Curie constant is about 104 degrees absolute,
whereas (8-4) gives 393/y, where y is certainly larger than unity. Besides,
the same objections as in Sec. 8-4 may be brought to bear.
Another type of theory that has been suggested does away with the
assumption of permanent dipoles and is based solely on electronic and
ionic displacements. The essential point of these theories consists of the
calculation of the internal field at the positions of the different ions.
We have seen already in the preceding chapter that the Lorentz field
E + (47T/3)P holds only when all atoms an: surrounded cubically by
others. This is the cas.e for the Ba2+ and TiH ions, but not for the oxygen
ions in BaTi0 3 . The interesting feature of this type of theory is that it
brings in explicitly the peculiarities of the perovskite structure. Calcu-
lations of the internal field, which will not be given here, indicate that in the
perovskite structure there exists a strong coupling between the TiH
and 0 2- ions, leading to internal field constants about eight times as large
as the usual 47T/3 factor.27 Thus the internal field at the position of the TiH
ion is very strong, and this, combined with the high charge and small
restpring force of the TiH ion, would lead to the conclusion that the
perovskite structure is particularly f~vorable for ferroeiectricity to occur.
It must be emphasized, however, that in the calculations referred to above,
the internal field is calculated at the position of the undisplaced ions.
Actually, one is interested in the internal field at the position of the
displaced ions. That this is a serious objection has been pointed out by
C;:ohen, who showed that this may lead to an appreciable overestimation of
the internal fields. 28 Also, the theories under consideration leave un-
explained the pertinent experimental fact that as the temperarure of BaTi0 3
is lowered, the direction of spontaneous polarization changes in the order
[001], [011], [Ill].
A model which explains in a natural fashion the existence of the three
transitions just mentioned is based on the assumption that the displacement
of oxygen ions is essential in the understanding of BaTi0 3 . 29 It was first
pointed out by Devonshire that the restoring force for small oxygen
displacements in a direction perpendicular to the plane of the four
surrounding Ba 2 + ions is probably very smal1. 30 This is a consequence of the
fact that the 0 2- ions are tightly squeezed between the BaH ions. Now,
with each unit cell one can associate three oxygen ions (because each of the
,. For a disclIssion see for example E. T. Jaynes, op. cit., Chap. 2.
" J. H. van San ten and W. Opechowski, PhysiCO, 14,545 (1948); J. C. Slater, Phys.
Rev., 78, 748 (1950).
,. M. A. Cohen, Pllys. Rev., 84, 368 (1951).
,. t. T. Jaynes, Pllys. Rev., 79, 1008 (1950).
30 A. F. Devonshire, Phil. Mo,!{., 40, 1040 (1949).
200 FERROELECTRICS [Chap. 8

six ions belongs to two unit cells), which may be denoted by Ox, Oy and 0 •.
As the crystal is cooled from above the Curie point, the cubic lattice
contracts and at the Curie point one of the three oxygen ions is squeezed
out of the plane of the barium ions, let us say the ion Oz. This produces a
dipole moment per unit cell along the z-axis, part of which is equal to
2edz , where d z is the displacement of the ion 0z relative to the plane of BaH
ions .. At the same time, this allows for a possible contraction of the
lattice in the plane of the barium ions. The direction of polarization
corresponds to the c-axis of the tetragonal structure and sets in along
one of the cube edges at the Curie temperature. As the temperature is
lowered further, the Oy and Ox ions are successively squeezed out of their
normal positions, leading to a polarization along a face diagonal [OIl] and
a body diagonal [Ill], respectively, (by combination of their own effect
with the polarization already existin~. This model is in agreement with
the changes of structure associated with the changes in polarization
direction mentioned in Sec. 8-2. Also, X-ray diffraction studies have
shown that the oxygen ions are indeed displaced by 0.08-0.1 A relative to
the BaH ions; the displacement of the TiH is about 0.06 A according to
these measurements (the cube edge of BaTi0 3 is 4.00 A).31 The essential
feature of this model is that it combines the mechanical forces with the
electric forces.
On the quantitative side, the following simple ar~ment may b(!
put forward: Experimentally it is found that in the tetragonal region
the contraction of the lattice is proportional to the square of the polarization
and satisfies the relation
dala = 1.2 X 1O-12P2 / (8-16)
where a is the cube edge just above the Curie point and da is the (vntraction
in the tetragonal phase. Now, in the cubic phase, the sum of the radii of the
BaH and 0 2- ions is equal to alv2. Suppose now that the oxygen ion is
displaced out of the plane of Ba 2+ ions by an amount z and let it be assumed
that the radii of the ions remain constant and that the oxygen and barium
ions remain in contact. With reference to Fig. 8-13 it then follows that if
(a - fla) is the new edge of the square of Ba2+ ions, we must have ___~_
(a - flan2 = a 2/2 - Z2 '. ."

As long as fla/a ~ I, this yields

flala = (zla)2 (8-17)
The dipole moment per unit volume resulting only from the displaced
oxygen ions is equal to Po, = 2ezla3 and it thus follows from (8-17) that

31
fla/a = .
(ct/4e2 )p'6 = 2.8 X 1O-12P5 . (8-18)
H. T. Evans, Acta Cryst., 4, 377 (1951); W. Kanzig, Helll. Phys. Acta, 24, 175
(1951). . . . , ;
Sec. 8-6] FERROELECTRICS 201

Comparison of (8-16), and (8-18) shows that both expressions are of the
same form, and that if po. represents two thirds of the total polarization,
the agreement is quantitative. Although the oxygen displacement theory
has attractive features, recent neutron diffraction studies suggest that the
oxygen octahedra suffer little distortion in passing through the transition,
in contradiction with the theory. One must therefore conclude that the
problem is still not solved satisfactorily. 32

8-7. Thermodynamics of ferroelectric

transitions

It is of interest to investigate the

behavior of a ferroelectric in the vicinity
of its transition temperature To on the
basis of thermodynamic arguments. A
thermodynamic theory has the advan-
tage of being independent of any par- Fig. 8-13. Relative position of
ticular atomic model and thus leads to barium ions and displaced oxygen
quite general conclusions. Although such ions in a (110) plane.
a theory does not provide the physical
mechanism responsible for the ferroelectric properties of a given material,
it does point to certain features one should look for in atomic models.
We shall now discuss the elements of the thermodynamic theory of
ferroelectricity developed by Devonshire. 33
Consider a solid which is ferroelectric for temperatures T < To;
'let' the external pressure be zero and let there be no applied electric field.
If the crystal is in equilibrium at a given temperature, the free energy of
the crystal F should be a minimum. For simplicity we shall assume that in
the ferroelectric region the spontaneous polarization occurs along a
single axis; this would be the case for the Rochelle salt, KH 2 P0 4 , and
for the upper transition of BaTiO~. Let Fo represent the free energy of the
un polarized crystal; the free energy F of the polarized crystal may then be
expanded as a power series in the polarization

(8-19)

The coefficients c are functions of temperature; the numerical factors

are introduced for later convienence. Note that since we want the
free energy to be the same for "positive" and "negative" polarization
along the polar axis, only even powers of P are included. In thermal
32G. Shirane, F. Jona, and R. Pepinsky, op. cit.
33For a review of this work see A. F. Devonshire, "Theory of Ferroelectrics,"
Advallces ill Physics (quarterly suppl. of Phil. Mag.), 3, April 1954, p. 85.
202 FERROELECTRICS Chap. 8
equilibrium (oF/? Ph = 0 so that the spontaneous polarization satisfies
the equation
(8:20)
It is observed that P" = 0 is always a root of this equation and that
this will correspond to a minimum of the free energy if cl is positive.
If cl , C 2 and c3 are all positive, the root Ps = 0 will correspond to the only
minimum of the free energy and thus spontaneous polarization would
not occur. However, if as a result of the temperature dependence the
coefficient cl would become negative, Fwoulcl have a maximum for P s = 0
and there would be at least one non vanishing value for p. for which F
would be a minimum, i.e., spontaneous polarization would occur.

_p

ta) tb) \
Fig. 8-14. Second-order transition. In (a) the free energy is given
schematically as function of polarization for var.iuus values of c,; in
(b) the spontaneous polarization is represented as function of Ct. The
critical temperature corresponds to Cl = O. [After Devonshire,
ref. 33]

Consequently, if C1 changes continuously with temperature from a positive

to a negative value, the equilibrium of the crystal d nges from an
un polarized to a spontaneously polarized state. In or& to discuss the
properties in the vicinity of the transition temperature, we shall consider
two cases of particular interest.

(i) Second-order transitions. If the coefficients c 2 , c3 , ••• are all posTIlve .

and the value of cl varies from positive to negative as the temperature is
lowered, one obtains free energy curves as illustrated in Fig. 8-14a.
The corresponding spontaneous polarization as function of temperature
is indicated in Fig. 8-l4b. The transition temperature corresponds to
c1 = O. Assuming in (8-20) that the term with c3 is negligible, one obtains
for the spontaneous polarization,
(8-21)
Note that P s is a continuous function of temperature; a transition of
this type is not associated with a latent heat but with a discontinuity in the
Sec. 8-7) FERROELECTRICS 203
specific heat and is called a second-order transition. We shall return to
this point below.
Let us now consider the susceptibility of the crystal above and below
the transition temperature. For this purpose it is necessary to apply a
small electric field to the crystal. Now, for a crystal under zero pressure
in an applied field E, we may write according to thermodynamics,

dF= -SdT+ EdP (8-22)

Hence the applied field may be written E = (oFloPh .. Above the tran-
sition temperature the polarization will be small for small applied fields,
and in this region we may neglect all terms on the right-hand side of
(8-19) except the first. We thus obtain for T> To,
.'
,.-.~-
,

E = 2FI2P = ciP and Ilx.. I( = dE/dP = C1 (8-23)

where Xa is the susceptibility above the critical temperature; the co-

efficient ci is evidently equal to the reciprocal of the susceptibility Xn'
However, we know that in this temperature range the susceptibility is
given by the Curie-Weiss law X" = C;(T - 0), so that c i = (T - O)/C,
where C is the Curie constant. However, since the transition at To
corresponds to CI = 0, we have 0 = To and thus

(8-24)

In the ferroelectric region we obtain likewise from (8-19) and (8-23),

(8-25)

where Xb is the susceptibility below the transition temperature; the

terms with powers :;::'6 have been neglected in (8-19). For small applied
fields, P P, in this region, so that according to (8-25) and (8-21) we
r--J

have
(8-26)

] f we assume that the temperature dependence of cIon the ferroelectric

side of Tc is still given by (8-24), we obtain

(8-27)

The temperature dependence of the reciprocal of the susceptibility on

both sides of the transition temperature as given by (8-24) and (8-27) is
illustrated in Fig. 8-15a. Note that the slope in the ferroelectric region is
twice that above the transition temperature.
In connection with the remark made above that the transition under
discussion is of the second order, let us consider the entropy associated with
204 FERROELECTRICS [Chap. 8
the spontaneous polarization. According to (8-22) and (~-19), the entropy
is given by .
.S = -(oFjoT)p = So - lP2(oc1 joT) - t P4(oc 2 joT) + ...
where So is the entropy of the un polarized crystal. To Q first approxi-
mation we may then write \"
i
(8-28)
Since P is a continuous function of temperature for the case under con-
sideration and since the slope of p2 has a discontinuity at T = Te, there

\
\
l/xa

I ""
() 'Tc
(a) (b) . :}< ,"l

Fig. 8-1S. Reciprocal susceptibility near the critical temperature",

(a) For a second-order transition; (b) for a first-order transition.
The corresponding spontaneous polarizations are indicated by the
dashed curves; in (a) P s is continuous, in (b) discontinuous at Te'

should be a discontinuity in the specific heat, but no latent heat, i.e ..

the transition is of the second order. This type of transition is observed
in Rochelle salt and in KH 2P0 4 •

(ii) First-order transitions. We have seen that spontaneous polari-

zation requires the coefficient c1 to be negative. Furthermore, we have
seen that if at the same time c2 is positive, a second-order transition results.
We shall now consider the case for which C 2 is negative and c3 is positive.
Under these circumstances it is possible for the free energy curves to have
a minimum value for a nonzero value of the polarization to coexist with
a minimum for P" = O. Assuming that c1 varies from positive to negative
values as the temperature is lowered, one obtains free energy curves of the
type indicated in Fig. 8-16a. A transition from the non polarized state to a
spontaneously polarized state will now occur when the minimum of the
free energy corresponding to P s = 0 becomes equal to the minimum
associated with a nonzero value for P s • It will be evident that in this case
the polarization jumps at the critical temperature from zero to some non-
zero value, i.e., the polarization as function of temperature exhibits a
Sec. 8-7] FERROELECTRICS 205

discontinuity at T = Tc as shown in Fig. 8-16b. According to (8-28),

the entropy will also be discontinuous at T = Tc and there will be a latent
heat, i.e., the transition is of the first order.
In the absence of an external field we obtain from the equilibrium
condition (oF/oP)T = 0 and from (8-19) for the nonvanishing value of the
spontaneous polarization the equation '
(8-29)
At the critical temperature Tc the quantity P,/Te) should satisfy (8-29)

--T

(a) (b)

Fig. 8-16. First-order transition. In (a) the free energy is represented

as function of P for different values of Cl' In (b) the spontaneous
polarization is given as function of T; note the discontinuity
at Te' [After Devonshire, ref. 33]

as well as the condition mentioned above that F(Te) = Fo(T). According

to (8-19) we thus have also
_ 1 2 1 -t. 1 6 ~{>~f,Uc :"t:}l
0- 2CIPs(Tc) + 4,C 2 P.(Te) + sc3 Ps(Tc) + ... (8-30)
From this equation and (8-29) as applied to the critical temperature we
then find the relations
P;(Tc) = -i(C 2 /C 3 ); C1 = 13S(c~/C3); P;(TJ = 3c 1/C 3 (8-31)

The first of these results shows that the polarization is discontinuous

at the critical temperature (Fig. 8-16b).
We shall now consider the susceptibility on both sides of the critical
temperature. As in case (i), the coefficient c1 in the region above the
temperature Tc is again equal to 1/xa- In this region the susceptibility
follows the Curie-Weiss law, so that
Xn = C/(T - 0) and c1 = (T - O)/C (8-32)
where 0 is somewhat smaller than Tn as mentioned in Sec. 8-1. We leave
it to the reader to show that by similar arguments as used under (i) and by
206 FERROELECTRICS [Chap. 8
making use of the relations (8-31) we find for the susceptibility below the
critical temperature,
(8-33)

At the critical temperature C1 is, according to (8-32), equal to (Tc - ()/C

and the susceptibilities just above and just below Tc are given by

l/X" = (Tc - ()/C and l/Xb = 4(Tc - ()/C for T = Tc (8-34)

The reciprocal susceptibility as one passes through the transition tempera-

ture is illustrated in Fig. 8-ISb.
We should mention here that decisive evidence as to whether a parti-
cular ferroelectric transition is of the first order may be obtained from
a so-called "double loop" experi-
p
ment in which the transition is in-
duced slightly above the critical
temperature Tc by application of a
strong electric field. Such an induced
transition was first produced by
Roberts in ceramic material and has
more recently been demonstIated for
a good single crystal of BaTi03 by
Merz. 34 A strong a-c field is applied
to the crystal a few degrees above its
normal transition temperature. At
zero applied field the crystal if
Fig. 8-17. Schematic representation of
a double hysteresis loop, of the type
non ferroelectric but at a critical
observed for BaTiO a, slightly above the value of the apphed field the polari-
transition tt:lllperature. zation increases rapidly and upon
reversal of the field hysteresis is
observed. The hysteresis loop is not complete, however, and for
low applied fields the behavior is normal again (see Fig. 8-17).
A double hysteresis loop obtained in this manner can only occur if the
transition is of the first order, as may be understood in the following
manner: In the absence of an applied field the transition occurs when in
Fig. 8-16a the minimum of the free energy for P s = 0 is equal to the
minimum associated with nonvanisning value of the spontaneous polari-
zation. For a crystal subjected to a field E, however, the induced transi-
tion occurs when F--EP rather than Fhas the same value as the minimum
at the origin. Such induced transitions can evidently occur only if the free
energy curves are of the type illustrated in Fig. 8-16a and not if they are
of the type corresponding to Fig. 8-14a. Hence the double loop experi-
ment distinguishes between first- and second-order transitions. Since a
at S. Roberts, Phys. Rev., 85, 925 (1952); W. J. Merz, Phys. Rev., 91, 513 (1953).
Sec. 8-7] FERROELECTRICS 207
double lo'op has been observed for BaTi0 3 , the upper transition of this
material is evidently of the first order. We should note that it is usually
not possible to obtain a clear-cut distinction between a first- or second-
order transition from measurement of the spontaneous polarization as
function of temperature, since P s rises rapidly just below Tc even for a
second-order transition. For further details on the thermodynamic theory
of ferroelectricity and for a treatment of antiferroelectric transitions we
refer the reader to A. F. Devonshire, op. cit.

8-8. Ferroelectric domains

It was mentioned in Sec. 8-2 that when a Rochelle salt crystal is cooled
to below the Curie temperature, spontaneous polarization along the
a-axis of the orthorhombic structure sets in. In general, however,
the direction of spontaneous polarization is not the same throughout the
crystal; certain regions are polarized in the +a direction, others in the
-a direction. These regions are referred to as domains. The boundaries
between domains are called domain walls. In a Rochelle salt crystal the
domains are polarized in opposite directions. For KH2PO~ there is also
only one axis along which spontaneous polarization takes place, viz., the
c-axis of the tetragonal structure. The domain structure is thus similar
to that of Rochelle salt. In the case of BaTiO:l , spontaneous polarization
may occur along anyone of the three edges, leading to six possible
directions for the spontaneous polarization. The domain structure for
BaTi0 3 is therefore more complicated than in the other two groups of
ferroelectrics.
The ferroelectric domains are the electrical analogues of the Weiss
domains in ferromagnetic materials, although there are certain interesting
differences in their formation and growth, as we shall see below. The
existence of domains, which has been confirmed by X-ray investigations and
optical studies 35 , explains the possibility for a crystal below the Curie
temperature to have a zero or very small total polarization. By applying
an dectric field to such a crystal, the number and size of domains polarized
in the external field direction may be increased. This process leads,
upon reversal of the field direction, to hysteresis in the P versus E curves,
and gives rise to dielectric losses. These losses are proportional to the
area of the hysteresis loop and to the frequency of the applied a-c field.
Optical observation of ferroelectric domains is possible since ferro-
electrics are birefringent. In BaTi0 3 for example, the optical axis coincides
with the direction of spontaneous polarization. Thus a domain polarized
in a direction perpendicular to the surface of a crystal plate looks dark
'" B. T. Matthias and A. yon Hippel, Phys. Rev., 73,1378 (1948); P. W. Forsbergh,
Phys. Rev., 76, 1187 (1949); Blattner, Kanzig, Merz, and Sutter, Helv. Phys. Acta, 21,
207 (1948); W. J. Merz, Phys. Rev., 95, 690 (1954).
208 FER ROELECTRICS •
. "" [Chap. 8
through a microscope between crossed nicols. On the other hand, adomain
polarized in a direction parallel to the surface appears bright between
crossed nicols, except when the direction of polarization of the light is
parallel or perpendicular to the domain polarization. It is thus possible
to see the domains and to study changes in the domain structure. In barium
titanate the direction of polarization of neighboring domains differs either
by 90° or by 180°; this is a consequence of the three mutually perpendicular
axes along which spontaneous polarization may occur. In this con-
nection one speaks of 90° and 180° walls. The latter can be observed
only when the crystals are strained, by an external electric field or
by mechanical stresses.
A number of interesting experiments on

-- the formation of domains and the motion of

domain walls in BaTiOa have been carried
out by Merz.36 His work shows that when an
electric field is applied in a direction opposite
to that of the spontaneous polarization, a
- large number of new needle shaped domains
of about 10-4 em width are created (Fig.
8-18). These new domains grow essentially
in the forward direction rather than sid&ways.
This behavior is quite different from that of
-t::====-
-- E
ferromagnetic materials, where the change in
direction of magnetization is accomplished by
the growth of domains which have the right
direction of magnetization, the growth result-
Fig. 8-18. Schematic repre- ing from a sidewise motion of the domain I

sentation of new antiparallel walls. This indicates that the forward coupling
domains resulting from appli- of the electric dipoles is much stronger than
cation of an external field E. the sidewise coupling. At this point the
reader may be reminded of the remarks
made at the end of Sec. 8-4, with reference to the calculations of Tisza and
Luttinger. 20 Merz has given some semiquantitative arguments which
confirm this behavior: when one estimates the energy per cm 2 of a domain
wall between antiparallel domains and minimizes this with respect to the
thickness of the wall, it is found that the wall thickness is of the order of a
few lattice distances. In contrast with this, the wall thickness in a ferro-
magnetic material is of the order of 300 lattice constants. Thus to move a
domain wall in BaTiOa sidewise over one lattice distance requires an
energy which is about equal to the energy of the wall itself. In a ferro-
magnetic material, it takes roughly 1/300 of the total wall energy to
displace the wall over one lattice distance.
For Rochelle salt and for KH 2 P0 4 it has also been found that
3. W. J. Merz, Phys. Rev., 95, 690 (1954).
Sec. 8-8] FERROELECTRICS 209
the wall thickness is considerably smaller than for ferromagnetic
materials. 37
In view of the absence, or at least infrequent occurrence, of a sidewise
motion of the domain walls in ferroelectric materials, the problem of
nucleation of the needle shaped new domains becomes of primary
importance for the understanding of the reversal of polarization in an
external field.
REFERENCES
W. G. Cady, Piezoelectricity, McGraw-Hili, New York, 1946.
A. F. Devonshire, "Theory of Ferroelectrics," Advances in Physics
(quarterly supplement of Phil. Mag.). Vol. 3, April 1954. p. 85.
P. W. Forsbergh jr., "Piezoelectricity, Electrosttiction and Ferro-
electricity," Encyclopedia of Physics, Springer, Berlin, 1956, vol. 17,
pp. 264-391.
E. T. Jaynes, Ferroelectricity, Princeton University Press, Princeton, 1953.
W. P. Mason, Piezoelectric Crystals and their Application to Ultrasonics,
Van Nostrand, New York, 1950.
G. Shirane, F. Jona, and R. Pepinsky, "Some Aspects of Ferroelectricity,"
Proc. IRE, December, 1955. p. 1738.

PROBLEMS
8-1. Let P be the spontaneous polarization of a ferroelectric solid and
let yP be the internal field. Show that the "extra specific heat" of the
material is given by C = -(y/2)(dp2/dT). For the dipole theory, draw the
curve for specific heat versus temperature and show that at the critical
temperature the specific heat is equal to 3k/2 per dipole.
8-2. In the theory of Mason and Matthias 25 of ferro electricity of
barium titanate it is assumed that the TiH ion has six stable positions
corresponding to small displacements from the center of the unit cell
toward the six surrounding oxygen ions. If the absolute value of the dipole
moment due to this displacement is p, show that in a field appJied parallel
to a cube edge, the polarization due to these dipoles is given by

where N is the number of unit cells per unit volume and Ei is the internal
field. Introduce the approximation pEi ~ kT and compare the result with
31 T. Mitsui and J. Furuichi, Phys. Rev., 90, 193 (1953); W. .Kiinzig and
R. Sommerhalder, Heir,. Phys. Act.a, 26,603 (1953).
210 FERROELECTRICS [Chap. 8

that for freely rotating dipoles. Assume further that the internal field is
given by Ei = +
E y(P,[ + rx.E;) where rx.
represents the polarizability
per unit volume with the exclusion of the Ti4+ displacements. Show that
spontaneous polarization can occur only below a critical temperature
Tc = (yN;-t2/3k)/O - yrx.). Show further that the dielectric constant of the
material is given by . . . \.

E=l+~(rx.+!'~)
1- yrx. y T- Tc
8-3. Discuss an experimental method for growing large platelike
single crystals of BaTi03 . (See l. P. Remeika, J. Am. Chem. Soc., 76, 940
(1954).)
8-4. Discuss the results of X-ray and neutron diffraction studies of
ferro- and antiferr.oelectric ~aterials. See, fOf example, G. Shirane,
F. lona, and R. Pepmsky, op. Cit. '

8-5. Consider a system of dipoles and assume that the field acting on a
given dipole is equal to the cavity field (8-1 1). If there are N dipoles percm3 ,
show that the dielectric constant of the system is
E = 1 + ! [47TNIX - 1 + ( 1 + 87TNIX/3 + 167T2N21X2)1/2]
where IX = ;-t2/3 kT. This shows that E remains finite for any finite tempera-
ture, i.e., the system is nonferroelectric. ..f ,
., .'1
-' ;)
Chapter 9

FREE ELECTRON THEORY OF METALS

fn this chapter the free electron theory of metals as developed by

Sommerfeld and others will be discussed. Conductivity, Hall effect and
other transport phenomena will be treated separately in Chapter II.
The discussions assume the reader's familiarity with the material pertaining
to Appendixes B, C, D, and E. A reference such as D-7 stands for formula
7, Appendix D, etc.
H must be emphasized that in the model employed below, the existence
of free electrons is assumed. The question dealing with the reasons for
the occurrence of conduction electrons in certain materials and not in
others is deferred until the next chapter.

9-1. Difficulties of the classical theory

The outstanding properties of metals are their high electrical and

thermal conductivities. Thus, soon after the discovery of the electron, a
number of investigators, in particular Drude and Lorentz, attempted an
explanation of these properties on the basis of the assumption that a
metal contains a certain number of "free" electrons. The free electrons
were supposed to be able to move through the lattice, thereby suffering
collisions with the atoms (see Chapter II). These theories were developed
at the turn of the century and, of course, employed Boltzmann statistics.
One of the greatest achievements of these theories was that they led to
semiquantitative agreement with the Wiedemann-Franz law, discussed in
Chapter II.
There existed, however, a number of serious difficulties in the classical
electron theory, one of which was the following: According to classical
statistical mechanics, the average kinetic energy of a free electron is 3kTj2.
Thus if a metal contains N free electrons per gram atom, the total kinetic
energy of the electrons should be 3NkTj2. Associated with this is a specific
heat of 3Nkj2 per gram atom. Now, from measured values of the optical
reflection coefficient of metals, one had to assume that the number of free
electrons is of the order of one per atom. This corresponds to an electronic
specific heat of 3Rj2 ,..._, 3 cal per gram atom per degree. On the other
hand, the specific heat (at high temperatures) associated with the lattice
vibrations is 3R per gram atom. One therefore concludes that the specific
heat of metals should be about 50 per cent higher than for insulators.
However, experiments show that any specific heat associated with the
211
212 FREE ELECTRON THEORY OF METALS [Chap. 9

electron gas is very small. Another difficulty encountered in the classical

" theory, and intimately related to the one just mentioned, pertains to the
magnetic properties of the free electrons. Each electron has a magnetic
moment associated with its spin, and classically, should therefore give rise
to a paramagnetic susceptibility inversely proportional to the temperature.
Experimental results, on the other hand, show that the paramagnetism of
metals is nearly independent of temperature.
We shall see below that both difficulties are removed when quantum
statistics is used. , .)

9-2. The free electron model

" ',\

An electron in a metal, or for that matter in any solid, finds itself in

the field of all nuclei and all other electrons. The potential energy for
Vac. such an electron may therefore be
expected to be periodic, the periodicity
being that of the lattice. In the model
employed by Sommerfeld, however, it
is assumed that the "free" electrons,
Fig. 9-1. The Sommerfeld model. i.e., those giving rise to the conduc-
E. is the energy difference between tivity, find themselves in a potential
an electron at rest inside j'te metal which is constant everywhere inside
and one at rest in vacuum. At the metaJ.1 Since one does not observe
T = 0, all energy levels up to E Fare
electron emission from metals at room
filled, all higher ones are empty
(see Sec. 9-3); the work function temperature, it seems evident that the
'" = E, - E F • potential energy of an electron at rest
inside the metal must be lower than that
of an electron at rest outside the metal. This is confirmed by relatively
simple theoretical arguments. 2 The change in potential energy of an
electron Es as one crosses the metal-vacuum boundary may, for a number
of problems, be considered abrupt (see Fig. 9-1). For some problems,
however, it is necessary to consider the variation of potential at the surface
in some more detail (see Sec. 9-8). One thus arrives at a physical model in
which the interior of the metal is represented by a potential energy box of
depth Es as indicated in Fig. 9-1; the energy of an electron at rest outside
the metal is used as a reference and is commonly referred to as the vacuum
level.
It may be of interest to note that Es may be determined experimentally
from electron diffraction experiments with slow electrons (a few hundred
ev). An electron impinging on the metal from the outside with an initial
1 A. Sommerfeld, Z. PhYSik, 47, I (1928); see also the article by A. Sommerfeld and
H. Bethe, Handbuch der Physik, Vol. 24{2.
2 See, for example, H. Fr6~lich, Elektronen Theorie der Metal/e, Springer, Berlin,

1936, p. II.
Sec.9-2J FREE ELECTRON THEORY OF METALS 213
energy Eo gains an amount E, upon entering the metal. It may be shown
(see Problem 9-1) that the position of the diffraction maxima is determined
by the quantity [(Eo +
E,)/ Eo]1/2. Thus from a knowledge of the lattice
structure and Eo, it is possible to determine E.,. for nickel one has found
in this way E., = 14.8 ev. 3 In general, E" is of the order of 10 ev.
In the Sommerfeld model, the free electrons are assumed to be the
valence electrons of the composing atoms. Thus the alkali metals are
assumed to contain one free electron per atom; aluminum supposedly
has three free electrons per atom.
The first problem to be discussed now is the energy distribution of a
"free electron gas" with a density of the order of 1O~~ per cm3 •

9-3. The Fermi-Dirac distribution

For convenience let us define the _----CEI,2

energy of a free electron at rest inside T=O
the metal as zero, i.e., we choose the
bottom of the potential energy box as a
reference. According to Appendix B the
possible energy levels for an electron
are then given by
E = p2/2111 = (fj 27T 2/2111 ]l2/3)(n; + n~ + Il~) Fig. 9-2. The curve CE* repre-
(9-1) sents Z(E) in accordance with (9-3):
the energy distribution N(E) is
where V is the volume of the metal obtained by lllultiplyingZ(E) by F(E).
and n;r' nlj' n z are integers;:?: l. Each
set of integers n"" ny, n z defines an allowed wave function of the spatial
coordinates x, y, z:. From this, it can be shown that the number of allowed'
wave functions corresponding to a momentum range between p and p dp +
is equal to 47Tp2 dp V/h 3 (see Appendix B). Taking into account the fact
that the electron has a spin which can accept two possible values, one
concludes that the number of possible states (i.e., wave functions including
the spin) corre~ponding to a momentum range dp is equal to
(9-2)
It is frequently convenient t~have an expreSsion for the number of allowed
states in an energy range between E and E + dE. This may readily be
obtained from (9-2) by replacing p2/2m by E, yielding
Z(E)dE=CEl!2dE with C=47TV(2m)3/2jh3 (9-3)

The function Z(E) is represented schematically il~ Fig. 9-2. To find the
states actually occupied by the free electrons at a temperature T, we must

,
3 C. Davissun and L. H. Germer, PhI'S. ReL"., 30, 705 (1927): H. Bethe, AIIII. Physik.
87, 60 (1928). ' . ,,~
. '
'OJ,
214 FREE ELECTRON THEORY OF METALS [Chap. 9

make use of Fermi-Dirac statistics because electrons obey the Pauli

exclusion principle. Denoting the number of electrons occupying states
between E and E + dE by N(E) dE, we find from (0-10),
. 1
N(E) dE = Z(E)F(E) dE wIth F(E) = -e-:X+~E~/k~T-+-1 (9-4)

where ex is a parameter and F(E) is called the Fermi function. Note that
F(E) simply represents the fraction of possible states which is occupied.
When there is about one free electron per atom in the metal, the electron
gas may be expected to be highly degenerate at room temperature. This
implies that e? < I and we shall therefore write (see Appendix D)

1'1E)
e? = e- EF / k1 ' (9-5)

t where Ep is called the Fermi energy;

l~----------~,,~~T=O its physical meaning will become clear
kT ~EF./" below. With this notation we may
.5 write
\
\, --+-E
OL---------------~~­
EFo
F(E) = e (E-E F )/k1' +1 (9-6)

Fig. 9·3. The Fermi distribution In discussing the energy distribution it

function F(E) at absolute zero and is convenient to distinguish between
at a temperature T <g;' Erik.
different temperature ranges: ....

1. T = O. At absolute zero, the Fermi function has the property

"F(E) = 1 for E<EFo

F(E) = 0 for E> EF o (9-7)

Thus at absolute zero, all possible states below EFo are occupied. all
those above EFo are empty. The physical meaning of EFo is, therefore,
that it represents the highest occupied energy level at T = 0 (see Figs.
9-2 and 9-3). It is of interest to calculate EF II in terms of the number of
free electrons per unit volume. In general, one must satisfy the condition

Jooo N(E) dE = Jooo Z(E)F(E) dE = N (9-8)

In view of (9-7) and (9·3) this gives

N = C I,rEF 0 E1!2 dE or "

h2 (3n)2/3
E., = __ (9-9)
.0 0 2m 81T
Note that Epo is determined essentially by the number n of electrons per
unit volume. Values for E Po calculated from (9-9) for a number of metals
are given in Table 9-1. It is observed that Epo is of the order of several
electron volts. This brings out the very significant difference between
'._
Sec. 9-3] FREE ELECTRON THEORY OF METALS 215
classical statistics and Fermi statistics. In the former case, all electrons
would have zero energy. For "classical electrons" to have an energy of
1 ev, a temperature of about 50000 K would be required.
Table 9-1. Fermi Energy Calculated from (9-9) and Work Function
cJl (Exp.) for Some Metals
Metal Valence EFo (ev) '" (ev)
Na I 3.1 2.28
K l' ~ - 2.1 _._2.~
Cu t 7.0 ;4:4f"-
Ag T-~ )' -;} - 5.5 . 4.46
Ba 2.1 3.8 _,--.l..S l __ ~__ .
Al 3 11.7 4.20

The average kinetic energy of the electrons at absolute zero may be

calculated from
(9-10)

From this and (9-9) one readily finds by eliminating C that

(Eo> = !EF o (9-11)
J j;;

2. kT ~ Ep. For all temperatures below the melting point of metals

kT is small compared with Ep (kT at room temperature is only 0.025 ev).
It follows from the definition of the Fermi function (9-6) that for E = E p ,
F= t. Hence the physical meaning of Ep may be stated: at the Fermi
level, the probability for ~ccupation is t. An example of the Fermi
function at T> 0 is given by the dashed curve in Fig. 9-3. For energies
below EF such that (Ep - E)';P kT, the value of F(E) is still practically
unity, i.e., the energy distribution in that region is the same as that for
T = O. It is only in the vicinity of Ep minus a few kT that F(E) begins
to drop below the value at T = O.
For energies above Ep , such that (E - Ep) ';P kT, one may neglect
the term I in the denominator of (9-6) and one obtains ~i! .:.

F(E),-...J e-(E-EF)/kT for E - Ep';P kT (9-12)

;fhus, in this region, the Fermi distribution becomes identical with a
Boltzmann distribution; one speaks in this connection of the "Boltzmann
tail." .
The Fermi level and the average kinetic energy of the electrons in this
case are determined by the integrals
roo dE
.N =.10 Z(E) e(E-E,)/kT + 1 (9-13)

I
1 roo EdE ) f
(E) = N10 Z(E) e(E E F )/k1' +1 (9-14)
216 FREE ELECTRON THEORY OF METALS [Chap. 9
The evaluation of these integrals may be found elsewhere and it may
suffice here to give the results;4

Ep ~ EFo [1 -7; (;TfJFo

\\ (9-15)

(E) ~ (Eo) [1 + ~~2 (;:rJ o

(9-16)

where the subscripts 0 refer to the quantities at T = O. It is observed that

as T increases EF decreases and (E) increases slightly. The smallness of
the changes follows immediately from the occurrence of the factor
(kT/Ep o)2. For example, with EF 0 '::::' 5 ev, this factor is ,......, 2 X 10- 5 at
room temperature. For many practical purposes, therefore, the Fermi
level may be considered a constant.

9-4. The electronic specific heat

The expression for the average energy of an electron (9-16) has an

important consequence for the specific heat problem mentioned in Sec. 9-1.
]n fact, it follows immediately from (9-16) that the specific heat at constant
volume per electron is given by

c" = d(E)/dT::::: 57T2k 2 T(Eo)/6E'j" o

Making use of (9-1 I) this may be written
CI' = 7T2(kT/2EF.)k = 7T2(T/2TF)k (9-17)

where Tp is the Fermi temperature defined by kTF = Ep. Thus for

Epo'::::' 5 ev one finds at room temperature an electronic specific heat of
about k/40, which may be compared with the 'Classical value of 3k/2. The
use of Fermi-Dirac statistics thus removes the specific heat difficulty
encountered in the classical theory. It is of interest to note that the
electronic specific heat rises linearly with T. Now, at low temperatures,
the specific heat'associated with the lattice vibrations is proportional to
P, so that the total specific heat of a metal may be represented by
Cv = AT+ BT3 (9-18)
• This expression is, at least qualitatively, in agreement with experiment.
At sufficiently low temperatures the linear term predominates and this
allows one to determine the electronic specific heat term from experiment.
For copper, for example, Kok and Keesom find' A = 1.78 cal/mole/deg2 • 5
• See, for example, F. Seitz, Modern Theory of Solids, McGraw-Hill, New York,
1940, pp. I 46ff. For numerical tables involving integrals of the type (9-13) see
J.McDougall and E. C. Stoner, Phil. Trans., A237, 67 (1929).
• J. A. Kok and W. H. Keesom, Physica, 3,1035 (1936); 4,835 (1937).
Sec. 9-4] FREE ELECTRON THEORY OF METALS 217
When one calculates the coefficient A on the basis of (9-17) and uses
Ep o = 7.04 ev, calculated from (9-9), one obtains A = 1.24, which is
appreciably smaller than the observed value. This is a difficulty which
one encounters also for other metals and is a consequence of the over-
simplifying assumptions made in the free electron model. From the
discussion to be given in Chapter 10 it may be concluded that the dis-
crepancy is in part a result of the fact that the effective mass of the electrons
may be larger than that of a free electron.
Qualitatively, the results obtained may be summarized as follows: As
a consequence of the Pauli principle, even at low temperatures most
electrons have appreciable kinetic energy. Thermal excitation of electrons
is possible only if they can be excited into unoccupied states: This is
essentially possible only for electrons in the vicinity of the Fermi level;
the electrons in the low-energy region require too large an excitation
energy. Thus only a relatively small number of electrons contribute to the
specific heat. ...,
,I
r\
9-5. Paramagnetism of free electrons

It is well known that when a certain charge distribution rotates about

an axis, a magnetic dipole moment results. Thus, as a consequence of the
angular momentum, or spin, each electron bears a magnetic dipole
moment. An imp<?rtant property of the electronic magnetic moment is
that in an external field H its component along the field direction is either
+ehj2mc or -enj2mc (see Sec. 18-2). In other words, the component is
either parallel or antiparallel to the external field direction. The magnitude
of the component
d.

ftB = eh/2mc = 0.917 X 10-20 ergjoe~ted 1 (9-18)

is called a Bohr magneton. The energy of a dipole in an external field is

equal to -fL' H, so that in the parallel orientation the energy is -P'nH,
+
and in the antiparallel orientation is ft nH.
In a metal, let there be n free electrons per unit volume. In the presence
of a magnetic field H let there be np with an orientation parallel to Hand
n" anti parallel to H. The magnetic moment per unit volume (the
magnetization) is then equal to lJ',:U

(9-19)

If we assume classical statistics M may be calculated in the same way

as the orientation polarization of electric dipoles in the Oebye-Langevin
theory. We leave it to the reader (Problem 9-4) to show that in that case,

.mi"" (9-20)
218 FREE ELECTRON THEORY OF METALS [Chap. 9
as long as flH ~ kT. The quantity X", is called the paramagnetic suscep-
tibility. Note that for freely rotating dipoles the average component in
the field direction is (flJd3kT)H. The fact that the factor 3 is missing in
(9-20) is a consequence of the fact that the dipoles can accept only two
possible orientations relative to H. If (9-20) were correct, one would find for
the susceptibility of metals at room temperature with n ~ 1022 per cm3 ,
Xv ~ 10-4 per cm3 • Also, Xv should vary as liT. Experimentally, however,
one finds Xv ~ 10- 6 per cm3 and practically no temperature dependence.
The disagreement with experiment disappears when one applies Fermi-
Dirac statistics, as was first shown by Pauli. 6 For simplicity let us first
consider the situation at T = O. Without external magnetic field all energy

ME)

Fig. 9-4. The number of occupied states N(E) as function of the

energy at T = O. In (a) an external field H is applied while keeping
the electrons in their original states; as a result of the shift in
energy, this situation is unstable. In (b) eq,uilibrium is established,
corresponding to an excess of parallel spins,

levels below E F 0 are occupied and all those above E F 0 are empty. Leaving
for a moment all electrons in their original state and applying an external
field H, all electrons with a magnetic moment parallel to H would suffer
a shift in energy of -flEH, all antiparallel ones of +flnH. This is indicated
in Fig. 9-4a. It must be noted that fl BH ~ E Fo; in fact, even for a field
strength of 10 5 gauss, flBH ~ 10-3 ev as compared with EFo ~ 5 ev.
The situation as depicted in Fig. 9-4a is, of course, unstable and a number
of anti parallel spins will enter the group of parallel ones. In equilibrium
both halves are filled to the same level, as in Fig. 9-4b. Now, according
to (9-3), the number of allowed states in each of the halves is per cm3
equal to
z(E) dE = 27T(2m)3/2El/2 dElh 3 (9-21)

• W, Pauli, Z Physik, 41, 81 (1927).

Sec. 9-5) FREE ELECTRON THEORY OF METALS 219
The number of antiparallel spins entering the group of parallel spins is
therefore
,
:;
'.
t

because fl IJH ~ E F'o The total excess of electrons with parallel orientation
is twice this, so that one finds by making use of expression (9-9) for EIi'.'
_ 47Tm
M - h2
(3n)1/:lflnH -
7T
2 _
XI,H (9-22)

This may be written in a more convenient form for purposes of comparing

the quantum result with the classical result (9-20) by multiplying top and
bottom by E F' This gives
" (9-23)
where Tp is the Fermi temperature defined by kTF = Epo Substituting
numerical values, one finds for the volume susceptibility,
Xv = 2.21 X 1O-14n1!3 ( :::'1':1. (9-24)
For temperatures different from zero, the theory must be extended.
However, because the influence of temperature on the Fermi distribution
is slight, one expects Xv to be nearly temperature-independent. It has
been shown by Stoner 7 that for kT ~ E p ,

Xv
= ~. nfl~
2 E Fo
[1 _ 12 (kT)2]
7T
E,
2
(9-25)
1'0

The factor in brackets is identical with that occurring in (9-15) for the
temperature-dependence of Ep. For T = 0, (9-25) reduces to (9-23).
With n ,..._, 1022 it thus follows from (9-23) that the paramagnetic suscep-
tibility of the free electron gas is of the order of 10-6 per cm3 , in agreement
with experiment. "I
A quantitative comparison between the results obtained above and
experiment is rather difficult. First of all, the magnetic susceptibility of a
metal consists of three contributions:
(i) The paramagnetic contribution of the free electrons
Oi) A diamagnetic contribution of the free electrons, first calculated
by Landaus
(iii) The diamagnetic contribution of the ionic cores
Thus, in order to obtain Xv' the last two contributions must be
subtracted from the total susceptibility measured. For completely free
electrons, contribution (ii) is equal to - Xv13. Contribution (iii) is usually
calculated from susceptibility data on ionic solutions; this involves the
7 E. C. Stoner, Proc. Roy. Soc. (London), A152, 672 (1935).

• L. Landau, Z. Physik, 64, 629 (1930).

220 FREE ELECTRON THEORY OF METALS [Chap. 9

assumption that the susceptibility per ion is the same in the solution and
in the metal. Furthermore, the experimental data are sometimes impaired
by the presence of ferromagnetic impurities. Finally, the free electron
model can be expected to hold in good approximation only for the alkali
metals, as we shall see in Chapter 10. ",\_,
For further details, we refer to the literature. 9

\
9-6. Thermionic emission from metals '

With reference to Fig. 9-1, let us define the energy of a free electron
at rest inside the metal as zero. In order to escape from the metal an
electron must have an energy perpendicular to the surface of at least E,.
Thus if x is the coordinate perpendicular to the surface, an electron must
have a momentum Px ;?: PX o in order to escape, where ';''';" \
P;')2171 = Es (9-26)
However, even if an electron at the surface has a momentum Px ;?: PX o' it
does not necessarily escape, but may be reflected by the potential barrier.
This is a phenomenon which follows readily from wave mechanics. lO
Thus the probability of escape for an electron satisfying the condition
Px ;?: Px is equal to I - r(px), where r(PT) is the reflection coefficient as
functio~ of Pr The reflection coefficient also depends on the shape of the
potential barrier. Suppose now that the number of electrons per unit
volume with a momentum between px and Pcc + • the metal is
dpJ' inside
equal to n(pJ') dp:r The number of such electrons arriving at the surface
per second per unit area is equal to 1';cn(Px) dpr From this it follows. that
the emission current density is equal to . 1 '
I = (elm) ('" Pxn(Px)[1 - r(px)] dp" (9-27)
'P.l'n

The term in brackets is usually replaced by a factor (l - r) in front of the

integral, where r represents a suitable average of the reflection coefficientY
One is thus left with the problem of calculating n(p,,); this quantity may
be obtained in the following manner: From (9-2) it follows that for an
isotropic momentum distribution, as presumably exists inside the metal,
the number of allowed states corresponding to an element dp", dpu dpz in
the momentum space is equal to
2 dpx dpy dpzfh 3
, N, F. Mott and 1-1. Jones, The Theory of the Properties of Metals and Alloys, Oxford,
New York, 1936, p. 184; A. 1-1, Wilson, The Theory of Metals, 2d ed., Cambridge.
London, 1953,Chap, 6.
)0 See, for example, N. F. Mott and I. N, Sneddon, Wave Mechanics and its Applica-

tions, Oxford, New York, 1948, pp. 13ff.

11 For a calculation, 5ee, for example, L. W. Nordheim, Proc. Roy. Soc, (London),

121,626 (1928); L. A. MacColl, Pllys. Rev., 56, 699 (1939).

"i,
Sec. 9-6) FREE ELECTRON THEORY OF METALS 221
per unit volume. The number of electrons occupying states with momenta
between Px, Px +
dpx; PY' py dpy; Pz, pz +
dp, is therefore +
2 dp:rdpydpz ,t!l (l!
n(p", Pv' pz) dpx dpy dp, = h3 • e(E - Ep)/O' +1 (9-28)
where E = (p; + p; + p;)/2m. Hence
2 f+ocl'-1W dpudpz
n(px) dpx = Iii dpx.l_ 'l] • - oc e(t: -Hp)/"], +1 (9-29)

Now we are interested only in those electrons for which Pr ;:::: P.r o' i.e., the
total energy of the electrons of interest is at least equal to E,. On the other
hand, E, - Ep = ¢?:> kTfor all metals at temperatures below the melting
point (see Fig. 9-1). Hence the term of unity in the distribution function
may be neglected; we are interested only in the Boltzmann tail of the
Fermi dis.tribution. The quantity ¢ is called the work function of the
metal; it represents the energy difference between an electron at the Fermi
level and the vaClJum level. ( __
One thus obtains from (9-29),

(9-30)

Substituting this expression into (9-27) one finds upon integration for the
emission current density,
.:L ),
1= A(I - r)T2 e -·</>lkT (9-31)

where A 47Tcmk 2 /h 3 = 120 amp/cm 2/deg 2 . This is the Dushman-

Richardson equation.
From the form of (9-31) one may be inclined to conclude that by
simply plotting log U/T2) versus liT olle obtains ¢ from the slope of the
resulting straight line and A(l -- r) from the interc,pt at I IT = 0 (see
Fig. 9-5). A number of complicating factors in the thermionic emission
of an actual metal must, however, be considered. 12
(i) The apparent work function increases if a negative space charge
exists in the vicinity of the emitter; the anode potential should
therefore be sufficiently positive to prevent space charge build-up,
i.e., one should work in the region of saturation-current density.
(ii) The apparent work function decreases with increasing external
field strength, as explained in Sec. 9-8. Thus J(T) should be
I; , measured for different external fields and then extrapolated by
means of a so-called Schottky line to zero field strength (see
Fig. 9-7).
12 For an evaluation ot thermionic emission data and a thorough discussion of the
theory, see C. Herring and M. H. Nichols, "Evaluation of Thermionic Data," Revs.
Mod. Phys., 2], 185 (1949).

'---...
222 FREE ELECTRON THEORY OF METALS [Chap. 9

(iii) As a result of thermal expansion, ~ itself is a function of

temperature, and so is (1 - r).
I
(iv) In the derivation of (9-31) it has been assumed that the work
function is the same over the whole area of the emitter; this
assumption is valid only if the emitter is a single crystal, because
~ varies from one crystaIIographic plane to another. 18

'\
2 t10lOg (l/T2)
\,
o \,
\,
\,
\,
-2 \,
\,
\,
-4 \, 'I'
\,
\, 'J
-6 \,
\,
,I'
-& 1'11' ~'" ; ~: f '

-10
-12

o .2

I
,/
Fig. 9-5. Richardson plot for tungsten. [After Herrmann and
Wagener, I.e., vol. 2, page 74]

(v) Small amounts of adsorbed gases may influence ~ strongly, as

explained in Sec. 9-9; thus the surface should be atomically clean.
(vi) The macroscopic area of the emitter is in general not equal to the
actual surface area. '
From these remarks it is evident that reliable conclusions regarding
~ and A( I - r) can be drawn only from extremely carefully controlled
experiments. Many of the' older experimental results in the literature are
worthless because of poor vacuum techniques. a
A few remarks may be made in connection with (iii) above. Let us
assume that r is temperature-independent and that ~ varies linearly with
T according to •
~ = ~o + (d~/dT)T (9-32)
where ~o is the work function at absolute zero. (This assumption is
J3 For an extensive study of this and other aspects of the thermionic emission of
tungsten, see G. F. Smith, Phys. Rev., 94, 295 (1954) .
.. Illustrative in this respect is a table of values for 4> and A(l - r) for platinum in
chronological order in G. Herrmann and S. Wagener, The Oxide Coated Cathode,
Chapman and Hall, London, 1951, Vol. 2, p. 78.

"I .I .:
Sec. 9-6] FREE ELECTRON THEORY OF METALS 223
probably inaccurate because the coefficient of expansion goes to zero as
T -+ 0.) Substituting (9-32) into (9-31), one obtains

log (I/T2) = log A + log (I - r) - (d</l/dT)/k - </lo/kT (9-33)

On the basis of this expression one thus determines from the slope of a
Richardson plot, such as represented for tungsten in Fig. 9-5, a value for
</lo rather than for cP. Also, it is evident that the constant obtained from
the intercept at liT = 0 may differ appreciably from A = 120 amp/
cm 2/deg 2• A number of experimental results obtained by various methods 15
indicate that for metals d</l/dT ~ 10-4 ev per degree. Work functions for
a number of metals are given in Table 9-2.
Table 9-2. Average Values of the Work Function of Mctals in cv.
'-ty"
For references to the original literature, see footnote 15

AI 4.20 Cs 1.93 Na 2.28

Ag 4.46 Cu 4.45 Ni 4.96
Au 4.89 Fe 4.44 Pd 4.98
Ba 2.51 K 2.22 Pt 5.36
Cd 4.10 Li 2.48 Ta 4.13
Co 4.41 Mg 3.67 W 4.54
Cr 4.60 Mo 4.24 Zn 4.29

9-7. The energy distribution of the emitted electrons

The energy distribution of the emitted electrons may be derived from

the results obtained in the preceding section as follows: According to
the Dushman equation (9-31) the total number of electrons emitted per
cm 2 per second is equal to
(9-34)
if we assume for the moment that the reflection coefficient r == O. Also,
the number of electrons arriving at the surface per cm 2 per second with
PI£ ;?: PXo and velocities normal to the surface in the range dVI£ may be
obtained from (9-30):

(9-35)

When Vel£ represents the velocity of an electron in the x-direction after

emission, we have
~mvex = ~mvx -
1 2 1 2 E.£!' - .J.
'I'
.' (9-36)
veo: dveo: = Vo: dvo:
IS For a review of methods to determine r/>, see Herrmann and Wagener, I.c. Chap. 2.
224 FREE ELECTRON THEORY OF METALS [Chap. 9

As each of the electrons of the group represented by (9-35) contributes

an external electron as described by (9-36), the velocity distribution
f( v,,,,) eVe," of the emitted electrons is obtained by dividing (9-35) by (9-34)
and substituting (9-36); this gives
\
f( veX) dv ex IN = (mv ex IkT)e- mv :,/2kT dv eX (9-37)

Thus the velocity distribution perpendicular to the surface exhibits a

Maxwellian form. It is left to the reader (Problem 9-6) to show that the
average energy of the emitted electrons perpendicular to the surface is
equal to
(E.:> = (m/2)(v;x) = kT (9-38)
Clearly, the velocities of the electrons in the y- and z-directions (parallel
to the surface) do not change upon crossing the surface potential barrier;
it can be shown (Problem 9-6) that (Ey) = (Ez ) = kT/2. One thus
concludes that the total average energy of the escaping electrons is equal to
(E) = 2kT (9-38a)
This result is basic to the so called "cooling method" employed to determine
the work function cp at any operating temperature. I6 To explain this
method, we have to refer to a result of the thermodynamics of a gas, in
this case the electron gas. The change in entropy dS resulting from a small
change in the number of particles dN and a small change in the total
energy dE is given by (see 0-8 and E-5) .,{,' .. I:,
dS = ~k dN + dE/T+ P dV/T (9-39)

where ~ is an undetermined multiplier, related to the Fermi energy in

accordance with (9-5) by
, (9-40)

Let us now apply this to the electron gas at constant volume, assuming
that one electron leaves the metal with an average kinetic energy of 2kT.

dN= -1, dE = -(El!' + cP + 2kT) (9-41) . - ---

From the last three equations one obtains for the heat lost by the metal
per emitted electron,17
dQ = T dS = cP + 2kT (9-42)

Note the important physical meaning of the work function in this result
16 C. Davisson and L. H. Germer, Pllys. Rev., 20, 300 (1922); 30, 634 (1927);
G. M. Fleming and J. E. Henderson, Phys. Rev., 58, 887 (1940).
17 A detailed thermodynamical study shows that an additional term must be added
to the right-hand side of (9-42), containing the Thomson coefficient; this term is of the
order of 10- 2 ev. See C. Herring, Pllys. Rev., 59, 889 (1941).
Sec. 9-71 FREE ELECTRON THEORY OF METALS 225
for the latent heat of evaporation per electron. The power consumed by
the emitter per cm 2 due to this process is thus
P = (I/e)(c/> + 2kT) (9-43)
From the power input and correcting for losses due to thermal radiation
and heat conduction, it is possible to determine c/> at a given temperature.
This method has been used to determine dc/>/dT.lB

9-8. Field-enhanced electron emission from metal..

In the preceding sections the metal-vacuur.l boundary has been

represented by a discontinuity in the potential. Actually, the potential

E ."":-';' <

--~'::

, ,. ,,
,
Fig. 9-6. Surface potential barrier and Schottky effect (greatly
exaggerated) .
.
changes smoothly, and this has some interesting consequences, as we shall
see. Let us define the potential energy of an electron far away from the
metal surface as zero. As we approach the metal with the electron, the
metal will become polarized and will exert an attractive force on the
electron. For distances x large compared with the interatomic distances,
the metal surface may be considered homogeneous, and the attractive
force is given by the well-known image force f2/4x 2. This leads to a
potential energy of the electron equal to
(9-44)
The image potential is represented by curve AB in Fig. 9-6. It will be
evident that (9-44) is not valid for distances smaller than several Angstroms;
in fact, this would lead to a potential energy of - CD for an electron at
rest inside the metal. Schottky suggested that the image potential holds
18 See, for example, F. Krueger and G. Stabenow, Ann. Physik, 22, 713 (1935).
FREE ELECTRON THEORY OF METALS [Chap. 9

> x o, where Xo is a critical distance; for the region 0 < x < Xo he

ned a constant force, i.e., the potential energy in that region would
linear function of x (see CA, Fig. 9_6).19 Wave-mechanical calculations
:ate that this model is rather good. 20 To obtain the order of magnitude
0' let us assume the total potential energy barrier to be Es = 10 ev.
x = Xo the image force is e2j4x&, so that the increase in potential
'gy along CA is e2j4xo. Also, the energy rise between A and B in
9-6 is e2/4xo, leading to E. = e2/2xo or xo ~ I A.
The existence of the image potential has some important consequences:
(i) It reduces the reflection of escaping electrons considerably relative
to that by an abrupt potential change.
(ii) It leads to a reduction in the apparent work function in the presence
of an external electric field; this phenomenon is known as the
Schottky effect and may be understood as follows :19
Suppose there exists a homogeneous electric field between the emitting
"
~tal surface and another metal plate which is made the anode. The
,tential fOf an electron due to the external field may then be represented
( a line such as PQ in Fig. 9-6. Combining this potential with the image
)tential, we obtain the dashed curve, so that it is now easier for electrons
, escape than without an external field. The total potential energy
orresponding to the dashed line may be represented by
V(x) = ~e2/4x - eEx (9-45)
vhere the last term corresponds to the external field. The maximum of
his curve occurs for x = xm and from (9-45) one finds Xm = He/E)l!'I..·
5ubstituting, one finds for the change in work function
/lrp = V(x m ) = -e(eE)l!2 (9-46)
Instead of the Dushman equation, we thus obtain
log (/jT2) = log A + log (1 - r) - rpjkT + e(eE)1/2jkT (9-47)

Thus, if one plots the logarithm of the saturation current for a given
temperature as fu'nction of the square root of the anode voltage, one
expects a straight line (the Schottky line). A comparison of theory and
experiment for tungsten is given in Fig. 9-7; the agreement is good for
anode voltages above 100 volts; the deviations below 100 volts are
ascribed to variations of the work function over the surface. 21
It should be noted that the actual change in the work function is
relatively small. For example, for E = 103 volts per em, one obtains
X lIl ~ 10- 5 em and /lrp ~ 0.01 ev.

19 W. Schottky, Physik z., 15, 872 (1914).

20 See, for example, J. Bardeen, Phys. Rev., 49, 653 (1936); 58,727 (1940).
Zl W. B. Nottingham, Ph,s. Rev., 47, 806 (1935); 58,927 (1940).
1 'I
Sec. 9-81 FREE ELECTRON THEORY OF METALS 227
Field emission. When the external electri<: field becomes of the order
of J06 volts per em, cold emission or field emission sets in. This pheno-
menon is quite different from the Schottky effect: in the latter case the
electrons cross over the potential barrier, in field emission they tunnel
through the barrier. For simplicity, consider a metal at absolute zero and
let us assume the surface potential barrier to be abrupt. The potential
energy of an electron outside the metal is then equal to -eEx, represented
by the line AB in Fig. 9-8. If the distance d in Fig. 9-8 is of the order of
10 Angstroms or less, electrons in the vicinity of the Fermi level will be

20
I;"
I . "";

----<-;:--e-
. ......___
.

.....
x
o
'0
.... 5
t
2~ ____- L_ _ _ _ _ _k -_ _ _ _ ~ B
o 10 20 30

.
__ IV )1/2
a
, Fig. 9-7. Schottky line for tungsten. Fig. 9-8. To illustrate high-field
[After Nottingham, ref. 21] emISSIOn; the distance d should
be 10 Angstroms or less for
,;; ", appreciable tunneling to take
place.

able to tunnel through the barrier.22 For <p '::::' 3 ev, this requires a field of
the order of tO i volts cm-I . As the field strength becomes larger, more
and more electrons below the Fermi level begin to contribute to the
emission current. According to Fowler and Nordheim, the emission
current as function of the field strength E for a triangular barrier may be
written in the form
(9-48)
where Band fJ are constants containing the wor~ function. 23 Note that
E plays the same role in this formula as T in the Dushman-Richardson
expression for the thermionic current. Thus if log (II E2) is plotted versus
lIE, a straight line should result. This has been confirmed by experiment. 2i
Usually, field emission sets in at fields of the order of 10 6 volts cm- I ,
probably as a consequence of high fields occurring at surface irregularities.
" See, for example, N. F. Mott and I. N. Sneddon, op. cit .
.. R. H. Fowler and L. Nordheim, Proc. Roy. Soc. (London), 119A, 173 (1928).
"See, for example, R. Haefer, Z. Physik, 116, 604 (1940).
228 FREE ELECTRON THEORY OF METALS [Chap. 9

It will be evident from the above discussion that field emission is not ......
strongly influenced by temperature. Of course, the temperature should
be kept low enough to assure the absence of thermionic emission.

9-9. Cbanges of work function due to adsorbed atoms 25 :\

It is well known that the work function of metals such as tungsten

can be lowered by surface adsorption of alkali or alkaline earth atoms.
The lowest value of the work function is obtained roughly for a monatomic

o .2 .4 .6 .8 1.0 1.2
-Ii

Fig. 9-9. The decrease :11> of the Fig. 9-10. A Be represents the
'0\ ork function of tungsten as func- potential energy of an atom as
tion of the fraction () covered with function of distance from the metal;
adsorbedCsatoms; () "'1 corresponds PQR corresponds to an ion.
to a monolayer. [After J. A. Becker,
TrailS. Faraday Soc., 28, 151 (1932)] i
layer of adsorbed atoms, as may be seen from Fig. 9_9. 26
It is observed
that the work function of tungsten (4.52 ev) may be lowered to 1.5 ev
by Cs-adsorption. Adsorption of oxygen usually increases the work
function of metals. We shall now investiga,te the reasons for such changes.
First consider the potential energy of an atom as function of its
distance from a metallic surface. 1t is convenient to think of the metal as
a huge molecule which is "perfectly" polarizable. Since any atom has a
certain polarizability, the atomic potential energy curve will be of the
type ABC in Fig. 9-10, the attraction resulting from van der Waals forces.
The energy D« corresponds to the energy required to dissociate the
adsorbed ~tom from the metal surface. Suppose now that in point A we
ionize the atom by supplying the ionization energy /. The electron is then
taken to the metal, yielding a gain in energy equal to the work function
cp of the metal (see 9-42). Thus the potential energy curve for the ion
starts (J - cp) above the atomic curve, in point P. When we now approach
the metal with the ion, it will be under influence of an image force, i.e.,
~; For an extensive discussion see J. H. de Boer, Electron Emission and Adsorption
Phenomena, Cambridge, London, 1935.
21' See also J. B. Taylor and l. Langmuir, Phys. Rev., 44, 423 (I933). "
Sec. 9-9] FREE ELECTRON THEORY OF METALS 229

the attraction potential will be a Coulomb attraction, proportional to the

reciprocal of the distance from the metal. On the other hand, the potential
curve for the atom AB is of the van der Waals type and varies with a
higher power of the distance. For the ion we thus obtain a curve such as
PQR, which intersects the atomic curve. In this curve, Di represents the
binding energy of the ion. Thus, if Q lies lower than B, the foreign atom
will be adsorbed as a positive ion rather than as an atom. The condition
for ionic adsorption is therefore
D; - I + cP > D"
Thus atoms with a low ionization energy may be adsorbed as positive
ions and experiments indicate that this is indeed the case for alkali and
alkaline earth atoms adsorbed on a metal with a relatively high work
function like tungsten. We may note that (I - cp) may be negative, so
that point P may be lower than point A in Fig. 9-10. This is the case for
example with Cs on tungsten: les = 3.9 ev and CPu- = 4.5 ev. This has
been confirmed experimentally by heating a tungsten wire in cesium
vapor; if the tungsten wire is made positive with respect to a surrounding
metal cylinder, one observes that the cesium is
ionized at the tungsten and evaporates as ions
rather than as atoms. 27 The same is true for
rubidium, which has an ionization energy of
4.2 ev. For sodium, on the other hand, the
ionization energy is 5.1 ev, so that for Na
adsorbed on tungsten point Pin Fig. 9-10 is indeed
• above point A. Sodium therefore evaporates in
the form of atoms from a tungsten surface, even
though it is adsorbed in the form of ions.
Let us now consider the influence of atoms
adsorbed as positive ions on the work function
of the base metal. Opposite the positive ions Fig. 9-11. Electric double
layer on a metal resulting
exists a negative surface charge on the metal, from the adsorption of
i.e., there exists a double layer (Fig. 9-11). atoms in the form of
According to electrostatics, the field outside the positive ions. The curve
double layer vanishes, but inside the layer, the underneath represents the
force on an electron is 47Tae where ae is the potential energy of an
. ' 'electron as it crosess the
surface charge denSIty. . layer; D.rp is the lowering
Thus as an electron IS taken from the of the work function.
interior of the metal into vacuum there is an
extra potential energy drop, resulting from the double layer, equal to
11q, = 47Taed = 47TNe 2d (9-49)
where d is the distance between the positive and negative charges and N
" J. B. Taylor and I. Langmuir, Phys. Rev., 44, 423 (1933); J. A. Becker, Phys. Rev ..

,
28, 341 (1926).
230 FREE ELECTRON THEORY OF METALS [Chap. 9
is the number of adsorbed ions per For example, if d = 10-8 cm,
cm 2.
one requires N ~ 0.5 X 1014 cm- 2 to produce a drop of 1 ev, which is
approximately a complete monoatomic layer. It is therefore easier for the
electrons to escape than without the double layer, and the effective work
function of the metal is lowered by !.l.4>. Similarly, if the double layer
consists of negative ions adsorbed on the surface, as in the case of oxygen
on tungsten, the work function is increased.
') !, . ' \

9-10. The contact potential between two metals

, i!~ If
Consider two different metals of work functions 4>1 and 4>2 at absolute
zero temperature. The energy levels of the electrons in the two metals
Vacuum
\

):,

(a)
,1 .. '
Fig. 9-12. Contact between two metals. In (a) no equilibrium
has been established yet; (b) represents the equilibrium situation,
showing the contact potential difference </>2 - </>,.

may then be compared with reference to the common "vacuum level."

Suppose now the two metals are brought in contact with each other so
that their separation is comparable to interatomic distances. Initially then,
the situation is as indicated in Fig. 9-12a. Assuming 4>1 < 4>2' the energy can
be lowered by taking an electron from metal 1 to metal 2, and evidently
the situation depicted by Fig. 9-12a is unstable. A certain number of
electrons will therefore move from I to 2 by tunnel effect or, for tempera-
tures different from zero, by thermionic emission. Consequently, the
surface of metal 2 will become negatively charged, that ofmetall positively.
Thus, as the number of electrons shifted from 1 to 2 increases, it becomes
increasingly more difficult for other electrons to move from 1 to 2. Finally,
an equilibrium will be established corresponding to Fig. 9-12b, in which
the two Fermi levels coincide as a consequence of the potential rise (for
electrons) across the gap associated with the surface charges. Obviously,
the potential rise V is given by
eV === 4>2 - 4>1 (9-50)
where V is called the contact potential. We note that V is determined only
Sec. 9-10] FREE ELECTRON THEORY OF METALS 231
by the two work functions and is independent of the depths of the potential
energy wells.
In connection with the great importance of the Fermi level in equilibria
between two or more sets of electronic energy levels, let us consider the
problem from the thermodynamic viewpoint. Suppose two sets of energy
levels, distinguished by the subscripts 1 and 2, are in thermal equilibrium
at constant pressure and temperature. This means, according to Appendix
A that the Gibbs thermodynamic potential of the combined systems should
be a minimum; i.e., when one electron is transferred from system 1 to
system 2, the resulting change dG = dG1 +
dG 2 should vanish. Now,
according to thermodynamics,
T dS = dE + p dV - fl dN (9-51)
where -fliT is the change in entropy per particle added at constant E
and V, ./"

fl = - T(oSloN)e,r (9-52)
At constant pressure and temperature, therefore,
I
dG = deE - TS + p V) = fl dN (9-53)
Applying this to the combined systems under consideration and keeping
in mind that dN1 = -dN2' we may write as the condition for equilibrium
at constant p and T, ,. . .

(9-54)
.Equilibrium thus requires that the fl'S of the two systems be the same.
However, from (9-39), (9-40), and (9-52) it follows that fl = E p , showing
that for two (or more) sets of electronic levels, the Fermi levels must be
the same in equilibrium. This conclusion is of importance in the discussion
of contacts between metals, semiconductors, and insulators.

Fig. 9-13. Simple circuit to measure conta~t potentials.

Measurements of contact potentials may be used to determine the

difference in work function of two surfaces and is thus important in cases
where one is interested in changes in work functions. In Fig. 9-13, let A
232 FREE ELECTRON THEORY OF METALS [Chap. 9

and B be two SL!ch surfaces with different w0rk functions. Thus, without
external voltage. the plates will be charged as explained above. A sudden
change in the distance between the plates (switch S open) will lead to a
voltage pulse resulting from the change in capacitance and can be measured.
]f an external voltage is applied by means of a potentiometer (S closed),
the levels of one metal are raised or lowered relative to those in the other.
For a particular value of the external voltage the charges on the plates
vanish and a change in distance (S open) will not yield a voltage pulse.
Clearly, the external voltage then just compensates thc contact potential
and thus (~.1 ~ ~JI) may be obtained. A method dcvised by Zisman
employs a vibrating plate so that a-c techniques can be used and work
functions can be measured in a matter of seconds. 28 ]n this way one has
measured. for example, the change of work functions with temperature,
with the result that for metals ~ increases with about 10-4 ev per degree.

9-11. The photoelectric effect of metals

]n the photoelectric effect, an electron absorbs a light quantum and is

thereby excited into a state of higher energy; if the energy in the excited
state is large enough, the electron may appear as a photoelectron outside
the metal. The photoelectrons may originate from: (a) the interior of the
metal (volume effect), (b) near the surface of the metal (surface effect),
(c) forcign atoms adsorbed on the metal surface.
To begin with, it must be pointed out that completely free electrons
cannot absorb photons; this may be shown from the expression for the
quantum mechanical transition probability.29 By means of the following
simple argument, one arrivcs at the same conclusion. Consider the
interaction between an elcctron and a photon as a collision in which
momentum and energy are conserved. Let En be the initial energy of the
electron and hv the energy of the photon. The energy of the electron after
absorption is then E = Eo + hi'. When p and Po represent the absolute
values of the momentum of the electron, respectively after and before the
absorption process, and remembering that hv/c is the momentum of the
photon, conservation of momentum requires that
p <;Po -+ hv/c (9-55)
or (2mE)1!2 <; (2I11Eo)1/2 + hv/c (9-56)
This may be rewritten in the form
hv/2111C 2 + (2Eo/111C2)1!2 ;?: 1 (9-57)
However, for the energies of interest we have hv ~ mc:! and Eo ~ mc2•
W. A. Zisman, Rev. Sci. IlIslr., 3, 367 (1932).
28

See, for example, H. Frohlich, Elcklronell Theorie del' Alelalle, Springer, Berlin,
29

1936, p. 122; A. Sommerfeld and H. Bethe in Handbllch dey Physik. Vol. 24/2.
Sec. 9-11] FREE ELECTRON THEORY OF METALS 233
One thus concludes that in the free electron approximation, the conserva-
tion laws cannot be satisfied and thus free electrons cannot absorb photons.
This argument would hold fot the electrons in the interior of the metal.
The reason that there actually exists a volume effect is a consequence of
the fact that the free electron approximation is not valid; even in the case
of the alkali metals, for which this approximation is better than for any

'i
f.... f,'i -r-l~
Vacuum
hv I

'-
hv

_J
E
t - E'"./e o
n(EI
(al

Fig. 9-14. Illustrating the photoelectric efrect: for a frequency

v the electrons in the shaded part of the Fermi distribution may
contribute to the emission (a); (b) represents the ph,)to current
as function of the collector voltage.

other metals, the volume effect may contribute to the surface effect (b).30
The discussion given below is confined to process (b); because of lack of
space, only some qualitative remarks will be made.
Notwithstanding the arguments given above, the free electron approxi-
mation applied to electrons near the surface leads to the possibility of
photon absorption for these electrons; this follows from the wave-
mechanical treatment of the problem. 31 One might say that the presence
of the potential barrier at the surface makes it possible to satisfy the
conservation laws in the sense that the surface itself acts as a possible
source or sink for momentum. In other words, the system under considera-
tion is no longer the electron plus a photon, but electron plus photon plus
surface. With reference to Fig. 9-14a the following conclusions may then
be drawn for the emission characteristics of a metal at absolute zero.
3<1 H. J. Fan, Phys. Rev., 68, 43 (1945). In the volume effect, the excitation of electrons

is governed by the selection rule that the transition should be "vertical" in the reduced
zone scheme (see Chapter 10).
31 K. Mitchell, Proc. Roy. Soc. (London), A 146,442 (1934); 153,513 (1936); I. Tamm

and S. Schubin, Z. Physik, 68, 97 (1931); A. G. Hill, Phys. Rev., 53,184 (1938); R. E. B.
Makinson, Pllys. Rev., 75, 1908 (1949).
/

234 FREE ELECTRON THEORY OF METALS [Chap. 9

The minimum energy perpendicular to the surface required for an electron

to escape from the metal is Ej.' + cpo Thus, if hv is the energy of the
incident photons, electrons in the shaded portion of the Fermi distribution
may contribute to the emission current. It is evident that the threshold
frequency V t of the incident photons is given by
\
(9-58)
For V < V t , no emission occurs. Evidently the work function of a
metal may be obtained by measuring the threshold frequency V t • At

Na

3600 4400 5200 6000 6800

I
_AinA
j
Fig. 9-15. Relative photoemissive current as function of the ,YO
wavelength of the incident light for alkali metals. [After E. F. Seiter,
Astrophys. J., 52, 129 (1920)]

temperatures different from zero, a method devised by Fowler may be

used to determine cp.32
As the frequency is increased beyond V t , more and more electrons can
contribute to the emission and thus the emission current rises with
increasing frequency; for hv ~ E F + cp, saturation occurs. However, the
transition probabilities decrease with increasing frequency, leading to a
maximum in the current versus frequency curves (see Fig. 9_15).31
Besides measuring the total number of emitted electrons, one frequently
measures the emission current for a given incident photon frequency as
function of a retarding potential applied to a spherical collecting anode
surrounding the target. The maximum energy with which an electron can
leave the target at T = 0 is, according to Fig. 9-14a, equal to
E,;, = hv - cp (9-59)
3. R. H. Fowler, Phyfo Rev., 38, 45 (J 931).
Sec. 9-11] FREE ELECTRON THEORY OF METALS 235
Thus for a potential -E~Je applied to the collector, all emitted electrons
are stopped and the collected current I = O. As the collector potential is
made less negative, the collector current increases until for zero collector
potential the current reaches its saturation value Is for the particular
incident frequency. The I versus V('()lkdor curve thus has the. form as
indicated in Fig. 9-14b; this is in agreement with the observations. 33 By
differentiation of such curves, the energy distribution of the emitted
electrons may be obtained.
Quantitatively, the theory may be set up in the following way: let
neE) dE be the number of electrons in the metal occupying states in the
energy range between E and E + dE. Also, let P(v,E) be the probability
that an incident photon of frequency v excites an electron from a state E
into the state E + hv. The number of electrons emitted by the metal
originating from the range E, E +
dE is then per incident photon,
n(E)P(v,E)Q(E + hv) dE (9-60)
where Q(E + hv) is the probability for an electron of energy E + hv to
escape. In most theories the assumptions made with regard to P(v,E) and
Q(E -+- hv) are such that expression (9-60) is proportional to
F(v)(E - Ep - 4» dE = F(v)E'dE' (9-61)
Here F(v) is a function of the frequency only, and E' is the energy of the
electron in the excited state relative to the vacuum level. From (9-61) an
expression for the collector current as function of the retarding potential
can be obtained. 33
'.

REFERENCES
L. Brillouin, Die Quantenstatistik, Springer, Berlin, 1933.
J. H. deBoer, Electron Emission and Adsorption Phenomena, Cambridge,
London, 1935.
H. Frohlich, Elektronen Theorie der Metal/e, Springer, Berlin, 1936.
R. H. Good jr. and E. W. Muller, "Field Emission," Encyclopedia of
Physics, Springer, Berlin, 1956, vol. 21, pp. 176-231.
C. Herring and M. H. Nichols, "Evaluation of Thermionic Data," Revs.
Mod. Phys., 21, 185 (1949).
G. Herrmann and S. Wagener, The Oxide Coated Cathode, Chapman and
Hall, London, 1951, Vol. 2, Chaps. 1,2.

33 For a discussion of the important difference in the slope of such curves for metals

and semiconductors, see L. Apker, E. Taft, and J. Dickey, Phys. Rev., 74, 1462 (1948);
we also refer the reader to this paper for many references to the existing literature.
236 FREE ELECTRON THEORY OF METALS [Chap. 9
N. F. Mott and H. Jones, TheO/)' of the Properties of Metals and Alloys,
Oxford, New York, 1936.
W. B. Nottingham, "Thermionic Emission," Encyclopedia of Physics,
Springer, Berlin, 1956, vol. 21, pp. 1-176.
F. Seitz, The Modern TheOlY of Solids, McGraw-Hili, New York, 1940,
Chap. 4.
Article by A. Sommerfeld and H. Bethe in Handbuch del' Physik, Vol. 24/2,
1933, p. 333. ".'·a¥'qt, )(1 i,,0.,

PROBLEMS

9-1. Discuss how one can determine E, in Fig. 9-1 from electron
diffraction experiments.
9-2. Calculate the average velocity of a conduction electron in sodium
at T = O. Compare the corresponding "classical temperature" with the
melting point of Na. What is the electronic specific heat at T = 300 K?
0

9-3. Show that the derivative of the Fermi function is symmetrical

about E]<' and that J('(F/aE)dE

-oc
= -1.

9-4. Give a derivation of the classical expression (9-20) for the

paramagnetic susceptibility of free electrons.
9-5. Assuming df/dT = 10-4 ev per deg, what is the ordinate intercept
of a Richardson plot? Compare this with A = 120 amp/cm 2/deg2 •
9-6. Show that the average energy of the thermionically emitted
electrons perpendicular to the surface is kT; show that the average energy
parallel to the surface is k T.
9-7. On the basis of expression (9-61) derive an expression for the
photoemission current as function of the retarding potential on the
collecting anode.
9-8. A nondegenerate gas obeys the gas law pV = RT; derive a
relation between p, V, and T for a degenerate electron gas. (Hint: first
show that in general p equals two-thirds of the kinetic energy per unit
volume).
9-9. Consider a gas of similar molecules in thermal equilibrium. Let
the energy levels for the individual particles be denoted by En' where
n = 0, I, 2, . . .. Let the energy level En correspond to Z" possible states
(wave functions including the spin) and let on the average N n of these
states be occupied in equilibrium. Consider a collision between two
particles such that before the collision their energies are Ek and E l , and
after the collision Em and En'
) .

Chap. 9] FREE ELECTRON THEORY OF METALS 237

(a) Assume that the number of transitions k, 1-+ m, n per second is
given by AN"N1Z 1Il Z n, and that the number of transitions m, n -+ k, 1 is
given by AN",N"Z"ZI where A is a constant. Show that the equilibrium
condition and the law of conser\:ation of energy lead to the distribution
function Nk = CZ"e~/lEk for all k. This is identical with the Boltzmann
distribution if fJ is identified with l/kT.
(b) Suppose the number of transitions k, 1-+ m, n per second is given
by AN"N/(Zm - NIIl)(Zn - N n). Show that this leads to the Fermi-Dirac
distribution function.
(c) Assuming that the number of transitions k, 1-+ m, n is proportional
to NkN1(ZIIl + N",)(Zn + N n), show that the same reasoning leads to the
Bose-Einstein distribution.
(d) Comment on the physical meaning of the assumed expressions for
the number of transitions k, 1-+ m, n for the three types of statistics.
9-10. For an ideally flat metal surface calculate the lowering of the
work function resulting from a field outside the metal of 104 volts per cm.
Also calculate the distance from the surface for which the potential
barrier has its maximum value.
9-11. Discuss the theory of high-field emission of electrons for a metal
at OaK on the assumption that the potential barrier through which
tunneling takes place is of a simple triangular form.
9-12. The equation of motion of a free electron in a metal under
influence of light polarized along the x-direction may be written (J2x/dt 2 +
27TY (dx/dt) = --(e/m)Eoexp( -27Th't), where the second term is a damping
term. Solve the equation for x and from it calculate the electric moment
per unit volume. From this, show that the real part of the dielectric
constant (0' = n2 - k 2 and the conductivity a are given by

where ne is the number of free electrons per cm 3 • Show that y = 1/27T7

where 7 is the relaxation time occurring in the static conductivity
a o = n ee 27/m. Also show that metals are transparent for frequencies
:;:1015 per second and that they are reflecting in the region 1012 :::, v;:S 1015
per second. For background see Secs. 6-9 and 11-2; see also F. Seitz,
op. cit., p. 638.

~ I
Chapter 10

THE BAND THEORY OF SOLIDS

10-1. Introductor~' remarks

In a solid one deals with a large number of interacting particles, and

consequently the problem o(calculating the electronic wave functions and
energy levels is extremely complicated. It is thus necessary to introd uce a
number of simplifying assumptions. In the first place we shall assume that
the nuclei in the crystalline solid are at rest. In an actual crystal this is of
course never the case, but the influence of nuclear motion on the behavior
of electrons may be treated as a perturbation for the case in which they are
assumed to be at rest. As we shaH see in the next chapter, the lattice
vibrations play an important role in the interpretation of electrical
resistivity and other transport phenomena. Even with the above assump-
tion, however, we are still left with a many-electron problem which can be
solved only by approximative methods. In the case of solids, the most
important approximative method which has been applied extensively is
the so-called one-electron approximation. In this approximation the total
wave function for the system is given by a combination of wave functions,
each of which involves the coordinates of only one electron. In other
words,' the field seen by a given electron is assumed to be that of the
fixed nuclei plus some average field produced by the charge distribution of
all other electrons. An extreme case of the one-electron approximation is
the Sommerfield theory of metals discussed in the preceding chapter.
There it was assumed that the potential seen by a given conduction electron
is simply constant within the metal. ,.
Within the framework of the one-electron theory there are two
different approaches to the problem of the electronic structure of molecules
and solids. One of these, the Heitler-London or valence bond scheme,
is accurate when the atoms are far apart, i.e., when the atomic properties
are pronounced. This scheme is thus based on atomic or localized orbitals.
Another approach is that of Bloch; it is closely related to the Hund-
Mulliken scheme which has been applied to molecules. I n the Bloch
scheme an electron is considered to belong to the crystal as a whole rather
than to a particular atom. One speaks in this connection of the crystal
orbital method and the discussion given below is essentially limited to this
scheme. For a recent review of the one-electron method and many
,'" 238

,l " , .
Sec. 10-1] BAND THEORY OF SOLIDS 239
references we refer the reader to the article by Reitz cited at the end of this
chapter. The problem as outlined above involves essentially that of the
behavior of an electron in a potential which has the periodicity of crystal
lattice. We shall see that this leads, among other things, to a natural
distinction between metals, insu)ators, and semiconductors.
Before discussing the actual problem it may be useful to point out the
analogy which exists between (i) electronic motion in a constant and a
periodic potential, and (ii) the propagation of elastic waves in a continuum
and in a periodic structure.
For elastic waves in a continuous medium the frequency is inversely
proportional to the wavelength, i.e., there exists a linear relationship
between frequency and wave number (or wave vector). This implies a
velocity of propagation which is independent of the wavelength. Further-
more, there exists no upper limit for the frequency of the vibrational
modes in a continuous medium. However, when one considers the modes
of vibration in a lattice of discrete mass points which form a periodic
structure, two characteristic features appear (see Chapter 2):
I. There exist allowed frequency bands, separated by forbidden
regions.
2. The frequency is no longer proportional to the wave number but a
periodic function of the latter.
Returning now to the motion of electrons, the reader is reminded of the
fact that in a constant potential (free electron theory) the energy of the
electron as function of the wave vector k is given by ;;,
E = 1i2k 2 /2m where k = 2771). = pili
Here i. is the wavelength associated with the electron and p is the momentum
of the electron; the potential energy has been assumed zero. In this case,
there is no upper limit to the energy, i.e., the energy spectrum is quasi-
continuous (quasi, because the limited dimensions of the potential box
produce closely spaced but discrete energy levels). However, if we
consider the motion of an electron in a periodic potential we arrive at the
following resulTs:
I. There exist allowed energy bands separated by forbidden regions.
2. The functions E(k) are periodic in k.
These results will be derived below. The analogy pointed out above is
not too surprising if one recognizes that in both problems one deals with
waves in periodic structures; in one case they are elastic waves, in the
other they are waves associated with the electrons. For further details
with regard to the general problem of wave motion in periodic structures
we refer the reader to Brillouin. l
1 L. Brillouin, Wave Propl{l{afion in Periodic Structures, Dover, New York, 1953.

The existence of energy bands for electrons in crystals was first pointed out by M. S. O.
Strlltt, Ann. Phvsik, 84, 485 (1927); 85, 12<J (1928). ,i~ ,

-
240 BAND THEORY OF SOLIDS [Chap. 10

10-2. The Bloch theorem

In the free electron theory one assumes that an electron moves in a

constant potential Vo leading to the Schrodinger equation for a one-
dimensional case: , \)
d 21p/dx2 + (2m/1i2)(E - Vo)1p = 0

This equation can be solved by plane waves of the type

1p(x) =e±ik.t (10-1 )
Upon substitution one obtains for the kinetic energy of the electron
E kin = E -- Vo = /i 2k2/2m = p2/2m ~
It
The physical meaning of k is that it represents the momentum of
electron divided by Ii. The complete solution for the wave function
containing the time is obtained by multiplying 1p(x) by exp (~-iu)t) where
(') = E/fi, so that actually solutions of the type (10- J) represent waves
propagating along the x-axis.
Let us now consider the Schrodinger equation for an electron moving
in a one-dimensional periodic potential. Thus, let the potential energy of
an electron satisfy the equation
Vex) = vex -+- a) ( 10-2)
where a is the period. The Schrodinger equation is then

d 21p/dx2 + (2m/1i2)[E - V(x)]1p = 0 ( 10-3)

With reference to the solutions of this equation there is an important

theorem which states that there exist solutions of the form

( 10-4)

In other words, the solutions are plane waves modulated by the function
uk(x), which has the same periodicity as the lattice. This theorem is known
as the Bloch theorem;2 in the theory of differential equations it is known as
Floquet's theorem. Functions of the type (10-4) are called Bloch functions.
Before giving a proof of this theorem we note that the Bloch function
1p(x) = exp (ikx)uk(x) has the property

1p(x + a) = exp [ik(x + a)] uix + a) = 1p(x) exp (ika)

since uk(x -+- a) = uk(x). In other words, Bloch functions have the
property that
1p(x + a) = Q1p(x) where Q = exp (±ika) (10-5)
2 F. Bloch, Z. Physik, 52, 555 (1928).

i j
Sec. 10-2] BAND THEORY OF SOLIDS 241
It will be evident that if we can show that the Schrodinger equation (10-3)
has solutions with the property (10-5), the solutions can be written as
.Bloch functions and the theorem is proved. This will now be done. 3
Suppose g(x) and f(x) are two real independent solutions of the
Schrodinger equation. Now a differential equation of the second order has
only two independent solutiorfs, and all other solutions are expressible as a
lin~ar combination of the independent ones. Then, since j(x a) and +
g(x + a) are also solutions of the Schrodinger equation, we must have the
relations
f(x + a) = ocd(x) + oc~(x)
( 10-6)
g(x + a) = PI/(x) + P~(x)
where the oc's and P's are real functions of E. The solution of the Schrl"i-
dinger equation may be written in the form
) .
1p(x) = Af(x) + Bg(x) I

where A and B are arbitrary constants. According to (10-6) we must have

+."
In view of what has been said above about the property (10-5) of the
Bloch functions, let us choose A and B such that , . , '.. ,,"" ":.IIi'

AocI + B{JI = QA
( 10-7)
Aoc 2 + BP2 = QB
where Q is a constant. In this way we have obtained a function 1p(x) with
the property
1p(x + a) = Q1p(x) (10-8)
Since equations (10-7) have nonvanishing solutions for A and B only if
the determinant of their coefficients vanishes, we have the following
equation for Q:

or (10-9)
Now, one can show that OC I {J2 - OC 2PI = 1 in the following manner:
from equations (10-6) one can derive that

f(X + a) g(x + a) 1 If(X) g(x) I lOCI oc 2 \ ( 10-10)

I
F(x -1- a) g'(x + a) = f'(x) g'(x) If1I f12
3 See H. A. Kramers, Physica, 2,483 (1935); F. Seitz, The Modem Theory of Solids,

McGraw-Hili, New York, 1940, p. 279; N. F. Mott and H, Jones, Theory of the Pro-
perties of Metals and Alloys, Oxford, New York, 1936, p. 57; A. H. Wilson, TheOl~v ol
... Metals, 2d ed., Cambridge, London, 1953, p. 21.
242 BAND THEORY OF SOLIDS [Chap. 10
where f' = djJdx, etc. If we multiply the Schrodinger equation
for g(x) by I(x) and the equation for I(x) by g(x), we find upon
subtracting, \
!
o = Ig" - gf" = (d/dx)(fg' - gf') ,

Hence the so-called Wronskian is in this case a constant: \

f(X) g(x) I
= constant
.-~
If'(x) g'(x)

This result, together with equation (10-10), leads to the conclusion that
'l.d12 - oc 2f31 = 1. Instead of (10-9) we may therefore write.

(10-11 )
\
where we should remember that (oc l +
132) is a real function of E. In
general then, there are two roots Ql and Q2' i.e., there are two functions
If'l(X) and 1J'2(X) which exhibit the property (10-8). Note that the product
QIQ2 = I. For certain ranges of energy E, viz., for those corresponding
to (OCt+ 132)2 < 4, the two roots will be complex, and since QlQ2 = 1
they will be conjugates. In those regions df energy we may then write

(10-12)

The corresponding functions 1J'l(X) and 1J'2(X) then have the property

and thus are Bloch functions (see 10-5). In other regions of the energy E,
viz., those corresponding to (oc l + 132)2 > 4, the two roots Ql and Q2 are
real and the reciprocals of each other. These roots correspond to
solutions of the Schrodinger equation of the type

"~heX) = e"l'u(x) and 1J'2(X) = e~!'l'u(x) --------------~

where f.l is a real quantity. Although such solutions are mathematically

sound, they cannot in general be accepted as wave functions describing
electrons, since they are not bounded. Thus there are no electronic
states in the energy region corresponding to real roots Ql and Q2' The
above discussion thus leads also to the notion that the energy spectrum of
an electron in a periodic potential consists of allowed and forbidden
energy regions or bands. This will be illustrated further in the next
section where we consider the motion of electrons in a particularly
simple one-dimensional periodic potentiaL

','
Sec. 10-3] BAND THEORY OF SOLIDS 243

10-3. The Kronig-Penney model

The essential features of the behavior of electrons in a periodic

potential may be illustrated with reference to a relatively simple one-
dimensional model first discussed by Kronig and Penney.4 It is assumed that
the potential energy of an electron has '
the form ofa periodic array of square wells,
as indicated in Fig. 10-1. The period of the
potential is (a +b); in regions Jiuch as
o < x < a the potential energy is assumed
equal to zero, in regions such as -b < x < 0 \
the potential energy is Vo. Each of the -b 0 a
_x
potential energy wells may be considered a
rough approximation for the potential in Fig. 10-1. One-dimensional
the vicinity of an atom. The Schrodinger Kronig-Penney potential.
equations for the two regions are
(10-14)
li21p/dx2 + (2m/1i2)(E - Vo)1p = 0 for -b < x < 0 (10-15)
We shall assume that the energy E of the electrons under consideration
is tmaller than Vo. Defining two real quantities 'Y.. and f3 by
I :x 2 = 2mE/1i2 and f32 = 2m(Vo - E)/1i2 (10-16)
and making use of the fact that the solutions must be Bloch functions of
the form eik.T uk(x), one obtains upon substitution into (10-14) and (10-15)
the following equations for uk(x):
+
d 2u/dx2 2ik(du/dx) +(oc 2 - P) U = 0 O<x<a (10-17)
d u/dx2
2
+ 2ik(du/dx) - (f32 + k 2) U = 0 -b < x < 0 ( 10-18)
The solutions of these equations are
u1 = Ae i (oc-k)2' -t- Be-i(x-l-k)I O<x<a
(10-19)
u
2
= Ce(P-ik)x + De-(fJtil')I -b<x<O
where A, B, C, and D are constants. These constants must be chosen in
such a manner that the following f!Sur conditions are satisfied:
u1(0) = u 2(O), u1(a) = u2(-b)
( 10-20)
(dUl/dx)x~o = (dU2/dx)x~o' (du1/dx)" = (du 2 /dx) "
, R. de L. Kronig and W. G. Penney, Proc. Roy. Soc. (London), ABO, 499 (1930);
see for an extension of this work D. S. Saxon and R. A. Hutner, Philips Research Repts.,
4,81 (1949); J. M. Luttinger, Philips Research Repts., 6, 303 (1951); G. Allen, Phys.
Rev., 91, 531 (1953). The case Vex) ~- A sin x has been discussed by Morse, Phys. Rev.,
35, 1310 (1930). For another calculable one-dimensional case see J. C. Slater, Phys.
Rev., 87, 807 (1952).
244 BAND THEORY OF SOLIDS [Chap. 10

The two conditions on the left are imposed because of the requirement of
continuity of the wave functions and of their derivatives; the two on the
right are required because of the periodicity of uk(x). It is evident that
application of (10-20) on (10-19) leads to four linear homogeneous
equations in the constants A, B, C, D; thus the wave functions may be
calculated. However, for our purpose we are more interested in determining
the values of the energy for which satisfactory solutions are obtained. The
four equations just mentioned have a solution only if the determinant of
the coefficients of A, B, e, D vanishes. It can be shown that this leads to
the following condition:
p-~ . .
'-----:-,- sinh flh sin xa
2xt)
+- cosh ph cos xa = cos k(a + b) (10-21)

To obtain a more convenient equation, Kronig and Penney consider the

case for which the potential barriers become delta functions. i.e .• Vo tends

aap SID. aa +cos aa

Fig. 10-2. The left hand side of (10-24) for P = 31T/2, plotted as
function of IXa. The allowed regions are heavily drawn. . \

to infinity and b approaches zero, but the product Vob remains finite. Under
these circumstances (10-2 J) reduces to
(m Vob/h 2 x) sin xa +- cos xa = cos ka iL (10-22)
Let us now define the quantity
P = m V oba/1i2 ( 10-23)
which is evidently a measure for the "area" Vob of the potential barrier.
In other words, increasing P has the physical meaning of binding a
given electron more strongly to a particular potential well. From the last
two equations we find that solutions for the wave functions exist only if
sin oca
P --
rxa
+- cos ,xa = cos ka • (10-24)

As an example, we have represented in Fig. 10-2 the left-hand side of this

Sec. 10-3] - BAND THEORY OF SOLIDS 245
equation as function of oca for the value P = 37Tj2. The reader is reminded
that ex2 is proportional to the energy E, i.e., the abcissa is a measure for the
energy. Furthermore, it is important to realize that the right-hand side
+
can accept only values between - I and I, as indicated by the horizontal
lines in Fig. 10-2. Therefore the condition (10-24) can be satisfied only for
values of exa for which the left-hand side lies between ± I.
From the figure, the following interesting conclusions may be drawn:
(a) The energy spectrum of the electrons consists of a number of
allowed energy banQs separated by forbidden regions.
(b) The width of the allowed energy bands increases with in-
creasing values of exa, i.e., with increasing energy; this is a consequence
of the fact that the first term of (10-24)
E
decreases on the average with increasing cxa.
(c) The width of a particular allowed band
decreases with increasing P, i.e., with increasing
"binding energy" of the electrons. In the extreme
case for which P--+ 00, the allowed regions become
infinitely narrow and the energy spectrum be-
comes a line spectrum. In that case, (10-24) has
only solutions if sin exa = 0, i.e., if exa = ±n7T
with n = 1, 2, 3,... According to this and (l0-16),
the energy spectrum is then given by o o
P/47r +- -+ 47r/P

Fig. 10-3. Allowed and

forbidden energy ranges
which one recognizes as the energy levels of a (shaded and open respec-
particle in a constant potential box of atomic tively) as function of P.
dimensions (see Appendix B). Physically, this The extreme left corre-
sponds to P = 0 (free elec-
could be expected because for large P, trons), the extreme right
tunneling through the barriers becomes im- to P = oc.
probable.
These conclusions are summarized in Fig. 10-3, where the energy
spectrum is given as function of P. For P = 0, we simply have the free
electron model and the energy spectrum is (quasi) continuous; for P = 00,
a line spectrum results as discussed under (c) above. For a given value of P
the position and width of the allowed and forbidden bands are obtained by
erecting a vertical line; the shaded areas correspond to allowed bands.
From (10-24) it is possible also to obtain the energy E as function of the
wave number k; the result is represented in Fig. 10-4a. This leads us to the
conclusion that
(d) The discontinuities in the'I'E' Jersus k curve occur for

k = n7Tja n = 1,2,3, ... ;·~ola f; hi,' (10-26)

•
246 BAND THEORY OF SOLIDS (Chap. 10
These k-values define the boundaries of the first, second, etc. Brillouin
zones. It must be noted that Fig. 1O-4a- gives only half of the complete E(k)
curve; thus the first zone extends from --7T/a to +1T/a. Similarly, the
second zone consists of two parts; one extending from 7T/a to 21T/a, as
shown, and another part extending between --1T/a and -21T/a.
A further important conclusion may be drawn from (10-24):
(e) Within a given energy band, the energy is a periodic function of k.
For example, if one replaces k by k + 27Tn/a, where n is an integer, the
right-hand side of (10-24) remains the same. In other words, k is not

15

10

5
I
00

vi
I
I

:
I
'(
," rh~ ':r;
I I
I

-7r /a 7r/a - k
1st 2nd 3rd
(al (bl

Fig. 10-4. In (a) the energy is represented as function of k for

P = 3Tr/2; the Brillouin zones are indicated (note that this is only
half the picture), In (b), E is plotted versus the reduced wave
vector.

uniquely determined. It is therefore frequently convenient to introduce the

"reduced wave vector" which is limited to the region
--~---- --
-7T/a ~ k ~ 7T/a (to-27)
,
The energy versus reduced wave vector is represented in Fig. 10-4b. It may
be noted here that the fact that k is not uniquely determined also follows
quite generally from the form of the Bloch function (10-8). Consider the
function eik,ruk(x) and introduce a new wave vector V - k 21Tn/a, +
where n is an integer. One may then write
(10-28)
It will be noted that uk.(x) is also periodic with the lattice so that (10-28)
is just as good a Bloch function as the initial function eik.ruk(x).
Sec. 10-3] BAND THEORY OF SOLIDS 247
The number ofpossible wave functions per band. So far, we have assumed
the crystal to be infinite, but it will now be necessary to investigate the
consequences of imposing boundary conditions. Since we have employed
the running wave picture, it will be convenient to use cyclic or periodic
boundary conditions (see Sec. 2-9 for the same problem in the theory of
elastic waves in a chain of atoms). For a linear crystal of length L the
boundary condition may be taken as
tp(X + L) = tp(x) (10-29)
Strictly speaking, this applies to a circular lattice, 4>ut it may also be
imposed on a linear lattice of macroscopic dimensions, as explained in
Sec. 2-9. Making use of the fact that we are dealing with Bloch functions,
this requires
eik(H L)Uk(X + L) = ei!-Xuk(x)

Because of the periodicity of Uk' we have uk(x + L) = uk(x), and the

boundary conditions thus require
k = 2-rrn1L with n = ±l, ±2, ... (10-30)
The number of possible wave functions (or k-values) in the range dk is
therefore
dn = L dkl2-rr (10-31)
Since k is limited in accordance with (10-26), it follows that the maximum
value of n in (10-30) is LI2a = N12, where N is the number of unit cells.
This leads to a very important conclusion:
(f) The total number of possible wave functions in any energy band is
equal to the number of unit cells N.
Now, as a result of the spin of the electrons and the Pauli exclusion
principle each wave function can be "occupied" by at most two electrons. 5
Thus each energy band provides place for a maximum number of electrons
equal to twice the number of unit cells. In other words, if there are 2N
electrons in a band, the band is completely filled. This conclusion, as we
shall see below, has far-reaching consequences for the distinction between
metals, insulators, and semiconductors.

10-4. The motion of electrons in one dimension according to the band theory

The Kronig-Penney model is evidently an oversimplification of the

actual potential encountered in real crystals. However, before we discuss
the results obtained for more realistic models, it will be useful to consider
the consequences of the conclusions reached so far for the motion of
electrons in the band theory. First of all, let us consider the velocity of an
electron described by a wave vector k. From the wavemechanical theory
S See Appendix C.
248 BAND THEORY OF SOLIDS [Chap. 10
of particles it follows that the particle velocity is equa'I to the group
velocity of the waves representing the particle,6 i.e.,

v = dw/dk (10-32)
\
Here w is the angular freq uency of the de Broglie waves; it is related to the
energy of the particle by the relation E = nu). Thus instead of (10-32),
one may write in general for the velocity of the particle,

D = n-l(dE/dk) (10-33)
E
This in itself shows the importance of the E
versus k curves. In the case of free electrons
E = n2k2j2m, and (10-33) simply leads to the
(a)
identity r = nk/m = p/m. In the band theory,
however, E is in general not proportional to k 2 ,
as may be seen from Fig. 10-4. Employing an
E(k) curve such as represented in Fig. 10-5a, one
(h) obtains, according to (10-33) for the velocity as
function of k, a curve of the type illustrated in
Fig. 10-5b. (Note that for free electrons v is
proportional to k.) At the top and bottom of
the energy band l' = 0, because from the peri-
(e)
odicity of the E(k) curves it follows that there
dE/dk = O. The absolute value of the velocity
reaches a maximum for k = ko, where ko cor-
respoJl\ls to the inflection point of the E(k) curve.
It is of importance to note that beyond this point
the velocity decreases with increasing energy, a
feature which is altogether different from the
behavior of free electrons.

The ejfectil:e mass of an electron. Let us now

consider what happens to an electron when an
external electric field F is applied. 7 It will be
assumed that the Brillouin zone under considera-
_k
tion contains only one electron, so that the
Fig. 10-5. Energy, velo- Pauli exclusion principle does not enter. Sup-
city, effective mass and pose the electron is initially in a state k. When
.I~ as function of k. The
dashed lines correspond to
the field has acted on the electron for a small
the inflection points in the time dt, it has gained an energy
E(k) curve.
dE = eFt' dt = (eF/Ii)(dE/dk)dt (10-34)
• See, for example, M. Born, Atolllic PhYSics, 5th ed., Hafner, New York, 1951.
, To avoid confusion with the energy, the electric field will be represented by F.
Sec. 10-4] BAND THEORY OF SOLIDS 249
where we used (10-33).8 Now dE = (dE/dk) dk so that as a result of the
applied field, the rate of change of the wave vector is given by
dk/dt = eF/1l (10-35)
To obtain the acceleration of the electron, differentiate (10-33) with
respect to t; this gives
, ,) ..,..' F- _,_ ~ I

a = dc/dt = (l/Il)(d E/dk 2)(dk/dt)

2 (10-36)
From the last two equations it follows that
a = (eF/1l2)(d 2E/dk2) (10-37)
It is illustrative to compare this result with the acceleration of a free electron
of mass m,
a = eF/m
From the last two expressions it follows that the electron behaves as if it
had an effective mass m* equal to (
( 10-38)
Thus the effective mass is determined by d 2E/dk 2 ; this result indicates
once more the importance of the E(k) curves for the motion of the electrons.
In Fig. 10-5c the effective mass is represented as a function of k; this
curve shows the interesting feature that m* is positive in the lower half of
the energy band and negative in the upper half. At the inflection points in
the E(k) curves, m* becomes infinite. Physically speaking, this means
that in the upper half of the band the electron behaves as a positively
charged particle, as will be explained further in Sec. 10-6. One arrives at
the same conclusion by considering the v(k) curve and making use of
(10-35). Suppose an electron starts at k = 0; when an electric field is
applied, the wave vector increases linearly with time. Until the velocity
reaches its maximum value, the electron is accelerated by the field;
beyond the maximum, however, the same field produces a decrease in v,
i.e., the mass must become negative in the upper part of the band.
It is frequently convenient to introduce a factor

( 10-39)

where j~ is a measure for the extent to which an electron in state k is "free."

If m* is large, h is small, i.e., the particle behaves as a "heavy" particle.
When h = I, the electron behaves as a free electron. Note that fk is
positive in the lower half of the band and negative in the upper half, as
shown in Fig. IO-5d.
8 Throughout this section, only the influence of the external field on the motion of the

electron will be discussed. Actually, the electron also interacts with lattice vibrations,
leading to resistivity. The problem of reSistivity is discussed in Chapter II.
\.
250 BAND THEORY OF SOLIDS [Chap. 10

It may be mentioned here that when the above treatment is extended to

three dimensions, the effective m~ss may be represented by

l/m* = O/h2) grad" grad" E(k)

\
where grad" grad" E(k) is a tensor with nine components of the general
form eJ2E/ok; ok; with i, j = x, y, Z.9

10-5. The distinction between metals, insulators, and intrinsic semiconductors

Although a proper distinction between these three groups of materials

is possible only by considering the results of a three-dimensional periodic
potential, it is instructive at this point
E to indicate how the band theory leads
naturally to the possibility of such a
distinction. To see this, let us con-
sider a particular energy band which
we shall assume to be filled with
electrons upto a certain value kl' as
- t r fa
tr fa k indicated in Fig. 10-6. As far as the
influence of an external electric field
Fig. 10-6. Energy band filled up to
is concerned one would like to know
states k, at T = o. with how many "free" electrons the N
electrons in the band are equivalent.
Presumably, once we knew the answer to this question, it would be
possible to draw conclusions about the conductivity associated with this
band. The effective number of "free" electrons in the band is in accordance "V
with the preceding section equal to "

(10-40)
I

where the summation extends over all occupied states in the band. Now,
according to (10-31) the number of states in an interval dk (excluding the
spin) for a one-dimensional lattice of length L is equal to L dlt/27T.
Because two electrons occupy each of these states in the shaded region of
Fig. 10-6, one may write instead of (10-40),

where we used (10-39). Thus the effective number of electrons in the band is

(10-41)

9 See, for example, F. Seitz, op. cit., p. 316.

;
,"
Sec. 10-5] BAND THEORY OF SOLIDS 251
From this result we draw the following conclusions:
(i) The effective number of electrons in a completely filled band
vanishes, because dE/dk vanishes at the top of the band.
(ii) The effective number of electrons reaches a maximum for a band
filled to the inflection point of the E(k) curve, because then dE/dk
is a maximum.

From the above discussion it follows that a solid for which a certain
number of energy bands are completely filled, the other bands being

?Z4V2ZZZZT/2l2Z/
Insulator Semiconductor Metal
(al (bl (el
i: '\
Fig. 10-7.Electron distribution at T = 0 in an insulator, intrinsic
semiconductor, and metal. The shaded regions are occupied by
electrons.

completely eJ11pty, is an insulator (see Fig. 10-7a). On the other hand, a

solid containing an energy band which is incompletely filled has metallic
character (Fig. 10-7c). It will be evident that the situation depicted by
v'. Fig. 10-7a can occur actually only at absolute zero, when the crystal is in
its lowest energy state. At temperatures different from zero, some electrons
from the upper filled band will be excited into the next empty band
("conduction band") and conduction becomes possible. If the forbidden
energy gap is of the order of several electron volts, however, the solid will
remain an "insulator" for all practical purposes. An example is diamond,
for which the forbidden gap is about 7 ev. For a small gap width, say
about I ev, the number of thermally excited electrons may become
appreciable and in this case one speaks of an intrinsic semiconductor.
Examples are germanium and silicon. It is evident that the distinction
between insulators and intrinsic semiconductors is only a quantitative one.
In fact, all intrinsic semiconductors are insulators at T = 0, whereas all
insulators may be considered semiconductors at T> O. It may be noted
here that the conductivity of semiconductors in general increases with
increasing temperature, whereas the conductivity of metals decreases with
increasing temperature. The properties of these materials will be further
discussed in later chapters. ~l :t,
252 BAND THEORY OF SOLIDS [Chap. 10
It must be noted that three-dimensional models allow" the possibility of
overlapping of bands (see Sec. 10-9); i.e., a solid which in the one-
dimensional mpdel should be an insulator may turn out to be a metal;
the divalent metals are an example in point, as we shall see later.

\
10-6. The concept of a "hole"

It has just been mentioned that in an intrinsic semiconductor at

temperatures different from zero, a certain numb~r of electrons may be
excited thermally from the upper filled band into the conduction band.
Thus some of the states in the normally filled band are unoccupied. We
shall see in the next chapter that these unoccupied states lie essentially
. near the top of the filled band. For the moment, let us consider a single
"hole" in the filled band of a one-dimensional lattice and consider its
influence on the collective behavior of this band when an external electric
field is applied. Denoting the charge of an electron by -e and the velocities
of the electrons by Vi' we may write for the current associated with all
electrons in a completely filled band in the absence of an external field,

1= -e ~
1
Vi = -e [Vj + '*)
.2:. Vi] = 0 (10-42)

Thus if the electron.i were missing, we should have

l' = -":_e '"
.~. v·t = ev·)
(10-43)
I rJ

Applying an external field F, the rate of change of the current l' due to the
field is
,. dl'ldt = e(dvjldt} = -e2 Flmj (10-44)
Now, since holes tend to reside in the upper part of a nearly filled band,
mj· is negative and the right-hand side of (10-44) becomes positive. In
other words, a band in which an electron is plissing behaves as a "positive
hole" with an effective mass Im·l.
This concept is of great importance in
the theory of conductivity and Hall effect as 'we shall see later. It explains,
for example, why certain materials show a positive rather than a negative
Hall coefficient (free electrons give a negative Hall coefficient}V

10-7. Motion of electrons in a-three-dimensionallattice

So far, the discussion has been limited to a simple one-dimensional

periodic potential. We shall now consider the motion of electrons in a
three-dimensional lattice from a general point of view. The results are
very similar, though more complicated, to those for the Kronig-Penney
ll1odel.
The most fundamental property of an infinite crystal with primitive
Sec. 10-7] BAND THEORY OF SOLIDS 253
translation vectors a 1 • a 2 • a 3 , is that if we make a translation corresponding
to any vector,
( 10-45)

where d1 , d 2 , d3 • are integers, we arrive at a point that is geometrically

equivalent to the point we started from. Thus the physical properties
remain unchanged when we make a translation defined by any vector of
the type d. For example, if the potential energy of an electron is given by
VCr), we must have
Vel') = vel' +d) (10-46)

Vectors such as d are called direct lattice vectors; the adjective "direct" is
included to distinguish such vectors from the "reciprocal" lattice vectors
to be introduced below. In order to di,scuss the behavior of an electron in
a periodic potential it will be convenient to consider first how one represents
periodic functions such. as (10-46) in terms of three-dimensional Fourier
series. For a one-dimensional periodic potential which satisfies the
condition
Vex) = Vex + d1a) where d1 = integer

one may of course always write

Vex) = L Vg exp (27Tigx/a) g = integer (10-47)

, "
where the summation extends over all integers from --00 to +00; the
coefficients Vq are the Fourier coefficients. That this series indeed satisfies
the periodicity requirement may readily be shown as follows. Replacing x
in (10-47) by x + d1a, where d1 is an integer, we obtain i

However, since gd1 is an integer, exp (27Tid1g) = 1 and the right-hand

side of this expression equals Vex).
Similarly, the potential in a cubic lattice satisfies the requirement

(10-48)

where d1 , d 2 , d 3 are integers. The reader may readily verify that V(x,y,z)
may be written in the form of the following three-dimensional Fourier
series.

Returning now to the general three-dimensional lattice for which the

primitive translations aI' 02' a 3 are not necessarily equal in magnitude, nor
perpendicular to each other, it is not immediately obvious how one
254 BAND THEORY OF SOLIDS [Chap. 10

represents a potential with the periodicity (l0-46) in terms of a three-

dimensional Fourier series. It can be done rather easily, however, if we
introduce the so-called reciprocal lattice. The reciprocal lattice is defined
by three primitive translations b I , b 2 , b 3 which satisfy the conditions

I if i = j \
bj = = 0 if i =1= j
(l0-50)
°i 0 °ij {

Thus the vector bi is perpendicular to the plane through the direct lattice
vectors 02 and 03' The explicit expressions for the b's are evidently of the
form
(l0-51)

from which the absolute magnitudes of the b's may be obtained in terms
of the primitive translations of the direct lattice. Any vector

(l0-52)

is called a reciprocal lattice vector. The end points of these vectors

define the reciprocal lattice points. The reader may show himself that the
reciprocal lattice of an f.c.c. lattice is b.c.c. and vice versa. IO
We shall now show that the three-dimensional Fourier series,

V(r) = ~ Vn exp (27Tin r) 0 (l0-53)

n

exhibits the periodicity requirement (10-46).n The symbol Vn stands for

VII I" ,11. and the summation extends over all integers nI , n 2, n3 from -00
to +00. The proof is as follows. Applying to (l0-53) a translation over a
direct lattice vector d, we obtain

V(r + d) = ~
n
Vn exp [27Ti(rno r + nod)]
However, nod according to (10-45), (10-50), and (10-52) is equal to nIdI +
n 2d 2+ n 3 d 3 , which is an integer. Hence the right-hand side of the last
expression is equal to V(r), which proves the statement.
Since we now have a method for representing periodic functions in
three dimensions in terms of Fourier series, let us consider some of the
general features of the motion of electrons in a potential of three-
dimensional periodicity. First of all, the Bloch theorem concerning the
form of the wave functions, discussed for the one-dimensional case in Sec.
10 For other properties of the reciprocal lattice, see, for example, Brillouin's book

quoted at the end of this chapter.

11 Some authors define the reciprocal lattice by means of the relations a i bi = 27T15ij;
0

with this definition the factor 27T in the exponential of (10-53) is absent.
Sec. 10-7] BAND THEORY OF SOLIDS 255
10-2, may be extended to three dimensions. The result is that the wave
functions are, in analogy with (10-4), of the type )Ci :t!,! ,,1

.\ (10-54)

where uk(r) has the periodicity of the lattice. Hence, in general, we may
write
uk(r) = ~ en exp (27Tin • r) (10-55)
n

where n is a vector in the reciprocal lattice. In analogy with what has been
said in connection with equation (10-28), one can show that any two Bloch
functions for which the wave vectors differ by 27T times a reciprocal lattice
vector are physically equivalent. For example, let n be a reciprocal lattice
vector and let us introduce instead of k another wave vector k' = k 27Tn +
in (10.54). We may then write
'I/'(r) = e:1:ik"'e T2 "in"Uk(r) = e±·ik"rUk · (r)

where uk,(r) as defined by the above expression is still periodic because

exp (±27Tin • r) is periodic, i.e., we are still left with a Bloch function.
We can say also that k is not uniquely determined and that k and k + 27Tn
correspond to physically equivalent states. In order to avoid the occurrence
of physically equivalent solutions with different k-values, it is convenient
to restrict the range of k-values. This can be done most conveniently by
limiting the components k 1 , k 2 , ka of k along the directions of b l , b 2 , b 3 to
the ranges
-7Tbl ~ kl ~ 7Tbl
-7Tb 2 ~ k2 ~ 7Tb 2 (10-56)
-7Tb 3 ~ ka ~ 7Tb 3

In this case we refer to k as the reduced wave vector; the region of k-space
defined by (10-56) is referred to as the first Brillouin zone or reduced zone.
As in the Kronig-Penney model, a given reduced wave vector k
corresponds to a set of energy values E1(k), E 2(k), ... , where the subscripts
refer to a particular energy band. Within each energy band the k-values
are restricted in accordance with (10-56). We shall now show that for a
finite crystal the number of possible reduced k-values within a single energy
band is equal to the number of unit cells contained in the crystal. This
statement is the analogue of conclusion (f) in Sec. 10-3 for the Kronig-
Penney model. Consider a crystal in the form of a parallelepiped with
edges N10 1 , N 20 2 , N 30 3 , where N 1 , N 2 , N3 are large integers. Employing
cyclic boundary conditions (compare 10-29), the wave functions should
satisfy the condition
( 10-57)
256 BAND THEORY OF SOLIDS [Chap. 10
Since lp(r) is a Bloch function of the type (10-54), for which uir) is periodic
with the lattice, this condition is equivalent with the requirement

k . (NIa l +N 2a 2 +N a 3 3) = 2rr times an integ!!r (10-58)

This implies that the possible k-values are given by \
k = 2rr[(n1/NI )b1 + (n 2 /N 2 )b 2 + (n3/N3)b31 (10-59)
where nl , n 2 , n3 are integers, since upon substituting this expression for k
into (10-58) the left-hand side of (10-58) reduces to 2rr(n1 n2 + n3); +
any k-value chosen not in accordance with (10-59) does not satisfy (10-58).
Now the components of k along the reciprocal lattice vector directions are
restricted in accordance with (10-56). From this and frol)l (10-59) it thus
follows that n 1 , n 2 , and n3 can accept a total of, respectively, N 1 , N 2 , N3
different values. In other words, the total number of k-values within an
energy band is given by the product N 1 N 2 N 3 , which is equal to the number
of unit cells in the crystal. Each k-value corresponds to one wave function
if we exclude the two possible spin directions; including the spin, the number
of possible electronic states within an energy band is therefore equal to
twice the number of unit cells in the crystal. The result obtained here may
be expressed also in the following way. Consider a crystal of unit volume,
the volume of the unit cell being a1 • (a 2 X a 3 ) = 0. The crystal then
contains N = 1/0 unit cells. We leave it to the reader as a problem to
show that the volume of a unit cell in the reciprocal lattice is given by
b I • (b 2 X b 3 ) = N. Since the whole reduced zone contains N possible
k-values, and since these values are uniformly distributed in the k-space,
the number of electronic states dn .. corresponding to a volume element
dO,. in k-space is, per unit volume of the crystal, 1· ."
dns = (2/8rr3 ) dO,. . (10-60)
The factor 2 arises from the spin. The quantity dns is referred to as the
density of states corresponding to the Hement dO" in k-space. In
subsequent discussions it will frequently be desirable to introduce the
number of states per unit volume of the crystal per unit energy interval.
Thus, consider in the k-space two surfaces of constant energy, one of E,
the other of E + dE. The volume element dD,. in k-space corresponding
to a differential area dS and bounded by the constant energy surfaces, is
then given by
dO,. = dS[lgrad,. E(k)IJ-I dE :rH

so that the density of states per unit energy interval is given by

, dS
dns/dE = (2/81T
3
) JIgrad"E(k) I • 1
(10-61)

where the integral extends over the whole area of the constant energy planes.
Sec. 10-8] BAND THEORY OF SOLIDS 257

10-8. The tightly bound electron approximation

As an example of evaluating the energy levels for an electron in a solid,
we shall discuss one particular approximation in some detail, viz., the
tightly bound electron approximation. In this approximation one starts
from the wave function for an electron in a free atom and then constructs a
crystal orbital, i.e., a Bloch function, which describes the electron in the
periodic field of crystal as a whole. This method is abbreviated LCAO,
since it is based on a linear combination of atomic orbitals. We shall see
that the discrete electron levels corresponding to a free atom will broaden

..
into energy bands as the atoms are brought together in the form of a
crystal. The approximation used .,..:' ~.

here is valid only for electrons cor-

Atom
responding to the inner electronic
shells in the atoms, as will become
clear below from the assumptions
r
that will be introduced. ... , /
...
I
Consider first an electron in a /
. / .
free atom. Suppose the potential a
I

energy of the electron in the field

_r
of the nucleus plus that of the other
electrons in the atom is given by
Fig. 10-8. Schematic representation of
Va( r), where r represents the distance the potential energy of an electron in an
from the nucleus. The potential has atom (fully drawn) and in a solid
a form as indicated by the fully (dashed curve).
drawn curve in Fig. 10-8. Let the
wave function of the electron in the free atom be cp(r) and let its energy
be Eo. . The wave function then satisfies the Schrodinger equation,
-(/i 2 j2m)V2cp + Va(r)rfo = Eo )'''flAM lC·i.s (10-62)

We 'shall assume that the level is nondegenerate, i.e., there is only one
wave function corresponding to Eo. Furthermore, we shall assume that
the wave functions are normalized. Suppose then that similar atoms are
brought together in the form of a crystal. The potential energy of the
electron in the crystal then looks like the dashed curve in Fig. 10-8; the
potential energy in this case will be represented by VCr), where V(r) has the
periodicity of the lattice. Taking a particular atom as the origin of our
coordinate system, the position of any atom may then be represented by a
vector R; where R; is a lattice vector. In the tightly bound electron
approximation it is assumed that the electron in the vicinity of a particu!.ar
nucleus j is only slightly influenced by the presence of other atoms, i.e.,
when the end point of the vector r lies in the vicinity of R j , the wave
function for the electron is approximately given by cp(r -- R j ) and the
258 BAND THEORY OF SOLIDS [Chap. 10
energy of the electron is still very close to the value Eo in the free atom.
Consequently, one calculates the energy of an electron with a wave vector k
in the crystal on the basis of a linear combination of the form

(10-63)

since this expression satisfies the approximation just mentioned: if

r lies close to R j all contributions in the sum will be small except that from
cjJ(r - R;). However, since we are dealing with an electron in a periodic
field, the wave function must be a Bloch function, and this restricts the
choice of the coefficients C j • lfin expression (10-63) we take the coefficient
clk) equal to exp (ik . R j ) we obtain

"Pk(r) = },: cjJ(r - R;} exp (ik • R;) (10-64)

:J

which indeed has the properties of a Bloch function. This can be seen by
applying a transformation corresponding to a lattice vector, say R "'.
This gives
"Pk(r +
Rm) =},: eik'RjcjJ [r - (R j - - Rm)]
.i
= i k ' Rm },: eik'(Rj-Rm)cjJ[r -- (R - R",)] j
.J

The sum in the last expression, however, is equal to "Pk(r), so that (10-64)
satisfies the characteristic property of a Bloch wave. We shall now calculate
the energy of an electron with wave vector k in the crystal, based on the
wave function (10-64). This can be done by starting from the expression
(10-65)

where :Yt' is the Hamilton operator for an electron in the crystal; the
denominator takes care of the proper normalization of the Bloch functions.
The denominator becomes
,I

.f1fJk"Pk d-r = },:) m},: eik ' (R r- R",) .fcp*(r - R ",)cjJ( r -- R j } d-r :) ~.i);;'P
.

Now cjJ(r - Rm} has appreciable y.alue only when the end point of the
vector r lies in the vicinity of atom m; similarly, cjJ(r - R;) has appreciable
value only in the vicinity of atom j. In other words, there is very little
overlap between the wave functions, even for nearest neighbors. To a
first approximation, therefore, we shall neglect all overlapping, so that of
the summation over j only the term j = m will be retained. Since we have
assumed that the atomic wave functions were normalized, we may then
write
J"Pk"Pk d-r = .2 J cjJ*(r - Rm)cjJ(r -. Rm) d-r = N (10-66)
In

where N is the total number of atoms in the crystal. Let us now consider
Sec. 10-8] BAND THEORY OF SOLIDS 259
the numerator of (10-65). The Hamiltonian of an electron in the crystal
may be written
£' = -(/i 2j2m)V2 + VCr) = -Wj2m)V2 + VCr) - Va(r -- R j )
+ Vir - R j) = -(/i2j2m)V2 + V'(r - R j ) + V" (r - Rj)
(10-67)
where we have introduced the quantity

1<, ,
V'(r - R;) = VCr) - Va (r - R;) ( 10-68)
The reason for this will become obvious below. The physical meaning
of V'(r - R j ) is that it represents the potential energy of the electron in the
crystal at the point r, minus the potential energy of the electron in the same
point if there were only a single atom, viz., the one located at R j • In other
words, V'(r - R j ) represents the potential energy of the electron in point r
resulting from the presence of all atoms excl!pt the one located at R j . It is,
in a sense, a perturbation potential. According to Fig. 10-8, V'(r - R j )
is a negative quantity. Substituting the Hamilton operator (10-67) into
(10-65), making use of (10-66), and realizing that
-Wj2m)V2cp(r - R j) + Va(r - Rj)cp(r - R j) = Eo q,(r - Rj )
where Eo is the energy of the electron in the free atom, we obtain njl,!

E(k) = (ljN) L L eik'(Rj-Rm)S cp*(r - Rm)[EO + V'(r - Rj)]cp(r - Rj) dT

j 'In

First consider the term containing Eo. Since the overlapping is small
anyway, we may neglect in the summation over m all terms except m = j.
Thus the term containing Eo' becomes " ,

(ljN) L Scp*(r - Rj)Eocp(r - R j) dT = Eo

j

In the term containing the "perturbing" potential V'(r - R;) we shall

neglect all overlap except for wave functions cp corresponding to nearest
neighbors. Furthermore, we shall assume that the atomic wave functions cp
are spherically symmetric, which would be the case if they corresponded to
s functions. Defining two positive quantities IX and y such that
IX = -Jcp*(r - Rj)V'(r - R;) cp(r - R j) dT (10-69)
Ul:ju,r.J. Y = -S cp* (r - Rm)V'(r - Rj)cp(r - R j) dT (10-70)
where the vector Rm is understood to correspond to the location of one of
the nearest neighbors of atom j, we may finally write
E(k) = Eo - IX -- Y~ eik'(Rj-R m ) (10-71)
m
where the summation extends over nearest neighbors of atom j only.
Note that IX and yare positive because V'(r - R;) is negative. It is
260 BAND THEORY OF SOLIDS [Chap. 10
observed that the energy of the electron in the crystal differs from the
energy of the electron in the free atom by a constant factor ex: plus a term
which depends on the wave vector k. It is this last part which transforms
the discrete atomic level into an energy band in the solid. In order to see
this more clearly, we shall apply this result to the case of cubic crystals in
the next section.
Another important approximation is the'so-called nearly free electron
approximation. In this case it is assumed that the Fourier coefficients of
the periodic potential are small relative to the constant potential. This
approximation may therefore be expected to be applicable to the conduction
electrons in monovalent metals. The energy versus wave vector curves
obtained for a one-dimensional lattice on the basis of this approximation
resemble closely those given in Fig. 10-4 for the Kronig-Penney model.
_For a discussion of the nearly free electron approximation as well as
other approximations we refer the reader to the literature.

10-9. Application to a simple cubic lattice

In order to appreciate the consequences of the results obtained in the

preceding section we shall first apply expression (10-71) to a simple cubic
lattice. In this lattice a given atom has six nearest neighbors, located such
that
R j - Rm = (±a, 0, 0); (0, ± a, 0); (O,O,±a)
Evaluation of the sum in (10-71) then yields for the energy of an s electron
in the crystal
E(k) = Eo - ex: - 2)'(cos krra + cos k~a + cos kza)' (10-72)
From this we may draw a number of important conclusions. In the first
place it is observed that the part of E(k) which depends on the wave
vector k is periodic with k. In order for k to b1 uniquely determined we
should restrict the components to the regions -Tria < k", < Tria, etc. Since
the reciprocal of a simple cubic lattice of edge a is again a simple cubic
lattice with edge b = Jla, this conclusion is in agreement with the general
expressions (10-56); see also (10-27). The first Brillouin zone in this case is
evidently a cube of edge 2Trla in k-space, the origin of k-space being located
at the centre of the cube. Furthermore, since the cosine terms vary between
± I, the energy levels are contained within an energy band of a total width
12?" The bottom of the energy band is given by
Ebottom = Eo - ex: - 61'
and the top is given by

From the definition (10-70) of I' it follows that the width of the band
Sec. 10-9] BAND THEORY OF SOLIDS 261

increases as the overlap of the wave functions on neighboring atoms

increases. Thus the inner electronic levels of the free atoms give rise to
narrow bands in the solid; as one proceeds to the outer shells the corre-
sponding band widths in the solid increase. This conclusion is in agreement
with conclusion (c) in Sec. 10-3 derived from the Kronig-Penney model.
By way of illustration we have represented in Fig. 10-9 the formati'on of
energy bands for sodium according to Slater. 12

'""---~" o
,~i·-,_I;

E -.2

f
-.4

-.6

o 2 6 10 12
l _r i
Fig. 10·9. Formation of the 3s and 3p bands in sodium. The energy
E is plotted in Rydberg units as function of half the distance
between nearest neighbors (in atomic units). The dashed line cor-
responds to the actual metal. [After Slater, ref. ) 2]

The bottom of the band corresponds to

cos kxa = cos kya = cos kza = 1
i.e., to k = 0 in this case. As long as k is small, the cosine terms may be
expanded. Retaining only the first approximation of this expansion, one
obtains from (10-72)
E t::::::'. Eo - 0( - 6y + ya 2k 2 for small k (10-73)
+ +
where k 2 = k x ky 2 k z2 • It is observed that with reference to the bottom
of the band, the energy of the electron is proportional to k 2 , as in the case
of free electrons; the constant energy surfaces are then spheres. Thus in
this region the electrons may be considered free electrons with an effective
mass m* determined by
(10-74)
As the band width decreases (decreasing y), the effective mass of the
electrons near the bottom of the band increases. This is consistent with the
qualitative notion that strongly bound electrons do not move readily from
12 J. C. Slater, Phys. Rev., 45, 794 (1934); 49, 537 (1936).
262 BAND THEORY OF SOLIDS [Chap. 10
one atom to another; they have a high effective mass, and the acceleration
produced by an electric field will be relatively small.
The top of the band corresponds to cos kxa = cos k lla = cos kza = -1,
i.e., to kx' k ll , k z = ±TT/a. Thus the corner points of the reduced zone
correspond to states at the top of the band. In the vicinity of such a
corner point we may expand the cosines again; for example, if we expand
about the point kx = ky = k z = TT/a we may write cos kxa = COS(TT - k~a)
where the new component k: = TTla - k" is measured relative to the
ky

(a) (h)

Fig. 10-10. Schematic representation of constant-energy curves for

a two-dimensional square lattice: (a) for the tightly bound electron
approximation; (b) for the nearly free electron approximation.
corner point. For small values of k~ we then obtain COS(TT - k~a) =
-cos k~a = -1 + (k'xa)2/2. Hence near the top of the band, (10-72)
leads to
E -::::: Eo - ex +
6y - ya 2k' 2 (near top) (10-75)
Thus, relative to the top of the band, the electron energy is proportional
to k' 2, where the new wave vector k' is measured from the corner point of
the Brillouin zone. Constant-energy surfaces in this region are therefore
again spherical, but with the corner point as center . .ijy way ofiIlustration
we give in Fig. 10-JOa a schematic representation of constant-energy
surfaces in k-space for a two-dimensional square lattice, based on the
tightly bound electron approximation. In the nearly free electron approxi-
mation, the proportionality with k2 of the energy relative to the bottom of
the band extends to much larger values of the wave vector than in the
tightly bound approximation. Here again, however, constant energy
surfaces near the top of the band are spherical relative to corner points of
the reduced zone. This is illustrated for comparison in Fig. 10-lOb.
I t is left as a problem for the reader to discuss in a similar manner the
application of the tightly bound electron approximation to body-centered
and face-centered cubic lattices.
Sec. 10-10] BAND THEORY OF SOUDS 263
10-10. Brillouin zones; density of states; overlapping of energy bands
In order to understand the electronic properties of solids the following
topics need some discussion: I. the structure of the Brillouin zones,
2. the shape of constant-energy surfaces in k-space, 3. the density of
states as function of energy, 4. the possibility of overlapping of energy
bands. Some of these topics have already been discussed to some extent
above; in 'the present section we shall consider these topics somewhat
further. The discussion will mainly be concerned with simple cubic lattices.
The structure of Brillouin zones.
In the preceding section we had
arrived at the conclusion that the first p
Brillouin zone of a simple cubic lattice
is given by a cube of edge 2TT/a, where "

a is the lattice constant. Although for

many purposes only the first or re-
duced Brillouin zone is sufficient, it
is sometimes desirable to introduce
higher zones. The structure of the Bril- • o 1st zone
R ~ 2nd zone
louin zones may be obtained on the
lIID 3rd zone
basis of the general discussion of Sec.
10-7 involving the reciprocal lattice. Fig. 10-11. The first three Brillouin
Consider the set of vectors 2TT(n l b l zones for a square lattice of edge ·a.
+
+ n~b2 n 3 b 3 ), where nl , n 2, n3 are
integers and bl , b 2 , b 3 are the primitive translations of the reciprocal lattice.
The end points of the vectors so defined form a lattice which may be
considered an enlarged reciprocal lattice, the enlargement factor being 2TT.
In this lattice we shall represent the k-vectors, choosing a particular lattice
point as origin for the k-space. Suppose now we draw vectors from the
origin to all other lattice points and that we draw planes which bisect these
vectors perpendicularly. The smallest volume enclosed by these planes
is then the first Brillouin zone. That this is consistent with our previous
discussion may be seen from the definition of the first Brillouin zone
according to (l0-56). In order to illustrate the procedure with regard to
higher zones, consider the case of a square lattice in Fig. 10-11. The
lattice points of the "blown-up" reciprocal lattice are separated by a
distance 2TT/a, forming again a square lattice. The first Brillouin zone in
this case is a square of edge 2TT/a. The second Brillouin zone is defined
by the area between the smallest and next smallest area enclosed by the
lines bisecting the lattice vectors. Higher zones are obtained in a similar
way. The zone boundaries are determined by the equations
(10-76)
where n,r and n. are integers. The first Brillouin zone is enclosed by the
264 BAND THEORY OF SOLIDS [Chap. 10
four lines corresponding to nx = ± I, ny = 0 and nx = 0, n1l = ± 1.
The square PQRS in Fig. 10-11 is determined by four lines corresponding
to the four sets of integers n x, ny = ± 1, ± 1. The area between PQRS
and the first zone forms the second Brillouin zone. Note that the areas
of the zones are equal.
The extension of this procedure to the simple cubic lattice is relatively
easy. The zone boundaries are in this case in analogy with (10-76) given
by the solutions of the equation
n.,k", + nyky + nzkz = 7T(n; + n; + n;)/a (10-77)
or, written in vector notation.
n . k = 7Tn2/a (10-78)
At the zone boundaries, the energy exhibits a discontinuity as in the
one-dimensional case (see Fig. 10-4). It is of interest to note that the values
of the wave vector satisfying (10-78) are those for which the electron
suffers a Bragg reflection.13 We leave it as a problem to show that this is
the case. An electron which satisfies the Bragg condition cannot penetrate
the lattice, since it suffers reflections. Such an electron therefore does not
correspond to a wave propagating through the crystal, but to a standing
wave. The energy discontinuities or energy gaps occurring at the Brillouin
zone boundaries represent the energy ranges for which it is impossible
for an electron to move through the crystal. This is clearly borne out by the
fact that if such electrons are incident on the crystal from the outside,
they are totally reflected and unable to penetrate into the crystal. For
the structure of Brillouin zones for various crystal structures we refer the
reader to the literature. 14
The denSity of states as function of energy. The number of electronic
states per unit volume associated with a volume element dn k in the
k-space is, according to (10-60), equal to (2/87T3) dn k • The density of
states per unit energy interval is given by the general expression (10-61).
Let us now consider the consequences of this for a si91ple cubic lattice.
In order to simplify the problem, let us assume that tne constant-energy
surfaces are spheres or parts of spheres around the center of the first
Brillouin zone. This situation is approached in the nearly free electron
approximation (see Fig. 1O-lOb), although even there it does not hold
in the vicinity of the corner points of the zone. With this assumption we
have, as for free electrons, E(k) = /i 2k2/2m*. Since the density of states
correspoflding to wave vectors for which the absolute magnitude lies
between k and k + dk is given by (2/87T 3 )47Tk2 dk, we obtain for the
density of states Z(E) dE, corresponding to an energy interval dE
Z(E)dE=CE 1 / 2 dE with C=47T(2m*/h2)3/2 (10-79)
13 See, for example, N. F. Mott and H. Jones, op. cit., p. 64 .
.. See, for example, N. F. Mott and H. Jones, op. cit., Chap: 5.
1...../(./-1

Sec. 10-10] BAND THEORY OF SOLIDS 265

Hence Z(E) increases as El/2; also note that as the effective mass increases,
Z(E) increases. For narrow energy bands, therefore, Z(E) rises more
rapidly than for broad bands. For the example under consideration,
expression (10-79) will hold up to values of the wave vector equal to
k = Tria because for this k-value the spherical constant energy surface
just touches the Brillouin zone boundary. For larger values of k and E,
only the corners of the cube are available for electronic states, and (10-79)
can no longer be used. In fact, for k = (Trla)v3 the density of states
becomes zero. One thus obtains a Z(E) curve as represented schematically
in Fig. 10-12; the energy E1 corresponds to k = Tria.
Z(El Z(E)

Fig. 10-12. Schematic representa- Fig. 10-13. Schematic representa-

tion of the density of states versus tion of the density of states as
energy for a simple cubic lattice, function of energy in an energy band.
assuming spherical energy surfaces;
the energy E. = 1T'fr 2 /2m·a 2 •

Actually, the E(k) surfaces are spherical around the point k = 0

only in the vicinity of the bottom of the band, as may be seen from Fig.
10-10. In general, therefore, the density of states as function of energy
exhibits a shape of the type indicated in Fig. 10-13. Close to the bottom of
the band, (10-79) holds (0 A); as one approaches the zone boundary
E does not change much with k (compare Fig. 10-4) and thus the density
of states increases relative to (10-79), leading to a peak (AB); the sub-
sequent drop (BC) is a result of the fact that only the corners of the zone
are available. Near the top of the band, Z(E) approaches zero as
(EtoJl - E)1/2 in agreement with the behavior expressed by equation (10-75).

Ol'erlapping of energy bands. In the one-dimensional model there

exists a clear-cut difference between metals and insulators: for a linear
lattice to be a metal, there must exist an incompletely filled band. If
the same simple picture were true for a three-dimensional lattice however,
all divalent metals should. be insulators, as will be explained further
in Sec. 10-11. That elements such as Be, Ca, Ba, etc. are metallic is a
result of overlapping of energy bands, a phenomenon which in the one-
dimensional model is absent. This may be explained with reference to
Fig. 1O-lOb, in particular by considering the energy corresponding to
the points A, B, and C. (A anq C lie within the first zone, B in the second
266 BAND THEORY OF SOLIDS [Chap. 10
zone.) Let these energies be denoted, respectively, by E A , E B , and E c .
In crossing the Brillouin zone from A to B, the energy changes discon-
tinuously by the amount t::..E = E B - E A' There exist now two possi-
bilities with regard to EB and Ec, viz.,
E B > Ec or E B < Ec \
In the former case all energies inside the first Brillouin zone are lower
than any of those in the second zone. This is likely to be the case when
the energy discontinuity t::..E is large. In the second case, however, the
lowest energy state in the second zone (ER ) lies below the top of the llrst
_ ' , .;. ~ mi. t,~ ~t

.,
'.'
Z{E)

Fig. 10-14. Electron distribution Fig. to-15. Schematic representa-

(shaded) for the case of partial over- tion of the density of states versus
lapping of the first and second energy in the case of two overlapping
energy bands; the number of holes bands. The shaded region may cor-
in the first zone equals the number respond to states occupied by
of electrons in the second zone if electrons in case each atom con-
there are two electrons per atom. tributes two electrons.

band (Ec). Thus the two bands overlap to some extent, and this may
possibly happen when t::..E is relatively small. It is instructive to consider
the consequences of this type of overlapping by filling up the available
states with electrons. Suppose we use twice as many electrons as there are
unit cells in the crystal; this number would just completely fill a band in
the absence of overlapping. With overlapping, the electron distribution
in the two-dimensional case would look as indicated in Fig. 10-14. The
first zone is partly empty, the second zone is partly filled, because there
are energy states available in the latter which lie below those at the top of
the first zone. It will be evident that under these circumstances conduction
becomes possible and the solid may behave as a metal, be it a "poor" one.
In Fig. 10-15 we have represented schematically the density of states
when overlap occurs.

10-11. The zone structure of metals

It is impossible within the scope of this volume to give a detailed
account of the zone structure of metals; we shall therefore confine
Sec. 10-11] BAND THEORY OF SOLIDS 267
ourselves to a few general remarks. 15 First of all, for not too complicated
structures such as the f.c.c., b.c.c., and hexagonal lattice, it is always
possible to choose the unit cell in such a fashion that there is one atom per
unit cell. For example, in the f.c.c. lattice one may use as translational
vectors those joining a given corner atom with atoms at the center of three
Or----,-12-r------------------------------.
~b!~d 3d band
i
/,

-.1

-.2

11- eu
il -.3
'§
'"
] -.4 Ni
-"i<
'<l

t -.5

---- -6- -----

-.6

-----4--------

o __
o --+- Z(EI

Fig. 10-16. The density of quantum states of copper in the 4s and

3d bands; the dashed lines indicate the highest filled levels for the
transition metals, assuming the Z(E) curves are the same as that for
Cu. [After H. M. Krutter, Phys. Rev., 48, 664 (1935); see also J. C.
Slater, J. Appl. Phys., 8, 385 (1937)] iiJ.Ii.Hl

faces (see Fig. 1-4a). Under these circumstances, each band can accom-
modate twice as many electrons as there are atoms in the lattice. It then
foHows that electronic shells which are filled in the atom will lead to
completely filled bands in the solid state (at least if T = 0). It is therefore
not difficult to understand that monovalent elements such as the alkalis,
Cu, Ag, Au are metallic because they contain a half-filled band. In the
1> For a review, see F. V. Rayn?r, Repts. Progr. Phys., 15, 173 (1952).
268 BAND THEORY OF SOLIDS· ."~ [Chap. 10
.
divalent metals such as Ca, Ba, Sr, etc. there is evidently overlapping
between the energy bands associated with the valence electrons.
The zone structure of the transition elements is of considerable interest.
For example, the elements of the iron group have an incompletely filled
3d shell in the atomic state. As the atoms are brought together, the
3d level· gives rise to a relatively narrow band; the 4s level broadens
much more strongly, as indicated in Fig. 10-16.1 6
As a consequence, both the 4s and 3d bands
are partly filled with electrons in these metals;
in copper the 3d band is completely filled. (The
3d band can accommodate 10 electrons per
atom because it consists actually of five
completely overlapping bands; the 4s band
contains at most two electrons.) The im-
portance of this type of structure for the
magnetic properties will be discussed in
Fig. 10-17. Illustrating the
process of X-ray emission Chapter 19. The electronic specific heat of the
by a metal after ionization transition. metals is abnormally high. This is a
of K or L levels. For the consequence of the fact that the effective mass
transitions indicated, the of the 3d electrons is very high (narrow band
width of the emitted energy width). For the same reason, the 3d electrons
spectrum is equal to the
width of the occupied
show a high paramagnetic susceptibility and a
region in the conduction low efficiency for conducting electric current.
band. Thus the conductivity of the transition metals
is determined essentially by the 4s electrons.

10-12. The density of states and soft X-ray emission spectra

It may be mentioned here that information about the density of states

and band width may be obtained from studies of the soft X-ray emission
spectra. For example, if one ionizes the relatively sharp K or L levels in a
solid by bombardment with fast electrons, electrons from higher bands will
make transitions to the vacated levels, with emission of X-fays.. It is evident
from Fig. 10-17 that the spectrum of the emitted radiation provides infor-
mation about the energy distribution of the electrons in the higher energy
bands. l ? Thus it is possible to determine the bandwidth of the upper bands,
atleastso far as they are occupied by electrons. One has found, for example,
that the conduction electrons in AI cover a range of '"'-'12 ev, in Li '"'-'4.2 ev,
and in Na '"'-'3.0 ev. This method may of course also be used to determine
16 N. F. Mott, Proc. Phys. Soc. (London), 47, 571 (1935); 49,258 (1937); 62,416

(1949).
17 For a review see, for example, H. W. B. Skinner, Repts. Prog. Phys., 5, 257 (1939);

Trans. Roy. Soc. (London), A239, 95 (1940). For recent work in this field see E. M.
Gyorgy and G. G. Harvey, Phys. Rev., 87, 861 (1952); 93,365 (1954).
Sec. 10-12] BAND THEORY OF SOLIDS 269
the bandwidth of the upper filled band in insulators. The exact shape of the
emission spectrum also depends on the transition probabilities.

10-13. The Wigner-Seitz approximation and the cohesive energy of metals

In view of its importance, a few words may be said here about the
Wigner-Seitz approximation, which is based on the following physical
mode}.l8 Imagine a number of straight lines joining the nucleus of a
particular atom in a metal with those of its
nearest and next nearest neighbors. A set of
planes bisecting these lines perpendicularly then
defines what is known as an atomic polyhedron.
An example is given in Fig. 10-18 for a body-
centered cubic lattice. These polyhedra evidently
fill the whole space occupied by the crystal.
Confining ourselves to monovalent metals, each
of the polyhedra contains a singly charged
positive ion; one of the aims of this approxi-
mation is to obtain information about the Fig. 10-18. Atomic poly-
behavior of the valence electrons in the field of hedron for a body-centered
these ions. Near the center of a polyhedron, cubic lattice.
the potential will be spherically symmetric;
in the vicinity of the boundaries of the polyhedron the field will be small.
In the Wigner-Seitz approximation it is assumed that the field is spherically
symmetric inside the whole polyhedron; also, the field is assumed to be
that of the singly charged positive ion at the center.
Consider now the wave function for an electron in the state k = O.
Then, because the wave function must be of the Bloch type, it follows that
1p = uk(r), i.e., the wave function itself must be periodic with the lattice.
One may thus require that on the boundary of the polyhedron o1p/on = 0,
where %n stands for differentiation normal to the surface of the poly-
hedron. For simplicity, Wigner and Seitz approximate the polyhedron
by a sphere of radius r0 such that (47T/3)r~ equals the volume of a polyhedron
and then use as a b<;lUndary condition,
(o1p/or)r=,. o = 0 (10-80)
The problem of calculati~g 1p(r) then reduces to solving the spherically
symmetric Schrodinger equation, .I
1 d2 2m
-;. . dr2 (r1p) + h2 [E - V(r)] 1p = 0 (10-81)

for the boundary condition (10-80). Note that because V(r) represents the
18 E. Wigner and F. Seitz, Phys. Rev., 43, 804 (1933); 46,509 (1934). See also J. C.

Slater, Phys. Rev., 45, 794 (1934).

270 BAND THEORY OF SOLIDS [Chap. 10
potential energy of an electron in the field of a free ion, the solution of
(10-81) with the boundary condition tp --70 for r --700 would be identical
with that for the valence electron in the free atom. As an example of the
results of such calculations, we reproduce in Fig. 10-19 part of the wave
function of a conduction electron (35) in sodium in its lowest state. It is
important to observe that the wave function is very flat over the region
between 2 to 4 hydrogen radii. This means that the wave function for
k = 0 is flat over about 90 per cent of the atomic volume; the total charge

.4

0
'/I
t
-.4
~. ,

-.8
0 1 2 3 4
-+r

Fig. 10-19. Part of the wave function of a conduction electron in

sodium for k = 0 as function of the distance from the center of
an atomic polyhedron (r is expressed in atomic units).

distribution corresponding to the flat region is nearly equal to e. Now

when a Bloch function for k = 0 is constant over a certain region of space,
we may conclude that the periodic part Uk of the Bloch function is constant,
i.e., the electron behaves as a free electron in that region. Thus the valence
electrons in sodium and in the other alkali metals behave very much like
free electrons. For copper and silver and presumably also for gold, the
flat part of the wave functions extends over a relatively small region,
and here the free electron model can hardly be applied. 19 It is interesting
in this connection to point out that the ratio of the ionic to the metallic
radii is much smaller for the alkali metals than for the monovalent noble
metals.
Li Na K Cu Ag Au
0.39 0.51 0.58 0.75 0.88 0.95

Thus Cu, Ag, and Au may be pictured as consisting of a system of hard

spheres (the ions) held together by the valence electrons. In the alkali
metals on the other hand, the ions are separated by relatively large
distances.

'9 N. F. Molt and H. Jones, 0p. cit., p. 79; R. Fuchs, Proc. Roy. Soc. (London),
At51, 585 (1935); 153, 622 (1936).
Sec. 10-13] BAND THEORY OF SOLIDS 271
In Fig. 10-20 we have plotted the energy Eo of the electron in sodium
in the state k = 0 as a function of the variable, o' The physical meaning of
Eo is clearly this: it represents the energy corresponding to the bottom of
the conduction band relative to the vacuum level. Thus the Wigner-Seitz
approximation allows one to determine what we denoted by Es in
Fig. 9-1.
A "complete" theory of metals should allow one to calculate, among
other things, the cohesive energy, the lattice constant, and the elastic con-
stants. Although these problems are necessarily very complicated, a great

E ~-----

.4
t
i,';
.2 .'" " I,;

I
I
,',; 0
.:. {: --
,.
-.2 "

-.4

-.6

o
Fig. 10-20. Curves for Eo, EF and Eo + ~EF (all in Rydberg units)
versus ro (in atomic units) for sodium.

deal of progress has been made towards solving them for simple metals.
We shall discuss here a simplified theory of the cohesive energy of metals
based on the Wigner-Seitz approximation. In general, the total potential
energy of the metal is determined by the interaction of the charges within
a given polyhedron plus the interaction of the polyhedra with each other.
Suppose now that the valence electrons are distributed such that each poly-
hedron contains one electron. In that case the polyhedra are neutral, and
to a first approximation the interaction between them may be neglected.
Doing this, the total energy of the crystal is then given simply by the sum of
of the kinetic energy of the electrons plus the potential energy of each
electron in the field of a positive ion. Now the latter quantity is given by Eo,
represented as function of '0 in Fig. 10-10. The kinetic energy of the
electrons may be obtained to a first approximation by assuming a free
electron model for the valence electrons, which for the alkali metals is
quite good as we have seen above. In the preceding chapter we have seen
that the average energy of suc~ a system is equal to ~EF' Now, according
272 BAND THEORY OF SOLIDS"", [Chap. to
",
to (9-9), EF may be expressed in terms of the density of electrons; making
use of the fact that lin = (47T/3),g one may write
E kin = iEF = :0 (1i2/mr~)(97T/4)2/3 (10-82)
This is represented for Na as function of '0 in Fig. 10-20 ~ the sum of
the curves Ekin(r 0) and E o(' 0) is also given. The position of the min~mum of
the curve Eo + iEF determines the calculated lattice constant. From these
results the cohesive energy may be obtained with reference to the system
of free atoms at infinite separation. When E] represents the ionization
energy of a free atom, the cohesive energy (positive quantity) in the metal
is, per atom, equal to
Erohesive = -(Eo iEF + +
E]) with '0 = (rO)min (10-83)
Here Eo is the only negative quantity; EF and E] are both positive, and
as they increase the binding becomes less strong. The abpve model is, of
course, too simple and a number of corrections are required. For example
it is estimated that the Coulomb energy between the valence electrons
gives a term 0.6e 2/ro; also, account must be taken of the fact that the
electrons tend to keep away from each other, an effect which depends on
the relative spin orientations of the electrons involved. Furthermore,
there are van der Waals forces between the ions. Although it is evident
that the problem is a very complicated one, it may be of interest to indicate
the extent to which theory and experiment agree; the following com-
parisons are from Seitz.20
Lattice spacing Sublimation energy
(A) (kcaIJmole)
Metal Calc. Obs. Calc. Obs.
Li 3.50 3.46 36.2 39
Na 4.51 4.25 24.S 26
K 5.82 5.20 16.S 23
In these figures, the.minimum in the total energy versus ro curve was used
to define the theoretical lattice spacing, and the cohesive energy was
calculated for this particular value of roo Calculations of the
compressibility are also .in reasonable agreement with' experiment. For
Na the observed \lnd calculated values are, respectively, 12.3 and 12.0 X
10-12 cm 2/dyne. 21
Attempts have also been made to explain the crystal structure of
metals in terms of the electronic structure; the differences in energy
obtained for different crystal structures are in general too small to draw
unique conclusions. For certain alloy structures, however, Jones has
been able to account for structural transitions associated with particular
compositions on the basis of the band theory.22
20 F. Seitz, op. cit., p.365.

21J. Bardeen, J. Chem. Phys., 6, 367, 372 (1938).

22H. Jones, Proc. Roy. Soc. (London), AI44, 225 (1934); Proc. Phys. Soc. (London),
49,243 (1937); Physica, 15, 13 (1949); Phil. Mag., 41, 663 (1950).
Chap. 10] BAND THEORY OF SOLIDS 273

REFERENCES
An elementary treatment of the band theory may be found in:
L. Brillouin, Wave Propagation in Periodic Structures; Electric Filters
and Crystal Lattices, 2d ed., Dover, New York, 1953.
A. H. Cottrell, Theoretical Structural Metallurgy, Arnold, London, 1948.
W. Hume-Rothery, Atomic Theory for Students in Metallurgy, Institute
of Metals, London, 1947.
W. Hume-Rothery, Electrons, Atoms, Metals and Alloys, Cornwall Press,
London, 1948.
Advanced discussions are given in:
H. Frohlich, Elektronen Theorie der Metal/e, Springer, Berlin, 1936.
N. F. Mott and H. Jones, Theory of the Properties of Metals and Alloys,
Oxford, New York, 1936.
N. F. Mott, "Recent Advances in the Electron Theory of Metals,"
Progr. Met. Phys., 3, 76 (1952).
G. V. Raynor, "The Band Structure of Metals," Repts. Progr. PhYs.,
15, 173 (1952).
J. R. Reitz, "Methods of the One-Electron Theory of Solids," in F. Seitz
and D. Turnbull (eds.), Solid State PhYSiCS, Academic Press, New
York, 1955, Vol. 1.
F. Seitz, The Modern Theory of Solids, McGraw-Hill, New York, 1940.
J. C. Slater, "Electronic Structure of Metals," Revs. Mod. Phys., 6,
209 (1934).
A. Sommerfield and H. Bethe, in Handbuch der PhYSik, 1933, Vol. 24/2,
pp. 333-622.
A. H. Wilson, Theory of Metals, 2d ed., Cambridge, London, 1953.
"International Conference on the Physics of Metals, 1948," special issue
of Physica, 1949.

PROBLEMS , T •

10-1. Let aI' a 2, aa and b 1, b 2 , b a represent the primitive translation

vectors of the direct and reciprocal lattice. In the direct lattice consider
a set of planes with Miller indices n l , n 2 , n3 • Show that the reciprocal
lattice vector n = nib i + +
n 2b 2 nab3 is perpendicular to these planes.
Also show that the distance ~etween consecutive planes is equal to 1/lnl. "
10-2. Consider an f.c.c. lattice with a cube edge a. Show that the
reciprocal lattice is b.c.c. with an edge 2/a. Also show that the reciprocal
lattice of a b.c.c. lattice is f.~.c. '
274 BAND THEORY OF SOLIDS [Chap. 10

10-3. Show that the volumes of a unit cell in the direct and reciprocal
lattices are the reciprocal of each other.
10-4. Suppose a beam of monochromatic X-rays is reflected by a
crystal, i.e., the beam satisfies the Bragg condition. Let So and s be unit
vectors in the direction of the incident and reflected beams. Show that
the Bragg condition is equivalent with the requirement that (s -- so)/).
must correspond to a vector in the reciprocal lattice ; J.. is the wavelength
of the X-rays.
]0-5. In Sec. ]0-10 we concluded that the band theory for cubic
crystals leads to discontinuities in the E(k) surfaces whenever k satisfies
the condition n· k = 7TnZja (see expression lO-78). Show that this
condition is equivalent with that for Bragg reflection of the electrons by
the set of planes with Miller indices n1 , n z, n 3 .
10-6. Show that in the tightly bound electron approximation the
energy E(k) for b.c.c. and f.c.c. lattices are given by
E(k) = Eo - oc - 8y cos kxa cos kya cos kza (b.c.c.)
t
E(k) = Eo - oc - 4y[cos kxa cos kya + cos kxa cos kza
+ cos kya cos kza] (f.c.c.)
where 2a is the cube edge. Show also that for small values of Ikl the energy
varies proportionally with ikj2. Discuss the shape of constant energy
surfaces in k-space.
10-7. Calculate the width of the energy region occupied by electrons
in the conduction bands of Li, Na, and Al on the basis of the free electron
theory of metals, assuming that each atom contributes as many electrons
as its chemical valence. With reference to the bandwidths quoted in Sec.
10-12, what average effective mass would one have to assume in order
to obtain agreement?
10-8. Discuss the nearly free electron approximation for a one-
dimensional lattice.
---::-:-:--:--- ..
Chapter 11

THE CONDUCTIVITY OF METALS

, --',-

In this chapter an elementary discussion is given of the electrical and

thermal conductivities of metals; a brief account of the thermal con-
ductivity of insulators is given in Sec. 11-9. Within the allowed space
it did not seem possible to discuss 6uperconductivity, thermoelectric,
galvanomagnetic, and thermomagnetic effects, although a simplified
derivation of the Hall effect is included as the last section.
I
11-1. Some features of the electrical conductivity of metals

Any theory of the electrical conductivity of metals must explain a

number of pertinent experimental facts. Apart from deviations in special
cases or under extreme conditions, the general features of the electrical
conductivity of metals are the following.
1. In accordance with Ohm's law, the current density in the steady
state is proportional to the field strength.
2. The specific resistivity of metals at room temperature is of the order
of 10- 5 ohm cm (1 ohm cm ~ 1.1 X 10-12 cgs unit)
3. Above the Debye temperature the resistivity of metals increases
linearly with temperature.
4. At low temperatures, but above approximately 20 o K, the resistivity
of many metals is proportional to T5; at liquid helium temperatures
some metals exhibit a minimum in the resistivity versus temperature
curve.
5. For most metals the resistivity decreases with increasing pressure.
6. According to Matthiessen's rule, the resistivity P of a metal
containing small amounts of impurities may be written
P = Po + p(T) (11-1)
where Po is a constant which increases with increasing impurity
content and p(T) is the temperature-dependent part of the resistivity.
7. The resistivity of alloys which exhibit order-disorder transitions
shows pronounced minima corresponding to ordered phases
(Fig. 11-7) ..
275
276 CONDUCTIVITY OF METALS [Chap. II
8. Above the Debye temperature the ratio of thermal to electrical
conductivity is proportional to T, the constant of proportionality
being approximately the same for all metals (Wiedemann-Franz lawf
9. A number of metals exhibit the phenomenon of superconductivity,
i.e., their resistivity disappears at temperatures abo\,e absolute zero.!

11-2. A simple model leading to a steady state; drift velocity and relaxation
time

In order to appreciate the essential problem in the theory of conductivity

it is useful to consider a simple model which shows the features of the
more sophisticated theory. From the macroscopic point of view, the
electrical conductivity of a metal is defined by .. ;
\ (11-2)

where Ix is the current density resulting from an applied electric field Ex

in the x-direction. In the case of an anisotropic solid, the conductivity
depends on direction, and (J becomes a tensor (see Sec. 1-12); we shall
assume an isotropic solid. From an atomic viewpoint, we may ascribe the
current to a flow of electrons, i.e.,

(11-3)

where n is the number of electrons per unit volume, -e is the electronic

charge, and (ox) is the average velocity of the electrons in the x-direction
(the average being taken over the electrons per unit volume). In the
absence of an external field, the velocity distribution is isotropic and (ox)
vanishes. Now, a free electron under influence of an external field E J •
obtains an acceleration ax = -eEx/m, and thus its velocity would continue
to increase with time. It is evident that the influence of the electric field
alone would not lead to a steady state as required by Ohm's law; it is
therefore necessary to assume the occurrence of some kind of "frictional"
process. This process together with the influence of the external field
should then lead to an average velocity (v x > which, according to (11-2)
and (11-3), should be proportional to Ex. The origin of the "frictional"
process must obviously be sought in a possible interaction of the conduction
electrons with the atomic lattice, since collisions between the electrons
themselves cannot provide the required result (the latter would not destroy
momentum in the field direction). f \.

1 This topic will not be discussed here; for an introductory survey and references to

the literature, sec C. Kittel, Introduction to Solid State PhYSics, Wiley, New York, 1953
Chap. 20. -;. . I g! 1
Sec. 11-2] CONDUCTIVITY OF METALS 277
In its simplest phenomenological form the interaction of the electrons
with the lattice may be described in the following manner: suppose the
probability for an electron to collide with the lattice during a small time
interval dt is dt/T. For the moment we shall assume for simplicity that T
is constant, independent of the energy of the electron and of the direction
of motion. Furthermore, let it be assumed that in a collision with the
lattice, the electron loses all the energy it has gained from the external
field and that its velocity after the collision is random (independent of the
direction of motion before the collision). In other words, the collisions
are assumed to be so designed that immediately after the collision the
electron has no memory of what happened before the collision. Under
the terms of the model specified above, we may argue in the following
way: The rate of change of the average velocity in the x-direction due to
the field alone is
(11-4)
)
Also, the rate of change of (rx> due to collisions with the ,'lattice alone is
( 11-5)

since I /T is the probability for a collision per second and after the collisions
the velocities are random. In the steady state we must have
(I 1-6)

From the last three equations it then follows that the average drift velocity
in the field direction is given by
(11-7)

From (11-3) and (11-7) it then follows that the conductivity is given by
(11-8)

Suppose that under influence of an electric field Ex the electrons have

a certain average drift velocity and that at the instant t = 0 the field is
suddenly switched off. As a result of the collisions with the lattice the
average drift velocity will gradually approach zero; since the rate of
change of (l'x> by collisions alone is given by (1l-5), the decay will follow
the expression
(11-9)

where (vx(O) is the average drift velocity at t = O. Because of the

exponential form of (11-9), the quantity T is called the relaxation time.
We may note here already that with n ~ 1022 cm- 3 , expression (11-8)
requires T'_' 10-14 second in order to obtain agreement with experimental
room temperature data (see point 2, Sec. 11-1).
For the particular type of collisions postulated above, T also represents
.
~
,{'.l~:tJ'
..... "
278 CONDUCTIVITY OF METALS [Chap. I I

the mean free time between collisions. This may be shown as follows:
Let pet) be the probability that t seconds after a certain collision has"
occurred, an electron has not yet collided again; P(t dt) represents the +
same quantity after (t + dt) seconds. Then

pet + dt) = pet) + (dP/dt) dt

On the other hand, we may also write

P(t + dt) = P(t)P (dt) = P(t)(l - dt/T)

where (l - dt/T) represents the probability for an electron not to collide

during the interval dt. From the last two equations one finds

pet) = f;-I/T

since P = 1 for 1= O. Hence the mean free time between collisions is

I' ,. ~ ,

(I) = foOD t (dP/dt) dt = ". (11-10)

It must be emphasized, however, that the relaxation time and the mean
free time between collisions are identical only if the velocity after collision
is random. For example, if the scattering is not isotropic and Te is the
mean free time between collisions, the relaxation time can readily be
shown to be
T = Te/(I - (cosf3» (11-11)

where (cos 13) is the average of the cosine of the scattering angle. 2 Thus
when nearly all collisions involve small angles, the electron has a rather
strong "memory" and it takes a relatively large number of collisions to
erase this memory, i.e., T ~ To in that case.
I
11-3. The Boltzmann transport equation

It will be evident that in a state of steady flow of heat or electricity,

the distribution function for the velocity components and spatial co-
ordinates of the electrons will be different from that in thermal equilibrium
in the absence of flow. Thus the theory of transport phenomena is
concerned with determining this distribution function for given external
fields. We shall see in this section that the determination of the distribution
function requires solving an integrodifferential equation, viz., the
Boltzmann transport equation. 3 IJiW.:ulj :)"'1

2 See, for example, W. Shockley, Electrons and Holes ill Semicollductors, Van

Nostrand, New York, 1950, p. 255.

3 L. Boltzmann, Vorlesullgell liber Gastheorie. Barth, Leipzig, 1923. Uf1J 'W ,
Sec. 11-3] CONDUCTIVITY OF METALS 279
Let PX' Py, P. represent the components of the momentum of an
electron and let
" ..." j(p",pyP. ;xyz ;t) dpx dpu dpz dx dy dz (11-12)

represent the number of electrons in the volume element dx dy dz which

at the instant t have momenta in the range dpx dpy dp •. The steady state
is then defined by
djjdt = 0 (I 1-13)

In order to obtain information about the function f, it is necessary to

consider the causes which, when operative by themselves, would tend to
produce a change of j with time. First of all, we must consider the rate
of change off resulting from the velocities of the electrons and from the
components X, Y, Z of the external forces which are assumed to act on
the electrons. Consider the group of particles defined by (11-12) at an
instant t + (Jr, where Ot is a very small time interval. The momenta and
spatial coordinates of this group of electrons at 1 01 are then to be+
found about the point
_J ~ •___ •

Px + X (Jt; py+ Yot; P. -/- Z 01

x + Px olJm; y + jJy otJm; z + P. otJm (11-14)

However, according to the definition of the distribution function (11-12)

+
the number of electrons which at the instant t Ot have their representative
points in an element dpx dpv dpz dx dy dz around the point defined by
(11-14) must be equal to

j(px -/- X dl, ... ; x + jJx oIJm ... ; t + Or) dpx dpy dp. dx dy dz (11-15)

Since (11-12) and (11-15) must be equal, one is led to the following result,
obtained by expanding (11-15),

oj oj of oj oj oj
(ojJOt)IlPhb= - - X--- Y---Z--VX--vy--V Z (11-16)
opx OPll opz ax oy 2z

where vx ' cu' v. represent the velocity components. In the steady state
there must be other processes which just balance the rate of change (11-16)
produced by fields and gradients. As we n~ted already in the preceding
section, such processes are provided by electron-lattice interactions. Thus
condition (11-13) may be written in the form
~

(ojJOt)flelclR + (ojIOI)('(l1I = 0 ( 11-17)

where the first term is given by (11-16) and where the second term refers
to electron-lattice scattering (compare 11-6). Since the force exerted on
280 CONDUCTIVITY OF METALS [Chap. II

an electron by a combined electric and magnetic field is given by the

Lorentz expression

F= -e( E + ~ ., X H) \

where., is the velocity vector, we may write ( 11-17) com\ined with (11-16)
in the general form

(o//Ot)('oll = ---e(,E + ~c ., X H) .grad p/ -+ V • grad r / (11-18)

which is the Boltzmann transport equation for electrons.

The left hand side of this equation involves an integral operator,
making the equation an integrodifferential equation; this may be seen as
follows: The number of electrons per unit volume which, due to collisions
with the lattice, change their momenta per unit time from the range
dp" dp. dpz to another range dp-: dp~ dp; can be represented by

f(p,r,t) dpx dpy dpz P(p,p',r) dp~ dp~ dp;

where the transition probability P(p,p',r) is determined by the type of

electron-lattice interaction. Similarly, the corresponding number of
electrons thrown from the range dP:r dp~ dp; into dpx dpy dpz per unit time is
,,
f(p',r,t) dl, dp~ dp; P(p',p,r) dpx dp. dpz h
,

The net difference between the above quantities integrated over dp~ dp~ dp~
determines (o//ot)ron, i.e.,

(o//ot),'OI! = JH [f(p',r,t)P(p',p,r) - /(p,r,t)P(p,p',r)] dp~ dp~ dp; (11-19)" ...

It is evident that since the left-hand side of (11-18) is given by expression

(11-19), containing the transition probabilities P, the distribution function
in the state of steady flow depends explicitly on the mechanism of inter-
action between the electrons and the lattice. From the atomic theory of
electron scattering it can be shown that under certain circumstances it is
possible to define a relaxation time such that (o//ot)eoll takes the form

(o"lot) = _ f(p,r) -- j~ (11-20)

'JI coil -r(p,r)

(compare 11-5). Here j~ represents the distribution function in thermal

equilibrium in the absence of external fields. The physical meaning of
the relaxation time -r(p,r) is analogous to that of -r introduced in the
preceding section: when the external fields are suddenly removed, (f - 10)
decays to zero in the fashion
(11-21)
Sec. 11-3] CONDUCTIVITY OF METALS 281
When for a certain problem a relaxation time exists, the treatment is
strongly simplified, since the integrodifferential equation then becomes
an ordinary equation. An example of this type will be discussed in the
next section.
Special cases for which a relaxation time can be defined consistently
may be mentioned here. 4 'J """ 'I.J ~'" "Jl '1''' ..."
>;'''....

(i) In processes whereby the electrons may be considered to be

scattered by elastic spheres; this is of importance for that part of
the resistivity which is due to impurity scattering.
(ii) From the (approximate) theory of the interaction between electrons
and lattice vibrations it follows that a relaxation time can be
defined when (fJjT)2 ~ 1, where fJ is the Debye temperature. This
simplifies the theory of electrical and thermal conductivities at
high temperatures.

11-4. The Sommerfeld theory of electrical conductivity

A theory of metallic conductivity based on average velocities, as

employed in Sec. 11-2, was developed by Drude in 1900. Lorentz in 1905
reinvestigated the problem, using the Boltzmann transport equation and a
simplified model for the collisions between the electrons and atoms in the
lattice. However, the use of classical statistics led to serious difficulties;
for a review of these theories we refer to the literature. 4 In 1928 Sommerfeld
recalculated the conductivities along the lines of Lorentz' theory, but
replacing classical statistics by Fermi-Dirac statistics." Sommerfeld did
not investigate the actual mechanism of interaction between the electrons
and the lattice any further, but assumed that a relaxation time can be
defined which is a function of the energy of the electrons only. As an
application to the Boltzmann transport equation we shall discuss below
Sommerfeld's theory of the electrical conductivity based on the free
electron approximation; the thermal conductivity will be discussed later.
The number of electronic states per unit volume associated with an
element dpx dp.y dpz in momentum space is (including the spin) (2/h 3 ) dp",
dpy dpz. In thermal equilibrium and in the absence of fields, let the average
number of occupied states be
(2/h 3 )Fo(p) dpx dpy dpz
where Fo is the Fermi distribution function in terms of the total momentum
p. Suppose we apply an electric field Ex along the x-direction, other
, See, for example, A. H. Wilson, The Theory of Metals, 2d ed., Cambridge, London,
1953, pp. 8, 264.
, A. Sommerfeld, Z. Physik, 47, I (1928); se:: also the article by A. Sommerfeld and
H. Bethe, in Handbuch de,. PhYSik, Vol. 24/2, 1934, or A. Sommerfelrl and N. H. Frank,
ReI'S. Mod. Phys., 3,1 (1931).
282 CONDUCTIVITY OF METALS [Chap. 11
fields or gradients being absent. When in the state of steady current the
average number of electrons per unit volume in the range dp", dpy dpz is
represented by
\
(11-22)
\
we may write immediately for the current density,
2e
Ix = - h3 Iff vx(F -- Fo) dpx dpv dpz (11-23)

which is a generalization of (11-3). The term Fo does not contribute

anything to the current, since it is spherically symmetric with respect to
p; it has been added, however, to emphasize the fact that the current is
essentially determined by the deviation (F - Fo) from the Fermi distri-
bution Thus, if one can calculate (F - Fo), Ix may be obtained.
Th~ Boltzmann transport equation (11-18) reduces for the case under
consideration to
(oF/ot)coll = -eEx(oF/opx) (11-24)
We shall now assume that there exists a relaxation time T such that

(oF/ol)coll = -(F -- FO)/T (11-25)

(compare 11-20). Thus, according to the last two equations,

(F - FO)/T = eEx (oF/opx) ~ eEx (oF%px) (11-26)

where the last approximation is valid for small fields so that (F - Fo) is
relatively small (physically speaking this assumption is equivalent with a
linear dependence of I on E). Making use of the fact that the energy of
the electrons is given by E = (p~ + +
p; p;)/2m, one may write instead
of 01-26),
(11-27)

Substituting (11-27) into (11-23), one obtains for the current density,

(11-28)

We shall assume that T is a function only of the energy and not of the
direction of motion (compare 11-20). Since OFO/OE is also a function of E
alone, one may transform (11-28) into a single integral by replacing by v;
v2/3 and dpx dpv dpz by 47Tp2 dp. Expressing the integrand in terms of E,
one obtains
(11-29)

Now we have seen in Sec. 9-3 that OFO/OE has an appreciable value only
in an energy range of a few kT about the Fermi level EF. To a good
Sec. 11-4] CONDUCTIVITY OF METALS 283
approximation 1' 3/27(1') under the integral sign may thus be replaced by
the quantity E:W7F in front of the integral. Furthermore,
fo'" (oF/oE) dE = -I :,' ,,~,

and if one substitutes EO F from formula (9-9), one finally obtains the
simple result, l (:

(11-30)
where n is the number of electrons per unit volume. It is interesting to
note that although all electrons take part in the conduction mechanism
only the relaxation time of the elec-
trons at the Fermi level occurs in
the conductivity. The reason for this
may be explained with reference
to Fig. II-I. The full circle repre-
sents the Fermi distribution for a
Vx
two-dimensional case in the absence
of an external field. In the presence
of a field along the x-direction, the
veloCity of all electrons is shifted
by an amount ~v (the average drift
velocity), leading to the dashed circle. Fig. 11-1. Exaggerated representation
It is evident that the distribution is of the influence of an electric field on the
changed only in the vicinity of the velocity distribution for a two-dimen-
sional crystal. The fully drawn circle
Fermi level, so that only the relaxa-
corresponds to the Fermi distribution in
tion time of electrons near EF is of the absence of a field; the field E;,
importance. produces a shift AD opposite to the field
Note that (11-30) is essentially the direction (dashed curve).
same as (11-8), except that 7 has
been replaced by 7F' Although the treatment given here was based on the
free electron approximation, a similar treatment may be given for the
band approximation. 6 The result of such a calculation is
a = n('ffe27F/m (11-31)
i.e., n is replaced by the effective number of free electrons neff as defined
in Sec. 10-5. It must be noted that (11-31) is based on the assumption
that the energy of the electron as well as 7 are functions of the absolute
value of the wave vector only.

11-5. The mean free path in metals

If we confine ourselves to the conductivity of metals in the temperature

•
region T ~ 0, the existence of a relaxation time is assured according to
• See, for example, N. F. Mott and H. Jones, Theory of the Properties of Metals and
Alloys, Oxford, New York, 1936, p. 258.
284 CONDUCTIVrTY OF METALS [Chap. II

what has been p;aid in Sec. 11-3. So far, however, we have not paid any
attention to til.: actual cause of resistivity, i.e., to the physical mechanism
which determines TF' On the other hand, it follows from the basic formula
(11-30) that features such as the temperature dependence, pressure
dependence, etc. must be hidden in the quantity TF'
Let us assume that the scattering of the electrons is isotropic; from
the discussion given at the end of Sec. 11-2 it then follows that we may
Introduce a mean free path AF between collisions for electrons at the
Fermi level by means of the relation !I" "en".

(11-32)
where I'F is the velocity of an electron with the Fermi energy. Hence
(11-30) may then be written
(11-33)
From experimental values of (} and from a knowledge of the Fermi level
(which is determined by n) one can thus calculate A F . Results of such
calculations at O°C are given for a number of monovalent metals in
Table II-I. The point of special interest is the fact that the mean free path
is of the order of several hundred Angstroms.

Table 11-1. Conductivity, Mean Free Path and Relaxation Time at O°C
for Some Monovalent Metals

Metal <1obs X 10" (esu) Ef' (ev) Af' (A) Tf' in IO- u sec

Li 1.1 4.7 110 0.9

Na 2.1 3.1 350 3.1
K 1.5 2.1 370 4.4
Cu 5.8 7.0 420 2.7
Ag 6.1 5.5 570 4.1

Before the development of the band theory by Bloch and others, this
fact presented a great difficulty. The electrons were supposed to move in
the spaces between the ionic cores, as illustrated in Fig. 11-2, and such a
model inevitably leads to a mean free path of a few Angstroms. This model
also led to unsurmountable difficulties in explaining the temperature
dependence, pressure dependence, influence of impurities on the con-
ductivity, etc.
In Chapter 10 we have seen, however, that the wave vector of an
electron moving in a perfectly periodic potential remains unchanged in the
absence of external fields. Thus, as a result of the wave nature of the
electrons, they can pass through a perfect crystal without suffering any

)
Sec. 11-5] CONDUCTIVITY OF METALS 285
resistance. This is a result of interference of the electron waves scattered
by the periodic potential representing the lattice. It may be compared
with the unattenuated passing of a light wave through a perfect crystal.
The important consequence of this is that if all nuclei were at rest, the mean
free path for electron scattering would be infinite. 7 The actual cause of
resistivity must therefore be sought in deviations from the periodicity of the
potential in which the electrons move. It is on this concept that the modern
theory of conductivity is based.
Deviations from the periodicity of the
potential causing resistivity may be due to:
(i) Lattice vibrations
(ii) Lattice defects, such as vacancies, in-
terstitials, and dislocations
(iii) Foreign impurity atoms
o o
Fig. 11-2 The classical model
(iv) Boundaries for electron scattering by the
atoms in a solid. This leads
It is interesting to note that Wien in 1913, to A c--- 10- 8 cm.
before the development of wave mechanics,
put forward the hypothesis that the resistivity in pure metals was due to
thermal vibrations of the atoms in the lattice. The justification of this idea
had to await the development of the band theory.

11-6. Qualitative discussion of the features of the resistivityB

Temperature dependence of p. For the moment we shall assume

scattering processes of the types (ii), (iii), and (iv) mentioned above to be
negligible and confine ourselves to the temperature dependence of the
resistivity. In the complete theory of the temperature-dependence of p
it is necessary to investigate the influence of the lattice waves on the
motion of the electrons. This is a complicated problem, and only on the
basis of a number of simplifying assumptions is it possible to calcul~te
the resistivity. One of the approximations involves the representation
of the lattice waves by a Debye model (see Sec. 2-6); furthermore, certain
assumptions must be made about the influence of such lattice waves on
the potential seen by the electrons. We shall simplify matters even
more strongly by assuming an Einstein model for the lattice vibrations
(see Sec. 2-4) and by considering the interaction between the electrons and
the atomic vibrations in a qualitative way. The results obtained in this
way are, for the high temperature region, in agreement with the advanced
theory and with experiment. In view of (11-33) we are particularly
interested in the scattering of electrons with the Fermi energy.
, This was first pointed out by W. V. Houston, Z. Physik, 48, 449 (1928); Phys. Rev.,
34, 279 (1929).
1

CONDUCTIVITY OF METALS {Chap. II

When v represents the vibrational frequency of the atoms in the

Einstein model, M the mass of an atom, and x its displacement from the
equilibrium position along a given axis, the equation of motion of the
atom is \
(11-34)

The average potential :,lergy associated with the vibration is equal to half

Na

16 K
'".....o
~ Li Ag
~ 12
b Ca
Cu

t 8
Au
Mg

Be

o 10
- Atomic number
Fig. 11·3. Values of a/M()2 versus atomic number obtained from
conductivity measurements at OQC (the values employed are those
given by Mott and Jones, I.e., page 246); a is expressed in ohm- 1
cm-', M in terms of the mass of a H atom.

the total thermal energy, i.e., equal to kT/2 for temperatures well above the
critical temperature (j = hv/k. Hence
27T2V 2 M(x 2 ) = kTj2 T}> (j (I 1-35)
The quantity (x 2 )
is of particular interest for the scattering of electrons.
In order to see this, we shall first introduce the "scattering cross section"
QF associated with an atom with reference to its capability of scattering
an electron with the Fermi energy. From the definition of AF it follows
that an electron traveling over AF has unit probability C,-_'1eing scattered.
Suppose we represent the atoms by obstacles with a cross section QF
perpendicular to the direction of motion of the electron. Then QF may
be defined by the relation
(11-36)
Sec. 11-6] CONDUCTIVITY OF METALS 287
where N is the number of atoms per unit volume. Since there is no scatter-
ing of electrons (Q J.' = 0) when the atoms are all in their equilibrium
position, one may expect that Qp is proportional to <x2 ) (both have the
dimensions of an area). Accepting this, it follows from the last two
equations that
Aj.' = const. M()2/T (11-37)

Combining (11-37) with (11-33), we may write the conductivity in the form

a = const. M02/T T'}>& (11-38)

Thus a varies as T-l, in agreement with the experimental fact (3) mentioned
in Sec. 11- I. Expression (11-38) may be brought in harmony with Bloch's
theory if 0 is interpreted as the Debye rather than the Einstein temperature;
this will be done from now on.
In comparing different metals, it is more meaningful to compare
a/M()2 values than the a values themselves. The reason is that the former
quantity is a measure for the conductivity per unit amplitude of vibration
of the atoms. In Fig. 11-3 we have plotted a/ M()2 as function of atomic
number for T = 300o K. It is observed that the alkali metals and the
noble metals with one outer electron exhibit large values of this quantity,
indicating a relatively small cross section for scattering. For the divalent
metals next to them in the periodic table, alM02 is smaller by a factor
between 2 and 4; this is a consequence of the small effective number of
free electrons in these metals. Note also the low values of alM02 for the
transition metals.
As a result of the expansion of the lattice and the associated reduction
in the binding forces, () decreases slightly at high temperatures; conse-
quently aT is not exactly constant but decreases somewhat at high tem-
peratures. The transition metals form an exception to this rule; they
exhibit an increase of aT with increasing T which may be explained on the
basis of the band structure of these metals. 8

Matthiessen's rule. When a metal contains impurities, the field in the

vicinity of the impurities is in general different from that near the host
atoms. The impurities thus produce deviations from the periodicity of the
potential and act as scattering centers for electrons. Thus electrons in an
impure metal are scattered by impurity atoms as well as by the thermal
vibrations of the atoms. Denoting the relaxation times associated with
each of these processes by T j and TtlI' respectively, the resulting relaxation
time T is given by
liT = I/Ti + I/ Ttl. (11-39)

because the probabilities for scattering in this simple model are additive
8 See also J. Bardeen, J. Appl. Phys., 11,88 (1940).
288 CONDUCTIVITY OF MET ALS~
, [Chap. II
and they are proportional to the reciprocals of the relaxation times.
Since the resistivity is proportional to T F 1, associated with electrons at the (
Fermi level, the impurity scattering leads to a constant term in Matthiessen's
rule (11-1). Actually, Ti will itself be slightly temperature-dependent, but
in general the temperature-independent part predominates strongly. For
not too high impurity concentrations, l/Ti is proportional to the impurity
concentration and so is Po in (I I-I). As an example, we give in Fig. 11-4
the resistivity of pure copper together with that of copper containing
small amounts of nickel, as function of temperature. 9

6 10 6 P '""
5
~. 15

~"
4 ;':i ~;
Q.
X
'§

~
3

2 t 5

~ o o 25 50 75 100
-200 -100
---+- Temp, I'CI Cu --.Atomic '.I; Au Au

Fig. 11-4. Specific resistivity (ohm Fig. 11-5. Fully drawn curve repre-
cm) as function of temperature for sents the resistivity of copper-gold
copper and copper-nickel alloys; alloys annealed at 200°C (ordered);
the numbers refer to atomic per- the dashed curve refers to alloys
centages. [After J. O. Linde, ref. 9] quenched from 650"C (disordered).
[After Barrett, ref. 10]

ReSI:ftivity of alloys. As an example of the behavior of the resistivity

of alloys, consider Fig. 11-5 for the copper-gold system. 10 The dashed
curve refers to alloys quenched from 650°C, leading to disordered systems.
The fully drawn curve refers to alloys which have been annealed at 200°C,
leading to at least partly ordered alloys. For low concentrations of gold
in copper (or copper in gold) the resistivity increases linearly with impurity
concentration for reasons explained above. Particularly noteworthy are
the resistivity minima corresponding to the ordered structures of the
composition Cu 3 Au and CuAu, and of course those corresponding to the
pure elements; in all these cases the potential seen by the electrons is
nearly periodic, in contrast with that of the disordered alloys. The amount
9 J. O. Linde, Ann. Physik, 15,219 (1932).
10 C. S. Barrett, Structure of Meta/s, 2d ed" McGraw-Hili, New York, 1952, p. 288.
",q
See. 11-6] CONDUCTIVITY OF METALS 289
of order in the lattice is thus clearly reflected by the resistivity of the
material,u

Resistivity due to vacancies and interstitia/so It may be remarked here

that resistivity measurements play an important role in the study of radia-
tion effects. For example, when a metal is exposed to a beam of neutrons
or other types of radiation, a certain number of interstitial atoms and
vacancies are formed. Each of these contribute to the scattering of
electrons, i.e., to the resistivity. From resistivity measurements it is
possible to obtain information about the numbers of defects produced,
about the time required for these defects to anneal out at a given tem-
perature, etc.

Variation of resistance with pressure. As mentioned under (5) in Sec.

11- I, the resistivity of most metals decreases with increasing pressure
(exceptions are Li, Ca, Sr, Bi). Qualitatively, this may be understood by
starting from expression (11-38). Under high pressures, the forces between
the atoms are stronger, and as a result (j increases. Hence
dajdp = d«(j2)jdp > 0 01-40)

The VarIatIOn of (j with pressure or, rather, the so-called Griineisen

coefficient d(log (j)jd(log V), where V is the volume, may be deduced from
the coefficient of expansion of the solid. Calculations carried out along
these lines give fair agreement with the observed changes in a. For a
discussion of the exceptional cases the reader is referred to the literature. 12

11-7. Thermal scattering described as electron-phonon collisions

Although the treatment followed in the preceding section gives a
qualitative insight into the causes of resistivity, it does not touch upon the
actual problem of calculating the perturbing influence of the lattice
vibrations on the motion of the electrons. The problem of the coupling
between the electrons and the lattice is a very complicated one, and in
order to calculate the conductivity, strongly simplifying assumptions must
be introduced. In a theory developed by Bloch the lattice vibrations are
described in terms of a Debye model, and the interaction of the electrons
with the lattice vibrations is assumed to be weakP Furthermore, it is
assumed that the lattice and the electronic system remain essentially in
II For a simplified treatment of the resistivity of completely disordered alloys see

N. F. Mott and H. Jones, op. cit., p. 297. Their treatment leads to Po = const. x(l - x),
where x is the atomic concentration of one of the elements and (I - x}.is that of the
other. This type of curve is in rather good agreement with experimental results; it gives
rise to the arch in Fig. 11-5.
]2 For references see N. F. Mott and H. Jones, op. cit., p. 272.

]3 F. Bloch, Z. Physik, 52, 555 (1928); 53,216 (1929); 59,208 (1930).

!HiifH')fr
290 CONDUCTIVITY OF METALS [Chap. 11
thermal equilibrium. For critical reviews of this subject and for the
details of the theory we must refer the reader to the literature. 4 A few
remarks will be made here in connection with the description of electron-
lattice interaction in terms of electron-phonon collisions.
Suppose an elastic wave of wave vector q and angular frequency Wq is
propagated through a crystal lattice. The displacement of an atom at the
lattice point r due to the vibrational mode may then be written in the form
(see Chapter 2), /

where Aq is the amplitude. For a transverse mode the displacement is

perpendicular to q; for a longitudinal mode it is parallel to q. At the
temperature T the average energy associated with this mode is given by
Planck's formula, ,. 1
liwq/[exp (liwq/kT - I)]
It is convenient to call1iwq·the energy of a "phonon," in analogy with the
photon concept in electromagnetic radiation. We may then say that the
vibrational mode at the temperature T corresponds to exp (liwq/kT - I)
phonons. Note that the energy of a phonon may be written
liw q = licsq
where Cs is the velocity of sound (if we use a Debye model, Cs is independent
ofq).
As a result of the atomic displacements, an electron of reduced wave
vector k sees a potential which is somewhat different from that corre-
sponding to the situation in which all nuclei are in their equilibrium
positions. Thus there exists a non vanishing transition probability for the
electron to be scattered into another state k'. In order to deal with this
type of problem, one usually applies time-dependent perturbation theory
to the system consisting of the electron plus the lattice vibrations. It turns
out that the transition probabilities vanish unless the following selection
rules are satisfied
ii'i E k • = Ek ± licsq ~. (11-41)
k' = k ± q + 27Tb (11-42)
where either the upper or the lower signs should be used. The vector b is
a vector in the reciprocal lattice and for a simple cubic lattice 27Tb =
(27T/a)n, where n is a vector with integer components. For the moment we
shall assume b = 0; in this case the selection rules have a simple physical
interpretation: (11-41) expresses the conservation of energy in an electron-
phonon collision, the + sign corresponding to absorption, the - sign
corresponding to emission of a phonon by the electron. Similarly, (11-42)
(with b = 0) may be considered as expressing the law of conservation of
momentum in an electron-phonon collision; the momentum of the

I 1
Sec. 11-7] CONDUCTIVITY OF METALS 291
electron is given by p = lik, the momentum associated with the phonon is
nq = IiwQ/c s in complete analogy with the momentum associated with a
photon. The selection rules have interesting consequences, a few of which
may be mentioned here. First of all, we may bear in mind that the values
of q are limited to the range 0 < q < qlltaX ~ 7T/a. Hence the energy of the
most energetic phonons is only licsqlllax ~ 0.01 ev, assuming c,,-..J 10 5 cm
secI. On the other hand, electrons near the Fermi level, the scattering of
which determines essentially the conductivity of metals according to
(11-30), have energies of several ev; hence when such electrons are scattered
their energy remains essentially unaltered, although they may be scattered
over large angles (when k ~ q). The angle fJ over which an electron is
scattered by phonon absorption or emission may also be found from the
selection rules.if the functions E(k) and E(k') are known. We leave it to
the reader to show that when E(k) = 1i2k2/2m* and the electron energy is
large compared to the phonon energy,
sin (fJ/2) ~ q/2k "
"t'
.( (1l-43)
Since the absolute value of the left-hand side of this equation is ~ 1, the
electrons can interact only with such phonons for which q ~ 2k. Thus
low-energy electrons with small k-values can interact only with a fraction
of the total spectrum of vibrational modes; electrons near the Fermi level
can interact with essentially the whole spectrum of vibrations.
At temperatures far below the Oebye temperature, there are essentially
only phonons for which the wave vector q satisfies the inequality
(11-44)

(k o is Boltzmann's constant); the higher-frequency modes require too

much excitation energy. Consequently, electrons near the Fermi level can
be scattered only over small angles when the temperature is low. In fact,
according to the last two equations,
(11-45)

A few remarks may be made here about the case for which b =f:: 0
in equation (11-42); such processes are called "Umklapp-Prozesse"
("reversal processes").14 For cubic crystals they are described by
k' = k ± q + (27T/a)n (11-46)
where n has integer components. Such processes, viz., with q = 0, we
have encountered in the preceding chapter; in fact, k' = k + (27T/a)n
represents the condition for Bragg reflection of an electron by a set of
atomic planes with Miller indices (n 1n 2n3 ). The only difference which
arises presently is that k +
q satisfies the Bragg condition rather than k
,. R. Peieris, Ann. Physik, 4, 121 (1930); 5,244 (1930).
292 CONDUCTIVITY OF :M'ETALS [Chap. 11

alone. Since q may accept a great variety of values, an electron in state k

has many more possibilities for such reflections. It is evident that in an
Umklapp process there is no conservation of momentum of the system
electron plus phonon. In fact, in such a process an electron absorbs a
phonon and thereby arrives in a state at the boundary of a Brillouin zone,
whereupon it suff{,~ a reflection. .
Peierls has suggested that Umklapp processes are essential in maintain-
ing thermal equilibrium in the phonon system when an electric current
flows at low temperatures. 15 The problem involved here is the following.
When there is an electric field in the positive x-direction, the electrons gain
momentum in the negative x-direction. This momentum is given off to the
lattice by the electron-lattice interaction, and thus the phonon equilibrium
is disturbed. In the theory of conductivity it is usually assumed that the
phonons are in thermal equilibrium; at normal temperatures the inter-
action between the phonons (due to anharmonic forces) is probably strong
enough to maintain essentially thermal equilibrium. However, at low
temperatures, the "self-relaxation" of the lattice may require long periods;
in that case the lattice waves would accumulate momentum in the direction
of the electronic current, and consequently further transfer of momentum
from the electronic system to the phonon systeJ? would be inhibited. In an
Umklapp process, however, electronic momentum may be destroyed
without the necessity of having this momentum absorbed by phonons;
thus Peierls suggests that these processes must be responsible for main-
taining phonon equilibrium at low temperatures. 15 His suggestion has
been criticized by Klemens, who claims that the anharmonicity of the
lattice forces is strong enough to maintain phonon equilibrium. 16 The
problem of "phonon-drag" has received much attention in recent years.

11-8. The electrical conductivity at low temperatures

From the Bloch theory,13 in which the interaction between the con-
duction electrons and the lattice vibrations is investigated by approximative
methods, it follows that for (TjO)2;y I, a relaxation time can be defined.
Thus once 'Tp has been calculated, the conductivity can be obtained
immediately from (11-30) (or from its more general torm). In that
temperature region his theory leads for free electrons to

(j = 2.83 X 1O-32n M()2jC2T (cgs) (11-47)

where n is the number of electrons per cm 3 , M is the atomic weight, () is

the Debye temperature, and C is a constant characteristic of the metal,
with the dimensions of an energy; C may be calculated from experimental
IS R. Peierls, Ann. Physik, 12, 154 (1932).
16 P. G. Klemens, Proc. Phys. Soc. (London), A64, 1030 (1951).
Sec. 11-8] CONDUCTIVITY OF METALS 293
a-values by means of (11-47) and turns out to be roughly equal to the
Fermi energy. The value of C is determined by the coupling between the
electrons and the lattice vibrations. We note that this formula confirms
expression (11-38) which we used in our qualitative discussion of the
conductivity in the high-temperature range.
At low temperatures (T <fJ), a relaxation time cannot be defined
consistently. It is, of course, always possible to define TF in accordance
with (11-30) by Tp = majne 2 ; however, if one defines Tp in a similar way
from the thermal conductivity, the two values of Tp are no longer equal
(for T < 0) and the concept has lost its usefulness. On the other hand, for
the electrical conductivity it is still possible to find a relatively simple
solution to the Boltzmann transport equation in the region T <
0; for the
thermal conductivity this is not the case (because it is a second-order
phenomenon). For low temperatures, Bloch's analysis leads to a resistivity
proportional to T5. In an oversimplified way, one may make the T5 law
plausible by the following arguments. First of all, at low temperatures the
specific heat of the metallic lattice is proportional to T3 (in the Debye
model); therefore the density ofphonons and the probability for scattering
are proportional to T3. Furthermore, the angle of scattering at low tem-
peratures is proportional to T according to (11-45). Now, if one sub-
stitutes (11-45) into (11-11) one finds that the influence of the small
scattering angles alone would lead to a factor T-2 in the conductivity, i.e.,
T2 in the resistivity. Consequently, p is proportional to T 3-r2 = T5. Since
this argument implies the existence of a relaxation time, it is not very
satisfactory; on the other hand, it points to the two essential causes for
the T5 law: the decrease in density of phonons and the decrease of the
scattering angle with decreasing temperature.
On the bases of certain approximations it is possible to obtain from
Bloch's theory a formula which covers the whole temperature range :17
this formula had been used previously by Griineisen18 on a semiempirical
basis and is of the form
5 .. "

peT) = ( 10 5 (OIT (eX

AT).Io
X dx
_ 1)(1 _ e-X) (11-48)

where A is a constant characteristic of the metal. Note that for T ~ 0 the

integral ~ HOjT)4, so that in that region p is proportional to T, in agree-
ment with experiment. For T <
0 we may replace the upper limit of the
integral by 00, leading to the T5 law. When one plots p(T)j p(O) versus
(TjO), one obtains from (11-48) the universal curve given in Fig. 11-6,
which represents the experimental data above ,.....,20 o K very well for many
metals. On the basis of (11-48) one may determine the Debye temperature
17 See, for example. M. Kohler, Z. Physik, 125,679 (1949).

,. E. Griineisen, Ann. Physik, 16,530 (1933).

294 CONDUCTIVITY OF METALS . [Chap. II

o from resistivity measurements; in fact, when two temperatures Tl and

T2 satisfy the condition Tl ~ e ~ T 2, one finds from (l1-48),
p(Tl )/ P(T2) = 497.6(Tl /e)4(Tl /T2) (11-49)
A comparison of Debye temperatures so obtained with those determined
from specific heat data is given in Table 11-2; the agreement is good.
.3 However, systematic studies by the
Leiden l9 and Oxford 2o low-tempera-
ture groups ha\,e shown that devi-
ations from (11-48) occur in the region
between 4° and 20°K. One type of
deviation is illustrated in Fig. 11-7,
which represents the "apparent"
t .1
Oebye temperature as function of T
for Rb; the apparent e at a given
temperature is calculated from (11-49)
on the basis of resistivity measure-
ments. It is observed that instead
o .2 .3 .4 .5
of being constant, e varies with T.
-T/8
Such discrepancies may be compared
Fig. 11-6. The reduced resistivity
p(T)1 p(f) as function of the reduced
with thos'e observed at low tempera-
temperature (Tlf), according to the tures for the apparent 0 calculated
Bloch-Grtineisen formula (11-48). from the T3 law of the specific heat
(see Sec. 2-13). The occurrence of
such deviations is not too surprising in view of the approximations involved
in the theory, in particular the use of the Debye appro~imation for the
lattice vibrations, which is known to be inaccurate at low temperatures.
Deviations of a more fundamental character in the region ~ lOoK were
first reported by de Haas, de Boer, and van den Berg ;19 they found a
minimum in the resistivity versus T curve of gold specimens, the minimum
shifting to lower temperatures as the sample becomes more pure. The
effect has since been observed in other metals as well; the explanation of
the effect is still in doubt.
Table 11-2. Comparison of Characteristic Temperatures in Degrees
Absolute Obtained from Specific Heat and from Resistivity Data. [After
D. K. C. MacDonald, Progress in Metal Physics, 3, 42 (1952).]

Metal Na Cu Ag Au Al Pb W Ta

o (sp. heat) 159 315~330 210~215 163~186 390 82~88 305~337 245
o(resist.) 202 333 223 175 395 86 333 228

19 Work by W. 1. de Haas, 1. de Boer, and G. 1. van den Berg has been reported

in Physico 1, W9 (1934); 1, )115 (1934); 2, 453 (1935); 3, 440 (1936); 4,683 (1937).
20 D. K. C. MacDonald and K. Mendelssohn, Proc. Roy. Soc. (London), A202,

523 (1950).
Sec. 11-9J CONDUCTIVITY OF METALS 295

200 l'{;l':!clJl'!5vf,it. ,', y,",,V';rl,\

160 . h·"" .,".> :' .'
8
t 120
.... , < .' , ; . -•

80 , i,
L -
40

o 20 40 60 80 lOO'K
-- T
Fig. 11-7. The "apparent" characteristic temperature () for Rb, as
deduced from resistivity measurements by employing (11-49). [After
MacDonald and Mendelssohn, ref. 20]

11-9. The thermal conductivity of insulators J

1
I '

A thermal gradient in a cubic crystal gives rise to a flow of heat in a

direction opposite to that of the gradient. Thus if there exists a thermal
gradient dT/dx along the x-direction and Q", is the resulting heat current
density, the thermal conductivity K is defined as
; ,",11: "

K = -Qx/(dT/dx) (11-50)
In normal insulators the heat flow is carried by lattice waves. In metals,
the thermal conductivity is, at least in principle, determined by the
conduction electrons as well as by the lattice waves. Usually the electronic
contribution dominates strongly in metals; however, in poor metals such
as bismuth, or in metals containing large amounts of impurities (alloys),
the lattice conductivity may be important. For the moment we shall
confine ourselves to the thermal conductivity in insulators to obtain some
insight into the lattice conductivity.
A theory of the thermal conductivity of insulators was developed in
1914 by Debye ;21 as in his theory of the specific heat (1912), he assumed
that the lattice vibrations may be described by a model in which elastic
waves are propagated through a continuum. Since solids expand upon
heating, these waves cannot be purely harmonic but must be anharmonic.
This anharmonicity was, according to Debye, the source of coupling
between the lattice waves, so that mutual scattering of the waves becomes
possible. (He pointed out that mutual scattering is not possible for purely
harmonic waves.) As a measure for the coupling, Debye introduced a
mean free path A, which measures the distance of travel of a wave required
to attenuate its intensity by a factor e.
21 P. Debye, Vortriige iiber die kinetische Theorie der Materie und der Elektrizitiit,

Teubner, Berlin, 1914, pp. 19-60. ,

296 CONDUCTIVITY OF METALS [Chap. II
These ideas were extended by Peierls and translated in terms of
phonon-phonon interaction. 22 When a temperature gradient is present in
a solid, the phonon distribution is different from that existing in thermal
equilibrium; the phonon-phonon collisions tend to restore this equilibrium,
the rate of the restoring process being the determining factor for the
thermal resistance. The selection rules for the collisions between two
phonons are similar to those for the collision between an electron and a
phonon (11-41) and (11-42); in fact, a collision between two phonons 1
and 2 is possible when
(11-51)

(11-52)

where a is the cube edge in a cubic crystal and n is a vector with integer
components. According to (II-51), two phonons may give rise to a single
phonon with an energy nW3 equal to the sum of the energies of t he original
phonons (conservation of energy). Ifin (11-52) we assume for the moment
n = 0, this equation expresses the law of conservation of momentum.
However, collisions of the type n = °
do not contribute to the thermal
resistance because after such a collision the energy is still flowing in the same
direction as before. On the other hand, when the vector n *- 0, the
direction of flow of energy has changed after the collision; these so-called
"Umklapp" processes (compare Sec. 11-7) are therefore responsible for
the thermal resistance in Peierls' theory. Since the vector n may accept
a number of directions in space, e.g., along the six directions corresponding
to the cube edges in a cubic lattice, the scattering may be considered
as approximately random.
In order to set up an expression for the thermal conductivity, we remind
the reader of a well-known formula for the thermal conductivity of a gas :23

K= ~CvA (11-53)
--f
11-.
where C is the specific heat (at constant volume) of the gas per unit
volume, v is the average velocity of the molecules, and A is the mean free
path. In analogy, we may write for the conductivity associated with the
Umklapp processes,24

K" = t ~~ C;jv;jA;j
, J
(11-54)

The subscript j refers to the direction of polarization of the phonons; the

summation over i extends over the complete frequency range of the
22 R. Peierls, Ann. Physik, 3, 1055 (1929).
23 For a derivation, see any textbook on the kinetic theory of gases.
24 See, for example, R. Berman, Advances in PhysiCS, 2, 103 (1953).
Sec. 11-9] CONDUCTIVITY OF METALS 297
vibrational spectrum. In a Debye model for the lattice vibrations the
velocities Vi; are all equal (to the velocity of sound cs ).
For a given solid the thermal resistance may arise as a result of a
variety of causes:
(i) Umklapp processes (Ku)
(ii) Scattering of phonons by boundaries (Kb)
(iii) Scattering by impurities and lattice imperfections (Ki) .'il

If we consider these processes independent, their scattering probabilities

may be added, and the resultant conductivity is then given by
IlK = IIKu + IIKb + IlK; (11-55)
For the moment we shall consider an ideal crystal of infinite dimensions,
and inquire about the temperature-dependence of Ku. As long as the
temperature is well above the Debye temperature, the specific heats e,; in
(II-54) are all the same and independent of T (viz., equal to ko per mode,
where ko is Boltzmann's constant). Furthermore, the mean free path for
a given phonon ij is inversily proportional to the density of all other
phonons with which it can interact. Since the number of phonons of a
given type is equal to kTjliw i ;, the density of all phonons is proportional
to T. We thus conclude that
Ai; oc T-I and Ku oc T-I for T?> 0 (11-56)
For macroscopic crystals which are well annealed, (ii) and (iii) may usually
be neglected in this range of temperatures. For example, for NaCl at
oDe, K = 0.017 cal cm- I degree- I sec-I; assuming K = K u, we find by
using the simple expression (11-53) that Au'__ 20 A on the basis of a
specific heat of 0.45 cal cm-3 and a velocity of sound of,....,5 X I05 cm sec-I.
When processes (ii) and (iii) lead to a mean free path of the same order
as Au or smaller, they can, of course, no longer be neglected. It is obvious
that (ii) and (iii) may be expected to become important at low temperatures
and in imperfect crystals.
In considering the Umklapp processes at low temperatures (T ~ (J),
we must point out that equation (11-52) indicates that Umklapp processes
can occur only when the phonons have an energy larger than a certain
minimum value. In fact, we want at least one of the q's to be of the order
Ija, corresponding to a phonon energy ,....,ko(J (k o is Boltzmann's constant).
Peierls takes as a threshold energy ko(Jj2.22 Now the number of phonons
with this energy is proportional to lj[exp (Oj2T) - 1]. From this we
deduce that the temperature-dependences of Au and Ku at low temperatures i

are essentially given by

(11-57)
Thus the Umklapp processes lead to a thermal conductivity which
298 CONDUCTIVITY OF METALS [Chap. II
decreases exponentially with T in the low-temperature region; in the
high-temperature region it decreases as T-l. Although Kit ~ CIJ for T -)- 0,
the total thermal conductivity remains finite even in a perfect crystal, as a
result of boundary scattering. Qualitatively, the influence of the latter at
low temperatures may be seen from (11-53): since the specific heat is ",
proportional to T3 and the mean free path Ab is determined by the
dimensions of the crystal, Kb is proportional to ra and to the crystal
dimensions. A quantitative calculation of this effect has been made by
-
~)Jin ,b~)'bbi.
K ................... \
t ···s~~ttering by electrons

Fig. 11-8. The fully drawn curve represents the general theoretical
. form of the thermal conductivity of an insulator; in metals,
phonons are scattered by electrons as well (dotted curve), leading
to the dashed resultant curve. [After R. E. B. Makinson, Proc.
Cambro Phil. Soc., 34, 474 (1938)]

Casimir. 25 The general form of the thermal conductivity of an ideal

insulating crystal is given by the fully drawn curve in Fig. 11-8, indicating
the occurrence of a maximum. In order to observe the exponential
behavior predicted by Peierls, one must measure K in the range between
0/10 to 0/20. The lower limit of this temperature region is determined
not only by the boundary scattering, which must be negligible, but also
by the fact that scattering by imperfections must be avoided. Results for
the mean free path obtained in this region are represented in Fig. 11-9
for sapphire, diamond, and solid helium. The conductivity in this range
fits a relation of the type K oc Tne01bT, where b is approximately 2 (compare
11-57). For further details on this topic we refer to the literature. 24 In
general, Peierls' theory combined with Casimir's calculation of the
influence of crystal size at low temperatures describes the experiments
satisfactorily.
2.; H. B. G. Casimir, Physica, 5, 595 (1938); see also H. B. G. Casimir, Mu,f{l1etis11I

at Very Low Temperatures, Cambridge, London, 1940.

Sec. 11-IOJ CONDUCTIVITY OF METALS 299

11-10. The thermal conductivity of metals

Although lattice conductivity may become important in metals under

certain circumstances (low T, high magnetic fields, large impurity content),
we shall assume for the moment that their thermal conductivity is deter-
mined solely by the conduction electrons. Thus, let there be a thermal
gradient dT/dx in a metal and a 5xlO- 3 Au (em) i~,
thermal current density Q",. Since
the gradient produces a drift velocity
t .--,;.;r-
of the electrons and since the heat
flow is determined under conditions
of zero electric current, a small
electric field must be set up intern-
ally to counteract the drift velocity
due to the gradient; this is achieved
by a slight redistribution of the
electrons. Thus, in the Boltzmann 10- 5
equation (I I - I 8) we must include, 5XlO- 6
besides the thermal gradient dT/dx
(which leads to a term oj/ax), a term
containing an electric field Ex. We 10- 6 ' - - - - ' - - - - ' - - - - ' - -
shall first consider the region T?> e, 10 15 20

since in this region one can define a Fig. 11-9. The mean free path for
relaxation time, which simplifies the Umklapp processes as function of OfT:
A, synthetic sapphire (0,.",980); B,
calculation of the conductivity diamond (0,.",1840), C, solid helium
tremendously. Using the notation (0, 22-35). [After R. Berman, F. E.
of Sec. I 1-3 we obtain for this case Simon, and J. Wilks, Nature, London,
from (11-18), 168,277 (1951)1

- ( f - jO)jT = -eE",(aj/apx) + v",(aj/ax)(aTjax) (II-58)

As long as the electric field and (aT/ax) are small, we may replacejon the
right-hand side by /0' as we did in calculating the electrical conductivity.
The thermal current density in terms of the distribution function F(pxpypz)
introduced in Sec. 11-4 is given by

(II-59)
i
where E is the energy of an electron. When Q", is calculated by solving
( II-58) under the condition that the electric current
300 CONDUCTIVITY OF METALS [Chap. II

vanishes, one finds for the electronic thermal conductivity K r ' in the free
electron approximation,26
T (11-60)
Here T F is again the relaxation time for electrons at the Fermi level. From
the theory of interaction of electrons with lattice vibrations one can show
that TF is proportional to T--I, so that
Kr constant T~ (j (11-61)
35 tK (watts cm- 1 deg- 1)
=

in good agreement with experimental

data. Note that combination of
30
(11-60) and (11-31) leads to the
Wiedemann-Franz law [see point
25
(8) in Sec. II-I].
20 L _ Ke/aT= (7T 2/3)(k/e)2
= 2.7 X 1O-13 cgs unit (T ~ () "
15 (11-6;:::~
Here L is called the Lorenz number;
10 the theoretical value is in rather good
agreement with experimental data in
5 the high-temperature region.
It can be shown that the existence
o 20 40 60 80 100 of a relaxation time is a sufficient
---+- T (OK) condition for the constancy of the
Lorenz number. Experimentally one
Fig. 11-10. The thermal conductivity
finds, however, that as the tempera-
of two samples of sodium; sample II is
purer than sample I. [After Berman ture decreases, L decreases, indicating
and MacDonald, ref. 27] that the concept of a relaxation
time cannot be extended to low tem-
peratures. At this point we may mention that, like the electrical resistivity,
the thermal resistivity associated with electrons may be considered to
consist of two parts: one due to scattering by lattice vibrations, another
due to scattering by impurities or other lattice imperfections. Denoting
these parts, respectively, by subscripts I and i, we may write, if they are
independent,
(J 1-63)

The last equality follows from the fact that for impurity scattering one
may always define a relaxation time (see the end of Sec. 11-3). Thus, by
plotting T/K, versus T, one can obtain liLa; from the intercept at T = 0
and Krl may be determined by subtraction.
In the case of the electrical conductivity one can, even in the low-
temperature region where no relaxation time can be defined properly,
•• See, for example, A. H'"Wilson, op. cit., pp. 18,20],
Sec. 11-10] CONDUCTIVITY OF METALS 301
arrive at a relatively simple solution for the Boltzmann transport equation.
For the thermal conductivity, which is a second-order phenomenon, this is
much more complicated; for a discussion of this subject we refer the
reader to the literature. As an example of the thermal conductivity of
metals we represent in Fig. 11-10 measured curves for two sodium samples
of different purity.27 The theory leads to curves of a similar type.
In alloys, the lattice conductivity must also be taken into account,
since the electronic thermal resistance is increased as a result of impurity
scattering. Furthermore, the lattice conductivity is modified as a result of
phonon scattering by electrons, as indicated in Fig. 11-8.
For pure metals, one may estimate
the ratio of the electronic and lattice
conductivities at high temperatures as
follows: according to (11-60) and (11-53) ++++++
we may write . :-. ,,
../-
/Hz ~Ey -vx

Kelectron.//("attice = -rr2kgTn'iF/m ACc.

Considering a monovalent metal for Fig. ll-ll. Illustrating the Hall
which the density of electrons n is effect, in a metal, produced by an
electric field Ex and a magnetic field
equal to the density of atoms, one H. perpendicular to the front face.
finds with a specific heat (at constant The electrons move with a drift
volume) of 3nko, a velocity of sound velocity v, as indicated; the Lorentz
c. ~ 5x 105 cm sec-I, 'iF ~ 3x 10-14 force acts downward along the
sec, and a phonon mean free path y-axis. For positive charge carriers,
E. will be reversed.
A ~ 100 A for this ratio .,",-, 102.
(

',:"

ll-ll. The Hall effect in metals 'U ~ .

Consider a slab of material subjected to an external field E", along the

x-axis and a magnetic field Hz along the z-axis as illustrated in Fig. 11-11.
As a result of the applied electric field, a current density /", will flow in
the direction of E",. For the moment let us assume that the current is
carried by electrons of a charge -e. Under influence of the magnetic
field the electrons will be subjected to a Lorentz force such that the lower
surface collects a negative charge, the upper surface a positive charge.
Ultimately, a stationary state is obtained in which the current along the
y-axis vanishes and a field E1I is set up. If the charge carriers were positive,
the upper surface would become negative relative to the lower surface,
i.e., E1/ would be reversed. From this it is evident that a measurement of
the "Hall voltage" in the y-direction gives information about the sign of
the charge carriers. Measurements of this kind are thus useful in semi-
conductor research. Furthermore, the density of the charge carriers may
27 R. Berman and D. K. C. MacDonald, Proc. Roy. Soc. (London), Al09, 368 (1952).
302 CONDUCTIVITY OF METALS [Chap. 1 I

be obtained, at least if the current is carried either by electrons or holes.

To illustrate this, let us assume a free electron model for a metal; the
derivation given here is strongly simplified, but leads to the same result
as obtained from the Boltzmann transport equation. 28 The force exerted
on an electron of charge -e by a combined electric and magnetic field is
given by the Lorentz formula,

(11-64)

F0r the configuration of Fig. II-II we have from Fy = 0 in the steady state
Ey = (IJc)vxHz
where r" is the average drift veiocity of the electrons. Also, the current
density may be expressed in terms of the number of electrons n per unit
volume as t" \ . rnnw vr;m
.-.----.-,-- -..--"'.".~~.::. Ix = -nel'""
From the last two equations one obtains for the Hall coefficient,
RH =c:= EyJlxH z = -IJnec (11·65)
Thus the Hall coefficient is determined essentially by the sign and density
of the charge carriers. Observed Hall coefficients for a number of metals
are given in Table 11-3. It is observed that a number of metals have
positive Hall coefficients. Qualitatively, this can be explained on the
basis of the band theory of metals, since a metal with a nearly filled band
is equivalent to a conductor in which the current is carried by positive
holes; this would change the sign of R. For further details on the Hall
effect see Chapter 13. We should mention that the same information as
obtained from Hall coefficient measurements can be obtained from the
thermoelectric force.

Table 11-3. Hall Coefficient of a Number of Metals at Room

Temperature, in volts/cm-abamp-gauss. (After Seitz, Modern
Theory o/So/ids, McGraw-Hili, New York, 1940, p. 183)
I I
1012R H 1012RH I0 12 RH
. --- I----~- --~---
--
Cu -5.5 Be 24.4" Fe 100
Ag 8.4 Zn 3.3 Co 24
Au 7.2 Cd 6.0 Ni -60
Li 17.0 AI 3.0
Na -25.0

Negative signs indicate electron conduction. positive signs indicate hole conduction.

,. See, for example, F. Seitz, The Modem Theory olSo/ids, McGraw-Hili, New York,
J940, p. 181.
Chap. II] CONDUCTIVITY OF METALS 303
REFERENCES
Besides the books referred to at the end of the preceding chapter, the
following review papers may be consulted:
J. Bardeen, "Electrical Conductivity of Metals," J. Appl. Phys., 11,88 (1940).
R. Berman, "The Thermal Conductivity of Dielectric Solids at Low
Temperatures," Advances in Physics (quarterly supplement of the
Philosophical Magazine), 2, 103 (1953).
P. G. Klemens, "Thermal Conductivity of Solids at Low Temperatures,"
Encyclopedia of Physics, Springer, Berlin, 1956, vol. 14, pp. 198-276.
D. K. C. MacDonald, "Properties of Metals at Low Temperatures,"
Progress in Metal Physics, 3, 42 (1952). ')<1)' ,

D. K. C. MacDonald, "Electrical Conductivity of Metals and Alloys at

Low Temperatures," Encyclopedia of Physics, Springer, Berlin, 1956,
vol. 14, pp. 137-197.
J. L. Olsen and H. M. Rosenberg, "On the Thermal Conductivity of
Metals at Low Temperatures," Advances in Physics, 2, 28 (1953).
"Proceedings of the International Conference on Electron Transport in
Metals and Solids," Can. J. Phys. 34, Dec. 1956, No. 12A.

PROBLEMS
11-1. From the observed. electrical conductivity of copper at room
temperature, calculate the relaxation time and the mean free path for
electrons at the Fermi level on the basis of (11-30); assume one free
electron per atom. Also calculate the average drift velocity of these
electrons in a field of I volt per cm and compare the result with the average
velocity in the absence of a field. ,\.....
11-2. Show that on the basis of the classical picture of electron
scattering by rigid spheres (the atoms) and on the assumption that the
electrons obey Boltzmann statistics, the electrical conductivity should be
proportional to T-1/2. How does this compare with experiment?
11-3. Set up a simple classical theory for the thermal conductivity
K ofa metal and show that in this theory KjaT= 3(kje)2 = 2.48 X 10-13 cgs
unit, where a is the electrical conductivity. This is the Wiedemann-Franz
law. See for example the first chapters of the books by A. H. Wilson,
0p. cit., and by N. F. Mott and H. Jones, op. cit.
11-4. Show that if the ions in a metal behave as rigid spheres with
respect to electron scattering, a relaxation time can be properly defined
(see, for example, A. H. Wilson, 0p. cit., p. 8).
304 CONDUCTIVITY OF METALS [Chap. II

) 1-5. Consider a group of similar particles which at the instant t = 0

all move in the x-direction with the same velocity VOX' Suppose the
particles are scattered by obstacles such that the average time between
collisions is 'T r • The scattering is not isotropic. Show that the average
velocity of the group measured along the x-direction decreases exponen-
tially to zero with a relaxation time 'T = Tr/(l - (cos fJ», where {J is the
scattering angle and (cos (J) is the average of cos (J.
11-6. Give a rough estimate of the density of vacancies or interstitial
atoms required in a metal such as copper to make the impurity resistivity
comparable to the resistivity associated with lattice vibrations at room
temperature; do ttys on the basis of mean free path considerations. Do
the same problem I. of liquid air and liquid helium temperatures.
11-7. In the simplified discussion of Sec. 11-6 it was assumed that the
cross section for scattering of an electron by an atom was proportional
to the mean square displacement of the vibrating atom. Calculate the
mean square displacement of a silver atom in the metal at room tempera-
ture, assuming that the frequency is equal to the Debye frequency. Also,
calculate the cross section QF for scattering per silver atom from the
observed conductivity at room temperature. Find the proportionality
factor relating QF and (x 2) for this case.
11-8. Consider a collision between an electron and a phonon in which
the phonon is absorbed by the electron. Assume that the energy of the
electron may be written E(k) = fi 2k 2 /2m, and that the electron energy is
much larger than the energy of the phonon. From the conservation laws,
show that sin (fJI2) ~ q/2k where {J is the angle over which the electron is
scattered and q is the magnitude of the wave vector of the phonon. Also,
calculate the scattering angle if the electron has an energy of 4 ev and
the phonon has a wavelength of loA; assume that the velocity of sound
is 10 5 cm sec l . For this case, what is the required angle between k and
q before the collision?
11-9. Consider a metal subject to an electric field and a constant
temperature gradient, both in the x-direction. Set up the Boltzmann
transport equation for this case and show that in the free electron
approximation, if a relaxation time exists, the thermal conductivity is
given by (11-60). See, for example, F. Seitz, op. cit., pp. 174 ff.
11-10. Define the thermoelectric effects: the Thomson effect, the
Peltier effect, and the Seebeck effect. Discuss these effects for metals on
the basis of the free electron approximation. See F. Seitz, op. cit., 178,
or A. H. Wilson, op. cit., p. 202.
a
11-11. Discuss the influence of magnetic field on the resistivity of
metals (magnetoresistance effect). For this and other galvanomagnetic
effects see A. H. Wilson. op. cit., or N. F. Mott and H. Jones. op. cit.
,,

Chapter 12' ,-.j~

THE ELECTRON DISTRIBUTION IN

INSULATORS AND SEMICONDUCTORS

The electrical properties of semiconductors are determined essentially

by the following quantities:
(i) The number of electrons and holes per unit volume.
(ii) The mobility of the electrons and holes.
It is therefore convenient to discuss the temperature-dependence of the
density of charge carriers for some frequently occurring cases before going
into the details of specific types of semiconductors.

12-1. The Fermi distribution

As shown in Appendix D, the number of electrons per unit volume

occupying states in the energy range between E and E + dE in any
electronic system in thermal equilibrum is given by .j: i ' ';.'t'

neE) dE = Z(E)F(E) dE (12-1)

where F(E) is the Fermi distribution function,

. (12-2)

and Z(E) represents the number of possible states per unit volume,
(including the spin). So far we have had an opportunity to employ this
distribution law only in the free electron theory of metals, in which case
Z(E) is proportional to E1/2 when E is measured from the bottom of the
potential well representing the metal. In that case, the physical meaning
of E]<' at T = 0 was simply that it represented the highest occupied state.
In the case of insulators and intrinsic semiconductors where Z(E) may be
a complicated function of E which vanishes in the forbidden energy ranges,
the physical meaning of E]<' may not be immediately obvious. In general,"
of course, we may say that E]<' corresponds to that .level which has a proba-
bility of t for being occupied; this follows immediately from (12-2).
However, Ep in the case of insulators and semiconductors is usually
located somewhere between the valence and conduction bands, i.e., in
305
306 ELECTRON DISTRIBUTION IN INSULATORS [Chap. 12

general E]<' is not a level which can actually be occupied by an electron.

The physical meaning in these cases is therefore somewhat more abstract
than that in the case of metals. The position of the Fermi level in any case
may be determined from the condition ;

, ~.
ji;;LI
SneE) dE = SZ(E)F(E) dE = n\ ( 12-3)

where 11 is the total number of electrons per unit volume. The general
procedure of calculating neE) for given Z(E) and T therefore is this: from
(12-3) one calculates E]<' and from it
:::;::====Ec neE) may be determined by substitu-
f tion into (12-1).
Eg - - ----EF

12-2. A simplified model of an insulator

Illlllllliillli Ev
In order to indicate the general
features of the electron and hole dis-
tribution in insulators and intrinsic
F(E) _ L - _ J _ _ _ _ J ==== semiconductors as functions of tem-
1 .5 0
perature, we shall first consider a
Fig. 12-1. Insulator with Fermi level simplified model. It will be assumed
half-way between valence and con- that the widths of the valence and
duction bands. The band widths are conduction bands are small compared
assumed small compared with Eg. The
with the forbidden gap between the
Fermi distribution function is indicated
on the left. two bands. In this case we may
associate a single energy Ec with all
states in the conduction band and a single energy Ev with all states in
the valence band (see Fig. 12-1). This situation resembles closely
the system of discrete energy levels in an atom. Let each band contain
Z possible states per unit volume; Z ~ 1022 per cm3 • At T = 0 the
electrons are in their lowest state, and because the solid is assumed
to be an insulator at this temperature, the valence band and all lower
bands are completely filled; the conduction band at T = 0 is completely
empty. At temperatures different from zero, the density of electrons in
the conduction band is given by
Z
n = --------- (12-4)
C exp [(Ec - EF)/kT] +1
Similarly, the density of electrons in the valence band is
Z
n = -------:-c:-:---::-- (12-5)
V exp [(Ev - EF)/kT] + 1
It will be evident that for gap widths of the order of several electron volts,
practically all electrons in the conduction band originate from the valence
Sec. 12-2] ELECTRON DISTRIBUTION IN INSULATORS 307

band, so that the presence of bands below the latter may be neglected. l
]n other words, we may write
(12-6)

Substituting (12-4) and (12-5) into this expression, one obtains an equation
for EF • leading to:
(12-7)

Thus, in this model, the Fermi level is located exactly halfway between the
valence and conduction bands. Also, its position is independent of tem-
perature in this approximation.
The density of electrons in the conduction band may now be found by
substituting EF from (12-7) into (12-4). Ifwe assume that the Fermi level
is more than about 4kT away from the conduction band, the term
unity in the denominators of (12-4) and (12-5) may be neglected to a good
approximation. In that case,

(12-8)

where Ey = Ec - Ev represents the width of the forbidden gap. This

result may be compared with the improved formula (12-19). The number
of holes in the valence band is, of course, equal to nco Note the occurrence
of half the gap width in the Boltzmann factor (see Problem 12-1). Clearly,
when log nc is plotted 'versus I/T, a straight line with a slope of -Eg /2k
results (see Fig. 12-6). In this connection it is of interest to note that the
conductivity of a material is given by

(12-9)
where fl represents the mob"ility of the charge carriers, (i.e., the velocity
per unit electric field); the subscripts e and h refer to electrons and holes,
respectively. In the case under discussion ne = nh = nco One speaks in
this case of intrinsic conductivity. Now we shall see in the next chapter
th;:tt flc and flh are much less strongly temperature-dependent than the
density of electrons and holes. The temperature-dependence of II in the
intrinsic region is therefore essentially given by (12-8); i.e., log II versus
I/Tyields a straight line with a slope of -- Eg /2k. We shall see below that
the same result is obtained with a more sophisticated model. Note that
the conductivities of insulators and intrinsic semiconductors increase with
increasing temperature. In contrast to this, the conductivity of metals
decreases with increasing T; the reason is that in metals the density
of charge carriers remains constant and the mobility decreases with
increasing T.
I The reader is reminded of the fact that at room temperature kT =0.025 ev; the
gap width in a good insulator is several ev.
308 ELECTRON DISTRIBUTION IN INSULATORS [Chap. 12
I~
~'

12-3. Improved model for an insulator and intrinsic semiconductor

It is evident that when the width of the allowed energy bands becomes
comparable with the width of the forbidden region, one is no longer
justified in using a single energy for a complete band. Thus, in general,
(12-4) should be replaced by

(12-10)

where Eo represents the bottom of the conduction band and Z(E) is the

I,-----Z(E)

Fig. 12-2. Schematic representation of the density of states in an

insulator. Near the bottom of the conduction band Z(E) is
proportional to (E - E,)1/2; near the top of the valence band Z(E)
is proportional to (Ev - E)lIZ. v
. ~

density of the states (see Fig. 12-2). Because we expect from the results
obtained above that EF lies roughly halfway between Ev and Eo, the
Fermi function F(E) decreases strongly as one moves up in the conduction
band. In other words, to evaluate the integral (12-10) it is sufficient to
know Z(E) near the bottom of the conduction band and one may then
integrate from E = Eo to E = 00. Near the bottom of the conduction
band we have, in accordance with (10-79),

(12-11)

where m: is the effective mass of an electron near Ec. Hence the density
of electrons in the conduction band is

_ (4 /h3)(2 * 3/2 ~ 00 (E - Eo)1I2 dE (12-12)

no - me)
7T
.' Ee e
(E-E )/11:7'
F' 1 +
,
For simplicity we shall assume that (Ec - E F ) ;., 4kT, in which case the
Sec. 12-3] ELECTRON DISTRIBUTION IN INSULATORS 309

term unity in the denominator may be neglected to a good approximation. 2

The integral (12-12) may then be reduced to the type

and one obtains

(12-13)

In order to find E F , which so far is an unknown quantity, we make use of

the fact that nc must be equal to the number of holes in the valence band.
To calculate the latter, we note that [I - F(E)] represents the probability
for a state of energy E to be unoccupied. The density of holes in the
valence band may thus be written

r
E,;

n,. = Z(E)[1 - F(E)1 dE (12-14) .

boil,om
i
where the integration extends over the valence band.
It is readily verified that the factor [1 - F(E)] decreases rapidly as one
goes down below the top of the valence band (i.e., the holes reside near
the top of the valence band). Hence, to evaluate the integral (12-14) one
is essentially interested in Z( E) near the top of the valence band. According
to the results obtained in Chapter 10, Z(E) varies in this region in the
following fashion:

(12-15)

where mtrepresents the effective mass of a hole near the top of the valence
band. Ifwe make the assumption that the Fermi level lies more than about
4kT above E", we may use the approximation
1 - F(E) ~ e(E-Ep )/k1' (12-16)

Substituting the last two expressions into (12-14) and integrating from
-00 to E", one obtains in the same way as above
(12-17)

Employing the fact that nc = nIl' it follows from (12-13) and (12-17) that

(12-18)

In case mt = m:, the Fermi level lies again exactly halfway between the
2 For numerical tables of integrals of the type (12-12), see J. McDougall and E. C.

Stoner., Phil. Trans., A237, 67 (1929). .

310 ELECTRON DISTRIBUTION IN INSULATORS [Chap. 12

top of the valence band and the bottom of the conduction band; (l2-18)
is then identical with (12-7). In general mt m:
> and the Fermi level is
raised ~ightly as T increases. This is indicated schematically in Fig. 12-5
by t~:; '~ntrinsic Fermi level."
The density of electrons in the conduction band nc and the density of
holes in the valence band nIL may be obtained by substituting (12-18) into
(12-13). This gives

(12-19)

where Eg represents the gap width. It is observed that the temperature-

dependence is the same as in the simplified model. The temperature-
dependence of nc is represented schematically by the curve labeled
"intrinsic" in Fig. 12-6. It is convenient to remember that at room
temperature \
\
(12-20)

where m is the mass of a free electron. Note that the constant in front of
the exponential in (12-8) is much larger than that in (12-19). We emphasize
again that (12- I 8) and (12-19) are good approximations only if the Fermi
level is more than a few kT away from the bottom of the conduction band
and from the top of the valence band.

12-4. Models for an impurity semiconductor

Most semiconductors owe their conductivity to impurities, i.e., either

to foreign atoms built into the lattice or to a stoichiometric excess of one
of its constituents. At absolute zero such a solid may contain a certain
concentration of occupied electronic levels which lie in the normally for-
bidden region between the valence and conduction bands. These electrons
are localized in the vicinity of the impurities and therefore do not con-
tribute to the conductivity unless they are excited into the conduction band.
Centers of this kind are called donor levels. In the energy level scheme
they are represented by a short bar, to indicate that they are localized (see
Fig. 12-3a). Similarly, an impurity semiconductor may contain a certain
density of holes which at T = 0 are trapped in levels lying in the forbidden
gap. Such levels are called acceptor levels because they may become
occ,upied by electrons excited from the filled band; these excited electrons
leave a hole in the valence band and conduction becomes possible in this
band (see Fig. 12-3b). The physical reasons for the existence and location
of donor and acceptor levels will be discussed in the next chapter.
We shall now consider the density of free electrons and holes for two
simple m o d e l s . . ,1""",,<, 11 ,H,:l.A • 1,1'''': \
.; ~ ,.
Sec. 12-4] ELECTRON DISTRIBUTION IN INSULATORS 311
(i) The simplest model for an n-type semiconductor consists of a
conduction band below which there are nd donor levels per cm3 of energy
Ei (see Fig. 12-3a).3 The influence of the valence band will be neglected
for the moment, i.e., the model may be applied only at relatively low
temperatures. Let us assume that at T = 0 all donor levels are filled with
electrons. At low temperatures, when only a small fraction of donors is
ionized, we expect the Fermi level to lie about halfway between the donor
levels and the bottom of the conduction band. We shall assume for

Cond. band Condo band

Ec ----..._-----'!1'--- -------------Ec
E;...I...

_~~-·l

Ev ~}$;~j@$$~
(a)
/
Fig. 12-3. Donor levels are indicated in (a); one of the donors
is ionized, leading to a free electron in the conduction band.
Acceptor levels are indicated in (b); one of them is ionized (i.e.,
occupied by an electron from the valence band), leading to a free
hole.

simplicity that EF lies more than a few kT below the bottom of the con-
duction band. In that case, the density of conduction electrons nc is given
by (12-13). This number must be equal to the density of ionized donors.
If we assume that EF lies more than a few kT above the donor levels,
the density of empty donors is equal to ... 'I .-'.'"

(12-21)

Equating (12-13) and (12-21), one obtains for the location of the Fermi
level the expression,

EF = i(Ei + Ec) + (kTj2) log [2(27Tm:~Tjh2)3/2] (12-22)

Thus at T = 0, Ep lies exactly halfway between the donor levels and the
bottom of the conduction band. As T increases, the Fermi level drops.
This is illustrated in Fig. 12-4 for the case Ec - E; = 0.2 ev for three
3 Semiconductors in which the current is carried predominantly by electrons are

called n-type semiconductors, (n = negative); a hole conductor is referred to as a

p-type (p = positive) semiconductor.
,~ ~
312 ELECTRON DISTRIBUTION IN INSULATORS [Chap. 12

~::ifferent values of nd. 4 Within the triangul~r region ABC the Fermi level
';. IS more than 2kT away from the conductlOn band and from the donor
levels; only in this region is (12-22) applicable (with an accuracy of about
8 per cent). Outside this region, the term unity in the Fermi distri-
bution entering in (12-21) must be retained. Note that for this model, EF
falls indefinitely; in an actual case, however, the presence of the valence

Cond. band \

\
-.3

-.4

o 200 400 600

-T('K)
Fig. 12-4. The Fermi level as function of T for a set of donor
levels 0.2 ev below the conduction band; the presence of the valence
band is neglected. The numbers next to the curves ~epresent the
number of donors per em'. Within ABC, the Fermi level is
more than 2kT away from the donors and from the conduction
band. [After Hutner, Rittner, and DuPre, ref. 4]

band would ultimately keep the Fermi level about halfway between the
valence and conduction bands (see Fig. 12~S).
For the region in which (12-22) is applicable, the density of free
electrons in the conduction band is obtained by substituting Ep into
(12-13), leading to
(12-23)

where t1E = Ec - Ei represents the ionization energy of the donors.

Note again the occurrence of t1Ej2 rather than t1E; also note that nc
is proportional to the square root of the donor concentration (see Problem
12-2).
The case of acceptor levels above the valence band may be treated in
• R. A. Hutner, E. S. Rittner, and F. K. DuPre, Philips Research Rep's' 5, 188,
(1950).
•. ,
•
~
'
Sec. 12-4] ELECTRON DISTRIBUTION IN INSULATORS 313
the same way. The density of holes in the valence band, making similar
assumptions as above, is given by an expression similar to (12-23). In this
case the Fermi level lies halfway between the acceptor levels and the top
of the valence band at T = 0; as T increases, the Fermi level rises (see
Problem 12-3 and Fig. 12-5).
'I "..-~." .,.

i
i·

Condo band

..._ .....
Donors

Fig. 12-5. Schematic representation of the Fermi level as function

of temperature; curve 1 for insulator with donors, curve 2 for
insulator with acceptors. The intrinsic Fermi level slopes slightly
upward, in accordance with (12-18). The dashed curve, 3, cor-
responds to the case in which the electron gas in the conduction
band is degenerate over a certain range of temperatures, as
discussed in Sec. 12-6.

From these results it follows that the logarithm of the density of carriers
plotted versus the reciprocal temperature should yield a straight line of
slope -!J..E/2k. However, as the temperature is increased to such values
that the intrinsic excitation becomes important, the slope changes gradually
to -Egap/2k. The reason is that the density of electrons in the filled band
is of the order of 1022 per cm3 , whereas the density of impurity centers is
usually '( 1019 per cm3 • This is illustrated schematically in Fig. 12-6.
Similar curves are encountered when the logarithm of the conductivity
is plotted against liT, as we shall see in later chapters.
(ii) The above model applies to a large extent to semiconductors such
as germanium and silicon, containing trivalent or pentavalent impurities;
the former produce acceptor levels, the latter donor levels. In other cases,
such as the alkali halides containing excess metal, the density of available
levels may be larger than the number of excess electrons. In other words, "
it is possible that at T = 0 only a fraction of the' available levels is occupied.
As an extreme case, we shall assume that the density of donor electrons nd
is very small compared with the density of available levels Zi' In this case,
314 ELECTRON DISTRIBUTION IN INSULATORS [Chap. 12

the Fermi level evidently lies below the donor levels. At any temperature
T, the number of filled "impurity" levels is equal to ,

Z \
Z.e (E,-E;l/kT
e(Ei-E,l/kT +I -
--;-;;;---;;-.,.;':,..;;;-_ _ r-J
,

where we assumed (E; - E F) .2: few kT. As long as the temperature is low,
the density of electrons in the im-
purity levels is large compared with
the density of electrons nc in the
conduction band and we may write
(12-24)
from which the Fermi level may be
, calculated. Substituting EF from
(12-24) into (12-13) we find for the
density of conduction electrons,
nc = 2(27Tm~kT/h2)3/2(nd/Zi)e-!J.E/kT
(12-25)
--..ljT
It is interesting to compare this
Fig. 12-6. Schematic representation of expression with (12-23); in the present
the logarithm of the density of conduc- case nc is proportional to nd (instead
tion electrons versus 1IT for an impurity of n~/2), and the exponential contains
semiconductor containing different
!!.E (instead of !!'E/2). This shows
donor densities, (nd1 < nd> < IId3)' At
high temperatures the slope is deter- that in some cases one must be careful
mined by Ega p/2k; at lower tempera- in interpreting the slope of the log
tures by !!.Ej2k. nc versus I IT curve as giving half the
ionization energy of the donors.

12-5. Thermionic emission from semiconductors

The importance of the Fermi level in the discussion of contacts between

conductors has been stressed in Sec. 9-10. It was shown there that in such
contacts the Fermi levels of the materials must coincide. We shall show
here another important aspect of the Fermi level, viz., the fact that it
determines the thermionic work function of a semiconductor.
In Sec. 9-6 we derived the Richardson expression from the free electron
model for the thermionic emission of metals;
1= (47Tmek 2T2/h 3)'e-4>lkT (12-26)
We neglect reflection for simplicity. We shall now consider the thermionic
emission from a semiconductor, assuming that the electrons in the con-
duction band may be treated as free electrons with an effective mass m*.
Sec. 12-5] ELECTRON DISTRIBUTION IN INSULATORS 315
Let the vacuum level (i.e., the energy of an electron at rest outside the
semiconductor) be higher than the bottom of the conduction band by an
amount X as indicated in Fig. 12-7; X is called the electron affinity of the
crystal. If x is the direction perpendicular to the surface, an electron needs
at least a momentum in the x-direction given by
(12-27)

in order to escape. As a result of thermal excitation let there be nc electrons

per unit volume in the conduction
band. If the Fermi level is assumed
to lie more than a few kT below the
Cond. band
bottom of the conduction band, the
conduction electrons have a Max-
wellian velocity distribution accord- Fenni level _j_
ing to the discussion of the preceding
sections. We leave it as a problem
to the reader to show that the Fig. 12-7. lllustrating the electron
density of electrons with momenta affinity X and the work function q,
in the range dpx, dp1l' dpz is then of a semiconductor.
equal to
n(px,P'll'pz) dpx dp'll dpz = [n c/(27rm*kT)3/2]e- p2 / 2"..kT dpx dp1l dpz (12-28)
Following the same treatment as in the thermionic emission of metals, one
may then write for the emission current density,

1= enc SSS(p /m*)e- P 2,,,_m ·kT drp drp drp (12-29)

/ (21Tm*kT)3!2 x x z
'II
•
The integra1ions over P1l and pz go between ±oo; the integration overpx
extends from
,
Po;0 to 00. This yields

1= enc 21Tm*k2T 2e- x/k7' (12-30)

(21Tm*kT)3!2

The value of nc is for intrinsic as well as for impurity semiconductors

given by (12-13). Substitution gives finally

(12-31)

where the work function f represents the energy difference between the
Fermi level and the vacuum level, as indicated in Fig. 12-7. It is observed
that (12-31) becomes identical with (12-26) if one replaces the effective
mass of the conduction electrons by that of a free electron. It is of interest
to note that according to (12-30) the thermionic emission is proportional
to nc, i.e., the emission current density is correlated with the conductivity
of the material. , :~
"
316 ELECTRON DISTRIBUTION IN INSULATORS [Chap. 12

12-6. Electronic degeneracy in semiconductors

]n the preceding sections it was assumed that the Fermi level was
located at least a few kT below the bottom of the conduction band. In
that case the electrons in the conduction band follow closely Boltzmann
statistics, i.e., the electron gas is nondegenerate. Under certain circum-
stances, however, the Fermi level may enter the conduction band and the
electron gas in the conduction band may become degenerate. From the
preceding discussions it should be clear that the conditions favorable for
such a situation are the following:
(i) Relatively high donor densities (,...., 1019 per cm3)
(ii) Sm::~_l donor ionization energy
(iii) Lc.. density of states near the bottom of the conduction band,
i.e., small effective electronic mass (see Sec. 10-9).
When these conditions are fulfilled, the Fermi level as function of
temperature varies as indicated by the dashed curve 3 in Fig. 12-5. As T
increases from absolute zero, the donors begin to ionize and as a result of
the low density of states, the lower energy states in the conduction band
become completely filled. The position of the Fermi level relative to the
bottom of the conduction band is then given by (9-9),
/'

where nc is the density of electrons in the conduction band. As long as

EF }> kT, the electron gas is degenerate. Clearly, as the effective electronic
mass is reduced, degeneracy may occur at lower electron densities. As T
is increased further, the degeneracy is removed and the Fermi level leaves
the conduction band again.
The circumstances described here are believed to occur in InSb,
containing donor levels in concentrations of about 1018 per cm3 ; the
effective mass of the conduction electrons is probably only about m/30 in
this case. ~
REFERENCES

J. S. Blakemore, "Carrier Concentrations and Fermi Levels in Semi-

conductors," Elec. Commun., June 1952, pp. 131-153.
R. A. Hutner, E. S. Rittner, and F. K. DuPre, "Fermi Levels in Semi-
conductors," Philips Research Repts., 5, 188 (1950).
F. Seitz, The Modern Theory of Solids, McGraw-Hili, New York, 1940,
pp. 186 ff.
W. Shockley, Electrons and Holes in Semiconductors, Van Nostrand,
New York, 1950.
Chap. 12] ELECTRON DISTRIBUTION IN INSULATORS 317

PROBLEMS

12-1. With reference to the problem discussed in Secs. 12-2 and 12-3,
consider the reaction
electron in valence band ~ electron in conduction band
+ hole in valence band
Applying the law of mass action as used in chemical reactions, show that
the equilibrium concentration of the conduction electrons is proportional
to exp ( -~ Egapj2kT). _" __ _
12-2. With reference to the problem discussed in Sec. 12-4, consider
the reaction
bound electron ~ free electron + empty donor
Making use of the law of mass action, answer the following questions:
(a) Assuming that at T = 0 all donor levels are filled, show that the
density of free electrons is proportional to nYz exp ( -I::iEJ2kT).
(b) Assuming that at T = 0 only a small fraction of the donor levels
is filled, show that the density of free electrons is proportional to Zi exp
(-I::iEjkT), where Z, is the density of impurity levels and I::iE is the ioniza-
tion energy of the donor levels.
12-3. For an intrinsic semiconductor with a gap width of 1 ev,
calculate the position of the Fermi level at T = 0 and at T = 300°, if
m: Sm:.
= Also, calculate the density of free electrons and holes at
T = 300° and at T = 600°.
12-4. Assuming a Maxwellian velocity distribution for the electrons in
the conduction band, derive expression (l2-28).
12-S. Assuming a valence band above which there are na acceptor levels
per unit volume, derive an expression for the Fermi level and for the
density of free holes in the valence band as function of T.
12-6. What is roughly the temperature range over which an electron
gas in the conduction band is degenerate if nc = 1018 per cm3 and
m: = mj30? Compare this with perfectly free electrons.
12-7. If the Fermi level in a semiconductor lies more than a few kT
below the bottom of the conduction band and more than a few kT above
the top of the valence band, show that the product of the number of free
electrons and the number of free holes per cm3 is given by
nenh = 2.33 X IQ3IT3 e -E.'kT

where Eo is the gap width. Note that this holds irrespective of the presence
of donors or acceptors in the gap, as long as the condition imposed on the
Fermi level is satisfied.
318 ELECTRON DISTRIBUTION IN INSULATORS [Chap. 12
12-8. Consider a crystal which at T = 0 is an insulator; the crystal
contains Nd donor levels per cm3 , which at T = 0 are all occupied, and
Nt electron traps per cm3 , which at T = 0 are all empty (the traps lie above
the donor levels). Discuss in detail the distribution of electrons at a
temperature T and the various approximations which may hold under
particular circumstances.
Chapter 13

NONPOLAR SEMICONDUCTORS

13-1. Introductory remarks

Semiconductors are characterized by an electrical conductivity

(associated with the motion of electrons or holes or both) which on the
one hand is considerably smaller than that of metals, and on the other
hand, is much larger than that of "insulators." Furthermore, the con-
ductivity increases with temperature, in contrast with the behavior of
metals at normal temperatures. The number of current carriers per unit
volume in a semiconductor is in general much smaller than the number
of atoms per unit volume. This situation is encountered, for example, in
a solid for which the forbidden energy gap between the highest normally
filled band and the conduction band is small, i.e., of the order of one
electron volt. At absolute zero such a solid is an insulator, and as the
temperature is raised, the density of free electrons and holes increases as
explained in the preceding chapter. In this case the density of free electrons
equals that of the free holes and one speaks of intrinsic semiconductors;
the properties are then characteristic of the solid itself. Semiconductor
properties may also be exhibited by solids which in the pure state are
good insulators, viz., when impurities are present which either donate
free electrons to the conduction band (donors) or free holes to the upper
filled band (acceptors); in this case one speaks of extrinsic or impurity
semiconductors. Impurity conductivity may of course be superimposed
on the intrinsic semiconductor properties of a solid.
The semiconducting elements are those appearing within the area
enclosed by the lines drawn in Table 13-1; this table represents the A
subgroup elements in a number of columns of the periodic table. Of
these, silicon and germanium have received a great deal of attention
because of their great technical importance, particularly in the field of
crystal diodes and transistors. The discussion in this chapter will be
concerned mainly with the properties of Si and Ge; the amount of
literature on this subject is so vast that the discussion is necessarily very
incomplete. A review which is up to date until the beginning of 1955
may be found in H. Y. Fan in F. Seitz and D. Turnbull (eds.), Solid State
PhysiCS, Academic Press, Ne~ York, 1955, Volume I.
319
320 NONPOLAR SEMICONDUCTORS [Chap. 13
Extensive studies have recently been initiated on intermetallic
compounds formed between the elements of the third and fifth columns
in Table 13-1; these will be discussed briefly in the last section of this
chapter.
\
Table 13-1. The A Subgroups of the 3rd, 4th,5th, 6th, and 7th Columns
. of the Periodic System of Elements
IlIA IVA VA VIA VIlA \ __
BeN 0
AI Si P S
Ga Ge Se
In Sn Te
TI Pb Po At

Of the semiconducting salts in which the binding is essentially ionic,

the alkali halides containing color centers have been investigated most
thoroughly; we shall return to these compounds in Chapter 15.

13-2. Some laCce properties of the elements of the fourth group

Structure. Diamond, silicon, germanium, and grey tin all have the
diamond structure represented in Fig. 13-1. Each atom is surrounded by
four others, occupying the corner points of a tetrahedron, to which it is
bound by electron pair bonds. The structure may be described by an
f.c.c. point lattice in which each lattice point corresponds to two atoms,
one located at (0,0,0) and another at (i,1-,t). The free atoms of the
elements have an outer electron configuration in which two electrons
occupy an s state and two others occupy a p state. In the solid state the
total of four outer electrons per atom is just sufficient to produce electron
pair bonds with four other atoms; in this configuration the sand p wave
functions. form hybrid wave functions giving rise to four equivalent
chemical bonds, the angle between any two of them being approximately
109°.1 This type of covalent binding may be contrasted with the ionic
bonds in crystals such as the alkali halides; in the latter, the particles are
charged and the field around a given ion is spherically symmetric, i.e.,
the restriction on the coordination number is essentially of geometrical
origin. In terms of a two-dimensional picture one arrives at an electron
distribution as indicated schematically in Fig. 13-2.
One expects the electrons taking part in ,the electron pair bonds to be
rather strongly bound, i.e., one expects that a certain amount of energy
is required in order to set them free to the extent that they can move about
in the crystal. This is in agreem.ent with the fact that at very low tempera-
tures these elements areinsulators. In terms of the energy band scheme,
I See L. Pauling, The Nature of the Chemical Bond, 2d ed., Cornell University Press,

Ithaca, 1945, p_ 81.

Sec. 13-2] NONPOLAR SEMICONDUCTORS 321
this means that at absolute zero the electron distribution is such that a
certain number of energy bands is completely filled, the higher ones being
completely empty.
f-···

0
••
0
..
j----
. . ..
'~~ ~

.
0
.~

.
0

.
0
•~·'t--~~-..- _- . -."
. .
..
0
-----
0
~.

0 . 0 0 0
Fig. 13-1. The crystal slructure of Fig. 13-2. Schematic two-dimen-
diamond, showing the tetrahedral bond sional representation of the elec-
configuration. [After W. Shockley.. tronic distribution in the diamond
Electrons and Holes in Semiconductors, structure, showing the electron
Van Nostrand, New York, 1950] pair bonds.

Physical constants. It is of interest to consider how some of the

physical properties of these elements vary in a regular fashion with their
position in the· periodic table. As the atomic number increases, the
interatomic distances increase, i.e., the binding forces become weaker, and
the solids become "softer." In Table 13-2 some physical constants are
given for diamond, silicon, and germanium to illustrate this. In this order,
the lattice parameter a (the edge of the f.c.c. lattice) increases, !he elastic
constants, the melting point, the Debye temperature, and the forbidden
energy gap decrease. Qualitatively, this regularity can be explained on
the basis of the relative strengths of the chemical bonds between the
atoms. It is also observed that the dielectric constant increases in the
order C, Si, Ge; this is to a large extent a result of the increase in the
number of electrons per atom, leading to a larger polarizability. With
reference to the quantities given in Table 13-2, some remarks should be
made. The lattice constants for Si and Ge are those obtained at 20°C by

Table 13-2. Some Physical Constants of Diamond, Silicon, and Germanium

(see text for details)

a (A)
m.p.
€
On Egap
C ll C12
c ..
eq ("K) (ev) (10 12 dynes/em)

C 3.561 3550 5.7 1800 -7 9.2 3.9 4.3

Si 5.43086 1420 12 658 1.21 1.674 0.652 0.796
Ge 5.65748 936 16 362 0.785 1.298 0.488 0.673
322 NONPOLAR SEMICONDUCTORS [Chap. 13

Straumanis and Aka from X-ray diffraction data; the coefficients of

expansion, measured between 10°C and 50°C, obtained by these authors
are 4.15 X 10- 6 and 5.92 X 10-6 per °C for Si and Ge, respectively. 2
The dielectric constant E given above is based on measurements of the
index of refraction in the optical region as well as on measurements of
the dielectric constant in the microwave region. 3 The Debye temperatures
for Si and Ge were obtained from specific heat measurements below 4°K
by Keesom and Pearlman;4 in this region the lattice specific heat is
proportional to P, and On may be calculated on the basis of formula
(2-37). The energy gap in Si and Ge is not a well-defined quantity because
of certain peculiarities in the band structure of these elements; we shall
return to this problem in Sec. 13-6. The values given in the table are
derived from the density of charge carriers in the intrinsic region. The
elastic constants have been obtained from measurements of the velocity
of propagation of elastic waves. 5 \

Influence of impurities. Of great interest is the fact that Si and Ge

can be "doped" with foreign elements. For example, Pearson and Bardeen
have shown that boron and phosphorus form substitutional solid solutions
in Si. 6 Evidence for this was obtained from the decrease in the lattice
constant with increasing concentration of these elements (the atomic radii
of Si, B, P are, respectively, 1.17,0.89, and l.l A). If the solute atoms were
incorporated interstitially, the lattice constant should have increased.
Thus, consider a phosphorus atom at a position which is normally occupied
by Si. The phosphorus atom has five outer electrons, one in excess of
the number required to form electron pair bonds with four nearest
neighbors. As a result, the extra electron is relatively weakly bound and
only a small amount of energy is required to set the electron free. In
terms of the energy band picture, this means that phosphorus and other
pentavalent atoms give rise to donor levels close to the conduction band.
The order of magnitude of the energy required to ionize the phosphorus
atom, i.e., the energy difference between the donor level and the bottom of
the conduction band may be estimated according to a suggestion by Bethe
as follows: the extra electron of the phosphorus atom may be pictured as
moving in the field of a single positive charge, i.e., the problem is somewhat
2 M. E. Straumanis and E. Z. Aka, J. Appl. Phys., 23, 330 (1952).
3 See, for example, K. Lark-Horovitz and K. W. Meissner, Phys. Rev., 76, 1530
((949); w. C. Dunlap and R. L. Watters, Phys. Rev., 92, 1396 (1953).
'P. H. Keesom and N. Pearlman, Phys. Rev., 9t, 1347 (1953); N. Pearlman and P.
H. Keesom, Phys. Rev., 88, 398 (1952).
, W. L. Bond, W. P. Mason, H. J. McSkimin, K. M. Olsen, and G. K. Teal, Phys.
Rev., 78, 176 (1950); H. J. McSkimin, W. L. Bond. E. Buehler, and G. K. Teal, Phys.
Rev., 83, 1080 (1951).
• G. L. Pearson and J. Bardeen. Phys. Ret'., 75,865 (1949); also F. H. Horn, Phys.
Rev., 97, 1521 (1955).
Sec. 13-2] NONPOLAR SEMICONDUCTORS 323
analogous to that of the hydrogen atom. 7 The difference is, however, that
the extra electron and the positive charge are embedded in a medium of
rather high dielectric constant (see Table 13-2). As a result, the radius of
the orbit covers several atomic distances and the binding energy is small.
In fact, if one employs for an estimate the simple Bohr picture modified by
taking into account the dielectric constant £ and the effective mass m*, one
obtains for the radius and the energy of the ground state
(13-1)
The energy Ed is measured relative to the bottom of the ionization
continuum, i.e., relative to the bottom of the conduction band. Assuming
for the moment the effective mass m* to be equal to the free electron mass,
one finds
, E" (Bohr)

Si 12 6.4 A- -0.0gev -0.05

Ge 16 8.5 A -0.05 ev -0.01

The last column gives the experimental ionization energy of the donor
levels for doping with P, As, or Sb. 8 A detailed calculation of the ionization
energy of donors by Kittel and Mitchell gives 0.009 ev as a lower limit for
germanium and 0.03 ev as a lower limit for silicon, in good agreement with
the experimental values. 9 These calculations made use of recent informa-
tion about the E(k) surfaces as revealed by cyclotron resonance experiments
(see Sec. 13-6).
Silicon and germanium may also be doped with trivalent elements such
as B, AI, Ga, and In. In these cases the added atoms are one electron short
for four electron pair bonds. Each added trivalent atom thus gives rise to a
vacant electron level slightly above the valence band. These levels are
acceptor levels because they may accept an electron from the filled band if
the electron is excited thermally. One may picture the acceptor level as a
hole describing a Bohr orbit about the impurity atom; the binding energies
are approximately equal to those for the donors. Ionization of the
acceptor level in this type of picture is equivalent to the excitation of a
valence electron into the hole. In the energy band scheme, electrons are
excited upward, holes downward (see Fig. 13-3).
From what has been said above, it is evident that ionization of donor
levels (P, As, Sb) gives rise to electronic carriers in the conduction band;
ionization of acceptor levels (8, AI, Ga, Sn) produces hole conductivity in
the valence band. In germanium at room temperature nearly all donor or
, G. Wannier, Phys. Rev., 52, 191 (1937); see also G. F. Koster and J. C. Slater,
Phys. Rev., 95,1167 (1954); 96,1208 (1954).
8 J. A. Burton, Physica, 20, 845 (1954).

• C. Kittel and A. H. Mitchell, PIlys. Ret'., 96, 1488 (1954).

324 NONPOLAR SEMICONDUCTORS [Chap. 13

acceptor levels will be ionized, because kT ~ 0.025 ev, which is larger

than the bindjng energy of donor electrons and acceptor holes. Also, the
ionization energy decreases with increasing concentration, as may be seen
from Fig. 13_4. 10 Thus, even at low temperatures the fraction of ionized
donors or acceptors may be rather large.

.08
fev
Cond. band

J
~ "Acceptors

~
Valence band

Fig. 13·3. Energy level scheme for Fig. 13-4. Ionization energy of ac-
donor and acceptor levels. ceptor levels in Si as function of the
acceptor density 11 0 , [After Pearson
and Bardeen, ref. 10]

Crystal growth. Single crystals of silicon and germanium, either doped

or not, can be obtained by placing a seed crystal in contact with the melt
and then withdrawing the seed slowly.ll The concentration of a particular 1
impurity in crystals so obtained is determined by the segregation coefficient
of the impurity under consideration; this quantity is defined as the ratio
of the impurity concentration in the solid phase to that in the melt in
thermal equilibrium. For most impurities the segregation coefficient is
~I, except for boron, which has a coefficient larger than unity in"
germanium. It will be evident that in general, therefore, the concentration
of impurities in the melt increases as the crystal is withdrawn, so that the
impurities are concentrated at the end of the crystal. Based on this prin-
ciple is the so-called zone-refining technique by which crystals of high
purity may be obtained: when one moves a heating coil slowly along a
crystal, the impurities are swept towards one end of the crystal; this
process may of course be repeated many times. 12 In this way it is now
possible to produce single crystals of Ge and Si with impurity concentra-
tions as small as one part in 1010 or 109 , at least if one considers the
,. For p-type Si, see G. L. Pearson and J. Bardeen, Phys. Rev., 75,865 (1949); for
II-type Ge, see P. P. Debye and E. M. Conwell, Phys. Rev., 93, 693 (1954).
11 G. K. Teal and J. B. Little, Phys. Rev., 78, (547 (1950); see also G. K. Teal and

E. Buehler, Phys. Rev., 87, 190 (1952). .

12 W. G. Pfann, J. Metals, 4, 747 (1952); W. G. Pfann and K. M. Olsen, Phys. Rev.,
89,322 (1953).
Sec. 13-2] NONPOLAR SEMICONDUCTORS 325
electrical resistivity a measure for the purity. It should be mentioned in this
connection that the use of crucibles and the contamination resulting from
the crucible material may be avoided by employing the so-called floating
zone technique_13 In this technique one produces a molten section in a
polycrystalline rod of the material (which is held vertically) by induction
heating. One end of the material is in contact with a single crystal seed
and the molten zone is moved slowly from that end to the other, leading
to recrystallization of the polycrystalline material.

Diffusion of impurities. We mentioned above that elements of the third

and fifth columns in the periodic system, used as doping material in Si and
Ge, are believeo to be incorporated substitutionally in the lattice. This
belief is supported by the fact that the diffusion coefficients of these
elements lie in the same range as those for self-diffusion, Le., the elements
probably diffuse by a vacancy mechanism. l4 There are, however, some
notable exceptions, viz., copper, nickel, and lithium. The diffusion co-
efficients of these elements in silicon and germanium are very high
(,,-,10- 5 cm 2/sec at temperatures of 700 0 or 8000 e) and it seems likely that
the diffusion process in these cases involves the migration of interstitials.
It is believed that copper migrates through germanium in the form of
positive ions. I5 At normal temperatures there is strong evidence that
copper ac~s as an acceptor for electrons, i.e., it should then be negatively
charged.

Influence of lattice defects. When a germanium crystal, doped with

donor impurities, is irradiated with high-energy particles, the conduc~ivity
initially decreases. Upon further irradiation with a sufficiently large flux it
may convert from n type (electron carriers) to p type (hole carriers) and the
conductivity may then increase. Irradiation effects of this type are evidently
associated with the formation of vacancies and interstitial atoms in the
lattice; in fact, when the crystals are annealed, the changes essentially
disappear. It is not unlikely that the interstitials correspond to donor levels
and the vacancies to acceptor levels, although several details of the
interpretation of irradiation effects are not yet settled.
Dislocations produced by plastic deformation of silicon and germanium
also produce pronounced effects on the electrical conductivity. In n-type
Ge, for example, plastic deformation leads to a reduction in the con-
ductivity, i.e., the deformation introduces acceptor levels. Is The physical
13 P. H. Keck and M. J. E. Golay, Phys. Rev., 89, 1297 (1953).
14 See, for example, H. Letaw, L. M. Slifkin, and W. M. Portnoy, Phys. Rev., 93, 892,
(1954); W. C. Dunlap, Phys. Rev., 94,1531 (1954). .
l ' c. S. Fuller, J. D. Struthers, J. A. Ditzenberger, and K. B. Wolfstirn, Phys. Rev.,

93,1182 (1954); F. van der Maesen and J. A. Brenkman, J. Electrochem. Soc., 102, 229
(1955). .
16 c. J. Gallagher, Phys. Rev., 88, 721 (1952).
326 NONPOLAR SEMICONDUCTORS [Chap. 13
picture of the acceptor levels according to Shockley and Read is the
following. Slip in these crystals takes place along the {Ill} planes and
along a (110) direction. The extra half plane associated with an edge
dislocation leads to a row of "dangling" bonds since the atoms of this row
have no neighbors on one side. An electron paired with one of those
dangling bonds would not be as "free" as an electron in the conduction
band, so that the corresponding level should lie below the bottom of the
conduction band. On the other hand, the paired electron is not as strongly
bound as one corresponding to a normal electron pair bond between two
neighboring atoms, i.e., the level associated with the dangling bond should
lie above the filled band. Consequently, an edge dislocation corresponds
to a row of acceptor levels lying in the forbidden energy region. For a
detailed discussion of the implications of this model for the electrical
properties of these materials we refer the reader to a series of three papers
by ReadY

J3-3. Conductivity and Hall effect in semiconductors with a single type of

charge carrier

Before discussing the electrical properties of Si and Ge, some remarks

on the conductivity and Hall effect of semiconductors should be made.
, In this section we shall limit ourselves to the case of a single type of charge
carrier. The conductivity of such a material is given by

a = nef-l (13-2)

where n is the density of carriers and f-l is their mobility (drift velocity per
unit field). It is observed that measurements of aCT) provide information
only about the product n(T)f-l(T), and in general do not allow one to deter-
mine these quantities separately. However, if we assume for the moment
that the Hall coefficient for a semiconductor is given by the formula
applicable to metals we would have (see 11-65),
RII = l/nec and caR H = f-l ( 13-3)

Thus RH(T) would provide information about n(T), and combined

measurements of Rn and a thus permit determination of nand f-l separately.
Although this type of analysis is indeed applied to semiconductors, there
are some modifications in the formula for Rn which will be discussed below.
Also, the temperature-dependence of f-l is diffetent from that for metals.
We shall give here a simple theory for n-type material based on the
assumption that the electrons in the conduction band behave as nearly
free electrons with an effective mass m*; this implies that constant-energy
surfaces in momentum space are assumed to be spheres. There exists at
"W. T. Read, Phil. Mag., 45,775 (1954); 45, 1119 (1954); 46. III (1955).
Sec: 13-3] NONPOLAR SEMICONDUCTORS 327
present a great deal of evidence (see Sec. 13-6) that this is not correct, but
in many instances the simple theory still gives rather good agreement with
the experiments. It is also assumed that the electron gas in the conduction
band is nondegenerate, and thus that it has a Maxwellian distribution.
As an example, consider a semiconductor in which the current is
carried only by electrons in the conduction band. Suppose an electric
field E", and a magnetic field Hz are applied to the materiai as indicated in
Fig. 13-5. The current density I", along the x-direction may then be obtained
from the Boltzmann transport equation in the same way as for metals.
Thus from (11-28) it foHows that

e 2 E", f<Xl 3Fo 2

1,,= --Jo a v T(E)(87T/h 3)p2dp
3 E (13-4)
The relaxation time T is assumed to z
be a function only of the energy of
the electrons, not of their direction
of motion. Now it can readily be
shown that the Fermi function Fo(E)
satisfies the relation
-( 3Fo/3E) = Fo(l - Fo)/kT ~ Fo/kT
(13-5)
The last approximation is valid
only if the density of the electrons Fig. 13-S. Showing the Hall effect; the
in the conduction band is small current I. flows only if front and back
enough so that Fo 4:,_ I, i.e., if the faces are connected; normally, this is
not the case and an electric field in the
system is nondegenerate. Recog- y-direction is set up. The electrons
nizing that 87Tp2 dp Fo/h 3 equals actually flow in the direction opposite
the number of electrons with momen- to the current vectors.
tum in the range dp, it follows that I
I
ne2E I
Ix = __'" (V 2T) = aEx = neftE" (13-6)
3kT

Here (V 2T) is the average value of V2T(E), the average being taken over the
Maxwellian distribution of the conduction electrons. Since 3kT = m*(v2 ),
one may also express the mobility as
i
e (V 2T)
(13-7)~
ft = m* . (V2)

Note that if T were independent of the velocity of the electrons, this would
reduce simply to ft = er/m*, as in the simplified model discussed in Sec.
11-2. We shall return to this ~xpression in the next section. ,;'J •. Ii' .
328 NONPOLAR SEMICONDUQORS [Chap. 13
The Hall effect may be discussed by considering the case for which the
front and back faces in Fig. 13-5 are short-circuited, allowing the flow of
a current along the y-direction. An electron of velocity u'" under influence
of the magnetic field Hz will develop a velocity along the y-direction such
that
(OUI[ot)H, = eu",Hz/m*e = WU'" ( 13-8)
On the other hand, due to collisions with the lattice,
(cvy/dt)roll = -VII /T
Hence, in the steady state,
VII = ev",HzT/m*c = WTV", (13-9)
In analogy, one may thus obtain the current along the y-axis by multiplying
the integrand of (13-4) by W'T. This finally leads to
\ (13-10)
Thus, although the electric field is applied along the x-direction, the
resultant current has a y-component due to the magnetic field. In fact, it
is convenient to define the Hall angle On (see Fig. 13-5), where
<V2T2)
tan On ':::' On = Iy/I", = W -2-
(V T)
(I3-11)

If the Hall contacts ar.: not short-circuited, a field Ell is set up to counteract
the influence of the magnetic field. The Hall coefficient then becomes
1 (V 2T2)(V 2 )
Rn = Ey/I", H z= ly/aI",H. = - ' --2-2 (13-12)
nee (V'T)
where a has been substituted from (13-6). Note that the sign of the carrier
in the above derivation is contained in e; for electrons RH is negative,
for holes it is positive. It should be mentioned that one frequently employs
the Hall mobility flH defined in analogy with (13-3) by
e (V 27 2 )
fln = eaRn =- -'-- .~_ (I3-13)
m*c <V27)
Comparing this with the "normal" mobility given by (13-7), it is observed
that in general flH is not equal to fl.
From the foregoing discussion it is evident that the relaxation time 'T
plays an essential role in the interpretation of conductivity and Hall effect
data. The relaxation time in general is determined by collisions of the
carriers with
(i) Lattice vibrations
(ji) Ionized impurities
(iii) Neutral impurities, dislocations, vacancies, and interstitials.
"-

Sec. 13-4] NONPOLAR SEMICONDUCTORS 329

]3-4. Mobility and Hall effect as determined by different scattering processes

(i) Scattering by lattice vibrations. From the theory of interaction of

thermal electrons with lattice vibrations in nonpolar solids,18 it follows that
(a) The scattering is isotropic.
(b) The mean free path A is independent of the velocity of the carriers.
(c) The mean free path is inversely proportional to T, down to tem-
peratures of the order of lOK.
The selection rules for electron-phonon interaction mentioned in
Sec. 11-7 play an essential role in arriving at these conclusions. For a given
temperature it thus follows from (a) and (b) that one may write19
T = A/v (13-14)
Substituting T into the results obtained in the preceding section, one is
thus left with the simple problem of finding averages over a Maxwellian
distribution of quantities on the type vn • Thus, jf only lattice scattering is,
present, (13-7) and (13-13) give
fl = teA /(27TmkT)l!2 and flH = (37T/8)fl (13-15)
Combining this result with (c) above, one concludes that the mobility fl
should be proportional to T-312 in this case. Bardeen and Shockl ey18 find
from their calculation of A,
eT (87T)1121i4cll
m* = fl = 3E12m*512(kT)312 = const. T-:-312 Ie (13-16)

Here, ell is the average longitudinal elastic constant, and E1 is the shift of
the edge of the conduction band per unit dilation; the temperature-
. dependence of both these quantities may be neglected. For holes, El
represents the shift of the edge of the valence band per unit dilation.
Experiments indicate that El ~ 10 ev for germanium. The formula
obtained by Seitz18 is written in terms of the Debye temperature (), the
mass M of the atoms, and their number per unit volume N, '
2l!2 X 61/3 Nl!3 eIi 2P()2M
fl = 47T5/6 • m*5/2C2(kT)3/2

The constant: C has the dimensions of an energy and is of the same order of
magnitude as E1 in the Bardeen-Shockley formula; it is a measure for the
electron-phonon interaction. The mebility determined by lattice scattering
alone is usually referred to as the "lattice mobility."
18 F. Seitz, Phys. Rev., 73, 549 (1948); J. Bardeen and W. Shockley, Phys. Rev., 80,
12 (1950).
19 Compare expression (J I-II) for the relation between collision time, relaxation

time, and scattering angle. (

330 NONPOLAR SEMICONDUCTORS [Chap. 13

The Hall coefficient as determined by lattice scattering for semicon-

ductors containing one or two types of carriers is given, respectively, by
377 d .. 377 nhfl~ - nefl;
R n = ± - an R Il = - - · 2 (13-17)
8nec 8ec (n"flh + n"fle)
where the subscripts e and h in the last formula refer to electrons and holes,
respectively. The conductivity for two types of carriers is of course equal
+
to (nee flc nhe flh)'

(ii) Ionic scattering predominates. When the concentration of ionized

donors is high, the charge carriers suffer Rutherford scattering due to the
;'"
presence of ions, as illustrated in
Fig. 13-6. If one assumes that the
ions are distributed throughout the
lattice in a regular fashion, the
average distance between the ions a i
at
is given by = llNi , where Ni is the
number of ions per unit volume.
Thus if v is the velocity of an electron,
the mean free time between collisions
Fig. 13-6. Rutherford scattering of an
is Tc c:::' adv. The relaxation time
electron by an ionized donpr. It can
be shown that tan (012) = e lEmv b,
2 2 according 10 (11-11) is in general
where to is the dielectric constant of the given by
material.
T = Tr/(l -- (cos 13»

where (cos 13) is the average of the cosine of the scattering angle. Making
use of the Rutherford scattering formula, Conwell and Weisskopf have
calculated an approximate expression for T with the result that

(13-18)

where E is the dielectric constant. 20 It is observed that this type of scattering

leads to a mobility which varies approximately as T3!2, in contrast with the
T-3/2 law for lattice scattering.

The Hall coefficient and Hall mobility associated with ionic scattering
are found to be 21
RH = ±1.93Inec, flH = 1.93fl (13-19)

(iii) Neutral impurity scattering. The scattering of charge carriers by

neutral impurities is quite similar to the scattering of electrons by hydrogen

20 E. M. Conwell and V. F. Weisskopf, Phys. Rev., 77, 388 (1950); see also W.

Shockley, Electrons and Holes, Van Nostrand, New York, 1950, pp. 258 If.; for a
quantum mechanical treatment, see H. Brooks, Phys. Rev., 83,879 (1951).
" W. Shockley, op. cit., p. 279.
Sec. 13-4] NONPOLAR SEMICONDUCTORS 331
atoms. Thus, by suitably modifying the theory of the latter, Erginsoy has
calculated the mobility associated with this type of scattering alone. 22
He finds ). , T
m*e3
er/m* = f.l = - - - (13-20)
~. 20Ndj3
"'1
where N is the density of neutral impurities and EO is the dielectric constant.
The relaxation time is independent of the velocity in this case, so that the
Hall coefficient is the same as that for metals, viz., RH = ± I/nec, as can
readily be seen from (13-12).
Dislocations are also scattering centers for charge carriers as a result
of the dilation they produce in the lattice. According to calculations by
Dexter and Seitz the probability for scattering is proportional to the number
of dislocation lines per cm 2 and proportional to the temperature T. 23
Scattering of charge carriers by vacancies and interstitials is used in
studying radiation effects in solids by resistivity measurements,
In general, lattice scattering. ionic scattering, and scattering by neutral
impurities are all present. The relaxation time for a given velocity of the
charge carriers may then be obtained from

(13-21)

because the probabilities for scattering are additive, each of them being
proportional to the reciprocal of the corresponding relaxation time,
._
13-5. Comparison with experiment

The first extensive investigation of the electrical properties of the

elements of the fourth group was carried out by Pearson and Bardeen on
silicon and silicon alloys containing boron and phosphorus,24 In these
experiments polycrystalline materials were used, More recently, the
electrical conductivity and Hall effect of single crystals of silicon containing
arsenic (n type) and boron (p type) have been studied by Morin and Maita
over a temperature range between WOK and l1OOoK,25 The mobilities in
single crystals are appreciably larger than those in polycrystalline materials
(see Table 13-3), Similar measurements on germanium crystals containing
arsenic have been reported by Debye and Conwell; these extend over the
temperature range between 11 OK and 300oK,26

2. C. Erginsoy, Phys. Rev., 79, 1013 (1950) . '.

•3 D. L. Dexter and F. Seitz, Phys. Rev., 86, 964 (1952) .
• 4 G. L. Pearson and J. Bardeen, Phys. Rev., 75, 865 (1949) .

•• F. J. Morin and J. P. Maita, Pllys. Rev., 96,28 (1954) .

• 6 P. P. Debye and E. M. Conwell, Phys. Rev., 93,693 (1954).
332 NONPOLAR SEMICONDUCTORS [Chap. 13

As an example we reproduce in Fig. 13-7 and 13-8 the resistivity and

Hall coefficient for some of the samples measured by Debye and Conwell,
(they actually measured eleven samples). The intrinsic resistivity is indi-
cated by the dashed line in Fig. 13-7. Sample 55 is nearly pure, whereas

\
- T('K)
300 20.4 10
78

- T('K)
300 20.4
78

107

10 6
55
p

t 55

103

.01 58 ,
10 2
.
10rr______~5~8~______

o .02 .04 .06 .08 .1 o .02 .04 .06 .08 .1

-1/T('K) --1/T('K)

Fig. 13-7. The specific resistivity Fig. 13-8. Hall coefficient (cm"/
in ohms cm for n-type germanium coulomb) versus T-' for arsenic
samples (doped with arsenic), as doped germanium. samples; the
function of T-'. [After Debye and numbers refer to the same silmples
Conwell, ref. 26] as in Fig. 13-7. [After Debye and
Conwell, ref. 26)

sample 58 contains enough arsenic to make the electron gas in the con-
duction band degenerate over most of the temperature range. The other
samples have intermediate impurity densities.
In accordance with (13-13), the Hall mobility may be obtained from
the relation flH = CRH/P; the results are given in Fig. 13-9. It is observed
that the nearly pure sample 55 follows closely the T-3/2 law down to the
lowest temperatures. The reason for this is that neutral impurity scattering
Sec. 13-5] NONPOLAR SEMICONDUCTORS 333
and ionic scattering are negligible for low impurity concentrations. As
the impurity concentration increases, ionized donors become important as
scattering centers at lower temperatures where the amplitude of the lattice
vibrations becomes small. Sample 61 contains a sufficient number of
ionized donors at low temperatures to give a positive slope for the ",(T)
curves. In most of the samples, ,,"
however, the slope gets steeper again
after the initial flattening resulting PH
from ionic scattering; the reason
for this is that electrons fall back 106
into donor levels at low temperatures,
thus reducing the influence of ionic
scattering. 10 5
A quantitative analysis of these
results shows that in the range where
scattering of electrons by the lattice
is predominant, the mobility varies
as T-I.64 rather than as T-I.5. This 10 3 - - - - - - - - - -
58
deviation from the simple theory is
probably in part due to the fact that
the constant energy surfaces in the 10 20 30 40 50 100 200 300
momentum space are not spheres. --+ T(OK)
We shall return to this in Sec. 13-6. Fig. 13-9. Hall mobility for some
Similar deviations have been ob- arsenic-doped germanium samples as
served by Morin and Maita for function of T; the sample numbers are
silicon. A summary of mobility data [he same as those in Figs. J3-7 and 13-8.
is given in Table 13-3. [After Debye and Conwell, ref. 26)

i - T a b l e 13-3. Mobilities in em 2 volt- 1 sec- 1

Room temp. /llattice (arbitrary temp.)

C (diamond), electrons· 900

Si (polycryst.) electrons 300
Si (polycryst.) holes 100
Si (single cryst.) electrons 1450 4.0 x looT-2.6
Si (single cryst.) holes 500 2.5 x 108T-2.3
Ge (single cryst.) electrons 3600 4.9 x IO'T-1.66
Ge (single cryst.) holes 1700 1.05 x 10oT-2.33
Sn (grey) electrons b 3000

• c. C. Klick and J. Maurer. Phy•• Rev. 81. 124 (1951).

b G'. Busch, I. Wieland, and H. Zoller, Hell'etla Phys. Acta, 24. 49 (1951).

Debye and Conwell conclude from their measurements that the

mobility associated with ionic scattering increases with a power of T
334 NONPOLAR SEMICONDUCTORS [Chap. 13

between 1.0 and 1.5, i.e., less rapidly than predicted by the Conwell-
Weisskopf formula. The Erginsoy formula for neutral impurity scattering
fits their data well for an effective electron mass equal to about mj3. They
find scattering by dislocations negligible in their samples.
\
13-6. Constant-energy surfaces and effective mass in silicon and germanium.

The theory developed in Sec. 13-3 and 13-4 was based on the assump-
tion that the energy of electrons near the bottom of the conduction band
or of holes near the top in the valence band could be represented by
1i2k 2 j2m*. This implies that constant-energy surfaces in k-space are spheres
and that m* is a constant independent of the direction of motion of the
carriers. It is presently believed that the discrepancies between theory and
experiment cited above are, at least in part, due to the fact that this
assumption is incorrect. Thus values of the effective mass calculated
indirectly from the electrical properties must be considered unreliable.
Measurements of the influence of a magnetic field on the resistivity of
single crystals of germanium also drew attention to the fact that the
constanf-energy surfaces cannot be spheres. 27
If the constant-energy surfaces are spheres, the effective mass is,
according to (10-38),

'.
However, if the energy is a function also of the direction of the wave
vector k, the effective mass is a tensor rather than a scalar, as was mentioned
in Sec. 10-4. Bya suitable choice of axes, this tensor may be diagonalized
in such a way that along the three principal axes the effective mass is
given by
m~ = 1i2j(d2E(k)jdkD where i = x, y, z (13-22)

For example, for motion along the x-axis, the electron behaves as a particle
of effective mass 1i2/(d2Ejdk;), etc. Until recently, experimental information
about the effective mass, and hence about the curvature of constant-energy
surfaces in the k-space, could be obtained only indirectly, viz., from
experimental results for transport phenomena in which m* occurs.
However, cyclotron resonance experiments of electrons and holes have
made it possible for the first time to measure m* directly.28 In this type
of experiment, electrons in the conduction band and holes in the valence
band describe spiral orbits about the axis of a constant magnetic field H.
27G. L Pearson and H. Suhl, Phys. Rev., 83, 768 (1951).
28Dresselhaus, Kip, and,Kittel, Phys. Rev., 92, 827 (1953); Lax, Zeiger, Dexter, and
Rosenblum, Phys. Rev., 93, 1418 (1954); Dexter, Zeiger, and Lax, Phys. Rev., 95, 557
(1954).
Sec. 13-6J NONPOLAR SEMICONDUCTORS 335
The angular frequency of rotation We can be obtained immediately from
the equality of the centrifugal force and the force due to the magnetic field:

m*v2 jr = ±Hevjc or We = ±eHjm*c (13-23)

where r is the radius of the orbit; the plus or minus sign indicates the
opposite senses of rotation for electrons and holes. Resonant absorption
of energy from a radio-frequency electric field perpendicular to the static

~-----

---._
..

I
«
i
o 1000 2000 3000 4000 5000 6000
,.- - H (oersteds)

Fig. 13-10. Typical cyclotron resonance absorption (arbitrary

units) for silicon near 24,000 mc/sec at 4°K; static magnetic field
in a (110) plane, 30° from an [001] axis. [After Dresselhaus, Kip,
and Kittel, Phys. Rev., 98, 368 (1955)]

magnetic field occurs when the frequency of the radio-frequency field is

equal to that determined by (13-23). Evidently, by measuring We for
different directions of H relative to the crystal axes, one measures essentially
the effective mass as function of direction. Usually, one employs a constant
frequency of the radio-frequency field and then varies H until resonance
is observed. A typical result is reproduced in Fig. 13-10 for an angular
frequency We ':::": 1.5 X lOll radians per sec for silicon at 4°K. The assign-
ment of a given peak to electrons or holes may be made on the basis of
a circularly polarized radio-frequency field or by using n- or p-type
material and exciting a particular type of carrier. The width of the lines
is determined by the relaxation time T of the electrons or holes. In order
to obtain distinct resonance peaks, it is necessary that WeT;:: I. Thus the
mean free path of the carriers should be large enough so that they can
cover at least one radian of a circle between successive collisions. Since
the relaxation times T are of the order of 10-13 or 10-14 second at room
temperature, it is necessary to work with high-purity samples 'at liquid
nitrogen or helium temperatures if one employs frequencies W ':::": IOll
radians per second.
Since it is not possible to enter into a detailed discussion of this subject,
336 NONPOLAR SEMICONDUCTORS [Chap. 13
it may suffice here to mention some of the results obtained for silicon
and germanium. 29 As. an example of the band structures obtained, we
give in Fig. 13-II the energy as function of the wave vector along the
(100) direction for silicon. It is observed that the minimum energy in the
conduction band does not correspond to k = 0 but that there are in all
six minima located somewhere along the six (100) axes. In the vicinity
of these minima, the constant energy surfaces are prolate ellipsoids of

E
. . t· Electrons

~
: :f
L
Forbidden band
' _1
I Eg

~
I 3

-k
I
; "1;

Fig. 13-11. Schematic representation of the energy band structure

in Si along a (100) axis. [After F. Herman, Proc. IRE, 43,
1703 (1955)Y

revolution. Similar minima occur for the conduction band in germanium

along the (Ill) axes. Choosing one of these minima as origin, the surfaces
of constant energy may thus be represented by an expression of the form

(13-24)

where m t and m l are called, respectively, the transverse and longitudinal

electron mass. For Si and Ge the cyclotron resonance experiments lead
to the following results at 4° K:
Silicon: mt = 0.I9m; m l = 0.98m
Germanium: m t = 0.082m; ml = 1.57m
where m is the free electron mass .
.. The energy band structure of Si and Ge derived from cyclotron experiments was,
at least in part, predicted by a theoretical study of F. Herman, Physica, 20,801 (1954);
Phys. Ret'., 95, 847 (1954). See also his excellent review in Proc. IRE, 43, 1703-1732
(1955) (solid state issue).
•
Sec. 13-6] NONPOLAR SEMICONDUCTORS 337

The maximum energy for the valence band in both silicon and
germanium occurs for k = 0, according to the results of cyclotron
resonance experiments; furthermore, this maximum is common to two
bands which meet at k = O. The constant-energy surfaces near k = 0 for
these two 'bands are warped and are given by the expression

where A, B, and C are constants. The negative and positive roots corre-
spond, respectively, to the highest (VI) and second highest (V2 ) valence
band. If one approximates the warped surfaces by spheres, one may
determine the average hole mass in the two bands from the experimental
values of A, B, and C. In this approximation, one obtains
Silicon: mtl = 0.49m; mt. = 0.16m
Germanium: mtr, = O.l~m; mtr. = O.OMm ,;
We should note here that the form of expression (13-25) was indicated by
the theory of spin-orbit splitting for these crystals. ao .
It is observed from Fig. 13-11 that there is a third valence band Va
which is separated from the VI and V2 bands as a result of spin-orbit
interaction. The maximum of the Va band lies slightly below that of the
two other bands. Near the maximum of the Va band, the constant energy
surfaces are spherical; the effective masses are:
Silicon: mt. = 0.24m (
Germanium: mt = 0.077m
• : ,·1

The energy difference between the top of the Va band and the common
maximum of the VI and V 2 bands has been estimated to be 0.035 ev for
Si and 0.28 ev for Ge. It will be evident that the relative hole populations
of the Va and VI' V2 bands is a function of temperature.

The energy gap. A few remarks may be made here about the conse-
quences of the above results for the concept of the forbidden energy gap
and its experimental determination. When an electron is thermally excited
from the. valence band into the conduction band, the electron absorbs a
phonon. This process is governed by the selection rules corresponding to
conservation of momentum and energy:
k' = k + q + 27Tn ...
(13-26)
E(k') = E(k) + liw q

30 G. Dresselhaus, A. F. Kip, and C. Kittel, Phys. Rev., 95, 568 (1954); 98, 368
(1955); R. J. Elliott, Phys. Rev., 96, 266 (1954); 96,280 (1954).
338 NONPOLAR SEMICONDUCTORS [Chap. 13
Here k' and k are, respectively, the final and the initial wave vector of the
electron; q is the wave vector of the absorbed phonon, and liwq is the
energy of the phonon; n is a vector in the reciprocal lattice, and 27Tn in
(13-26) guarantees that k' is a vector in the reduced zone. The "cheapest"
thermal excitation of an electron from the valence band to the conduction
band evidently involves a phonon of energy ;W)q = Eg where Eg is tl}.e
energy difference between the highest electronic level in the valence band
and the lowest level in the conduction band (see Fig. 13-11). Thus Eo
may be obtained from the variation of the carrier concentration with
temperature, We should note here that Eg itself is a function of temperature
(resulting from the expansion of the lattice).
Let us now consider what one measures if one determines the long
wavelength threshold for optical excitation of an electron from the valence
band into the conduction band in substances such as Si and Ge. If one
considers the optical excitation as a collision between an electron of wave
vector k and a photon of wave vector a the selection rules require

k' = k +a and E(k') = E(k) + hv ( 13-27)

where hv is the energy of the photon. Now, the wavelength of a photon

corresponding to infrared or visible radiation is large compared to a lattice
constant. Hence a may in general be neglected in comparison with the
electron wave vector k. In other words, optical transitions of this kind
occur "vertically" in the reduced zone scheme because we then have
k' = k. It is evident from Fig. 13-11 that the "cheapest" vertical transition
involves always more energy than Eo because the minimum of the conduc-
tion band occurs for a different k-value than the maximum of the valence
band. In other words, the optical threshold energy should be larger than
Egap. However, the observed threshold photon energies correspond closely
to the energy gap E. determined from the variation of carrier concentration
with temperature. Hall, Bardeen, and Blatt have therefore suggested that
the observed optical threshold is determined by an indirect or nonvertical
transition in which the absorption of a photon is accompanied by the
absorption or emission of a phonon. 31 Under these circumstances the
momentum and energy conservation laws for an optical transition are:

k' = k + a ± q + 27Tn ~ k =i:~ q + 27Tn

(13-28)
E(k') = E(k) + hl' ± limq

where the symbols have the same meaning as above. The presence of the
phonon momentum q thus makes it possible for the transition to be non-
vertical. The +
and - signs refer, respectively, to absorption and
emission of a phonon. It is of interest to recognize that at very low
at L. H. Hall, J. Bardeen, and F. J. Blatt, Phys. Rev., 95, 559 (1954).
Sec. 13-6] NONPOLAR SEMICONDUCTORS 339
temperatures few phonons are present and thus absorption of a phonon
becomes improbable. Thus at T = 0 we shall have an optical threshold
frequency Y t such that

At high temperatures, on the other hand, there are sufficient phonons

present to make optical transitions possible at a threshold frequency Y I
such that

In other words, the optical threshold frequency will vary with temperature.
,
Transport phenomena. It will be evident that the above results for the
energy-band structure have an important bearing on the theory of electrical
conductivity, Hall effect, magneto resistance, infrared absorption, etc. In
fact, the resulting energy-band scheme and the numerical values for the
effective mass parameters are consistent with magneto resistance measure-
ments on n-type germanium and silicon. 32 Deviations from the T- 1 .5 Iaw for
the mobility may also be explained as a result of the nonisotropic mass.

Infrared absorption. A few remarks may be made here about the

infrared absorption of charge carriers in Ge and Si. For the moment,
consider a charge carrier with an isotropic mass m* under influence of an
electromagnetic field. Suppose the electric field is along the x-direction
and let the magnetic field be neglected. The velocity component V,r of the
charge carriers then varies with time according to

dV"jdt = (ov,jot)fleld + (ov.jot)coll = (ejm*)Eoe iw1 - V"JT

The stationary solution of this equation is

. t I
v = (eTjm *)E etc" - - - (13-29)
x . 0 I iwt +
As long as the angular frequency of the field w ~ IjT, Vx varies in phase
with the external field, and the conductivity of the material containing N
carriers per unit volume is equal to the static conductivity <J o, where

(WT ~ I)

In the general case, however, it follows from (13-29) that the conductivity
is complex; the real part varies with frequency as

32 S. Meiboom and B. Abeles, Phys. Rev., 95, 31 (1954); I. Estermann and A. Foner,

Phys. Rev., 79, 365 (1950); G. L. Pearson and C. Herring, Physica, 20, 975 (1954).
340 NONPOLAR SEMICONDUCTORS
.
[Chap. 13
The absorption coefficient of .the radiation K is of course proportional to
the real part of the conductivity, and in fact equal to

where n is the index of refraction and c is the velocity of light. When

(IJT?>I, this may be written approximately as

(13-30)

where p. is the mobility of the carriers. Now if the constant-energy surfaces

are prolate spheroids, one can use
(13-30) by replacing m* by an average
50
effective mass m:v given by

where m l and m t are the longitudi-

nal and transversal mass parameters.
Thus by measuring K as function
of (I), m:v may be determined from
known values of p.. In Fig. 13-12
.1
we have represented the absorption
.05 ~~_~_L--.L.....Jc.......-,-~-u coefficients of n-type germanium
1.5 2 3 4 5 6 8 10 12 samples in the infrared, as deter-
mined "by Fan and Becker.33 The
Fig. 13-12. The absorption coefficient resistivity of the samples at room
of n-type Ge. [After Fan and" Becker, temperature is indicated. The sharp
ref. 33) rise in the Kversus wavelength curves
is associated with transitions of
electrons from the valence band to the conduction band. For wave-
lengths > 6 micron (w < 3 X 1014 radians per second), K varies
approximately as 1/(1)2 in accordance with (I 3-30). From the four
curves given in Fig. 13-12, Kahn finds by applying (13-30) for the
average effective mass of the electrons, 0.11, 0.12, 0.20, and 0.14, taking
the mass of a free electron as unit. 34 Using the values for m t and m l for
electrons in Ge as determined from the cyclotron resonance expenments,
one finds from (13-3 I) that m:v = 0.14m, in reasonable agreement with
the experimental values. The infrared absorption bands observed in p-type
Ge can be interpreted in terms of transitions of holes between the three
energy bands lying near the top of the valence band, as suggested by the
cyclotron resonance experiments.
33 H. Y. Fan and M. Becker, Proc. Reading Conference, Butterworths Scientific

Publications, London, 1951, pp. 132-147.

3' A. H. Kahn, Phys. Rev., 97, 1647 (1955). ":(~.: .. ,e
Sec. 13-7] NONPOLAR SEMICONDUCTORS 341

13-7. The lifetime and diffusion of minority carriers

Consider a semiconductor containing a relatively high concentration

of donor levels so that the conductivity is essentially due to electrons in
the conduction band (n-type). The electrons are then called the majority
carriers. There are, of course, always some holes in the valence band as a
result of thermal excitation of electrons from the filled band, but at not
too high temperatures the number of holes is relatively small. The holes
are called the minority carriers in this case. In thermal equilibrium the
number of holes recombining with electrons per second is equal to the
number of electron pairs produced per second by thermal excitation. The
concentration of minority carriers may be increased artificially in a number
of different ways.35 For example, if a metal in contact with n-type material
is made positive relative to the semiconductor, holes are injected into the
latter, as will be explained further in Sec. 14-4. Also, the semiconductor
may be exposed to light; absorption of photons by electrons in the filled
band will then lead to the formation of electron-hole pairs. The minority
carriers so produced will diffuse about in the crystal; however, because
the density of the minority carriers is not equal to the equilibrium con-
centration, they will ultimately disappear by recombination with the
majority carriers. Suppose now that a certain number of minority carriers
is produced during a short time interval somewhere in a crystal. As long
as the excess concentration is small compared with the equilibrium con-
centration, the rate of recombination is proportional to the excess concen-
tration, i.e., the excess number will decay according to exp (-t/T), where
T is the lifetime of the carriers (the lifetime should not be confused with
the relaxation time). Measurements of the lifetime of minority carriers
are of interest, since by varying the conditions under which the experiments
are carried out, one obtains information about the factors determining
the recombination process. Experiments of this kind essentially involve
the following idea: minority carriers are injected from an emitter into a
crystal; the carriers diffuse away from the emitter, and their arrival at
another point is detected by a collector. For a given number of injected
carriers the collector pulse decreases with increasing distance from the
emitter as a result of the disappearance of a fraction of the carriers on
their way to the collector. Frequently an electric field is used to drive the
carriers !"rom the emitter toward the collector.
The interpretation of this type of experiment is based on some
fundamental principles, which will now be considered. In an n-type semi- ,
conductor let the equilibrium concentration of holes (minority carriers) be
no, and let the actual concentration be n h • The basic equation governing
3. See Shockley, op. cit., p. 60; F. S. Goucher. Phys. Rev., 81, 475 (1951); R. Bray,

Phys. Rev., 76, 152,458 (1949).

342 NONPOLAR SEMICONDUCTORS [Ch~p. 13
the behavior of these carriers under conditions in which nh is a function
of space and time is the continuity equation,
(13-32) .
The terms on the right-hand side have the following meaning: the first
represents the number of holes leaving unit volume per unit time due to
the hole current density I h ; the second represents the number of holes
disappearing per second per unit volume due to recombination (Th is the
lifetime of the holes); the last represents the number of holes generated
per unit volume per second by external means (injection).
The hole current is made up of two terms: one results from the
external electric field E, the other is due to the diffusion of the holes. The
diffusion current is proportional to minus the gradient of the hole
concentration so that
(13-33)
where Dh is the diffusion coefficient of the holes and Ilh is the hole mobility.
There exists a fundamental relationship between the diffusion coefficient
and the mobility. According to elementary diffusion theory,
D = (A/3)(v) (13-34)
• where A is the mean free path for scattering and (v) is the average velocity
.i!' of the carriers. On the other hand, it follows from (13-7) and (13-14) that
-:"A M2 (13-35)
Il - m (v )

For thermal holes, m(v2 ) = 3kT, so that we obtain the Einstein relation,
IlID = e/kT (13-36)
The same relationship is obtained from (13-33) by considering an equili-
brium situation in which I" = 0. Under these circumstances, we should
have, according to Boltzmann,
n" = Ae-- e1 ' jkT
where V is the electrostatic potential and A is a constant. Combining
this with (13-33) for In = 0, we may write

0= ellhnhE -- eD"n h ( - keT grad V)

which leads immediately to (13-36).

Equations (13-32) and (13-33) govern the theory of the lnJection
experiments; a simple one-dimensional example may be given here. 36
a. For further examples, see Shockley, op. cit., pp. 3 t81f. ~Z 1 ..~
Sec. 13-7] NONPOLAR SEMICONDUCTORS 343
Consider an infinite medium consisting of n-type material in which at
t = °
a number of holes is produced by a plane source at x = 0. Let
n(x,t) be the excess hole concentration and T the lifetime of the holes.
Assuming that no electric field is present, we have, according to (13-33),
Ix = -e Dan/ax
(we leave out the subscripts h). In (13-32), the term gh is zero for t > 0,
so that
an/at = D o2n/ox2 - n/T (13-37)
The solution of this equation is
N '- "c~,",--'_:'" _ ~
t) = (13-38)
, n(x ,
e-xO/4Dt-t/T ",_j.-.'"
(41T Dt)1/2 "- ." ,
where N measures the strength of the source. It is recognized that the
finite lifetime of the carriers produces a factor exp (-t/T) which does not
occur in the "normal" solution for Brownian motion (T = 00). We leave
it to the reader as a problem to show that the average distance relative to
the point of origin traveled by the carriers during life is equal to
L = (DT)1/2 (13-39)
where L is called the diffusion length of the carriers. It may be compared
with the well-known expression (X2) = 2Dt for the mean square displace-
ment of a particle carrying out a one-dimensional random walk. Clearly,
the distance between collector and emitter in an injection experiment
should be of the same order or less than L in order to detect the arrival
of the carriers at the collector.
Results of injection experiments show that recombination takes place
not only in the bulk of the sample, but also at the surface. In fact, the
surface treatment influences the lifetime in many instances. A few examples
of lifetimes of holes in an n-type single crystal of Ge are given below;
the resistivity of the sample was 19 ohm em at room temperature. 37 The
dimensions indicated refer to the cross section perpendicular to the
direction of current flow. The values Tg refer to roughly ground surfaces,
T, to carefully etched surfaces. li,

Table 13-4. Hole Lifetimes for Ground and Etched Surfaces

Dimensions of
Ty (microsee) T, (microsec)
cross-section (em")

0.371 x 0.737 144 280

0.202 x 0.716 78 340 .,
0.100 >: 0.705 16.5 290
0.071 x OA8 9.2 280
0.036 x 0.48 3.1 235

37 D. Navon, R. Bray, and H. y, Fan, Proc. IRE,40, 1342 (1952).

344 NONPOLAR SEMICONDUCTORS [Chap. 13

This shows clearly the important role played by the surface in the
recombination process in the roughly ground samples. The exact nature
of the centers at which the electron-hole recombination takes place is not .
understood. Estimates of direct recombination of electrons and holes
under photon emission indicate lifetimes of the order of one second. 3s
So far, the longest lifetimes observed are of the order of 10-3 second,·
indicating that the direct recombination process is relatively unimportant.
It seems, therefore, that centers are required which act as a catalyst in
the recombination process. It is of interest to note that when a Ge crystal
is heated to higher temperatures and then quenched, the lifetime of the
carriers decreases. 37 This implies that certain types of frozen-in lattice
defects are at least in part responsible for recombination.

:f : 'i
13-8. Intermetallic compounds

As a result of the search for new semiconductors with properties

similar to those. of silicon and germanium, Welker successfully initiated a
study of intermetallic compounds consisting of the elements of the third
and fifth column in the periodic system. 39 Presently, a great deal of effort
is being expended in studies of the physical properties of this new group
of semiconductors. From Table 13-1 it is observed that column IliA
~ contains elements with an outer electron configuration in which two
)d-' electrons occupy an s state and one occupies a p state; similarly, the
elements in column VA have an outer electron configuration consisting
of two s electrons and three p electrons. One may then expect a close
relationship in structure and physical properties of compounds of the
type AJIIBV with elements such as Si, Ge, Sn. Of particular interest are
combinations of the six elements
AI P
Ga As , '. t·
In Sb

The nine compounds which can be made by combination of the elements

of one group with those of the other all crystallize in the zincblende
structure, which is closely related to the diamond structure; in fact if the
elements in the zincblende structure are made identical, the diamond
structure results. The nearest neighbor distances in Angstroms for these
compounds are given below; for comparison, those of Ge, Si, and grey
Sn are included.
AlP 2.36 GaP 2.36 InP 2.54 Si 2.34
AlAs 2.44 GaAs 2.44 InAs 2.62 Ge 2.44
AISb 2.62 GaSb 2.62 InSb 2.80 Sn 2.80
3. See Shockley, op. cit., p. 69.
3' H. Welker, Z. Natur(orsch., 7a, 744 (1952); 8a, 248 (1953).
Sec. 13-8] NONPOLAR SEMICONDUCTORS 345
The binding in these compounds is to a large extent homopolar, as in the
fourth group elements; however, as a result of the somewhat larger
electronegativity of the fifth group elements, there is a small ionic contri-
bution to the binding energy. The essentially covalent character of the
bonds is consistent with the fact that the interatomic distances are
approximately equal to the covalent radii of the atoms; the sum of the
ionic radii is considerably smaller. Thus the trivalent atoms and the
pentavalent atoms contribute an average of four electrons to the formation
of four electron pair bands per atom. From this model one may expect
that it is rather difficult to replace a pentavalent atom by a trivalent one.
In other words, it should not be too difficult to grow crystals of nearly
stoichiometric composition. That this is indeed the case is confirmed by
the fact that InSb can be made to conform to the chemical formula so well
that at room temperature the conductivity is essentially intrinsic.
A method of growing large single crystals (several cm) has been
described by GremmCImaier and Madelung. 40
In order to vary the electrical properties of these materials, one can
add elements of the second group such as Cd, Zn, or elements of the sixth
group, such as Se, Te; in the former case the compounds become hole
conductors, in the latter electronic conductors.
For InSb, measurements of the electrical conductivity and Hall
coefficient show that the electron mobility as a function of temperature
can be represented b y41 . I

fl. = 65,OOO(T/300)-1.66cm2/volt sec.

Thus at room temperature the electron mobility in InSb is about 20 times

that in germanium. This is presumably a consequence of a very small
electronic mass in the conduction band. In fact, Burstein has explained
the anomalous behavior of optical properties of this material on the basis
of m: = 0.03 m.42 If m: is small, the curvature of the E(k) curves near
the bottom of the conduction band is strong; consequently, the density
of states is low and the electron gas degenerates at relatively low densities.
This leads to a shift in the long-wave optical absorption edge to smaller
values as the density of electrons increases beyond the degeneracy density.
According to Madelung and Weiss the forbidden gap in InSb is
given btl
Egap = 0.27 - 3 X 10-4T (ev)

New information on the properties of intermetallic compounds IS ~

to R. Gremmelmaier and O. Madelung, Z. Naturforsch., 8a, Heft 5 (1953).

41 O. Madelung and H. Weiss, Z. Natu~rorsch., 9a, 527 (1954).
42 E. Burstein, Phys. Rev., 93, 632 (1954); M. Tanenbaum and H. B. Briggs, Plrys.

Rev.; 91,1561 (1953).

346 NONPOLAR SEMICONDUCTORS [Chap. 13
being obtained at a rapid rate and this may be expected to continue for a
number of years to come. Some further references are given below. 43
I

REFERENCES \
\
H. Y. Fan, "Valence Semiconductors, Germanium and Silicon," -in
F. Seitz and D. Turnbull (eds.), Solid State Phvsics, Academic Press,
New York, 1955, Vol. I, pp. 284-3'67. _.
F. Herman, "The Electronic Energy Band Structure of Silicon and
Germanium," Proc. IRE, 43 1703-1732 (1955) (solid state issue).
W. Shockley, Electrons and Holes, Van Nostrand, New York, 1950.
Proc. IRE, 40, (1952) (transistor issue); 43, (1955) (solid state issue).
"Semiconducting Materials," Proc. Reading Conference, Butterworths
Scientific Publications, London, 1951.

PROBLEMS
13-1. Calculate the distance between nearest neighbors in the germa-
nium and silicon lattices.
~ 13-2. Consider an n-type semiconductor contamlng Nd donors per
cm3 ; let there also be Na acceptor levels per cm3 , close to the conduction
band. Discuss the density of electrons in the conduction band as function
of temperature. !
13-3. Discuss how the elastic constants given in Table 13-2 can be
obtained from measurements of the velocity of elastic longitudinal and
shear waves.
13-4. On the basis of the Debye approximation, calculate the Debye
temperature for Si and Ge from the elastic constants given in Table 13-2;
compare the results with eD obtained from specific heat measurements.
13-5. From the dielectric constants given in Table 13-2 calculate the
polarizability per Si and per Ge atom in the crystalline state, assuming for
simplicity an internal field of the Lorentz type.
13-6. A germanium crystal contains 10-4 atomic per cent of arsenic;
assuming all donors are ionized, calculate the resistivity at room
temperature.
" For JnSb. see R. G. Breckenridge el al., Phys. Rev., 96, 571 (1954); for GaSb,
R. F. Blunt, W. R. Hosler, and H. P. R. Frederikse, Phys. Rev., 96, 576 (1954); and,
D. P. Detwiler, Phys. Rev., 97,1575 (1955); for AISb, R. F. Blunt, H. P. R. Frederikse,
J. H. Becker, and W. R. Hosler, Phys. Rev., 96, 578 (1954).
Chap. 13] NONPOLAR SEMICONDUCTORS 347
13-7. On the basis of the Rutherford scattering formula, rederive the
Conwell-Weisskopfformula by formulating your own simplifying assump-
tions; compare the result with expression (13-18).
13-8. Show that the Hall coefficient for a semiconductor in which the
current is carried by electrons as well as holes is given by expression (13- 17).
13-9. Consider an electron in the conduction band of a semiconductor
with the average thermal energy at room temperature. Discuss the
collision between this electron and a phonon on the basis of the laws of
conservation of momentum and energy. Show that the energy gain or loss
for the electron is always relatively small compared with its initial energy.
See Sec. 1I -7 for details.

'Ii
, "-,
i

Chapter 14

RECTIFIERS AND TRANSISTORS

\
14-1. Rectifying properties of a barrier layer between two metals

Although in solid-state rectifiers one usually employs one semicon-

ducting contact, semiconduction itself is not essential for the rectification
process. This may be illustrated by considering two metals of different
work function separated by a thin vacuum gap. As we haY\! seen in
Sec. 9-10, the Fermi levels of the two metals must. coincide in thermal
equilibrium, leading to the situation depicted in Fig. 14-1a; the metal
of low work function acquires a positive surface charge, the other acquires
a negative surface charge. The total potential drop across the gap is
10 -

\
(al " (bl
Fig. 14-1. (a) Shows the equilibrium between two metals of
different work functions separated by a thin vacuum gap. In (b) a
forward voltage is applied (metal 2 negative).

equal to (4)1 -- 4>2)!e. It is convenient to consider this situation a dynamic

equilibrium in which the electronic current from I to 2 is equal to that
from 2 to 1. Let us denote this current density by 10 , Suppose now metal
2 is made negative with respect to 1 by applying an external voltage
smaller than the voltage drop (4)1 - 4>2)/e. The energy levels of 2 are
then raised relative to those in 1, and the situation corresponding to
Fig. 14-1 b results. The current 11--+2 is still equal to 10 because the barrier
viewed from the position of metal 1 has not changed. On the other hand,
the potential energy hill as viewed from metal 2 is lowered by an amount
e V, which makes the probability for an electron to cross the hill larger
by a factor efl'/kT. Hence the net electron current is
(14-1)
Similarly, if the applied voltage has such polarity as to make metal 2
348
Sec. 14-IJ RECTIFIERS AND TRANSISTORS 349
positive with respect to I, we have again 11-+2 = 10 , However, the
current from 2 -+ I is now Ioe-eV/kT, yielding a net current of
(14-2)

where If and Ir are referred to, respectively, as the forward current and the
reverse current. Now If increases exponentially with the voltage applied
in the forward direction; In on the other hand, saturates rapidly to the
low value 10 , The current-voltage characteristic of the contact is similar
to that 'given in Fig. 14-8 and can be used for rectifying purposes.

14-2. The Schottky theory of a metal-semiconductor contact ~,- -

j ,-:j ,;; ::1,

A simple theory for the contact between a metal and a semiconductor

has been developed by Schottky.1 It leads to the formation of a physical

Cond. band

(a)

Fig. 14-2. (a) Refers to a metal-semiconductor contact not yet in

equilibrium; X is the electron affinity of the semiconductor. In
(b) equilibrium has been established by the formation of a Schottky
layer; the total potential drop is (<Pm - <p.)/e.

barrier layer at the metal-semiconductor interface as explained below.

Such barriers must be distinguished from chemical barrier layers which
may be present between the metal and semiconductor as a result of
chell!ical preparation.
To explain the nature of the physical barrier layer, consider an ideal
contact between a metal of work function 4>m and an n-type semiconductor
with an electron affinity X.2 Before equilibrium has been established,
the energy band scheme may be represented by Fig. 14-2a. According
to Sec. 12-5, the effective work function of the semiconductor is given by
the energy difference between its Fermi level and the vacuum level; let
this difference be 4>s. Thus, if 4>s < 4>m, electrons will flow from the
1 W. Schottky, Z. Physik, 113,367 (1939).
2 The electron affinity is defined as the energy required to transfer an electron from
the bottom of the conduction band to vacuum,
350 RECTIFIERS AND TRANSISTORS [Chap. 14

semiconductor into the metal. Consequently, the metal acquires a negative

surface charge and the semiconductor charges up positively. Now,
because the density of donors is relatively small, the donors will be come
ionized over a region which extends into the semiconductor, i.e., a space
charge rather than a surface charge is created (see Fig. 14-2b). The
thickness of the barrier layer thus formed may be estimated as follows ~
Let us assume that all donors in the region between x = 0 and x = xo
in Fig. 14-2b are ionized. The potential energy of an electron 4> in this
region is then determined by the Poisson equation
(14-3)
where nd is the donor concentration and € the dielectric constant. Taking
4> = 0 at x = 0 and 4> = 4>m - 4>. at x = xo, one readily finds that the
thickness Xo of the barrier must satisfy the relation
4>m - 4>. = (27TjE)nde2x~ \ (14-4)
Thus, for a given value of the required potential energy drop, Xo varies
as n,II/2. A few examples may be given here for 4>m - 4>. = 1 eV and
£ = 10.

na 1015 1017 1019 per cm3

Xo 10-4 10- 5 10- 6 cm
It is observed that an externally applied voltage changes the potential
drqp across the barrier and hence results in a change in the thickness
of the barrier. For example, if the semiconductor is made positive, the
··J,__':icness increases and is determined by
4>m - 4>. + e V = (27T/€)nde2x~ (14-5)
For an applied voltage in the opposite direction, Xo decreases. Note
that the barrier thickness increases with increasing dielectric constant.
If the dielectric constant of the material is known, the thickness of the
barrier can be determined from capacitance measurements with a small
ac signal for a given bias. To a first approximation the equivalent circuit
of the contact may be represented by a voltage-dependent capacitor
in parallel with a nonlinear resistor, the combination being in series
with the bulk resistance of the semiconductor. Changes as indicated by
(14-5) can indeed be observed.
The above model is admittedly simplified and neglects, for example,
the influence of the image force; for high dielectric constants (~1 0)
he image force has little influence. Also, the influence of surface states
has been neglected; these may play an important role.
The Schottky barrier layer forms an essential factor in the theory
of rectifying contacts as we shall see below. It is left to the reader to
discuss the barrier formed at a metal-p-type-semiconductor contact.
Sec. 14-3] RECTIFIERS AND TRANSISTORS 351

14-3. Single-carrier theories of rectification

As an example of the rectifying properties of a metal-semiconductor

contact we represent in Fig. 14-3 the current-voltage characteristic of
a metallic point contact on p-type AlSb. 3 In general, the forward current
is observed under the following circumstances: for n-type material the
semiconductor should be negative, for p-type material the semiconductor
should be positive. mA
In th{' conventional theories of rectifica- ''-'''' ~pw~ ~ 2 t
tion it is assumed that either electrons or
holes take part in the current flow across
the barrier'; i.e., they are single-carrier
theories. In order to explain certain pro- 1
perties of Ge rectifiers, a two-carrier theory
has been developed. In the present section
we shall consider only the single-carrier case.
10
The tunnel theory. The oldest theory of 5
rectification was developed in 1932 by v,.--
Wilson and Nordheim.' These authors
assumed that for an n-type semiconductor Fig. 14-3. The current in mA
the electrons crossed the barrier by tunnel as function of forward and
reverse voltage (in volts) for
effect, i.e., the carriers penetrate through a point-contact AISb rectifier.
rather than cross over the potential barrier. [After Welker, ref. 3)
Such a mechanism of course requires thin
barrier layers ('"'-'10- 7 cm); as we have seen above, the barrier is
usually considerably thicker. The strongest objection against the tunnel
theory is, however, that it predicts the wrong sign for rectification.
For example, the reader can readily convince himself that for a metal-
n-type-semiconductor contact, the tunnel theory predicts the forward
current when the metal is negative. This is simply because the number
of electrons available for tunneling in the metal is much larger than
that in the conduction band of the semiconductor. The tunnel theory
will therefore not be discussed here, although it should be kept
in mind that under special circumstances tunneling may well occur.

The MOlt-Schottky theory for thick barriers. A new theory ~f rectifi-

cation in which it is assumed that the carriers surmount the potential
barrier by thermal excitation was proposed by Mott 5 and further developed
by Schottky.6 Mott was particularly concerned with selenium and with
Cu-Cu 20 rectifiers. In these rectifiers, as a result of the chemical way in
3 H. Welker, Z. Naturforsch" Ba, 248 (1953),

• H. Wilson, Proc. Roy, Soc, (London), 136,487 (1932); L. W. Nordheim, Z. Physik,

75,434 (1932), ,'I'H';1 "iP"
352 RECTIFIERS AND TRANS[STORS [Chap. 14

which they are prepared, the density of donors (or acceptors) is very
small near the metal and gradually increases to a constant value as one
moves into the semiconductor. In some instances one produces deliber-
ately an insulating layer between the metal and the semiconductor by
chemical means.
As an idealized model for this type of system we shah consider the
following case. s An n-type semiconductor contains nd donors per cma.
The semiconductor is separated from the metal by a layer of 10-4_10-5
em thick of the same material but without donor levels. We shall further

Fig. 14-4. Metal-insulator-semiconductor contact; the voltage

drop across the insulating layer in equilibrium is Vo = (<Pm - <p.)/e.
With an applied forward voltage Vi the voltage drop is (Vo - V) as
indicated by the dashed conduction band.

aSStlme that any potential difference between the metal and semiconductor
ey(~ essentially across the insulating layer, the field strength in the
layer being constant (see Fig. 14-4).6 Since the thickness of the layer Xo
is large compared with the mean free path for scattering of the electrons
by lattice vibrations, the electron current through the layer is due to
(I) the electric field and (2) diffusion. Let E represent the field strength
for a unit negative charge, and let [ be the electronic current density.
We may then write
[ = n(x)eflE - De dn/dx (14-6)
where n(x) is the density of electrons. The diffusion coefficient D in
'terms of the mobility fl is given by the Einstein relation D = flkTfe.
Integrating (14-6), one thus obtains
n(x) = [/tuE + CeeEX/kT ,,~ (14-7)
where C is a constant. In order to calculate the current [, we make use
S N. F. Mott, Proc. Roy. Soc. (London), A171, 27 (1939).
6 W. Schottky, Z. Physik, 118, 539 (1942); also, W. Schottky and E. Spenke,
Wiss. Veroffentl. Siemens Werken, 18,225 (1939). These references also take account of
the space charge region in the semiconductor.
Sec. 14-3] RECTIFIERS AND TRANSISTORS 353
of the following boundary conditions: for x • 0, the density of electrons
is equal to that in the conduction band in the bulk semiconductor n(O).
Also, the density of electrons for x = Xo in the absence of an external
field must be equal to
'l n(x o) = n(O)e-(4>m-4>,l/kT = n(O)e-eVof kT (14-8)

where CPm and CPs are the work functions of the metal and insulator,
respectively; the total voltage drop is then Vo = (CPm - cps)/e. We shall
assume that n(xo) is not influenced by the current flow resulting from an
external field, although this is only approximately true. The first boundary
condition leads to C = n(O) - 1/fleE. Substituting this into (14-7)
and applying the second boundary condition in the form (14-8), one
obtains for the current density,
n(O)eeExo/kT - n(xo)
I = fleE eeExo!kT _ I (14-9)

Now when V is the applied voltage in the forward direction as indicated

in Fig. 14-4, Exo = -(Vo - V); also, as long as we are interested in
cases for which the potential barrier is large compared with kT, the
denominator in (14-9) reduces to -I. Thus (14-9) may be written in the
furm ' ,l",~." ,', ,\,' ",,:
I(V) = [fle(Vo - V)/xo]n(xo)(eeVlkT -- 1),-...J A(e·V/kT - 1) (14-10)

where A is approximately constant. The form of the current-voltage

characteristic is thus essentially the same as (14-1); for the reverse current
one obtains a relation similar to (14-2). For the type of rectifiers for
which this theory is developed (thick barriers), it is generally in accord
with the experimental results; refinements involving the image force may
be found in footnotes 5 and 6.

The diode theory.7 In germanium and silicon rectifiers the barrier

layer thickness is of the order of 10-6 em, i.e., comparable with the mean
free path of the carriers. In that case, the diffusion theory cannot be
applied, and the so-called diode theory has been developed. In this
theory it is assumed that collisions of carriers with the lattice are absent
and the problem reduces to that of two thermionic emitters facing each
other. We leave it to the reader to show that the electronic current
density from the semiconductor to the metal in this case is given by
(t)n(O)e(v)e-e(V o - V)/kT (14-11)
where (v) = (2kT/7Tm)1/2 is the average thermal velocity of the electro~s
in the conduction band of the semiconductor; the other symbols have
1 See, for example, H. C. Torrey and C. A. Whitmer, Crystal Rectifiers, McGraw-

Hill, New York, 1948, p. 81.

354 RECTIFIERS AND TRANSISTORS [Chap. 14

the same meaning as above. The electronic current density from the
metal to the semiconductor is obtained by putting V = 0 in expression
(14-11), since for V = 0 the two currents are equal and opposite. The
resultant current is then . _\ ' i'
leV) = mn(xo)e(v)(eeV/kT - l) = A'(eeV/kT - I) (14-12)

Comparing this with (14-10), it is observed that the form of the two
expressions is essentially the same. However, (v) may be considerably
smaller than pE, leading to A' ~ A. For example, at room temperature
(v) :::: 10 7 cm sec l ; for a: barrier of 10- 6 cm and a voltage drop of 1 eV,
E:::: 106 volts per cm, and with p:::: 103 cm per volt sec, we obtain
pE:::: 109 cm sec-I. It should be remarked here that V represents the
voltage across the barrier, i.e., it is equal to the applied voltage minus
the voltage drop across the bulk semiconductor.
Although the diode theory has been applied in the past to interpret
the rectifying properties of germanium and silicon diodes, a number of
observations remained unexplained. For example, according to the
above theory, the magnitude of the currents should depend strongly on
the work function of the metal because n(xo) is proportional to exp
(-eVolkT) and Vo is determined by (4),,, - 4>J. Thus, for a variation of
0.5 ev in the work function of the metals used, the currents should vary
by a factor of ,..._,10 8 . Experiments indicate variations by a factor of 10
or less for different metal points. The origin of this discrepancy will
be discussed in the next section.

14-4,.:surface states on semiconductors

",;..;;..'
4"

In 1948 Shockley and Pearson reported the following relatively simple

but crucial experiment. 8 Consider a thin layer of n-type germanium on
an insulating support. Opposite the layer and separated from it is a
metal plate, the system as a whole forming a parallel plate condenser.
When the metal plate is made negative relative to the germanium layer,
a negative charge is induced in the latter, which, if it were free to move,
should enhance the conductivity of the layer. For example, if the applied
field is 3 X 1()4 volts cm- 1 the induced charge per cm2 corresponds to
about 3 X 1010 electrons. On the other hand, if the layer is 5000 A
thick and contains 1015 electrons per cm3 , the number of electrons per cm2
of the layer without exterhal field is 5 X 1010. It should thus be possible
to measure this effect. The experiments indicated, however, that only
about one-tenth of the total induced charge contributed to the increase
in conductivity. It was proposed by Bardeen that the immobile fraction
of the induced charge resides in electronic states at the surface of the
S W. Shockley and G. L. Pearson, Phys. Rev., 74, 232 (1948). ,;, '
Sec. 14-4] RECTIFIERS AND TRANSISTORS 355
material. 9 Such states, which may lie within the normally forbidden
region, may arise partly as a consequence of the sudden departure from
periodicity of the potential at the surface or in part from adsorbed atoms.
In other words, the simple band picture which one normally employs
for the bulk properties is in general not applicable close to the surface.
Thus a certain number of these surface states may be occupied without
giving rise to an excess surface charge. When the material is placed
opposite a positively charged metal, more surface states may be filled by
the induced charge. ii' 1 , :;<' '>F ;,;
<-:-"h

Condo band
E.-r------

--+------_.._- Fermi
H+---::----'+l level
.~

:;/-<"

la) (b)

Fig. 14-5. In (a) there is no equilibrium; a number of surface ~"'~'

states are filled but no surface charge exists. In (b) equilibrium is
established, leading to a surface charge equal to the space charge
extending over Xo.

The existence of surface states has an important consequence for

the electron distribution near the surface of a neutral germanium crystal.
The reason is that the Fermi level associated with the surface states
should coincide with that of the bulk material. Thus, in the absence of
a net surface charge, let the surface states of an n-type Ge crystal be
filled up to the level E = 0 as indicated in Fig. l4-5a. Let the conduction
band be located at Es. Evidently, electrons in the conduction band will
tend to fill up more surface states until a potential drop Vo is built up such
that the highest filled surface state coincides with the Fermi level of the
bulk material (see Fig. l4-5b). Let the density of surface states in the
vicinity of E = 0 be equal to ns per cm 2 per electron volt. The neutrality
of the crystal then requires that per cmz the number of ionized donors
extending over a thickness Xo must equal the excess number of electrons
in surface states. Thus, if we assume that the bottom of the conduction,
band practically coincides with the Fermi level in n-type Ge, we'may write

(14-13)
• J. Bardeen, Phys. Rev., 71,717 (1947).
356 RECTIFIERS AND TRANSISTORS [Chap. 14
According to (14-4) we also have
eVo = 27Tnde2xUE (l4-14)
so that Xo may be eliminated, leading to
ns2-_ nr/EeVo/ 27Te2(Es - eVo)2\ . (I4-15)
We note that for very small values of n." the voltage drop Vo is very
small because a small number of extra electrons will bring the Fermi
level at the surface up to that of the bulk material. For very large values
of n." Vo becomes approximately equal to Es/e. According to Sno~kley
and Pearson, n, is of the order of 5 X 1013 cm- 2 volts-l.
From what has been said above it follows that due to the presenc~
of surface states, a layer of depleted conductivity is formed below the
surface. Under these circumstances, the space charge layer is a property
of the material itself and not particularly sensitive to the work function
of a metal which may be brought in contact with the surface. This
argument has been used by Bardeen to explain the fact that the properties
of point-contact germanium rectifiers are rather insensitive to the metal
used. 10 The presence of surface states also playa role in the interpretation
of contact potential measurements across n-p junctions. l l

14-5. The two-carrier theory of rectification

In Sec. 14-3 we have seen that if V is the applied voltage in the forward
direction the forward current of a rectifying contact should be given by
$- 1= A[e,,(V-II) - I] (14-16)

withe r is the bulk resistance of the rectifier. Although this formula

is in agreement with results obtained for germanium point-contact
rectifiers up to about 0.2 or 0.3 volts, deviations occlir at higher voltages;
these deviations are such that they require a decrease in the resistance r.
This difficulty has been explained by Bardeen and Brattain in terms of
the model represented in Fig. 14-6.12 They assume that as a result of
surface states the Fermi level in n-type material crosses the surface neat
the top of the valence band. From Fig. 14-5b it may be seen tha.t this is
possible if the density of surface states per unit energy interval is suffici-
ently large. Under these circumstances, the concentration of holes in the
valence band near the surface will be larger than the concentration of
electrons in the conduction band. Hence a thin layer of the n-type material
10 J. Bardeen, Phys. Rev., 71, 717 (1947); see also S. Benzer, J. Appl. Phys., 20, 804

(1949).
!l W. H. Brattain, "Semiconducting Materials," Proc. Readin,r: Conference, Butter-

worths Scientific Publications, 1951, p. 37.

12 J. Bardeen and W. H. Brattain, Pllys. Rev., 74, 230, 231 (1948).
Sec. 14-5] RECTIFIERS AND TRANSISTORS 357
will become p-type. Suppose now that the semiconductor is made negative
relative to a metal in contact with it. Thi's will lead to an Increase in
the electronic current from the semi-
conductor into the metal but at the
same time a hole current will begin
to flow from the surface into
the semiconductor. In other words,
two types of carriers contribute to
the current. This has the effect of p-type 1
I
I
. ...
n-type
decreasing the apparent value of r t+--.:....::-i-----=-:.._---+- Fenni
in (14-16), because r is based on level
electronic conductivity only. Because
of lack of space it is not possible
to discuss the quantitative aspects
of the two-carrier theory for point
contacts hereP It will be evident
that this model also explains the
Fig. 14-6. As a result of surface states,
hole injection into n-type material the valence band at the surface lies
by metals biased in the forward close to the Fermi level; this gives rise
direction, as referred to in Sec. 14-6. to a thin p-type layer near the surface of
n-type material.
14-6. The p-n junction rectifier

When a piece of p-type material is in contact with an n-type region,

one speaks of a p-n junction. Such junctions may be made in several
ways; in germanium they have been produced by converting part of an
n-type region into p-type by heating or by nuclear bombardment. In
other cases, these junctions are formed during the growth of single
crystals as a result of segregation of impurities. In general, the acceptor
concentration and the donor concentration will not change abruptly
at the junction, but for simplicity we shall assume this to be the case
(Fig. 14-7a). The Fermi level in the bulk p-type is located close to the
top of the valence band; the Fermi level in the n-type region lies close
to the bottom of the conduction band. As a consequence, the situation
of Fig. 14-7b is unstable; electrons will flow from n to p and holes from
p to n until two space charge regions are established, producing a voltage
drop Vo (see Fig. l4-7c). The space charge in the n-region results from
ionized donors, that in the p-region from ionized acceptors. The voltage
drop Vo is approximately equal to the width of the forbidden gap. For
an ideal case, assuming a simple variation of donor and. acceptor'
13 J. Bardeen and W. H. Brattain, Phys. ReL'., 75, 1208 (1949); J. A. Swanson,

J. Appl. Phys., 25, 314 (1954); for a discussion of the reverse characteristics of high
inverse voltage point contacts on Ge, soe J. H. Simpson and R L. Armstrong, J. Appl.
Phys., 24, 25 (1953).
358 RECTIFIERS AND TRANSISTORS [Chap. 14

concentration at the junction, the potential may be calculated in a way

similar to that used in a metal-semiconductor contact (Sec. 14-2).
It is convenient to consider the equilibrium situation in the absence
of an external field as a dynamic one. Thus, there must be a certain
hole current lho flowing from P to n and an equal but, opposite one from
)

(a)

:r:
cond ' band Fermi
level
(b)
Fermi'
level
Valence band

Fig. 14-7. (a) p-n junction; (b) non-equilibrium energy band

~.
scheme; (c) equilibrium energy band scheme with space charge
regions; (d) full curve represents the potential energy for a
hole in equilibrium and the two compensating hole currents 1"0
are indicated; the dashed curve represents the potential energy
for a hole when the junction is biased in the forward direction;
in that case the hole current to the left remains 1.". the hole
current to the right equals 1"0 exp (e V/kT).

n to p (Fig. 14-7d). The same is true for the equilibrium electron current
Ic o' This implies that there must be a certain concentration of holes
in the n-region as well as a certain concentration of electrons in the
p-region. This is a result of the continuous thermal creation of electron-
hole pairs, the creation being compensated by recombination. For ex-
ample, if g is the rate of production of pairs and nco and n". are the equi-
librium concentrations anywhere, we must have rn,> nil = g. where ,.
is the recombination coefficient. Thus in either regio~, n,> onil II = glr.
which is constant at a given temperature. If one assumes that the ratio
g!r is independent of the donor or acceptor concentration. g!r must also
Sec. 14-6] RECTIFIERS AND TRANSISTORS 359
be equal to nT, where ni is the density of carriers in intrinsic material.
Under these circumstances
(14-17)

Suppose now that a negative voltage - V is applied to the n-region.

If we assume that the voltage drop is essentially across the space-charge
region, the hole current from n to p is still I/i,,' However, holes going

ma/cm 2 o
100

,.,... ~_f ""-,,,t _rl~.

;'):}d
Fig. 14-8. Current-voltage characteristic of a p-n junction. The
}t!! ni
circles are experimental points, the curve is theoretical. [After
W. Shockley, ref. 14]

from p to n have to climb a smaller potential hill (Fig. 14-7d) and will
give rise to a current Ih exp (eV/kT). Hence
f) fl.') r~i$ 1}Hri (H '~:J.D:~;,>

(14-] 8)

For the electron current one finds a similar expression and the total
forward current across the junction should be

(14-19)

For positive voltages applied to the n-type region the reverse current is
obtained,
I = (I + I )(1 - e-eV1k7') (14-19a)
r "0 eo

In Fig. ]4-8 we have represented the experimental points obtained for a,

p-n junction characteristic ;14 the fully drawn curve is the theoretical
one. The agreement is very good indeed.
H W. Shockley, ProC'. IRE,40, 1289 (1952).
360 RECTIFIERS AND TRANSISTORS [Chap. 14
Let us now consider the rectification process in some more detail;
we shall discuss only the hole current because a similar reasoning may
b~ given for the electron current. We shall use the following symbols:

Vo = equilibrium potential drop

- V = voltage applied to n-region \
no = equilibrium density of holes in bulk n-region
n,,(x) = actual density of holes in n-region
np = density of holes in p-region
n(x) = nh(x) - no = density of excess holes in n-region
The point x = 0 indicated in Fig. 14-7d corresponds to the point
where the derivative of the potential vanishes. The general equations
governing the motion of holes are (13-32) and (13-33). If in these equations
we put gh = 0 (no external pair generation) and assume the electric
field to be negligible for x > 0, we obtain for the steady state (an/at = 0)
in that region.
(14-20)

where T" is the life time of holes in the n-region. The solution of this
equation is
n(x) = n(O)e-:r / Lh where L~ = D"Th (14-2l)

where Lh is the diffusion length of the holes. Thus the excess hole density
in the n-region decreases by a factor l/e over a distance L h • According
to equation (13-33) the hole current density diffusing across the junction
is equal to
.~
Ih = -eDh(onhlox)x=o = (eD"ILIt)n(O) (14-22)
;->-i-
in order to .find an expression for nCO) in terms of the applied voltage,
we make use of the fact that according to Boltzmann, .'
(14-23)
From the last two equations it then follows that

_eDit (-J7jkT
I ,,--noe _ I) (14-24)
Lit

Comparing this with (14-18) it is observed that the equilibrium current

1"0 = eDhnolL" = enOL,J-rh' This result has a simple physical interpre-
tation: no/T" represents the number of holes recombining per second in
equilibrium, and hence also represents the rate of creation of holes. The
created holes diffuse about and recombine at an average distance L"
from their point of origin. Therefore the holes diffusing across the barrier
are essentially those created within a range Lh on the right of x = 0
,;1
,\.1>,
Sec. 14-6] RECTIFIERS AND TRANSISTORS 361
(Fig. 14-7d). For electrons in Ge, the diffusion constant D ':::' 100 cm2/sec
and a typical lifetime is 10-4 sec. This gives a diffusion length of the order
of 0.1 cm.
The correctness of the diffusion theory for the rectifying p-n junction
has been tested further by using junctions as a photoconductive device.
For example, let photons of sufficient energy to create electron-hole

Emit.

~ n

L, +
e
'1 , , \ ,

Ia:l
'l:) n n
f"',
. n. '{'Y"
i t . ' ",( 1'l~
>"'14 ,.
d J(,~,,>._
, •• , ••

~
p..,

t
-Distance
(bl

Fig. 14-9. (a) Represents schematically an n-p-n junction transistor

with the emitter biased in the forward direction, the collector in the
reve£se direction. Actually, the p-region is much narrower than
indicated. In (b) the potential energy of an electron is represented
for the biased transistor.

pairs be incident on the n-type region at a distance x from x _:_ O. Accord-

ing to what has been said above, the current response should vary as
exp (-x/L) and this has indeed been verified experimentally by Goucher
and coworkers. I5 Also, the value of L so obtained is consistent with the
one required by the rectifier equation (14-24). When the light is incident
at the junction itself, the electron and hole are separated by the strong
field at the junction and a current of one electron per absorbed photon
may be obtained.

14-7. Transistors
,.
An n-p-n junction transistor is built up of two n-type regions separated
by a thin layer of weakly p-type material. It is mainly this type of transistor
which will be discussed below. The same reasoning applies to p-n-p
15 F. S. Goucher el al., Phys. Rep., 78,816 (1950); 81,637 (1951).
362 RECTIFIERS AND TRANSISTORS [Chap. 14
junction transistors. When the junction transistor is used as an amplifier,
one of the n-p junctions is biased in the forward direction, the other in the
reverse direction, as indicated in Fig. 14-9a. The former is called the
emitter because the corresponding n-type region emits electrons into the
,,-region (the base); these electrons are collected at the junction with the
reverse bias (the collector). The discussion below deals with the reasons
for the amplifying action of the transistor.
Let W be the width of the p-type base region and De the diffusion
coefficient of electrons in the base. The time required for an electron
to cross the base, if it stays "alive" during the crossing, is equal to
t = W2j2Dp; this follows from the elementary theory of diffusion. Thus
the probability for an electron to recombine with a hole during the crossing
of the base is given by

( 14-25)

where T,. is the lifetime of electrons and Le is their diffusion length in

the base material. In most cases, tlTe ~ I because the width of the base
is small compared with Le; we shall assume this to be the case in the
remainder of this section. In other words, we shall assume that
all electrons emitted by the emitter are collected by the collector.
Let us now consider the current flow between the emitter and the
base. The total current is made up of two parts: (a) a hole current
I" from the base into the emitter; (b) an electron current Ie from the
emitter into the base. The ratio of these currents is important for the
amplifying action of the transistor, and we shall now show that IelI"
= L"a,IWa", where ae and a" are the conductivities of the emitter and
<:~e regions. and L/i is the diffusion length of holes in the emitter
region.
According to (14-24), the hole current is given by

I -- eDit e' - 1)
n (eVlkT (14-26)
It - L" It"

where V is the applied voltage between base and emitter and nho is the
equilibrium concentration of holes in the emitter region. Because of
what follows it is important to realize that I" is determined by the diffusion
length of holes in the emitter region. In the same way, the electronic
current from emitter to base is determined by the diffusion length of
electrons in the base region. However, because the width of the base
region is W ~ Le, one should usc W rather than Le for the electronic
current. Hence
(l4-26a)
Sec. 14-7] RECTIFIERS AND TRANSISTORS 363
where np n is the equilibrium density of electrons
_ in the base. From (14-26a)
and (14-26) it then follows that
(14-27)
We may now apply expression (14-17) to the base and emitter regions,
giving
(14-28)
where n i is the density of carriers in intrinsic material, nit is the density

+ +
Base

Fig. 14-10. Equivalent circuit of Fig. 14-11. A point-contact tran-

the transistor. sistor.

of holes in the base, and ne is the density of electrons in the emitter.

Substituting into (14-27) we obtain
(14-29)
Here we have made use of the fact that in general a = neJi and Ji = De/kT,
where Ji is the mobility.
Suppose now that the base potential is altered; this will give rise
to a change in the hole current from the base to the emitter, and at the
same time, to a change in the electron current from the emitter into the
base. However, the latter is collected completely by the collector, and it
thus follows that the current gain is simply given by {I 4-29) ; the current
gain so obtained may be 100 or more. Other factors also favor a high
gain. The collector impedance is very high because of the reverse bias;
it is evident from the reverse junction characteristic in Fig. 14-8 that for
voltages larger than a few times kT/e, the collector current is essentially
independent of the bias, i.e., the impedance would approach infinity.
Actual collector impedances are of the order of 10 6 ohms or higher.
Furthermore, the resistance r. of the emitter is very low; in fact, it follows
from the forward characteristic that
'e = (kT/el)
where I is the emitter current. For 1= 1 rna, this gives at room tempera-
ture, f< = 25 ohms. l
364 RECTIFIERS AND TRANSISTORS [Chap. 14
From the above discussion one arrives at the equivalent circuit
represented in Fig. 14-10. Here re is the emitter junction resistance.
rb represents the resistance. of the thin p-type base region. and rc is the
resistance of the collector junction. These resistances are, of course.
functions of the bias voltages. The collecting action may be represented
by a current generator rxi" where ie is the emitter alternating current and
IX is the fraction of the emitter current collected by the collector. For a

good junction transistor, rx is nearly unity, as was assumed above.

A point-contact transistor (called type A) is represented schematically
in Fig. 14-11. The emitter and collector in this case are metallic points
pressed on the surface of a small die of n-type material. The base contact
is simply a large area contact at the bottom of the die. The emitter is
positive relative to the n-type material, and thus injects holes into the
germanium. The holes diffuse towards the collector under influence of
the electric field. This hole current adds to the electron current flowing
from the collector into the germanium as a result of the reverse bias of the
collector. At the same time the presence of the holes near the collector
enhances the electronic current. The ratio of the collector current increase
to the emitter current increase is again denoted by rx; in point-contact
transistors rx is therefore larger than unity (see table below). Since the
collector current flows through the high collector impedance, whereas
the emitter current is injected through the low emitter impedance, one
also obtains a voltage gain. Some typical values for a point-contact
type A transistor and a junction transistor are given below; the resistances
are in ohms.
Junctioll POillt-COllt{/CI
r, 2S 125
:-S
71·
rb 200 75
2 x IO~
r, S x 10"
oc 0.95--0.99 2-3
" .

RE'FERENCES

J. Bardeen and W. H. Brattain, Phys. Rel'., 75, 1208 (1949); Bell System
Tech. J., 28, 239 (1949).
J. S. Blakemore, A. E. De Barr, and J. B. Gunn, "Semiconductor circuit
Elements," Repts. Progr. Phys., 16, 160 (1953).
H. K. Henisch, Metal Rectifiers, Oxford, New York, (1949).
Proc. IRE., 40, (l952) (transistor issue).
W. Shockley, Electrons and Holes in Semiconductors, Van Nostrand,
New York, 1950.
H. C. Torrey and C. A. Whitmer, Crystal Rectifiers, McGraw-Hill,
New York, 1948.
Chap. 14] RECTIFIERS AND TRANSISTORS 365

PROBLEMS.,

14-1. Two metallic surfaces with work functions of 3 and 4 ev are

separated by a gap of 10 A. Calculate the surface charge density in
equilibrium at room temperature in terms of a number of electrons.
14-2. A metal with a work function of 3 ev is in contact with a semi-
conductor with an electron affinity of 1 ev; the semiconductor contains
1016 donors per cm3 close to the conduction band. Calculate the capaci-
tance of the barrier layer per cm2 for zero applied voltage, when the
dielectric constant is 12. Do the same problem for a reverse bias of 5
volts.
14-3. Consider a block of semiconducting material with a large area
contact on one of its faces; the opposite face has a small circular point
contact of radius a. Show that the bulk or spreading resistance of the
system is r = 1/4aa, where a is the conductivity of the semiconductor.
14-4. Consider an idealized p-n junction in which the acceptor con-
centration is constant for x < 0, and the donor concentration is constant
for x > o. Find an expression for the barrier thickness in terms of the
acceptor and donor concentrations and the forbidden energy gap; assume
that the donor and acceptor levels lie very close, respectively, to the
conduction and valence bands. Also discuss the variation of the barrier
thickness with an applied voltage.
14-5. Repeat Problem 14-4 for a junction consisting of a p-type region
containing N acceptors per cm3 and an n-type region containing N donors
per cm3 , the two regions being separated by a transition region in which
the concentrations vary linearly with x. Assume that the transition region
is large compared with the physical barrier layer.
14-6. Consider a p-n junction with an area of 0.25 cm 2 in which the
current is carried mainly by holes. Given that for small forward voltages
the junction resistance is 800 ohms, calculate the density of holes in the
n-region if the life time of the holes in this region is 10- 4 sec and their
mobility is 1800 cm 2 volt- I sec-I.

f,)

j !
Chapter 1!j

ELECTRONIC PROPERTIES OF
ALKALI HALIDES

In the class of solids which may be referred to as ionic semiconductors,

the alkali halides have been investigated more thoroughly than any other
group. In this respect they occupy a place similar to Si and Ge in the class
of nonpolar semiconductors. The reason for this is twofold: in the first
place large single crystals of the alkali halides may be grown with relative
ease; second, they have a simple structure. In the present chapter some
of the most outstanding electronic properties of these materials will be dis-
cussed. This discussion is necessarily very incomplete, and for further
details we must refer the reader to the bibliography at the end of this
chapter.

15-1. Optical and thermal electronic excitation in ionic crystals

In this chapter much of the dischssion will be devoted to the excitation

of the electronic system of ionic crystals. Electronic excitation may be
accomplished in various ways: I

I
(i) The electrons may be excited thermally. t !

(ii) They may absorb photons.

: : (iii) They may absorb energy from incident charged particles.
The eXCItation processes are discussed in terms of energy level diagrams,
and a few words may be said about the use of such diagrams.
First, the reader is reminded that in ionic crystals one must distinguish
between the high-frequency dielectric constant EO and the static dielectric
constant Ex' The former is a result of electronic displacements only, the
latter is due to electronic displacements plus ionic displacements (see
Chapter 6). For ionic crystals Eo< is considerably larger than EO' These
quantities enter in the discussion of energy level diagrams as a consequence
of the so-called Franck-Condon principle, which states that when an
electron is excited optically, the nuclei of the ions may be considered to
remain at rest during the process. l In other words, an optical excitation
process takes place in a time interval small compared with the period
I J. Franck, Trans. Faraday Soc .. 21, 536 (1925); E. U. Condon, Phys. Rev., 28,

1182 (1926); 32,858 (1928).

366
Sec. 15-1] ELECTRON[C PROPERTIES OF ALKALI HALIDES 367

associated with lattice vibrations. The const?,quences of this principle may

first be illustrated with reference to the optical excitation of a diatomic
molecule XY; later we shall generalize the picture to apply to a solid.
In Fig. 15-1 let the curve ABC represent the potential energy of the
molecule as function of the separation r between the X and Y atoms.
Similarly, let curve PQR represent the potential energy of the electronically
excited atom y* as function of its distance relative to atom X; the point
R lies above C by an amount equal to the excitation energy Q,. of the free

D E
B _r

Fig. 15-1. Illustrating the Franck-Condon principle (see tex!).

Y atom. In general, the minima Band Q will not correspond to the same
separation. Suppose now the molecule XY is in the state B. It may then
absorb a photon hv, after which its representative point will arrive at B',
in accordance with the Franck-Condon principle (the separation between
the nuclei does not change during the transition). However, point B'
represents a highly excited vibrational state of the XY* molecule and
ultimately the system will move toward a point on the PQR curve near Q,
by energy exchange with the surroundings. In other words, some of the
optically absorbed energy is wasted in the sense that after the optical
transition a certain fraction of it is transformed into heat. The thermal
activation energy is simply given by the energy difference between Band
Q; evidently the optical activation energy is always larger than or equal
to the thermal activation energy. This was first pointed out by de Boer
and van GeeJ.2
We should note that actually the atoms in the XY molecule vibrate ,
relative to each other, even at T = O. Thus, let the molecule XY be in the
vibrational level DE" Depending on where the representative point finds
itself along the DE level, the optical excitation energy may lie anywhere in
2 J. H. de Boer and W. Ch. van Geel, Physico, 2, 286 (1935).
368 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

the shaded region of Fig. 15- 1. Thus the absorption spectrum is a band
spectrum in contrast with the line spectra observed for single atoms. The
band width W will increase with increasing temperature.
The same reasoning may be applied to an electronic transition in a
solid by interpreting the coordinate r as representing the configuration of
the nuclei in the vicinity of the position in the crystal where the transition
takes place. It follows from the above discussion that when one introduces
an energy-level diagram, it is necessary to specify whether one is talking
about optical or thermal transitions, because the diagrams will in general
be different for the two cases.
To iIIustrate the role of the static and high-frequency dielectric constant
in the case of optical and thermal electronic transitions in ionic crystals,
consider the following much simplified model. 3 Suppose an electron is
trapped in an ionic crystal by all impurity of a certain radius R, the charge
of the impurity being e. Let the electron be removed optically from the
impurity to a point in the lattice far fro-m the impurity. Since only the
electronic displacements are able to follow the optical electronic transition,
the field about the impurity immediately after the transition is equal to
El = e/Eor2. After a time interval equal to a few times the period associated
with lattice vibrations has passed, the ions have adjusted themselves to the
new situation, and the field ultimately drops to E2 = e/Esr2. The process
of adjustment of the ions corresponds to the motion of the representative
point in Fig. 15-1 from B' to Q. The energy given off by the system during
this process may be estimated as follows. The energy per unit volume in
the dielectric is given by (E·D)/87T. In our example E and D are both radial
vectors; hence, per unit volume there is a change in energy .equal to
l

Integrating this from r = R to r = 00, one obtains for the difference

between the optical and thermal activation energy in this model,

(15-1)

This may be of the order of a few ev when R ~ I A.

We may note that in nonpolar crystals such as silicon and germanium,
the optical and thermal activation energies are equal within the experi-
mental error; this is a result of the fact that the atoms are neutral and any
atomic displacements occurring after an optical transition give off a very
small amount of energy indeed.
3 See N. F. Mott and R. W. Gurney, Electronic Processes in [onie Crystals, Oxford,

New York, 1940, p. 160. _ .. .

(,

"
Sec. 15-2] ELECTRONIC PROPERTIES OF ALKALI HALIDES 369

15-2. The upper filled band and the conduction· band in ionic crystals

In the present section it will be assumed that the crystals under con-
sideration are perfect in the sense that they are of stoichiometric com-
position and that they do not contain lattice defects of any kind. Although
such crystals do not actually exist, it is useful to consider the properties of
an idealized model as a starting point; the influence of lattice defects on
the electronic properties will be considered later.
Ionic crystals such as the alkali and silver halides, the oxides of the
alkaline earth metals, etc. are usually good insulators. Thus, according to

i 3p (occupied)
Cond. band

Cl-
Na+ t=:::::><
3s (empty)

Fig. 15-2. Schematic representation of the variation of the

occupied 3p-levels and the empty 3s-levels in NaCI as function of
the separation between the ions. The actual lattice constant is a,
le_!lding to the filled band and the conduction band as indicated on
the right., lille energy X required to take an electron from the bottom
of the conduction band to vacuum is called the electron affinity.

the band theory, the electron distribution may be represented by a system

of completely filled and completely empty energy bands, at least at T = O.
For many purposes in this chapter it will be convenient to discuss the
electronic properties by considering the crystals as a system of interacting
ions rather than from the collective electron viewpoint. Thus, in this
section, the upper filled band and the empty band (conduction band) will
be associated with certain electronic states of the composing ions.
As a particular example, consider NaCl. Suppose a NaCI lattice is
uniformly expanded so that the separation of the ions is large enough to
consider the ions as free. In order to locate the electronic levels we shall
take the energy of a free electron at rest as zero.4 The lowest unoccupied •
level of a free Na+ ion is a 3s state, located below the zero level by an
amount equal to the ionization INa energy of a sodium atom, i.e., located
at --5.12 ev (see Fig. 15-2). The highest occupied state of the CI- ion is a
• NaC! has been discussed by W. Shockley, Phys. Rev., 40, 754 (1936). 'iL
370 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. I~

3p level, located below zero by an energy din'erence equal to the electron

affinity Eel of the CI atom, i.e., at -4 ev. Thus, in the infinitely expanded
lattice, the empty 3s level lies below the occupied 3p level by an amount
INa - Eel = 1.12 ev; this is true for the "optical" energy level diagram as
well as for the "thermal" one. As the ions are brought together, however,
the relative position of these levels varies as indicated schematically in
Fig. 15-2, where r represents the shortest interionic distance. The reason
for this change may be understood by asking the following question: What
is the energy required to transfer an electron from a CI- ion to a remote
Na+ ion, when the ions are incorporated in an ionic lattice? For the
moment let us neglect any polarization effects associated with the dielectric
constant of the lattice. Under these circumstances the answer to the above
question is

( 15-2)

where Ec(r) is the Coulomb energy of one ion in the field of all others;
according to Sec. 5-2, Ec(r) = Ae2 /r, where A is the Madelung constant
(1.75 for the NaCl lattice). The reason for the occurrence of the Ec(r)
terms is the following. When an electron has been taken from a CI- ion,
the Coulomb interaction is lost, because the resulting atom is neutral.
Hence, to remove an electron from a Cl- ion in the lattice one requires an
energy ECI + Ec(r). In a similar way, the energy gained by putting an
electron on a Na+ ion is IN" - Ec(r) because again the Coulomb energy is
lost. Thus, as r decreases, FcCr) increases, leading to the variation of the
energy levels as indicated; for a certain value of r they cross over, and for
still smaller values of r the occupied 3p levels fall below the empty 3s levels.
Actually, the Ec(r) terms should be corrected for polarization effects.
"",Thus, when an electron is excited optically from a certain Cl- ion to a
r remote Na-i ion, one should subtract from (15-2) the polarization energy
around the neutral CI and Na atoms, using the high-frequency dielectric
constant EO' If the excitation is thermal, the polarization energy must be
calculated on the basis of the static dielectric constant Ea' Here again the
thermal excitation energy will be smaller than the optical excitation energy.
Hence one arrives at two possible electron level schemes: an optical one
and a thermal one.
When the lattice parameter r reaches values such that the wave functions
of neighboring ions of equal sign begin to overlap, the discrete atomic
levels broaden into bands (see Chapter 10). The actually observed lattice
parameter r = a determines the distance between the bands as well as the
widths of the bands, as indicated on the right in Fig. 15-2.
One thus arrives at the conclus'ion that the upper filled band in NaCI is
associated with the occupied 3p levels of the CI- ions, the empty band
corresponding to the unoccupied 35 levels of the Na+ ions. Similar
Sec.15-2} ELECTRONIC PROPERTIES OF ALKALI HALIDES 371

identifications may be made in other ionic crystals. Actually, the con-

duction band in ionic crystals probably"corresponds to an ionization
continuum, i.e., other empty bands will overlap with the one identified
above.
Information about the width of the upper filled band may be obtained
from soft X-ray emission spectra, as explained in Sec. 10-12. Results of
such studies for a number of ionic and semi-ionic crystals are given in .
Table 15-1. 5 It is observed that the band width for the alkali halides and

Table 15-1. The Width of the Upper Filled Band in ev

for a Number of Solids

LiF 2.1 LiBr 1.2 Li,O 12.8

NaF 1.7 NaBr 0.75 CaO 10.8
KF 1.5. KBr 0.55 SrO 9.2
RbBr 0.45 BaO 8.4
AgBr 1.1

silver halides is of the order of I ev; for the oxides it is of the order of
JO ev. From this one might expect the effective mass of ~ hole to be larger
in the halides than in the oxides.
The energy difference between an electron at rest in vacuum and an
electron at the bottom of the conduction band is called the electron
affinity X of the crystal (see Fig. 15-2), For alkali halides r. is probably of
the order of 0.5 ev or less.

15-3. The ultraviolet spectrum of the alkali halides; excitons

A great deal of experimental information about the electronic structure

of ionic crystals has been obtained from optical absorption measurements. 6
As an example we give in Fig. 15-3 the absorption spectrum of KBr.7 The
alkali halides are transparent in the visible region of the spectrum, and the
absorption spectrum associated with electronic transitions lies entirely in
the ultraviolet. It consists of a number of absorption peaks which are best
resolved at low temperatures. In the vicinity of the peaks, the absorption
coefficient is of the order of 10 6 per cm, so that thin evaporated layers are
used in these experiments. The high energy region is very difficult to
investigate experimentally so that virtually nothing is known about the
5 N. F. Mott and R. W. Gurney, op. cit., pr. 75, 79. -,
• For a review, see R. W. Pohl, Physik. z., 39, 36 (1938); E. G. Schneider and H. M.
O'Bryan, Phys. Rev., 51, 293 (1937); L. Apker and E. Taft, Phys. Rev., 81, 698 (1951).
New studies, with emphasis on the range from 950 A to 1700 A are presently being
carried out at Cornell University by Hartman, Siegfried, and Nelson.
, R. Hilsch and R. W. Pohl, Z. PhYSik, 59,817 (1929).
,72 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

short wavelength tail of the absorption region. The tail on the long-
wavelength side is at least in part due to imperfections, as will be explained
further in Sec. 15-5; it is therefore
temperature-sensitive.
It is important to note that when
A photons are absorbed in the long wave-
length tailor in the first absorption peak,
no photoconductivity results. This indi-
cates that the first absorption peak does
I \ not give rise to an electronic transitior.
v from the filled band into the conduction
band. It is believed, therefore, that the
first absorption peak gives rise to an
excited state of the halogen ions, i.e., an

\ 1"---_
electron from the filled band is raised to
a level below the conduction band. This
160 180 200 220 ml' situation may be compared with the excited
_A states of an atom. Complete ionization
of an atom may then be compared
Fig. 15-3. Absorption spectrum
of pure KBr. [After Bilsch and with the transition of an electron from
Pohl, ref. 7) the filled band into the conduction band.
It is for this reason that the energy
band scheme of a perfect ionic crystal contains a number of narrow
"exciton bands" below the conduction band, as indicated in Fig. 15-4.
One may also look at this by saying that when a photon corresponding
to the first absorption peak is absorbed by an electron in the filled band,
the excited electron is still bound to some extent by the Coulomb field
produced by the hole it left behind. This will be further illustrated in the
... ;'.~xt section. The combination of an electron in an excited state and the
~ssociated hole is called an exciton; the unit as a whole is neutral. It has
been suggested that an exciton may be thought of as resulting from an
electronic transition from a negative ion to a nearest neighbor positive ion.
A transition from the filled band to the conduction band in this type of
picture then corresponds to an electron transfer from a negative ion to a
faraway positive ion. This is probably an oversimplification, although it
illustrates the electron-hole interaction.
At present it is not known where the ultraviolet absorption spectrum
goes over from exciton bands into the ionization continuum. A rough
estimate may be made on the basis of the following simplified model.
Consider the exciton as an electron and a hole revolving about each other
as a result of Coulomb interaction. The energy of this system may be
estimated from the analogy with a hydrogen atom in the ground state.
Two modifications are required: (1) the mass of the electron is approxi-
mately equal to that of the hole; (2) the field between the two particles is
Sec. 15-3] ELECTRONIC PROPERTIES OF ALKALI HALIDES 373
reduced by a factor equal to the high-frequency dielectric constant EO'
Now the binding energy of an electron in tffe hydrogen atom is 13.54 ev.
Introducing the two modifications
suggested above, one obtains for the
Condo band
binding energy of the exciton in elec-
tron volts 13.54/2E~. This is of the Exciton
}
order of 1 ev for most ionic crystals.
=:IF=F====== bands

One thus estimates that the band-to-band

transitions should occur approximately
I ev beyond the first absorption peak.
From these arguments it follows that
as EO increases, the exciton bands should Filled
band
be crowded into a smaller energy region.
The first absoJPtion peak shifts to
Fig. 15-4. Energy band scheme of
higher values as the temperature is an insulator, showing exciton bands
lowered. This is a result of the thermal below the conduction band. The
contraction of the lattice, leading to combination of an electron in an
larger binding energies. Also, the peaks excited state (black dot) and the hole
broaden at higher temperatures as a left behind in the filled band (open
circle) is called an exciton.
result of the increased amplitudes of
the lattice vibrations.
As an example we give in Table 15-2 the position of the first
absorption peak for a number of alkali halides,. together with the
corresponding photon energy in ev. It is observed that as the ions
become larger, the absorption peak shifts generally to lower energy
values, as one might expect. It is of great importance to realize that
once an exciton is produced at the location of a certain halide ion,
it will in general not stay there. In fact, there is a great deal of
experimental and theoretical evidence that excitons move about in
the lattice. Thus an excited haliee ion may transfer its energy to
the next halide ion and by repeated transfers of this kind the exciton
is propagated through the lattice. In the earlier work on this topic

Table 15-2. Position of the First Ultraviolet Absorption Peak at Room Temperature
for a Number of Alkali Halides

Salt A ev Salt A ev Salt A ev

LiCI 1430 8.6 .~

NaCI 1580 7.8 NaBr 1900 6.5
KCl 1620 7.6 KBr 1890 6.5 KI 2200 5.6
RbCl 1660 7.4 RbBr 1930 6.4 RbI 2230 5.5
CsCl 1620 7.6 CsBr 1870 6.6
374 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

by Frenkel 8 and by Slater and Shockley 9 the possibility of exciton pro-

pagation was related to the overlapping of the excited-state wave functions
on neighboring atoms. More recently, Heller and Marcus have shown that
even if the overlap is small, the propagation of excitons may be good as a
result of the dipole coupling between the excited ion and a neighboring
identical atom .in the ground state_Io Thus an exciton may be represented
as a neutral "particle" with a certain effective mass m*, its motion being
characterized by a wave vector k. If the exciton is produced by the absorp-
tion of a photon, the initial wave vector of the exciton will be the same as
that of the incident photon (conservation of momentum). In this case, the
dipole moment of the exciton will be perpendicular to the direction of
propagation. As the exciton propagates, it may interact with lattice
vibrations or imperfections, and scattering results. Excitons for which the
dipole moment is parallel to the direction of propagation are also possible
and the two types can be converted into each other by scattering processes.
The optical lifetime T of an exciton, i.e., the average period elapsing between
the production of the exciton and the instant that the electron and hole
recombine under emission of a photon, is probably of the order of 10-8
second (corresponding to the emission of dipole radiation). However,
long before the optical lifetime is up, the exciton may give off its
energy to lattice imperfections. For example, an exciton may transfer
its energy to an F center, thereby raising the trapped electron into
the conduction band. Excitons may also transfer their energy to
an electron in the filled band in the vicinity of a negative ion vacancy,
leading to the production of an F center. These matters will be further
discussed in Sec. 15-9. According to Marcus and Heller, the effective
mass of an exciton is given by

m* ~ m(31T/4n)I/3/".Inaae (15-3)

where n is the number of ions per unit volume, m is the free electron mass,
a. is the effective Bohr radius of the excited atom, and In is the oscillator
strength connecting the ground state and the excited state." When In. ~ 1,
as it is in the alkali halides, it follows from (15-3) that m* ~ m. Hence
at room temperature the velocity of an exciton is approximately equal to
that of a thermal electron, i.e., V ~ 10 7 cm/sec. During the optical lifetime
the total path covered by an exciton is thus of the order of 10 7 X 10-8
~ 0.1 cm. As a result of the scattering by phonons and imperfections, the
path is actually curled up as in any type of Brownian motion. If one
8 J. Frenkel, Phys. Rev., 37, 17, 1276 (1931); Phys. Z. Sowjetunion, 9, 158 (1936);
see also G. H. Wannier, Phys. Rev., 52, 191 (1937).
9 J. C. Slater and W. Shockley. Phys. Rev., 50, 705 (1936).
). W. R. Heller and A. Marcus. Phys. Rev .• 84, 809 (1951).
Sec. 15-3] ELECTRONIC PROPERTIES OF ALKALI HALIDES 375

assumes a mean free path for scattering A. -::: 10 Angstroms, one finds for
the mean square displacement
(r2) = 2DT = iA.VT,-...J 10-8 cm2 (15-4)
Thus, during the optical life, the excitons may on the average undergo a
displacement of approximately 10-4 cm relative to point of origin.

15-4. Illustration of electron-hole interaction in single ions

In view of the importance of the concept of an exciton, it maybe useful
to consider the following example of the Coulomb interaction between an
electron and a hole. To remove the 3s electron in a free sodium atom, the
ionization energy (5.12 ev) is required. To remove a second electron,
another 47 ev is required, as illustrated in Fig. 15-5a. At first sight one
o 0------
-5.1--jl.- - 3s
E(ev)
-14 -,-, .... -,T 3s . ':
1 ~.., t r

-47-_'_-2p
,.;
(al (bl
Fig. 15-5. Schematic representation of the energy levels of a singly
charged sodium ion (a); the excitation of the 2p-electron into the
3s-level requires only 33 ev (b) rather than 42 ev, illustrating the 1../,,:1
::Ill'<, j'l!? 'H:'~ electron-hole interaction.

might thus expect that an energy of about 42 ev would be necessary to

excite the 2p electron in·a sodium ion into the 3s level. However, experi-
mentally one finds only about 33 ev. This leads to the electron level
scheme for the excited ion given in Fig. 15-5b. Thus the electron in the
3s level is now more strongly bound than in the atom as a result of the
Coulomb interaction between the electron and the hole in the 3p level.
In this case, the interaction energy is approximately 9 ev.
~;:il ':!Ill "(':., :,1A:,! in'}?

15-5. Qualitative discussion of the influence of lattice defects on the

electronic level.. . ,,
So far, we have considered only perfect crystals. However, as we have
seen in previous chapters, any crystal contains a certain number of lattice
defects of various kinds (vacancies, aggregates of vacancies, interstitials,
dislocations) quite apart from chemical impurities. The presence of such
defects will alter the charge distribution and one expects a change in the
electronic levels in the vicinity of the defects. As a simple example,
376 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

consider a positive ion vacancy in a lattice such as NaCl. The 3p electrons

of the Cl- ions neighboring the vacancy will not be so strongly bound as
they normally would be, because the positive ion vacancy acts as a negative
charge. Thus it should be easier to ionize or excite an electron from such
Cl- ions (A in Fig. 15-6) than is normally the case. In other words, the
outer electrons of these Cl- ions do not reside in the filled band but occupy
levels above the filled band. This is indicated in Fig. 15-6; the levels are
+ + +

+ + + Condo band
B
+ BOB + + _g_B
B
+ + +
A A....L.
+ -A OA- +

+ +
A
+
~
+ + +
Fig. 15-6. The outer electrons associated with negative ions
surrounding a positive ion vacancy occupy levels above the filled
band (A); the empty levels corresponding to positive ions surround-
ing a negative ion vacancy lie below the conduction band (8). The
excited states of levels such as A have been omitted.

represented by a short bar, and it is understood that this implies that the
level is localized in the vicinity of a particular vacancy. Each positive ion
vacancy gives rise to six of these levels because there are six Cl- ions
surrounding the vacancy. To a lesser extent, similar considerations hold
for the next-nearest Cl- ions; the levels for the 3p electrons on these ions
will be much closer to the filled band.
It may be noted that if in some way or other a free hole should be
created in the filled band, the hole may be trapped at one of the A levels
mentioned above. This is not surprising, because a position where a
positive ion is missing would be a favorable site for a positive hole to
reside. The trapped hole may then be represented as a Cl atom neighboring
a positive ion vacancy. Actually, the hole will probably be shared by the
six surrounding halogen ions, because they are all equivalent. Trapped
holes of this kind are called V centers; these will be discussed in Sec. 15-12.
The situation around a negative ion vacancy may be discussed in a
similar way. Suppose by some means one had created a free electron in the
conduction band. A likely place for this electron to get trapped would be
a negative ion vacancy; the latter has an effective positive charge and thus
attracts the electron. In this case the electron is shared by six surrounding
Na+ ions and the resulting center is called an F center. In the energy level
Sec. 15-5] ELECTRONIC PROPERTIES OF ALKALI HALIDES 377
scheme this means that the empty 3s states of the Na+ ions surrounding a
negative ion vacancy (8 in Fig. 15-6) do not lie in the conduction band but
below it.
Summarizing, we may say, that positive ion vacancies give rise to occu-
pied electronic levels above the filled band; negative ion vacancies give
rise to unoccupied sta,tes below the conduction band. It will be evident
that as a result of these changes in the energy level scheme, new absorption
bands will arise, the extent of the absorption being proportional to the
density of lattice defects. More complicated lattice defects, such as pairs,
triplets, etc., will also change the absorption spectrum. Usually the new
absorption bands lie in the tail of the first fundamental absorption band.
Thus, although changes in the tail may be observed, for example, by
variations in temperature, it is difficult to resolve the new bands. At low
temperatures, however, one has observed the so-called (1. band, which is
believed to be associated with the presence of single negative-ion
vacancies. 11

15-6. Nonstoichiometric crystals containing excess metal

A great deal of fundamental information about semiconducting ionic

crystals has been obtained by studying the properties of nonstoichiometric
crystals, i.e., crystals containing an excess of one of their constituents.
For example, when an alkali halide crystal is heated in the vapor of its
metallic constituent, an excess of metal is incorporated in the crystal.
Some properties resulting from the excess metal will now be discussed.

F centers. In the first place, crystals heated in the metal vapor and
quenched to room temperature show an absorption band in the visible or
ultraviolet, whereas the original crystals were transparent in that region.
This absorption band is called the F band (the German word for color is'
Farbe). As an example we show in Fig. 15-7 the Fband in KBr at various
temperatures according to Mollwo. 12 The width of the band increases
and its position shifts to lower energies when the crystals are heated. At
room temperature the position of the F band peak in the alkali halides is
as given in Table 15-3. It is interesting to note that according to Mollw012
the F-absorption frequency VEt' is related to the shortest interionic distance
a by the approximate expression

(15-5)
11 Delbecq, Pringsheim, and Yuster, J. Chern. Phys., 19, 574 (1951); 20,746 (1952);

see also W. Martienssen. Z. Physik, 131,488 (1952); W. Martienssen and'R. W. Pohl,

Z. Physik, 133, 153 (1952).
10 E. Mollwo, Z. Physik, 85, 56, 62 (1933); the fact that 1', is essentially determined
hy a and only very slightly by the dielectric constant of the material may be explained
on the basis of calculations by L. Pincher!e, Proc. Phys. Soc. (London), 64, 648 (1951).
378 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

As a result of the presence of the F band, the crystals have a colored

appearance; for example, LiF containing excess Li looks pink; KCI with
excess K looks violet, NaCl with excess Na looks brown-yellow, etc.
The peak height of the absorption band at a given temperature is
proportional to the number of F centel'S per unit volume. From dispersion
theory, Smakula has derived the following formula for the F-center
density nF : 13

fl:w finF =.I 31 >(, 1017 (n +

2
n 2)2 KIllilX H per cm'3 ( 15-6)

where f is the oscillator strength, n

Abs. is the index of refraction, Kmax is the
t absorption coefficient in cm-I at the
peak, and H is the half width of the
band in ev. By measuring the excess
metal chemically and comparing the
result with formula (15-6), Kleinsch-
rod obtained an oscillator strength
f = 0.81 for KCI.14 When f is not
known, formula (15-6) can be used
1.0 only to determine the order of
magnitude of the F center density.
Fig. 15-7. The optical absorption as
It should be added that the deriva-
function of photon energy for KBr
resulting from an excess of potassium, tion of Smakula's formula is some-
measured at various temperatures CCl. what doubtful in the light of recent
[After Mollwo, ref. 121 results obtained from,spin resonance
studies. ls 4t. l'<,··.1.

F center density as function of metal vapor pressure and temperature.

The absorption of alkali metal by the crystal can be described as a diffusion
phenomenon, as will be explained further below. For a given temperature
of the crystal and a given number of metal atoms (alkali vapors are
monatomic) per unit volume in the container, a certain saturation density
of F centers is obtained. Some results obtained for K in KBr by Rogener
Table 15-3. F-Center Absorption Energies in ev for the Alkali Halides

LiF 5.0 NaF 3.6 KF 2.6

LiCI 3.1 NaCI 2.7 KCI 2.2 RbCI 2.0 CsCI 2.0
LiBr 2.7 NaBr 2.3 KBr 2.0 RbBr 1.8
KI 1.8 Rbi 1.6

13 See R. Hilschand R. W. Pohl,Z. Physik, 68, 721 (1931); F. Seitz. Revs. Mod. Phys.,

18, 384 (1946); 26, 7 (1954).

14 F. G. Kleinschrod. Ann. PhYSik, 27, 97 (1936).

15 See, for example, F. Seitz, Revs. M?d. Phys .• 26, 7 (1954).

Sec. 15-6] ELECfRONIC PROPERTIES OF ALKALI HALIDES 379

are represented in Fig. 15-8. 16 It may be noted tltat he assumed f = I in

formula (15-6), so that actually the F center'densities are somewhat larger
than in the figure. Several conclusions may be drawn from these measure-
ments. In the first place, the saturation value, for brevity simply denoted
by np', is pro~ortional to the number of K atoms per unit volume nv in the
' ~ i 'I
',"

,)"

"~,:,"'.-' ,... ..1

10
10 17

~
ir.. 5
'"
~

10 16
t 2
/~
,./.
_ nv 1
1.6 1.4 1.2 1.0
1016 \ 10 17 -+- lOOOIT

Fig. 15-8. The saturation density of Fig. 15~9. The ratio 11,/11, (plotted
F centers in KBr as function of
(II F ) logarithmically) versus the reciprocal
the density of atoms in the metal absolute temperature for KBr and
vapor (II,,), for a crystal temperature KCI. [After Rogener, ref. 16]
of 4400C and 680'C. [After Rogener,
ref. 16]

vapor. Hence the chemical reaction corresponding to the incorporation

of excess metal may be written

metal atom in vapor ~ F center

According to the law of mass action, we then have

kT
nF/nv = const. e-<I>I (l5-7)

where 1> is the e~ergy required to take an atom from the vapor and incor-
porate it as an F center in th.e crystal. In Fig. 15-9 we h.ave plotted nF1nv
as function of T-1 as given by Rogener for KBr and KC[.l6 From the
slopes it follows that

for K in KBr 1> = -0.25 ev

for Kin KCI 1> ~-= -0.10 ev

Note that in both cases 1> is negative, i.e., energy is released by taking an
atom from the vapor into the crystal. It is observed that n F > n~ for these
crystals.
,. H, Rogener, A 1111, Physik, 29, 386 (1937),
380 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

The F-center model. Although some other interpretations had been

given previously it is now generally accepted that an F center is an electron
trapped at a negative ion vacancy. This model was first suggested by de
Boerl7 and was further developed by GI)rney and Mott. IS In the light of
this model the incorporation of excess metal by the crystal may then be
pictured in the following manner. The first step is the adsorption of a metal
atom from the vapor on the surface of the crystal, for example, at point A
In Fig. 15-10. The atom may then split up into a positive ion and an
electron. A negative ion from the lattice
+ + + such as B may then jump into a position
next to A to form the beginning of a new

+ -
+
:;(: :
- ) + ; -B +
layer on the surface of the crystal. The
electron and the negative ion vacancy
produced at B diffuse into the crystal,
and the electron will become trapped in a
region where the potential is such that it
_A(;': /
+ ,
-
,
,
Adsorbed
provides
band.
a level below the conduction
Evidently a lattice site where a
atom negative ion is missing provides such a
Fig. 15-10. Possible mechanism region. The trapped electron is shared
for the incorporation of excess by the six positive ions surrounding the
metal in an alkali halide (see text) .. vacancy. We emphasize that in the above
picture the number of "empty" negative
ion vacancies remains constant, because for each electron added, a
negative ion vacancy is created. Seitz has pointed out that the actual
mechanism of the formation of F centers may be somewhat different
in the sense that positive and negative ion vacancies tend to associate to
pairs or higher aggregates because of Coulomb attraction. 19 However,
if an electron meets a pair of ion vacancies, the electron may first be
trapped by the pair, whereupon the positive ion vacancy wanders off,
because the binding energy of an electron and a negative ion vacancy
(",,2 ev) is larger than the binding energy of a pair of vacancies (,...._, lev).
In other words, a negative ion vacancy prefers an electron as a partner
over a positive ion vacancy. The result of such a mechanism is, of course,
the same as the one described above.
This F-center model is confirmed, for example, by the fact that heat
treatment of KCI in sodium vapor produces exactly the same absorption
band as excess K in KCI, i.e., the Fband is independent of the added metal.
Also, the same band is formed when the stoichiometric crystals are
irradiated with ultraviolet, X-rays, or other types of radiation which

" J. H. de Boer, Rec. trav. chim., 56, 301 (1937).

18 R. W. Gurney and N. F. Mott, TrailS. Faraday Soc., 34, 506 (1938).
,. F. Seitz, Revs. Mod. Phys., 18, 384 (1946).
Sec. 15-6] ELECTRONIC PROPERTIES OF ALKALI HALIDES 38 I

produce free electrons. Such free electrons ultimately become trapped at

negative ion vacancies, forming F centers. ..
Also in agreement with the above F-center model is the observation by
Witt that the'density of the crystals decreases when excess metal is intro-
duced. 20 Within the experimental error, the observed decrease in density
of KCl is compatible with the notion that one negative ion vacancy is
created for each F center formed.
Although the experimental evidence will be given later, it may be noted
here that the F-absorption band is believed to be due to the. excitation of
the F-center electron into an excited state
close to the conduction band (see Fig. 15-11),
but not into the conduction band. In this
connection it is of interest to note that Klein-
schrod observed that the F band has not a
Cond. band

T-
Fim ~ci"" ...te
F-absorption

Ground state
simple bell shape but possesses a shoulder
and a tail on the short-wave length side. 21 Fig. 15-11. Energy level dia-
Seitz has suggested the name "K band" for gram for an F center. The
F-absorption band arises from
this shoulder. The K band itself may corre- a transition from the ground
spond to transitions of the electron to excited state to the first excited state
states lying between the first excited state below the conduction band.
and the conduction band; the tail may be
associated with transitions from the ground state of the F center
into the conduction band.

Theoretical calculations on F centers. Theoretical calculations of the

motion of an electron in the field of a negative ion vacancy have been
carried out by a number of investigators. 22 In these calculations self-
consistent field methods must be used because the potential in which the
electron finds itself is a function of the wave function of the electron.
Because of lack of space it is not possible to discuss these models here,
and we refer the reader to the literature on this topic. In all papers except
the last one mentioned in footnote 22, the electron is assumed to move in
a spherically symmetric field. In the spherical approximation, the ground
state of the electron in an F center is a Is state, and the F absorption band
corresponds to transitions form Is to 2p. The calculated absorption
frequencies are in fair agreement with the experimental values.
We mentioned above that the width of the F band increases with
temperature, the peak shifting at the same time to lower energies. Although

z" H. Witt, Nllchr. Aklld. Wiss. GOtlillgell, 1952, 17.

" F. Kleinschrod, AIlII. Physik. 27, 97 (1936).
zz S. R. Tibbs, TrllllS. FllYlldllY Soc., 35, 1471 (1939); 1. H. Simpson. Proc. Roy. Soc.
(Londoll). A197, 269 (1949); L. Pincherle, Proc. Phys. Soc. (London). 64, 648 (1951);
J. A. Krumhansl and N. Schwartz. Phys. ReL'., 89,1154 (1953); T. Inui and Y. Uemura.
Progr. Theoret. Pllys. (Japan), 5, 252, 395 (1950).
382 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

qualitatively this can be understood on the basis of lattice vibrations and

lattice expansion, the first serious attempt to interpret these effects quanti-
tatively W; . made not earlier than 1950. 23 It is not possible to discuss here
the ra t.':" complicated calculations on this topic that have been published
since 1. t time.

Magnetic properties ofF centers. Since an F center contains an unpaired

electron, one expects the crystals additively colored with metal to be
paramagnetic; the static paramagnetism has been observed by Jensen. 24

E}. KCI RbCI KBr KI

t

1.8 Jl

Fig. 15-12. F-center lumi: ;cence emission spectra for some'

alkali halides at 20oK. [After Botden, van Doorn and Haven,
ref: 26)

More recently, spin resonance techniques have been employed to study

the structure of F centers. 25 The gyromagnetic ratio g, which determines
the splitting of the energy levels per unit magnetic field, is 1.995 ± 0.001
rather than 2.0023 corresponding to a free electron. This result, together
with results obtained from measurements of the line width, show that the
F-center electron overlaps to a considerable extent the surrounding
positive and negative ions, as one might have expected. For details
concerning the interpretation of such experiments we refer to the literature.

Luminescence of F centers. One might expect that an excited F center

would return to the ground state with emission of a photon. From the
foregoing discussions it is evident that experiments attempting to detect
this type of luminescence should be conducted at low temperatures,
23 K. Huang and A. Rhys. Proc. Roy. Soc. (London), A204, 406 (1950); see also H.

J. G. Meyer, Physica, 20,181 (1954); 20,1016 (1954); 21.253 (1955).

" P. Jensen, Alln. Physik, 34, J61 (1939).
2.' C. A. Hutchison, Phys. ReI'., 75, 1769 (1949); C. A. Hutchison and G. A. Noble.
Phys. Rev., 87, 1125 (1952); E. E. Schneider and T. S. England, Physica, 17, 221 (1951);
M. Tinkham and A. F. Kip. Phys. Rev., 83, 657 (1951); A. H. Kahn and C. Kittel,
Phys. Rev., 89, 315 (1953); Kip, Kittel, Levy, and Portis, Phys. Rei'., 91.1066 (1953);
A. M. Portis, Phvs. Rel'., 91,1071 (1953).
Sec.. 15-6] ELECTRONIC PROPERTIES OF ALKALI HALIDES 383

because otherwise the electron will not remain in the excited state but
will be further excited thermally into the conduction band. The lumines-
cence of F centers in additively colored alkali halides has r 'ently been
c

observed by Botden, van Doorn, and Haven. 26 The crystals were,; ,diated
with light in the F band and luminescence in the infrared was ot ::rved at
200 K and at nOK. In Fig. 15-12 we
reproduce the emission spectra at 9 F
20oK. The energy of the emitted
0
photons at 20 K are given in ev below,
together with the corresponding ~

'e 6 A
photon energy for F absorption at ~

room temperature. It is observed :.c:

that the absorption frequency is t
3
nearly twice the emission frequency,
/" \
and this difference would actually be , I
F'
/
larger if the absorption energies were ---------.. . -!!
referred to 20oK. This illustrates 3 2.5 2 1.5 ev
again clearly the importance of the
Fig. 15-13. Formation of the F' band
Franck-Condon principle in ionic
at the expense of the F band, by irra-
crystals. After the optical excitation diation of an additively colored crystal
has taken place, the ions in the vicinity "'ith F light at 173°K. [After Rilsch
of the excited F center will adjust and Pohl, ref. 271
themselves to the new charge dis-
tribution, thereby giving off energy (corresponding to the representative
point moving from 8' to Q in Fig. 15-1). When the electron returns to
the ground state after this ionic displacement has taken place, an infrared
quantum is. emitted. ,i
Table 15-4. F-Center Absorption and Emission Energies (ev)

. Absorption Emission

KCI 2.2 1.25

RbCI 2.0 1.10
KBr 2.0 0.96
KI 1.8 0.85

15-7. The transformation of F centers into F' centers and vice versa

When an additively colored crystal containing F centers is irradiated

with light in the F band, a new band appears at the long-wavelength .>ide
of the F band. The new band grows at the expense of the F band and is
called the F' band. For example in Fig. 15-13, curve A represents the
26 Th. P. J. Botden, C. Z. van Doorn, and Y. Haven. Philips Research Rep/s .• 9, 469

(1954).
384 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

optical abso,ption spectrum of a KCI crystal containing 1.6 X 1016

F centers pe'" cm 3 , measured at 38°K.27 After irradiation with F light at
173°K, the F band has decreased and the F' band appears (curve B, Fig.
J 5-13, measured again at 38°K). The F' centers are stable only at rather
low temperatures, because the electrons causing F' absorption are more
loosely bound than those in the F
centers. Thus at higher temperatures,
the F' centers dissociate thermally and
form F centers again. To investigate
the transformation of F centers into
F' centers and vice versa, Pick carried
out a number of interesting experi-
ments on the quantum efficiency of
these processes at different tem-
peratures. 28 For example, Fig. 15-14
gives the number of destroyed F
~ 10
centers as function of the number of
t absorbed F center quanta for KCI at
different temperatures. The slope of
the curves give the quantum yield,
i.e., the number of destroyed Fcenters
o 5 10 15x1014 per absorbed quantum. We note that
0
above 140 K the curves start off with
- No. of absorbed quanta
a quantum yield of 2, i.e., in that
Fig. 15-14. The number of destroyed region one destroys tw~ F centers for
F centers as function of the total number
each absorbed quantum. This sug-
of absorbed F quanta at various tem-
peratures. [After Markham, ref. 281 gests the following interpretation: at
temperatures above about 1400 K (but
below the temperature above which F' centers become unstable) each
absorbed F quantum produces an electron in the conduction band;
the free electron wanders about in the crystal and is then trapped
by another F center, forming an F' center. Hence an F' center then
corresponds to two electrons trapped at a negative ion vacancy.
Because the negative ion vacancy is equivalent to a single positive charge,
the two electrons are only weakly bound (see Fig. 15-'15). More evidence
for the correctness of this picture has been obtained from photocon-
ductivity measurements, which will be discussed in the next section.
Markham has shown that from Pick's data one can conclude that the
capture cross section for an electron in the conduction band to form an
F' center is much larger than the cross section to form an F center from a
negative ion vacancy.
27 R. Hilsch and R. W. Pohl, Z. Physik, 68, 721 (1931).

"" H. Pick, Ann. Physik, 31, 365 (1938); 37, 421 (1940). The interpretation given
here is due to J. J. Markham, Phys. Ret'., 88, 500 (1952).
Sec. 15-7] ELECTRONIC PROPERTIES OF ALKALI HALIDES 385

The rather sudden drop in the quantum yield in the beginning of the
irradiation with F light at temperatures below 1400 K is explained as
follows: an F center corresponds to an electron trapped at a negative ion
vacancy, so that for large distances the electron moves in an electric field
-e2 /Eor 2 , where EO is the high-frequency dielectric constant. 29 As in a
hydrogen atom, there must therefore be a number of excited states below
the ionization continuum, Le., below the conduction band. Mott assumes
that the absorption of an F quantum raises the electron from the ground

+hVF- ...L!.-F'
F--'- F-·- F--Empty

Fig. 15-15. Schematic diagram of the reaction 2F --+ F'. The

reaction proceeds only if the temperature is high enough so that
absorption of an Fphoton produces a free electron in the conduction
band, which may then be captured by another F center. At the
same time the temperature should be low enough for the F' center
,,';' -
to be stable.

state to the first excited state, which is close to but not in the conduction
band (Fig. IS-II). At temperatures above 1400 K the thermal lattice
vibrations are intense enough to provide the additional energy required
to raise the electron from the excited state into the conduction band, but
at low temperatures the probability for the electron to fall back to the
ground state takes over. Hence, at low temperatures, absorption of an
F quantum does not liberate the electron, leading to the drop in quantum
yield of the reaction 2F -+ F'.
The decrease in quantum yield as the time of irradiation increases is a
result of the increase in the number of negative ion vacancies; this increases
the probability for an electron in the conduction band to be trapped by a
negative ion vacancy.
Another set of interesting data has been obtained by Pick employing an
additively colored KCl crystal in which 80 per cent of the F centers had
been transformed into F' centers. In such crystals one can study the
reverse process viz., the transformation of F' centers into F centers by
irradiating with F' light. In Fig. 15-16 we reproduce Markham's representa-
tion of Pick's data for the number of F centers formed as function of the
number of F' photons absorbed. 28 It is observed that at low temperatures
up to about 90 0 K two F centers are formed per absorbed F' photon, at
least in the beginning of the irradiation. This is in agreement with the model
of an F' center discussed above: an F' center from which an electron is
released is transformed into an F center; the free electron captured by a
negative ion vacancy produces the second F center. The drop in the
2. N. F. Mott, Proc. Phys. Soc. (London), 50, 196 (1938).
386 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

quantum yield at higher temperatures may be explained by considering

the trapping of an electron by a negative ion vacancy as a two-step process:
the electron is first captured in the excited state; it may then drop to the
ground state or may be released again by absorbing energy from the lattice
vibrations. Thus, as the temperature increases, the capture cross section

- No. of absorbed quanta

Fig. 15-16. The number of rebuilt F centers as function of the total

number of F' quanta absorbed. [After Markham, ref. 28)

for a free electron to form an F center from a negative ion vacancy decreases.
The decrease of the quantum yield as the irradiation proceeds is a conse-
quence of the increase in the number of F centers and the decrease in the
number of negative ion vacancies.

15-8. Photoconductivity in crystals containing excess metal

We have seen above that absorption of an F photon by an F center

produces a free electron if the temperature is not too low. Thus when a
crystal containing F centers is irradiated with F light and at the same time
an electric field is applied to the crystal, a photocurrent is observed.
However, if only ·the electrons are mobile. a space charge will soon be
built up in the crystal, thereby lowering the field and the current. The space
charge may be neutralized by electrons entering the crystal from the anode.
or by electrolytic conduction in the crystal. If this is not the case, space
charge difficulties may be avoided by employing low light intensities for a
short period. Before discussing briefly some classical experiments by
Pohl's group it may be useful to make some general remarks on the
Sec. 15-8] ELECTRONIC PROPERTIES OF ALKALI HALIDES 387
process of photoconductivity, assuming that space charge effects have
been avoided. ..
An electron liberated from, say, an Fcenter, will carry out a random
motion in thl.! conduction band. In the presence of an electric field E, it
will drift in the direction towards the anode with a velocity.

where fl is the mobility. After a certain time it will be trapped at some

lattice imperfection and for the moment it will be assumed that it remains
trapped, so that we may associate
Photon '! ~ __ -'-..
with the electrons in the conduction
band a certain life time T. The
distance over which the electrons
drift· in the field direction is then
+
(15-8)

unless the electron has arrived at the .....- - L

anode before being trapped. Suppose
the electron is liberated at a distance
Xo from the anode, and let L be the
distance between the electrodes (Fig.
15-17). The charge passing through Fig. IS-17. Illustrating the displace-
ment x associated with the drift of a
the external circuit is then ex/L or photo electron 'during a lifetime T in an
eXo/L, depending on whether x < Xo external electric field.
or x > xo' Let NIl represent the
number of photons absorbed by the crystal per second, and let rJ be the
probability that an absorbed photon actually produces a free electron.
On the assumption that x < Xo for all electrons under consideration, we
find by using (15-8) for the current,

( 15-9)
Hence I should be proportional to the field strength E. However, as E is
increased, x increases, and x may become larger than Xo' One thus expects
that the I versus E curve will saturate for high field strengths. In fact, for a
crystal illuminated in a thin slab at a distance Xo from the anode we shall have
(15-10)
Similarly, for a uniformfy illuminated crystal

Im"x = rJ N "e/2 (15-100)'

1t seems that for alkali halides saturation occurs only for crystals that are
too thin to be used in photoconductivity experiments. Saturation has been
observed, however, in the silver halides. in zinc sulfide, and in diamond.
388 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

The above considerations are based on equation (15-8), i.e., on a mean

lifetime T of the liberated electrons. Tn other words, free electrons that
have been trapped are not supposed to contribute any longer to the
current unless they are liberated again by absorption of energy. Such
currents are called "primary currents." However, suppose that an electron
liberated by absorption of a photon from, say, an F center, is ultimately

40 :--A I
B C---t
I
I F.light I Dark F-light I
I I I
I I I
20
J:I. 30'C I
~ I

'"'0
....
....X
E
::s
<.>
WL[l SO'C

ts;
'_t,· _\ - 'J:)-" -_,:"

~
i

t 40 ( ~ . ',,-

125'C
20

o 5 10 15 20 25 sec

Fig. 15-18. Time dependence of the photocurrent in NaCl con-

taining 8 x 10 15 excess Na atoms per em', at various temperatures_
[After Glaser and Lehfeldt, ref. 30]

trapped by another F center so as to form an F' center. If the temperature

is high enough, it may become free again by thermal excitation. Evidently,
such processes would increase the effective lifetime; the resulting "excess"
current is called a "secondary current." It is obvious that the magnitude
of the secondary current will depend strongly on temperature, contrary to
the primary current.
As a specific example, we shall briefly discuss some of the classical
experiments on the photoconductivity of alkali halides' containing F
centers resulting from an excess of the metallic constituent. In Fig. 15-18
we have represented the photocurrent observed in a colored NaCi crystal
as function of time for different temperatures. 30 During the interval A the
crystal is irradiated with light in the F band. Then follows a dark interval
(B) and finally the crystal is irradiated with light in the F' band (C). At
temperatures below 30°C one observes a constant current during the
'0 G. Glaser and W. Lehfeldt, Nachr. Akad. Wiss. Gottingell, 2, 91 (1936); see also
R. W. Pohl, Physik. z., 39,36 (1938). "c: . .
Sec. 15-8] ELECTRONIC PROPERTIES OF ALKALI HALIDES 389
interval A. This is a true primary current for which relation (15-9) holds.
Thus the quantity 'Y/x/E should be independent of the field strength, in
agreement with the experiments. From what has been said in the pre-
ceding sectioo one expects F' centers to be formed during the irradiation
with F light. That this is indeed the case may be seen from the intervals C,
which also indicate a larger production of F' centers at lower temperatures,

1+-")
,
10- 9
","-

..~--
> 10- 10
.§.
10- 11
~
...
Ii

10-12
t
10- 13

-200 -150 -100 -50 O·C

- Temp.

Fig. 15-19. The quantity 1}x/E as function of temperature for a

KCI crystal containing 2.7 x 1016 F cente'rs per cm'. [After Pohl,
ref. 301

as expected. The increase in the current during interval A at higher

temperatures is a result of the thermal liberation of electrons from F'
centers; this effect produces the secondary current mentioned above.
For the same reason there is still some current flow at higher tempera-
tures during the dark interval B.
The existence of an excited state of an F center close to the conduction
band (see preceding section) is confirmed by Fig. 15-19 where the quantity

(15-11)

has been plotted as function of temperature for a KCl crystal containing

F centers. The sharp drop below -140°C is a result of a drop in the
quantum efficiency 'Y/ for liberation of an electron from an F center. The
increase in the effective displacement above room temperature is a conse-
quence of thermal excitation of electrons from F' centers. The region
below _. 180°C probably corresponds to photoelectrons liberated from'
colloidal sodium particles.
Another result of great interest which confirms the conclusions of the
preceding section is represented in Fig. 15-20 where x/ E for KCl has been
plotted as function of the density of F centers n F for a fixed temperature
390 ELECTRONIC PROPERTlES OF ALKALI HALIDES [Chap. 15

of -100 0 e. At this temperature, 1] may be taken equal to unity. We note

that the slope of the line in this double logarithmic plot is 45°, showing that
for the region of F center densities involved, x is inversely proportional to
nF . From (15-8) it thus follows that the mean free path for capture of an
electron is proportional to nF \ indicating again that F centers are efficient
•. ft'" :i~'~'f~~01'" ~'~'.'i.: r,
, 0,

10- 11
t x/E (m 2 /volts) ,J,"
I
•
\.-----

Fig. 15-20. The quantity xl E for KCl as function of the F center

density nF at -IOO'C. [After Pohl, ref. 30]

traps for free electrons. We leave it to the reader to show that from Fig.
15-20 one may estimate a capture cross section of about 1O-lL lO-15 cm2 .

15-9. The photoelectric effect in alkali halides

Although the photoelectric effect of insulators has not been studied

very thoroughly, some recent experiments by Apker and Taft31 on alkali
halides show that such investigations can provide useful information about
the behavior of imperfections in crystals. As in the study of this effect
from metals, one can measure the number of photoelectrons emitted per
incident quantum as function of the frequency of the light employed, and
the energy distribution of the emitted electrons. In pure alkali halides, the
energy required to produce a free electron in the conduction band is of
the order of 8 ev, and in order to observe the photoelectric effect, photons
of an energy of this order of magnitude are required. On the other hand,
if F centers are present in the crystal, i.e., electrons trapped in levels about
2 ev below the conduction band, one expects an appreciably lower
threshold frequency. That this is indeed the case may be seen from Fig.
) 5-21, representing the photoelectric yield in electrons per quantum for
potassium iodide containing F centers. For hv:::: 2.3 ev, about 10-8
31 For a review of this work see the article by Apker and Taft in W. Shockley (ed.),
Imperfections in Nearly Perfect Crystals, Wiley, New York, 1952, p. 246.
Sec. 15-9] ELECTRONIC PROPERTIES OF ALKALI HALIDES 391
electron is emitted per incident quantum, but the curve rises rapidly to a
plateau with a yield of 10-4 . The sample ~~ntained about 1019 F centers
per cm3 produced by electron bombardment. The rise beyond the plateau
is interpreted as follows. The first fundamental absorption peak of KJ
occurs at hv = 5.66 ev at room temperature. Thus photons of 5 ev

3000 K

6 6

4 5 6
--+- hv lev)

Fig. 15-21. Spectral distribution of the photoelectric yield in

electrons per quantum for KI containing F centers. In the inset the
fundamental optical absorption of KI at 29JOK is given for com-
parison. [After Apker and Taft, ref. 33J

correspond to irradiation in the tail of this band and therefore produce

excitons in the crystal. The excitons may diffuse through the crystal as
mentioned in Sec. 15-3 and may give up their energy to an F center, thereby
giving rise to an electron in the conduction band of several ev. From Fig.
15-2 I we see that this process of ionization via excitons increases the yield
by a factor of 20. This reasoning is confirmed by the fact that the shape of
the peak in Fig. 15-21 is the same as that of the first fundamental absorp-
tion band. The Apker-Taft experiment constitutes the most direct experi-
mental evidence for the motion of excitons. For a quantitative treatment
of these results, we refer the reader to a paper by Hebb. 32 .

It has also been observed that excitons may interact with negative ion
vacancies in such a manner than an F center and presumably a free hole
3. M. H. Hebb, Phys. Rev., 81, 702 (1951).
392 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

are formed. Thus, when a crystal which initially contains no color centers
is irradiated with light in the first fundamental absorption band, the
excitons produce F centers which may thereupon be ionized' by other
excitons. One thus expects a build up of the F-center concentration as
function of time, and associated with this, an increase in the photoemission
current. This is shown in Fig. 15-22 according to Apker and Taft. 33 In
the same figure, the decay of the photoemission resulting from heating the
crystal is represented.

:
...,
I')
<lI
!::::> •
()

....00
..<::
p..
\
t
o 10 20 30 40 min
-Time

Fig. 15-22. Curve A represents the growth of the photocurrent

(arbitrary units) in KI by irradiating with 5.66 ev photons at 300o K.
Curve B represents the decay obtained by raising the temperature
to 400'K, leading to bleaching of the F centers. [After Apker and
Taft, ref. 33]
I

I
15-10. Coagulation of F centers and colloids r"

When a crystal containing F centers is irradiated with F light at room

temperature, a number of bands on the long-wavelength side of the Fband
appear. It is believed that the negative ion vacancies produced by the
ionization of the F centers join with positive ion vacancies, forming pairs.
These pairs are highly mobile (see Sec. 7-5) and thus provide a vehicle for
the transport of negative ion vacancies. The observed absorption bands
are probably due to aggregates of F centers and vacancies. The first
products of this type of coagulation are the so-called Rl and R2 bands and
the M band (see Fig. l5-24).
Related to the coagulation mentioned above is the formation of
colloidal particles of metal in the crystals. We have seen in Sec. 15-6 that
when an alkali halide is heated in the metal vapor at, say, 600°C and then
quenched, F centers are observed. However, if the crystals are cooled
slowly, or when a quenched crystal is heated at higher temperatures (say
above 250 o q, the atomically dispersed F centers condense in the form of
33 L. Apker and E. Taft, Phys. Rev., 79, 964 (1950).
Sec. 15-10) ELECTRONIC PROPERTIES OF ALKALT HALIDES 393

colloidal particles. At high temperatures the colloids are again transformed

into F centers. In other words, there exists an equilibrium between the
colloidal particles and the Fcenters. For details on this topic, see F. Seitz,
Revs. Mod. PIlys., 18, 384 (1946); 26,7(1954).

15-11. The Hall effect and electron mobility

The Hall effect of NaCI containing excess sodium has recently been
measured by Redfield, using a technique which is partic~larly suitable for
relatively high resistivity materials. 34 The electron mobility measured at
82°K is 260 ± 30 cm2 fvolt sec; at 200 0 K he finds 40 ± 20 in the same
units. According to MacDonald, the electron mobility at room tempera-
ture in NaCl is equal to 12.5 cm 2fvolt sec. 3S It may be noted here that a
theoretical calculation of the electron
mobility in ionic crystals has been
carried out recently by Low and
Pines. 36 Earlier calculations of the ...
's
mobility of electrons were made by ..£ 1.0
Frohlich and Mott. 3 ? l<
t .5
15-12. Color centers resulting from
excess halogen
5 4 3 2 ev
In the preceding sections we have
been mainly concerned with the :~11~;23;n T~~; ~~~~:i~~;rv::c:!s
electronic properties associated with bromine. The main peak is designated
excess metal. In some cases, however, as the V. band, and the unresolved peak
it is also possible to obtain an excess on the left as the Va band.
of halogen in alkali halides. For i ;'.' .)~ "
example, heat treatment of KI in iodine vapor results in new absorption
bands in the ultraviolet, as shown bv Mollwo. 38 Similar bands observed
by Mollwo for KBrwhen heated in Br 2 vapor are represented in Fig. 15-23.
Color centers of this type are referred to as V centers, and the reason for
their presence may be understood on the basis of a picture analogous to
that used for F centers.
The excess bromine is presumably incorporated in the lattice in the
form of negative ions, occupying normal lattice sites. Thus the intro-
duction of each extra bromine atom leads to the formation of a positive
34 A. Redfield, Phys. Rev., 91,244,753 (1953).
a·l. R. MacDonald, Phys. Rev., 92, 4 (1953). -,
.6 F. E. Low and D. Pines, Phys. Rev., 91,193 (1953) .
., H. Frohlich, Proc. Roy. Sec. (London), A160, 230 (1937); H. Frohlich and N. F.
Mott. Prcc. Roy. Soc. (London), 171, 496 (1939); see also F. Seitz, Phys. Rev., 76, 1376
(1949).
38 E. Mollwo, Ann. Physik,S, 394 (1937).
394 ELECTRONfC PROPERTrES OF ALKALI HALIDES [Chap. 15

hole. These holes are most likely to be found near a positive ion vacancy
where they can be trapped. The optical absorption associated with a
trapped hole may be, for example, the transition of an electron from the
filled band into the hole. A hole trapped at a positive ion vacancy is called
a VI center. There is good evidence to believe, however, that the dominant
peak observed by Mollwo is not of this simple type. The reason for this is
the following. According to Mollwo's experiments the saturation density
+ + + + +
~ ~F

+
+
D +
Ol

+LJ+~+

+ + +
+

- r=olVi
L_j - ~
Vz
+ 0

0
- + "[fJV:1
- +
0
- +

+ - + - + + - +

~~~@~C!J:
+ + + + +
Fig. 15-24. Models for a number of color centers. The squares
indicate ion vacancies, the dots electrons, and the open circles holes.

of color centers for a given temperature is proportional to the number of

Br2 molecules in the vapor. According to the law of mass action, each
molecule absorbed from the vapor must therefore give rise to one color
center in the crystal. Seitz has therefore suggested that the centers corre-
sponding to the main peak are of a molecular type, i.e., two holes are
trapped by a pair of positive ion vacancies, as shown in Fig. 15-24. These
centers are called V 2 centers. The details of the properties of V centers
are at present not so well understood as the corresponding ones for F
centers. For a review of the present situation we refer the reader to F.
Seitz, Rers. Mod. Phys., 26, 7 (1954).

15-13. Color centers produced by irradiation with X-rays

When an X-ray quantum passes through an ionic crystal it will usually

give rise to a fast photoelectron with an energy of the same order as that
of the incident quantum. Such electrons, because of their small mass, do
Sec. 15-13) ELECTRONIC PROPERTIES OF ALKALI HALIDES 395
not have sufficient momentum to displace ions and therefore lose their
energy by producing free electrons and holes, excitons, and phonons.
It is evident that this will give rise to trapped electrons as well as trapped
holes. Hence; color centers of both the F type and V type are formed. In
contrast with the additively colored crystals, the color centers in X-ray
irradiated crystals are not permanent. They can be bleached by irradiation
with light or by heating, because,ultimately the excited electrons and holes
will recombine. Without going into details, it will be evident that studies
of the coloration, photoconductivity, '
and bleaching at various temperatures K ~j' nJ ' F
provide information about the pro- t
HI ~f;. ' ~ :~'~
perties of the color centers and their
interaction. As an example, we give
in Fig. 15-25 the absorption spectrum
induced in KCl by irradiation with
X-rays at 20°C. 39
It is of interest to note that measure-
ments of the change in density of
6 5 4 3 2 ev
alkali halides during X-ray irradiation
show that the lattice starts to expand Fig. 15-25. The F and V bands pro-
as soon as the irradiation begins. It duced in KCI by irradiation with X-rays
thus seems that during the irradiation at room temperature. [After Dorendorf
vacancies are formed. 40 Eventually and Pick, ref. 39J
the expansion saturates, a typical
value being 5 X 10-5 cm for a crystal with dimensions of I cm. At present
tbe interpretation of the production of vacancies upon X-ray irradiation is
still rather speculative, although it seems very likely that dislocations play
an important role in the process. 41
,I

REFERENCES
J. H. de Boer, Electron Emission and Adsorption Phenomena, Cambridge,
London, 1935. I
N. F. Mott and R. W. Gurney, Electronic Processes in Ionic Crystals,
Oxford, New York, 1940.
R. W. Pohl, Proc. Phys. Soc. (London), 49 (extra part), 3 (1937); Physik. Z.,
39, 36 (l938).
F. Seitz, Revs. Mod. Phys., 18, 384 (1946); 26, 7 (1954). (These papers
constitute the most extensive review of the properties of alkali halides.)
39 H, Dorendorf and H. Pick, Z. Physik, 128,106 (1950).
40 K. Sakaguchi and T. Suita, Technol. Repts. Osaka Ulliv., 2, 177 (1952).
41 See J. J. Markham, Phys. Rev., 88, 500 (1952); also, F. Seitz, Revs. Mod. Phys.,

26, 7 (I 954).
396 ELECTRONIC PROPERTIES OF ALKALI HALIDES [Chap. 15

PROBLEMS

15-1. Assume that the first characteristic absorption peak for KCl
(observed at 7.6 ev) is due to the transfer of an electron from a Cl- ion to
a neighboring K + ion. Calculate the energy required for this process on
the assumption that the positions of the nuclei remain fixed and that there
is no polarization. Compare the answer with the observed value, and from
this calculate the polarization energy.
15-2. Assume that the second characteristic absorption peak for KCI
(observed at 9.4 ev) is due to the transfer of an electron from a Cl- ion to
a distant K+ ion. Assuming that the nuclei remain fixed and that there is
no polarization, calculate the energy required for the transfer. Compare
the result with the observed value and calculate the polarization energy.
15-3. (a) Show that for a monatomic gas at a temperature T the free
energy is given by
... F = - NvkT[Jog (27TmkT/h2)3/2 +I - log nv] i1

where nv is the number of atoms per unit volume and Nv is the total
number of atoms in the system; m is the mass per atom.
(b) What is the configurational entropy of an alkali }lalide crystal
containing N ion pairs and nF F ~enters, relative to the crystal without
F centers?
(c) Consider an alkali halide crystal containing N ion pairs in equili-
brium with the vapor of the alkali metal at a temperature T. The vapor
contains nv atoms per cm 3 ; the crystal contains nF F centers per cm 3 . Set
up an expression for the change in the free energy !1F of the system crystal
plus vapor if one atom is transferred from the vapor to the crystal;
neglect thermal entropy changes. Show that because !1F = 0 in equilibrium,
27TmkT) -3/2
nF'""
-
Nn v ( - -
h2 - e-~/kT for ~ N
n F'~

where cP is the energy required to take an atom from the metal vapor into
the crystal, thereby forming an F center. Compare the result with equation
(15-7).
15-4. Calculate the paramagnetic susceptibility of KCl at room tem-
perature containing 5 X 1017 F centers per cm3 and compare this with the
diamagnetic susceptibility. Do the same for liquid air and for liquid
helium temperatures.
15-5. From the data given in Fig. 15-20, estimate the cross section for
capture of an electron by an F center and compare the result with that
stated at the end of Sec. 15-8.
Chap'. 15] ELECTRONIC PROPERTIES OF ALKALI HALIDES 397

15-6. Assuming that the thermal ionization energy of an F center is

0.94 ev, estimate the electronic conductivity of a sodium chloride crystal
containing 1017 F centers per cm3 at room temperature; for mobility data
see Sec. 15-U.
15-7. Discuss the derivation of Sma kula's formula (15-6). See for
example F. Seitz, The Modern Theory of Solids, McGraw-Hili, New York,
1940, p. 661. i
Chapter 16

LUMINESCENCE

16-1. General remarks

When a substance absorbs energy in some form or other, a fraction

of the absorbed energy may be re-emitted in the form of electromagnetic
radiation in the visible or near-visible region of the spectrum. This
phenomenon is called luminescence, with the understanding that this
term does not include the emission of black-body radiation, which obeys
the laws of Kirchhoff and Wien. Luminescent solids are usually referred
to as phosphors.
Luminescence is a process which involves at least two steps: the
excitation of the electronic system of the solid and the subsequent emission
of photons. These steps mayor may not be separated by intermediate
processes. This will be further discussed in the next sections. Excitation
may be achieved by bombardment with photons (photoluminescence),
with electrons (cathodoluminescence), or with other particles. Lumines-
cence can also be induced as the result of a chemical reaction (chemi-
luminescence) or by the application of an electric field (electroluminescence).
When one speaks of fluorescence, one usually has in mind the emission
of light during excitation; the emission of light after the excitation has
ceased is then referred to as phosphorescence or afterglow. These defini-
tions are not very exact since strictly speaking there is always a time lag
between a particular excitation and the corresponding emission of a
photon, even in a free atom. In fact, the lifetime of an atom in an excited
state for which the return to the ground state is accompanied by dipole
radiation is ,._, 1O-I! second. For forbidden transitions, involving quadru-
pole or higher-order radiation, the lifetimes may be 10-4 secolld or longer.
One frequently takes the decay time of ,._,10-8 second as the demarcation
line between fluorescence and phosphorescence. 1 Some authors define
fluorescence as the emission of light for which the decay time is temperature-
independent, and phosphorescence as the temperature-dependent part. 2
In many cases the latter definition is equivalent to the former, but there
are exceptions.
1 See, for example, G. F. J. Garlick, Luminescent Materials, Oxford, New York,

1949, p. I.
2 See, for example, F. A. Kroger, Some Aspects of the Lumillescence of Solids,

Elsevier, New York, 1948, p. 36.

398
Sec. 16-1] LUMINESCENCE 399
One of the most important conclusions reached already in the early
studies of luminescence, is that frequentli the ability of a material to
exhibit luminescence is associated with the presence of "activators."
These activators may be impurity atoms occurring in relatively small con-
centrations in the host material, or a small stoichiometric excess of one of
the constituents of the material. In the latter case one speaks of self-
activation. The presence of a certain type of impurity may also inhibit
the luminescence of other centers, in which case the former are referred
to as "killers." Since small amounts of impurities may play such an
important role in determining the luminescent properties of solids, studies
aimed at a better understanding of the mechanism of luminescence must be
carried out with materials prepared under carefully controlled conditions.
A great deal of progress has been made in this respect during the last
two decades.
A number of important groups of luminescent crystalline solids may
be mentioned here.
(i) Compounds which luminesce in the "pure" state. According to
Randall, such compounds should contain one ion or ion group
per unit cell with an incompletely filled shell of electrons which is
well screened from its surroundings. 3 Examples are probably the
manganous halides, samarium and gadolinium sulfate, molybdates,
and platinocyanides.
(ii) The alkali halides activated with thallium or other heavy metals.
(iii) ZnS and CdS activated with Cu, Ag, Au, Mn, or with an excess
of one of their constituents (self-activation).
(iv) The silicate phosphors, such as zinc orthosilicate (willemite,
Zn 2Si04 ) activated with divalent maganese, which is used as
oscilloscope screens.
(v) Oxide phosphors, such as self-activated ZnO and AI 20 a activated
with transition metals.
(vi) Organic crystals, such as anthracene activated with naphtacene;
these materials are often used as scintillation counters.
".:

16-2. Excitation and emission

Before discussing the properties of specific luminescent materials, it is

perhaps useful to consider first some simple models which, at least in
principle, could give rise to luminescence. This will be done in the present
section and the next; the results may then be used as a guide in the
interpretation of the mechanism of luminescence in specific cases. For
3 J. T. Randall, Trails. Faraday Soc., 35, 2 (1939); Proc. Roy. Soc. (London), A170,

272 (1939).
400 LUMINESCENCE [Chap. 16
the moment let us assume that the luminescence is associated with the
presence of activator atoms. The incorporation of an activator atom in a
crystalline solid will in general give rise to localized energy levels in the
normally forbidden energy gaps. These localized levels may be classified
into two categories: (i) levels which belong to the activator atoms them-
selves and (ii) levels belonging to host atoms which are under the perturbing
influence of the activators. The levels of group (ii) may be associated
with host atoms in the immediate vicinity of the impurity atoms, but they
may also be associated with lattice
defects (e.g., vacancies) whose exis-
,r - + - " tence is tied up with the incorporation
A-'- of the activator. For example, if
Mn4+- ions were incorporated on sites
normally occupied by Zn2+ in a ZnS
G-+- lattice, there may be localized levels
associated with the Mn4+- ion, levels
(a) (b)
associated with the S2- and Zn 2+
ions in the vicinity of the MnH
Fig. 16-1. The ground state G and an ion, and levels associated with ions
excited state A of a luminescence in the vicinity of a positive ion
center. In (a) excitation takes place by
vacancy (produced as a result of
direct absorption of a photon hi'".
In (b) excitation is achieved by capture the presence of the Mn4+- ion to
of a hole at G and of an electron at A. compensate for the excess positive
charge).
I n terms of the energy band picture of Fig. 16-1 let G and A be two
levels corresponding to one of the categories (i) and (ii) mentioned above.
In the ground state, level G is occupied by an electron and A is empty;
in the excited state the reverse is true. The excitation from G to A may
be accomplished in at least three ways:
(a) It is possible that an incident photon of the proper frequency is
absorbed directly by the electron in level G, whereupon it arrives in A
(sel: Fig. 16-1 a). As a result of lattice vibrations the absorption will
correspond to a band centering about a certain frequency VII"
(b) The excitation process may also involve the diffusion of an exciton
(see Sec. 15-3). Suppose, for example, that in some part of the crystal an
exciton is produced; since the exciton may diffuse about in the crystal, it
may reach a center such as AG, whereupon it may give off its energy to
the center, resulting in excitation of the electron. This consideration is of
importance, since it provides a mechanism whereby energy can be trans-
ferred from the exciting source to the impurities via the host crystal. In
other words, the exciton mechanism makes it possible for the activators
to receive more energy than they ought to on the basis of their relative
concentration in the lattice.
Sec. 16-2] LUMINESCENCE 401

(c) The excitation process may also involve the motion of free electrons
and holes. For example, let electron-hole p-airs be created somewhere in
the crystal, as for example, by bombardment with photons or electrons.
If the center'l4G is in its ground state, the level G may capture a hole
from the valence band and A may trap an electron from the conduction
band. In this way, excitation of the center has been achieved, as indicated
in (Fig. 16-lb). Evidently this type of excitation process should be
associated with conductivity, ~n contrast with processes (a) and (b).
E .F:

f t ~--~...--'.

'---'.

-q
(a)

Fig. 16-2. Energy of the ground state G and of an excited state A

as function of a configurational coordinate q. The situation (a)
gives luminescence; (b) corresponds to dissipation in the form of
heat.

The Franck-Condon principle. From the simple energy level diagram

of Fig. 16-1 one might get the impression that the return of the electron
from the excited state A to the ground state G should be accompanied
by emission of a photon of a frequency equal to the absorption frequency.
This is not the case, since the Franck-Condon principle must be taken
into account, as discussed in Sec. 15-1. In Fig. 16-2 we have represented
the levels A and G as function of a configurational coordinate q; each
value of q corresponds to a particular configuration of the nuclei in the
vicinity of the luminescence center. During the optical excitation from G
to A the nuclei remain essentially at rest, leading to an absorption energy
/11'". After the absorption act the nuclei do not occupy the equilibrium
position proper for the excited state, and the system will move gradually
to the minimum of the A curve, with emission of phonons. This process
is possible since the lifetime of the excited state is ,.._, I 0- 8 second, as
compared with periods of the order of 10-13 second associated with lattice
vibrations. The emission act itself, like the absorption act, takes place
vertically in Fig. l6-2a, so that Ve < v". Thus luminescence centers are
in general transparent, or nearly so, with respect to their own emission
bands. ;.~:\ .: <,w~c,y! ':;
402 LUMINESCENCE [Chap. 16

Radiationless transitions. An excited center in a crystal can return to

the ground state either with or without the emission of a photon. A model
corresponding to the former case is the one represented in Fig. 16-2a.
For nonluminescent materials Seitz has suggested a model in which the
return to the ground state of an excited center can take place by means of
a radiationless transition. 4 Thus in Fig. 16-2b the system may move after
the absorption act from A to A' and then cross the narrow gap to point
G' associated with the ground state (perhaps with emission of a low-
frequency photon). In this way the energy of the absorbed photon GA is
essentially transformed into heat, i.e., into vibrational energy.

Temperature-dependence of luminescence. With reference to Fig. 16-2a

we note that the excited center might also return to the ground state by
means of a radiationless transition, viz., via the route A' A"G"G. Such a
model has been suggested by Mott and Gurney to explain the observed
decrease in the luminescence efficiency of phosphors at high temperatures. 5
When P, represents the probability per second for an excited center to
return to the ground state with photon emission, and Ph represents the
probability for energy dissipation in the form of heat, the luminescence
efficiency 1] may be defined as ) nil
(16-1)
Since it seems reasonable to assume that Pc is nearly temperature-
independent, Pit must be mainly responsible for the temperature effect.
For a model such as in Fig. 16-2a the probability Ph is determined by
the probability to find the excited state in a vibrational level corresponding
to A" or higher; one may then write Ph = vexp(-€/kT) where € is the
energy difference between A" and A', and v is a frequency. Thus for this
model Ph increases as T increases and the efficiency decreases. A detailed
account of the temperature-dependence of luminescence may be found in
F. A. Kroger, op. cit.

16-3. Decay mechanisms

One of the aims of studies of luminescent materials is the identification

of the luminescence centers and their energy levels. A good deal of
information for this purpose can be obtained from the decay characteristics,
and it is therefore useful to consider some simple decay mechanisms for
further reference.

Temperature-independent exponential decay. A model of luminescence

centers exhibiting a tempe.ature-independent exponential decay of the
, F. Seitz, Trails. Faraday Soc., 35, 74 (1939) .
.; N. F. Mott and R. W. Gurney, Electronic Processes ill IOllic Crystals, 2d ed.,
Oxford, New York, 1948, p. 221.
Sec. 16-31 LUMINESCENCE 403
intensity of luminescence after excitation has ceased can readily be set up.
let the instant at which the exciting source is removed be denoted by
t = O. Suppose at any instant t the number of electrons in excited states
such as A in "Fig. 16-1 is given by n(t). Let us assume that the probability
for an electron in A to return to the ground state G \s 1IT per second, and
that such a transition is associated with the emission of a photon. If the
center is well screened from its environment, the average lifetime T of the
excited state is independent of temperature and of the number of other
excited centers. Hence the intensity of lumi- --:,' _,'
nescence l(t), i.e., the number of photons
emitted per unit time, is given by
E
I(t) = -(dnldt) = nIT (16-2)

This leads to n(t) = no exp (-tIT) and to

(16-3)

where 10 is the intensity at t = 0. If the transition

___JL-_---''----_G
from A to G is associated with dipole radiation,
T'_' 10- second.
8 \
In some cases, e.g., in ammorlium uranyl Fig. 16-3. Schematic re-
presentation of a center
phosphate and in uranyl nitrate, T may be of the with a metastable level M.
order of milliseconds; one then presumably deals
with quadrupole or higher-order radiation. 6.~,,~ '"
"

(ii) Temperature-dependent exponential decay. In certain phosphors,

e.g., in the thallium-activated alkali halides, one observes exponential
decays of the form (16-3) but with T of the order of several minutes;
furthermore. T decreases exponentially with ,increasing temperature. A
model of a luminescence center which exhibits such properties involves
the existence of a "metastable" state, as illustrated schematicaIfy in Fig.
16-3. The physical nature of such states will be further explained in the
next section. Suppose that the excitation act involves a transition of an
electron from G to A and that from A it may either return to G with
emission of a photon or it may fall into the metastable state M. We shall
assume that the direct transition from M to G is forbidden. When the
exciting source is removed at the instant t = 0, a certain number of
electrons no will reside in the metastable M levels. These electrons can
presumably return to the ground state only via level A. If the energy
difference between M and A is equal to E, the probability per unit time,
for an electron in M to be excited into A will be given by an expression
of the type
(16-4)
OJ J. T. Randall and M, H. F. Wilkins, Proc. Roy. Soc. (Londoll), AI84, 379 (1945).
404 LUMlNESCENCE [Chap. 16

"
where l/To represents a frequency. Let us assume that once an electron
has arrived in a level such as A, the probability of returning to the ground
state G with emission of a photon is much larger than the probability of
falling back into M. Under these circumstances the intensity of the
luminescence at any instant is simply determined by the rate at which
transitions from M to A take place. Hence (16-2) and (16-3) are still valid.
but since T depends on T in accordance with (16-4), one obtains

(16-5)

1f the temperature is low, the intensity will be low; at high temperatures

the electrons in M levels may be "boiled off" at a high rate.

(iii) Power-law decay. The simplest model leading to a power-law

decay is the following: suppose that upon excitation of a particular type
of luminescence center the electron is released into the conduction band.
Let us further assume that the emission of a photon requires the recombina-
tion of a free electron and an empty center. If there are n free electrons
and n empty centers, the intensity would be given by an expression of
the type
let) = -(dnfdt) = rxn2 (16-6)

Such a process is called bimolecular, in contrast with a monomolecular

process described by an equation of type (16-1). From (16-6) one finds

net) = no/(noa.t + I) and let) = rwM(noa.t + 1)2 ( 16-7)

For large values of t, the intensity decays as t- 2 • Several variations of

this mechanism may be found in the literature involving trapping of the
released electrons. It is evident that the same equations hold if holes are
released in the valence band. Other power-law decays may be obtained
by superposition of processes of type (ii). For example, let the metastable
levels M in (ii) be distributed in energy such that after the excitation is
removed the number of occupied M levels with activation energies in the
range dE is given by no(E) dE. One then obtains for the intensity of the
luminescence instead of (16-5),

(16-8)

If one now assumes that TO is essentially independent of E and that no(E)

is given by an exponential distribution C exp (-(JE), it is shown In
Problem 16-11 that for large t,

l(t) = const./t(f3kT+ 1) (16-9)

Sec. 16-3] LUMINESCENCE 405
Thus power-law decay does not exclude the occurrence of exponential
decay of individual components. <ir

Thermoluminescence and glow curves. Let us again consider lumi-

nescence centers involving a metastable state M as discussed under (ii)
above. For simplicity we shall assume a single level M of an activation
energy E bel.ow level A in Fig. 16-3. Suppose that the centers are excited at
a low temperature To such that the rate of decay at To is very small. Let
the crystal now be warmed up at a uniform rate dT/dt = O. Qualitatively
one expects the following behavior of the intensity of the luminescence as
function of time. As long as the temperature is low such that kT E, <
the intensity will remain low; when kT ~ E, the intensity should become
high, and finally it should drop as a result of the depletion of the M levels.
Thus I(t) is expected to have a bell shape in the vicinity of kT ~ E. If
there are several discrete M levels of different E values, one will presumably
obtain a superposition of such curves. The emission of light resulting
from heating after excitation is referred to as thermoluminescence. A
curve of I versus t resulting from a uniform rate of heating is called a glow
curve; in studies of luminescence such glow curves are often used, since
they provide information about the energy of the metastable levels
involved as well as about the occupation of such levels at t = O.
For centers with a single metast';lble level M located in the energy-level
scheme of Fig. 16-3 below A by an amount E, the glow curve is governed
by the following equations:
1= -(dn/dt) = (n/To)e- E /H '

Since dt = dT/O, this leads to

(n) =
log -
no
- -I (1' e- E /k7 ' dT
OTO' To
(16- 10)

Since the temperature To has been chosen such that kTo <{ E, the lower
limit of integration may be replaced by zero. One thus obtains

1= (n o/To)e- E/k1' exp [-(I/OTo) f.T e- E/k1' dT] (16-11)

,0

where we have assumed throughout that E and TO are independent of T.

For further details we refer to Randall and Wilkins, 6 and to Garlick and
Gibson. 7 It can be shown that the temperature at which maximum
emission occurs is approximately proportional to the energy E. Also, the
area under the curve is a measure for the number of electrons occupying
the metastable levels at t = O. An example of an experimental glow curve
may be found in Fig. 16-5.
G. F. J. Garlick and A. F. Gibson, P,·OC. Phys. Soc. (London), A60, 574 (1948).

..
"
406 LUMINESCENCE [Chap. 16

164. Thallium-activated alkali halides

When "pure" alkali halides are irradiated with X-rays one observes in
the dark a faint luminescence. The decay of the phosphorescence may be
followed with sensitive equipment for several hours and has been studied
by a number of investigators. 8 The interpretation of these experiments is
somewhat difficult in view of the possible role played by small amounts
of unknown impurities. On the other hand, alkali halides activated with
thallium freqm:ntly exhibit high efficiencies for luminescence; studies of
these materials have provided a fairly detailed uQ.derstanding of their
luminescent properties. Although it
is impossible to enter into a detailed
5
discussion of this subject here, some
's 4 of the most important features may
E3 be mentioned, in particular those of
::.: KCI :TI (we shall adopt this notation
t 2 to indicate the host crystal and the
activator).
1800 2000 2200 2400 2800
_;\ The absorption spectra. The ab-
sorption spectra of the alkali halides
Fig. 16-4. Optical absorption spectrum
of KCl containing 2 x 10- 3 atomic
without additives have been dis-
percent Tl+. [After P. D. Johnson and cussed in Chapter IS. When a small
F. E. Williams, ref. 14] amount of thallous halide is added
to the melt of an alkali halide, mixed
crystals can be obtained with the usual growing techniques. Since the Tl+
ion is fairly large (its radius is ,_,1.5 A as compared with 1.3 A for K+,
for example), it seems reasonable to expect that the TI+ ions occupy
positions normally occupied by the alkali ions rather than interstitial
positions. Measurements of tht lattice constant of these mixed crystals by
X-ray diffraction methods seem to indicate that this is indeed the case. 9
The incorporation of the TI+ ions leads to new absorption bands, as
ill ustrated in Fig. 16-4 for KCI :TI? the Tl+ ions being present in an atomic
concentration of2 X 10-3 per cent. Other thallium activated al~ali halides
give similar spectra, i.e., they all show two strong peaks indicated by A
and C in Fig. 16-4 and a weak one, B. The rising part of the absorption
curve at the extreme left of Fig. 16-4 marks the onset of the first character-
istic absorption band of KCI. The positions of the peaks are roughly the
• M. L. Katz, Phys. Z. Sov.)elunioll, 12, 273 (1937); H. N. Bose, Indiall J. Phys.,
29,29 (1947); C. A. Boyd, J. Chern. Phys.,17, 1221 (1949); A. H. Morrish and A. J.
Dekker, Phys. Rev., 80,1030 (1950); G. W. Williams. S. R. Usiskin, and A. J. Dekker,
Php·. Rev., 92,1398 (1953).
'" O. Stasiw and E. Saur, Verhandl. deuf. physik. Ge.1 , 19,4(1938).
Sec. 16-4] LUMINESCENCE 407
same in all alkali halide host crystals, the maximum shift being I ev.l0
For KCI :TI the bands measured at r<fom temperature occur at the
following energies and wavelengths.
.... A (-. 'c
£(ev) ........ . 4.9 5.9 6.3
A(A) ........ . 2470 2060 1960
Transition .. . 150 ->- 3Pl IS" - .. IP 1

The transitions associated with A and C have also been indicated. It is of

interest to note that similar bands are observed in solutions containing
Tl+ ions as well as in the thallous halides. This indicates that the transitions
occur in the TI+ ions and that the
ions are fairly well screened from
their surroundings in this respect.
Seitz was the first to attempt an I
interpretation of the luminescent
properties of these materials on the
t ).

basis of electronic transitions taking

place within the TI+ ions_11 More
recently, Williams et al. have con- 100 200
tributed a great deal to the under~ -T('k)
standing of many details of this Fig. 16-5. Thermoluminescence curve
process. 12 From a computation of of KCI containing 0.05 atomic percent
the radial charge density of the free TI+. [After Johnson and Williams,
TI+ ion in the ground state ISO and ref. 14]
in the excited state 3Pl' Williams
found that the outer electron shell is quite localized in both cases; this
indicates that even in the excited state the ionic picture may be a good
approximationP According to calculations by Johnson and Williams, the
ground state ISO of the TI+ ion in KCl lies approximately at the top of
the filled band. 14 Since the bottom of the conduction band in KCl lies
approximately 9.4 ev above the top of the valence band, the excited states
3p 1 and lp 1 lie several ev below the conduction band, i.e., the excited
electron is strongly bound to the activator atom.

Emission spectra. The two principal emission bands of KCI :TI center
around 3050 A and 4750 A. The former has been identified with the
transition 3P 1 --+ ISO; the 4750 emission is due to IP 1 --+ ISO' An example
of a glow curve obtained by Johnson and Williams is given in Fig. 16-5. 14
10For a summary of data, see, for example, G. F. J. Gallick, op. cit., p. 50.
11F. Seitz, J. Chern. Phys., 6, 150 (1938). .
12 For a brief review and references to this work see F. E. Williams, "Solid State

Luminescence," Advances in Electronics, 5,137 (1953).

13 F. E. Williams, J. Chern. Phys., 19,457 (1951):

If P. D. Johnson and F. E. Williams, J. Chern. Phys., 21, 125 (1953). 'J£, . ,

408 LUMINESCENCE [Chap. 16

From the two peaks they conclude the existence bf two metastable levels
with activation energies of 0.35 ev and 0.72 ev; these must probably be
ascribed to the 3Po and 3 P 2 states. From these and other detailed studies
Johnson and Williams suggest the energy diagram as function of the radial

E
t 3

'1,'
1

-.6 -.4 -.2

_q

Fig. 16-6. Energy as function of configurational coordinate for

the ground state ('So), the emitting states (IPI and 3P I ) and the
metastable states ("P. and 3PO) of KCI:TI. The configurat~onal
coordinate q corresponds to the radial displacement of the Cl-
ions relative to the perfect KCllattice. [After Johnson and Williams,
ref. 14]

displacement of the six neighboring CI- ions represented in Fig. 16-6.

The metastable states are indicated by the dashed lines, which have been
drawn in such a way as to obtain agreement with experiment.

Concentration-dependence of the luminescence efficiency. If one defines

the luminescence efficiency 'Yj as the number of emitted photons per incident
photon absorbed by the material, one obtains experimentally for many
luminescent materials a curve for 1] versus atomic activator concentration
c which exhibits a maximum for a certain activator concentration (Fig.
16-7). For the particular case in which the excitation of the luminescence
center is achieved by the direct absorption of a photon, such as in the
Sec. 16-4] LUMINESCENCE 409
thallium-activated alkali halides, the efficiency versus concentration curve
may be interpreted on the basis of a simple modeJ.15 Suppose that an
activator atom, which has absorbed an incident photon, returns to the
ground stat~ with emission of a photon only if there is no other activator
atom within a sphere of radius R
around the central activator atom. 11
In other words, we assume that the t
activator atoms interact with each
other in such a way that if the
distance between them is ~R, they
quench each other. Thus, around a
given Tl+ ion let there be Z metallic
positions within the sphere of radius
R: if any of these Z positions is o~---------------------
occupied by another Tl+ ion, we
assume that neither of them will act Fig. 16-7. Schematic representation of
as a luminescence center. Due to the luminescence efficiency as function
the quenching effect then, 1] will of activator concentration.
be proportional to e(1 - e)Z, where
c represents the probability that a given metallic site is occupied by a Tl+
ion.. Furthermore, 1] will be proportional to the probability that a photon
absorbed by the material as a whole is actually absorbed by a Tl+ ion;
this probability is given by an expression of the type

~ejf~e + {J(I - e)J = ejfe + ({3j~)(l - e)J

where {Jj~ is the ratio of the capture cross section of a photon of given
wavelength by a lattice atom and by a TI+ ion. Evidently, the ratio {3j~
will be a function of the wavelength of the exciting radiation; it also
depends on temperature. Thus,

(16-12)
1] = e + ({3j~)(l - c)

For small concentrations of the activator, 1] increases proportionally with

c; at high concentrations, the mutual quenching takes over, leading to a
decrease in 1]. According to .Johnson and Williams, KCI :Tl satisfies
equation (16-12) quite well, with a value of Z c:::::: 70 at room temperature. I6
The maximum efficiency is obtained for a mole fraction of approximately
0.002 Tl+ ion. .' \ \ , f, .; " ,. • '

,.; For the more complicated case of excitation by electrons or X-rays, see, for
example, P. D. Johnson and F. E. Williams, J. Chern. Phys., 18, 1477 (1950).
,. P. D. Johnson and F. E. Williams, J. Chern. Phys., 18, 1477 (1950).
.,'.,
410 LUMINESCENCE [Chap. 16

16-5. The sulfide phosphors

Because of their practical importance, the zinc sulfide and cadmium

sulfide phosphors have received a good deal of attention. Although
several models of the luminescence centers in these materials have been
proposed in the past, it is only since the last few years that a coherent
picture has been developed; this is due in particular to the researches of
Kroger and Klasens and their collaborators_!7 We shall see below that
the physical chemistry of these materials plays an important role in the
interpretation of the luminescence.
The sulfide phosphors exhibit a number of properties which distinguish
them from other luminescent materials. In most luminescent materials
properties such as the emission spectrum and the decay are determined
mainly by the activator atoms. We have seen an example of this in the
thallium-activated alkali halides. In the sulfide phosphors, however, these
properties seem to be associated more with the lattice itself than with the
activators. For example, when in zinc sulfide activated with Ag, Au, or
Cu, the zinc atoms are gradually replaced by cadmium, the position of
the emission bands gradually shifts to longer wavelengths in approximately
the same manner as the forbidden gap between the valence band and the
conduction band. Furthermore, the position of the emission peaks in ZnS
activated with Ag, Cu, or Au vary.only between about 4000 and 5000 A.
Incidentally, since the gap width in ZnS associated with optical transitions
is 2.9 ev, it follows that the wavelength of the emission lies very close to
the long-wavelength absorption edge. One speaks in this case of "edge
emission." Such edge emissions are also observed in ZnO and CdS; the
ultraviolet emissions from Al z0 3 and certain silicates are probably also
of this type. 18 The excited state from which emission occurs by return to
the ground state lies presumably close to the bottom of the conduction
band. This is confirmed by measurements on the luminescence efficiency
as function of activator concentration; it seems that the efficiency can be
represented by a formula of type (16-12) with Z c::::' 4000, indicating a
large spatial extension of the excited states. 19

The principle of charge compensation; coactirators. Zinc sulfide is

usually obtained by precipitation from a solution of a zinc salt with H 2 S
or (NH4 hS. The actual phosphor is then prepared by firing the mixture
of components at sufficiently high temperatures so that diffusion of the
activators and recrystallization of the material may take place. To obtain
" For recent re~iews and references see H. A. Klasens, J. Electrochem. Soc., 100,
72 (1953) and F. A. Kroger, Proc. IRE, December 1955 (solid state issue), p. 1941;
Brit. J. Appl. Pllys., Supplement 4, 1954, p. 58.
18 See, for example, F. A. Kroger, op. cit., p. 49.

19 F. E. Williams, Advances in Electronics, 5, 153 (1953).

Sec. 16-5] LUMINESCENCE 411

a reasonable rate of recrystallization, one requires under normal circum-

stances temperatures of the order of 1200°(;. However, if one adds a flux.
temperatures of, say, 800°C may be sufficient, and for practical reasons
this is usualI)' done. For example, for activation of ZnS with monovalent
metals such as Cu, Ag, Au, salts like NaCI or CaCI 2 are found to be
suitable fluxes. It seems that the important role played by the flux material
in the preparation of sulfide phosphors was never fully realized until some
years ago. In fact, Kroger and collaborators have shown that the
incorporation of activators such as Ag, Cu, Au, Li, Na in zinc sulfide is
governed by the so-called principle of charge compensation, which will
now be explained. 20
First consider what may occur when zinc sulfide is fired with another
divalent sulfide, say MnS. Since the valences of the metal atoms are the
same and since their radii do not differ too much (Mn2+ is approximately
10 per cent larger than Zn2+), one may expect a substitutional mixed
crystal to be formed in which Mn2+ ions have replaced Zn2+ ions. Consider
now, however, a solid solution of ZnS and Ag 2 S in which Ag+ ions occupy
positions normally occupied by Zn2+ ions. Tn order to conserve charge,
the crystal must contain one sulfur vacancy for each two silver ions
incorporated in the lattice. Since the creation of a vacancy requires a good
deal of energy, the amount of silver incorporated in the lattice will be
strongly limited. Similarly, a mixed crystal of ZnS and ZnCI 2 , in which
Cl- ions occupy lattice sites normally occupied by S2- ions, must contain
positive ion vacancies. The formation of vacancies may be avoided,
however, ifin the case of ZnS :Ag a monovalent negative ion is incorporated
for each Ag+ ion. For example,

and no vacancies are required. One speaks here of charge compensation.

The lack of positive charge associated with the Ag-;o ions is compensated
by the lack of negative charge on the Cl- ions. Since no vacancies 'have
to be formed, this explains why a flux such as NaCI is so effective in
producing good phosphors of ZnS activated with monovalent metals.
The chlorine ions presumably enhance the solubility of the monovalent
metallic activator ions, resulting in a good phosphor. Similar results are
obtained with bromides as a flux. The Cl- or Br- ions are referred to as
coactivators. From the principle of charge compensation it follows that
trivalent metal ions such as AI3+ and Ga3+ should also he suitable co-
activators for monovalent metal activators. This is indeed the case; the
lack of positive charge is then compensated by an excess 'of positive
charge. 20
20 F. A. Kroger and J. Dikhoff, Physica, 16, 297 (1950); F. A. Kroger and J. E.

Hellingman, J. Electrochem. Soc., 93,156 (1948); 95,68 (1949).

412 LUMJNESCENCE \ [Chap. 16
!
The nature of the luminescence centers in impurity-actiwted sulfide
phosphors. As mentioned above, the spectrum of the luminescence
depends only slightly on the nature of the activator ions. This indicates
that the activator ions themselves are probably not the luminescence
centers, but that they disturb the host lattice in the immediate vicinity
in such a way that levels for a luminescence
center are created. Furthermore, the spec-
trum seems in many cases independent of
the coactivator ion; this indicates that the
T activator and coactivator ions are relatively
2 far apart. Since the activator and coactivator
ions attract each other (the former has
an effective negative charge, the latter an
effective positive charge), the pair presum-
ably dissociates at the firing temperature
and this situation may remain frozen in to
a large extent upon cooling. In some cases,
Fig. 16-8. Schematic represen- however, there seems to be a partial asso-
tation of the electronic levels ciation between activator and coactivator
in a zinc sulfide phosphor; ions. In any case, the facts given above lead
see text. one to suspect that the charge of the activator
ions is more essential than their chemical
species. One thus arrives at a model which is closely related to that em-
ployed in the discussion of the influence of lattice defects on the electronic
levels in alkali halides (see Sec. 15-5). Consider, for example, a sulfur
ion neighboring a monovalent metal ion such as Ag+. Since the electrons
of the S2- ion are not so strongly bound as when the Ag+ were replaced
by a Zn 2+ ion, localized electron levels will occur which lie somewhat
above the valence band (see level C in Fig. 16-8). This picture is supported
by the observation that after activation of ZnS, a new absorption band
appears on the long-wavelength side of the fundamental absorption. 21
This absorption seems to give rise to photoconductivity, indicating
that any excited states lie either just inside or very close to the conduction
band. The excitation of C in Fig. 16-8 by direct absorption is indicated
by arrow (1); emission cor.responds to (2). The center may also be excited
by capture of a hole from the valence band (3).
From the hyperbolic decay of the phosphorescence and from the
thermoluminescence of the sulfide phosphors, one must conclude that
the excited electrons may become trapped in the crystals. Since coacti-
vator ions such as A13-t or Cl- have an effective positive charge, these
may provide at least one type of electron trap; such traps have been
represented by the level T in Fig. 16-8.
21 F. A. Kroger and J. E. Hellingman, J. Electrochem. Soc., 93, 156 (1948); 95,68

(1949); J. H. Gisolf, W. de Groot, and F. A. Kroger, Physica, 8, 805 (1941).

i ,
Sec. 16-5] LUMINESCENCE 413
The presence of vacancies, even though they occur in relatively small
concentrations, also leads to localized-levels in the normally forbidden
energy range. The production of positive ion vacancies in ZnS may be
promoted by the ihcorporation of atoms such as aluminum or chlorine.
For example. the blue emission band characteristic of self-activated
ZnS is probably due to Zn2+ vacancies; it is observed particularly in
ZnS phosphors prepared with the addition of ZnCl z or AI 2Sa. For a long
time this emission was believed to be associated with interstitial zinc
atoms. The reader is referred to the literature for a discussion of the
present situation on this topic. 22

16-6. Electroluminescence

The direct transformation of electrical energy into light is attractive

from the practical standpoint and has a variety of applications. Since
the last few years the subject has therefore become of much wider than
purely academic interest .. Although the theoretical interpretation of the
details of electroluminescence is still in a state of flow, there are some
basic ideas which seem generally accepted. The term electro luminescence
covers a variety of phenomena which can occur when a luminescent
material is subjected to an electric field and some of these will be discussed
below.

The Gudden-Poh( effect. In 1920 Gudden and Pohl discovered that

a momentary flash of light is emitted when an electric field is applied to a
zinc sulfide phosphor during the after glow (phosphorescence).23 When
a d-c field is applied, a flash is observed; the same is true when the field
is switched off. This indicates that after application of the field, an
internal field is set up, due to polarization, which rapidly counteracts
the external field. When the latter is removed, the polarization field
itself produces a flash and decays rapidly to zero. The momentary flash
may also be observed when the field is applied during excitation with
photons. Luminescence associated with the application of a field during
or after photo-excitation is referred to as electro-photoluminescence.
The Gudden-Pohl effect is evidently due to the emptying of electron
traps. This may occur as a result of tunneling of electrons from the traps
into the conduction band or it may be due to ionization of the filled traps
by free electrons accelerated by the field in the conduction band. In any
event, the effect is somewhat analogous to thermoluminescence, the
O. See, for example, R. H. Bube, Phys. Rev., 80, 655 (1950); J. Chern. Phys., 20, 708
(1952); R. H. Rube and S. Larach, J. Chern. Phys., 21, 5 (1953); F. A. Kroger and H.
J. Vink. J. Chern. Phys., 22, 250 (1954); F. A. Kroger, Brit. J. Appl. Phys., Supplement 4,
58 (1954) .
•• B. Gudden and R. W. Pohl, Z. Physik, 2, 192 (1920).
414 LUMINESCENCE [Chap. 16
action of the field taking the place of the action of thermal vibrations.
For further details of the present situation we refer the reader to the
literature. 24

The Destriau effect. The emission· of light by a phosphor resulting

solely from the action of an electric field applied to a suspension of lumines-
cent particles in an insulator was first discovered by Destriau. 25 In this
case one may speak of intrinsic electro luminescence, since the effect does
not involve previous photo-excitation, nor the injection of charge carriers
from an external source. An electroluminescent cell is usually made in
the form of a parallel-plate capacitor of which at least one of the con-
ducting plates is transparent. In order to transfer power to the dielectric
consisting of the luminescent powder embedded in an insulator, alter-
nating voltages or pulses must be used. For sinusoidal voltages the average
brightness B increases rapidly with increasing amplitude. Several empirical
formulas have been introduced to describe the observed brightness versus
voltage curves, for example,
B = aV n exp (-h/V) (I 6-13)
where a, h, and n are constants. The curve shown in Fig. 16-9 has been
obtained by Roberts 26 for a copper-activated zinc sulfoselenide phosphor
embedded as a powder in a variety of dielectric materials. If one assumes
that the luminescent particles are spheres, one can show that the local
field £2 in the phosphor is given by the expression
3€lE
E2 = -----=----- (16-14)
2€1 + €2 - 11(£2 - £1)

where E is the applied field, £1 is the dielectric constant of the phosphor,

£2 is the dielectric constant of the matrix, and f~ is the fraction of the
volume occupied by the phosphor particles. By using various matrices
of widely different dielectric constants, Roberts showed that the observed
brightness is a function only of the local field £2' The brightness varies
only slightly with temperature, indicating that thermal excitation is of
little importance in the mechanism. Electroluminescence becomes
visible for fields of about 3000 volts per cm; for high brightness one
requires fields approximately ten times as strong. A possible explanation
of intrinsic electro luminescence presumably involves the emptying of
traps by the field, subsequent acceleration of electrons in the conduction
band, and excitation of centers by these electrons .
•• For a review and many references to electroluminescence, see G. Destriau and
H. F. lvey, Proc. IRE, December 1955 (solid-state issue), p. 1911. In the same issue
applications are discussed.
25 G. Destriau, J. chim. phys .. 33, 620 (1936); 34, 117 (1937).

2. S. Roberts, J. Opt. Soc. Amer., 42, 850 (1952).

Sec. 16-6] LUMINESCENCE 415
Piper and Williams have studied_ the electroluminescence of single
crystals of ZnS : Cu, clamped between two electrodes. 27 . From the non-
ohmic behavior of this system they conclude that there exists a Schottky
barrier "'at the crystal-metal interface. With an applied external field,
I the local field in the barrier may well be of the order of 10 6-107 volts per cm.
Although such fields are appreciably larger
than the breakdown field of insulators
103
('"'-'10 5 volts per cm), breakdown does
not occur because the Schottky layer is
thin ('"'-'10- 5 cm). When electrons in the
Schottky layer are accelerated by the B 10 2
field, they may produce luminescence
by impact with luminescence centers. t
Carrier-injection luminescence. When 10
a p-n junction of germanium or silicon
is biased in the forward direction, electrons
from the n-region penetrate into the
p-region and holes flow from p to n.
The minority carriers so injected will o
-+ E2 (volts/micron)
recombine with their counterparts and
one might expect emission of photons.
This has indeed been observed by Haynes Fig. 16-9. The brightness in
and Briggs. 28 The emitted radiation has a microlarnberts as function of the
local field strength for zinc sulfo-
wavelength which agrees well with the selenide. The curve fits experi-
optical absorption associated with band- mental data for the powdered
to-band transitions. For Ge and Si the phosphor in polystyrene (E =
radiation lies in the infrared (,1. = 1.77 fl 2.56), lUcile (e = 3.59) and poly-
and 1.12 fl, respectively). The emission is vinyl chloride (E = 7.05). [After
Roberts, ref. 26]
localized in the junction region.

REFERENCES
G. F. 1. Garlick, Luminescent Materials, Oxford, New York, 1949.
F. A. Kroger, Some Aspects of the Luminescence of Solids, Elsevier,
New York, 1948.
H. W. Leverenz, Luminescence of Solids, Wiley, New York, 1950.
P. Pringsheim and M. Vogel, Luminescence of LiqUids and Solids, Inter-
science, New York, 1943.
F. E. Williams, "Solid State Luminescence," Advances in Electronics.
Academic Press, New York, 1953, Vol. 5, p. 137.
27 W. W. Piper and F. E. Williams, Phys. Rev., 87,151 (1952).
2. J. R. Haynes and H. B. Briggs, Phys. Rev., 86, 647 (1952).
",
'7
416 LUMINESCENCE [Chap. 16
Solid Luminescent Materials, Symposium held at Cornell University
(1946). Wiley. New York, 1948.

PROBLEMS

16-1. Suppose an X-ray tube is operated at 60 kv and 10 mao Assume

that energywise 2 per cent of the electric energy is transformed into X-rays.
The luminescence efficiency of a good phosphor under X-ray excitation is
,_,10 per cent. Estimate the number of photons emitted by the phosphor
for an excitation energy ,....,5 ev; take into account a reasonable geometry
for the coupling between the X-ray source and the phosphor.
16-2. With the most intense light sources one can obtain a beam of
photons with energies ~ 3 ev corresponding to ,..._.1019 per cm2 per second
incident on a phosphor. Suppose the phosphor contains lOIS luminescence
centers per cm3 . Assuming that the host lattice does not absorb the in-
cident photons, estimate the penetration depth of the photons and from
it the average number of primary photons available per activator per
second. Does this explain why saturation effects have not been observed
for photoluminescence? Assume a lifetime of an excited center of 100s
second.
16-3. Suppose a cathode-ray tube operating at 25 kv delivers 2.l()4
watts per cm 2 to a phosphor screen: Calculate the penetration depth of
the electrons from the simplified Bethe formula [Ann. Physik, 5, 325
(1930)], x = £2j47TNZe4, where E is the energy of the incid~nt electrons,
N is the number of atoms per unit volume, and Z is the average number
of electrons per atom. Assume further that the primary electrons expend
approximately 30 ev per excitation of a luminescence center (this includes
losses of several kinds). Estimate the number of excitations available per
center per second if the density of the latter is 1018 per cm3 • Show that this
may lead to saturation effects, in contrast with the photoluminescence
in the previous problem.
]6-4. It was noted in this chapter that the concentration-dependence
of the luminescence of KCl :Tl can be described by formula (16-12) with
.Z ':::' 70. What does this imply for the lower limit of the distance between
two TI+ ions required to prevent quenching? .
16-5. Suppose that the decay of a luminescent material may be
described by a bimolecular mechanism of the type dnjdt = -rxn 2 • If
at t = 0 the exciting source is switched off and the luminescent intensity
is then 10 , show that the time required for the intensity to reach half its
initial intensity is given by (Vl - I)j(/orx)1I2. (Note thatt l / 2 depends on 10)'
For the same phosphor discuss the build-up of the intensity ofluminescence
under constant illumination. .~'! .~ H
Chap. 16] LUMINESCENCE 417
16-6. Give a proof of expression (16-14) for the local field in spherical
particles of a luminescent material embedded in a homogeneous dielectric.
16-7. FQr spherical particles of dielectric constant El and resistivity
p embedded'in an insulator, show that the field in the particles leads the
field in the insulator by an angle rp such that tan rp = 2/EIPV, where v is
the frequency of the applied field. r ,
16-8. Discuss the properties of scintillation counters. These were
first described by H. Kallmann, Natur and Technik, July 1947; for a
review and references to the literature see G. A. Morton, Advances in
Electronics, 4, 69 (1952).
16-9. Discuss a model for the killer action of certain impurities,
such as Ni in ZnS : Cu [see M. Schoen, Naturwiss., 31, 203 (1943);
38, 235 (1951); W. Hoogenstraaten and H. A. Klasens, J. Electrochem.
Soc., 100, 366 (1953)]. ~-' (

16-10. Discuss the topic of cathodoluminescence (see, for example,

G. F. J. Garlick, Proc .. IRE, December 1955, p. 1907).
16-11. Give a derivation of expression (16-9).
·;:(1
Chapter 17 .. ", h·

SECONDARY ELECTRON EMISSION

When the surface of a solid is bombarded with charged particles

of sufficient kinetic energy, emission of electrons by the solid may be
observed. This phenomenon of secondary electron emission was discovered
by Austin and Starke in 1902 in a study of the reflection of electrons
by metals; they observed that under certain circumstances more electrons
were emitted than were incident, indicating that the bombarding primary
electrons liberate electrons from the solid_! Unless otherwise stated,
it will be assumed in the present chapter that the bombarding particles
are electrons. However, emission of electrons may also result from
bombardment with heavy charged particles such as ions. 2 The theory of
secondary emission under electron bombardment is completely different
from that under ion bombardment. The reason is that in the former case
the bombarding particles penetrate into the solid, thus producing a bulk
effect; in the latter case, however, one deals essentially with a surface
effect. For a survey of the field of secondary emission we refer to the
bibliography at the end of this chapter. Some of the basic principles
involved in the secondary emission process will now be discussed.

17-1. Secondary electrons t

When a beam of primary electrons strikes the surface of a solid,
a certain fraction is elastically reflected and the remainder penetrates
into the solid. The primaries that enter the solid will lose energy by
exciting lattice electrons into higher energy levels. The latter may then
move toward the surface and a certain fraction will escape from the solid
as secondaries. It is also possible that a primary electron, which has
lost part of its energy inside the solid, returns to and escapes from the
surface as a result of Rutherford scattering; such electrons are called
inelastically reflected primaries. Although it is common to employ the
term "secondary electrons" with reference to all electrons emitted by the
surface and collected by a positive collector electrode, the above remarks
, L Austin and H. Starke, Ann. Physik, 9, 271 (1902).
2 An extensive study of this topic has been made by H. D. Hagstrum, Phys. Rev.,
89,244 (1953); 91,543 (1953). See also J. H. Parker, Jr., Phys. Rec., 93. 1148 (1954)
and L J. Varnerin, Jr., Phys. Rev., 9J. 859 (1953).
418
Sec. 17-IJ SECONDARY ELECTRON EMISSION 419

show that one may distinguish between ~hree categories of electrons

leaving the surface:
(a) Elastically reflected primaries
\ (b) Inelastically reflected primaries
(c) "True" secondaries
I
This may be illustrated by considering as an example the energy distribu-
tion of the electrons emitted by silver upon bombardment with primary
electrons of 155 ev, as shown in Fig. 17-1 according to Rudberg. 3 (Such

o 50 100 150
-E(ev)

Fig. 17-1. The energy distribution of secondary electrons emitted

by silver. [After Rudberg, ref. 3]

energy distributions may be determined either with a magnetic analyzer

or with a retardihg potential applied to a spherical collector with the
target at the center.) The presence of the elastically reflected primaries is
evident from the sharp peak (a) at the primary energy. Close to the peak
(a) are a few small maxima (b), the positions of which relative to (a) are
characteristic of the material and independent of the primary energy.
These maxima evidently correspond to inelastically reflected primaries
which have lost discrete amounts of energy before escaping from the
surface. The majority of the emitted electrons have relatively low energies,
corresponding to the broad peak (c). The maximum of this part of the
curve lies for most solids in the vicinity of a few ev. It is important to note
that the energy distribution of these slow electrons is practically indepen-
dent of the primary energy. One therefore speaks of these slow electrons
as true secondaries. On the other ha-nd, it is impossible to draw a sharp
distinction between true secondaries and inelastically reft.ected electrons;
in fact, from Fig. 17-1 it is evident that the flat region of the curve consists
3 E. Rudberg. Proc. Roy. Soc. (London). A127, III (1930): Phys. Rev., 4, 764 (1934).
420 SECONDARY ELECTRON EMISSION [Chap. 17

of a mixture of the two categories. Somewhat arbitrarily, the term "true

secondaries" usually refers to all those electrons with an energy below
about 50 ev. \I -.
For primary energies below about 10 ev, no' true secondaries are
produced; i.e., 10 ev is roughly the threshold value for the secondary
emission process. A considerable
.8
fraction of the incident primaries is
I'.. elastically reflected in that case. As
..... 1'-- w the primary energy increases, the
.6
number of reflected electrons de-
w
•..fIo
..... _-
/"
...... - - creases; for a primary energy of 100
ev for example only about 10 per
"{ .4 " cent is reflected. For very high
primary energies, i.e., above say 50
' ......... kev, the fraction of elastically plus
.2 AI -
inelastically reflected primaries in-
- - Ai-
-...
creases again. To illustrate this, we
have reproduced in Fig. 17-2 results
o 100 200 300 obtained b)' Trump and van de Graatf
-Epo (kev) for tungsten and aluminum.· The full
curves represent the ratio of the total
Fig. 17-2. Number of emitted electrons
per incident primary versus primary
secondary current and primary current
energy for tungsten and aluminum. .as function of the primary energy £,,0'
The full curves correspond to all The dashed curves refer to the case
emitted electrons; the broken curves to where only. electrons emitted with
emitted electrons with an energy energies above 800 ev are collected.
>800ev. [After Trump and van de
Graaf, ref. 4J
We note that the dashed curve
increases with increasing £})o.

17-2. Experimental yield curves I

The secondary yield () is commonly defined as the number of emitted

electrons per incident primary electron. According to this definition,
the yield includes all three categories of emitted electrons discussed in
the preceding section. If the experiment is set up in such a manner that
the velocity distribution of the emitted electrons can be measured, a
rough correction for the elastically and inelastica11y reflected primaries
can be made.
One of the most important relationships in secondary emission, both
from the experimental and theoretical point of view, is that between the
secondary yield () and the energy £ pO of the incident primaries. Examples
of such yield curves are given in Figs. 17-3, 17-4, and 17-5 for magnesium
• J. G. Trump and R. J. van de Graalf, J. Appl. Phys., 18,327 (1947).
Sec. 17-2] SECONDARY ELECTRON EMISSION 421

oxide, 5 germanium, 6 and platinum. 7 Apart Jrom quantitative differences

the yield curves for all materials exhibit the same general shape. For
low primary ,energies the yield increases, then goes through a maximum

'" 8

7 .........
6 ,£- ~

"-
'\.
~

t
5

4
/
"'-"-
"
~ ~o'c
I ~ i'--- r--
---r-r--
3

2 I
1
II

o 1.0 2.0 3.0 4.0 5.0

-+ Epo (kev)

Fig. 17-3. Secondary yield '0 versus primary energy (kev) for a'
single crystal of MgO. The upper curve refers to room temperature,
the lower one to 740 C (see Sec. 17-9). [After Johnson and McKay.
ref. 5]

1.2

1.0
r; ~
1
h

t
.8
V
II
"~ ~ ~20'C
.6
~t--
t· .4
I 'c
.2
o 1.0 2.0 3.0 4.0 5.0
-Epo (kev)

Fig. 17-4. Secondary yield t5 versus primary energy in kev for a

germanium single crystal. The upper curve refers to room tem-
perature, the lower one to 525°C. [After Johnson and McKay, ref. 6]

value bm corresponding to a characteristic energy Epm of the primaries,

and finally decreases for high primary energies. In Table 17-1 we give
values for bm and Epln for some metals, semiconductors, and insulators by
way of illustration. In all cases the primaries were incident perpendicular
:, J. B. Johnson and K. G. McKay, Phys. Rev., 91, 582 (1953).
6 J. B. Johnson and K. G. McKay, Phys. Rev., 93,668 (1954).
, P. L. Copeland, Thesis, University of Iowa, 1931.
"
",
422 SECONDARY ELECTRON EMISSlON [Chap. 17
to the surface; the same is true for the examples given in Figs. 17-3,
J 7-4, J 7-5. We note that the maximum yield of metals is of the order of
unity, the largest value having been observed for platinum (l.8).7 The
intrinsic semiconductors Ge and Si also have a maximum yield of about
unity; according to Johnson and McKay, the yield of Ge is independent

2.0

1.8

1.6
v - t-- t--
r-- t--
~ 1.4
/
t 1.2 1/
1.0 I
.8 /
.6
o 400 800 1200 1600 2000
-Epo (ev)

Fig. 17-5. Secondary yield <I versus primary energy in ev for

platinum. [After Copeland, ref. 7]

of the donor or acceptor concentration up to ,-....,1019 per cm3 • 6 Insulators

generally show a yield between about 3 and 10. The maximum yield of
21 for MgO, included in Table 17-1, has been obtained for crystals cleaved
in vacuum (R. G. Lye, Phys. Rev. 99, 1647 (1955). This value is con-
siderably larger than ~m for the crystal corresponding to Fig. 1'7-3, indi-
cating that surface conditions (electron affinity!) are of great importance
for the yield of insulators.

Table 17-1. Values of the Maximum Yield and the Corresponding

Primary Energy for a Few Substances

Substances
I <1m
I
ED'" (ev)

Ag 1.5 800
AI 1.0 300
Cu 1.3 600
Fe 1.3 350
Pt 1.8 800
Ge 1.1 400
Si 1.1 250
NaCI 6 600
MgO 21, 1100
Sec. 17-3] SECONDARY ELECTRON EMISSION 423

17-3. Elementary theory of secondary emissiow, universal yield curves

In the theo.,{y of secondary emission it is convenient to distinguish

between two stages in the process. In the first stage one considers the
production of secondaries, resulting from the interaction between the
primary beam and the lattice electrons. In the second stage one is -inter-
ested in calculating the probability for the secondaries so. produced to.
escape frDm the surface. Thus, in a simplified way and withDut paying
attention to. the velDcity distributiDn Df the secDndaries, Dne may write
fDr the secDndary yield,S
b = f n(x)j(x) dx (17-1 )

Here n(x) dx rep~esents the number of secDndaries produced by one

primary at a depth between x and x +
dx belDw the surface; j(x) repre-
sents the prDbability fDr such a secDndary to. mDve tDward and escape frDm
the surface. The integral extends over the thickness of the sample,
although only a thin layer of the order of 100 A participates in the process.
To. calculate <5 the fDllowing assumptions will be made:
(a) The primaries, as they penetrate the sDlid, mDve alDng straight
lines alDng the directiDn Df incidence; this assumptiDn thus neglects
elastically and inelastically reflected primaries. .<l !

(b) The primaries are incident perpendicular to. the surface.

(c) The energy IDSS Df the primaries per unit path length is given by
WhiddingtDn's law 9
dEp(x) A
---- (17-2)

where A is a CDnstant characteristic of the material.

(d) The number ofsecDndaries produced in layer dx by a single primary
is proportional to dEp/dx, i.e., "",'
1 dEl)
n(x) = - - . - (17-3)
Ee dx
where Ee represents the average excitation energy required to produce a
secDndary.
(e) The probability fDr a secondary prDduced at a depth x to escape
from the surface is determined by an exponential absorption law,
f(x) = !(O)e-= = !(O)e-·r /.r, (17-4)

• See, for example, H. Bruining, Physics and Applications ol SecolldtJry ElectrOIl

Emission, McGraw-Hill, New York, 1954; also H. Salow, Z. tech. Phys., 21: 8 (1940);
Phys. Z., 41, 434 (1940).
• For relativistic energies, E" should be replaced by mv'j2, where III is the relativistic
mass; this must be borne in mind in interpreting the secondary yield data obtained for
high energies of the primaries, such as those of Trump and van de Graalf, Fig. 17-2.
424 SECONDARY ELECTRON EMISSION [Chap. 17
where 1(0) represents the probability of escape for a secondary produced
at or very near to the surface; x. = I/a. may be considered as the range
of the secondaries.
From (17-2) it follows that if E"o is the energy of the primaries as
they strike the surface, the primary energy as function of depth is given by
E;(x) = £;0 - 2Ax
5
1 We note that the approximate maxi-
mum depth of penetration x" of the
...~
I
'it 3
) primaries is obtained by putting
E" = 0, i.e.,
Jt
I
V (17-5)
t 2
./

1
l--""V Hence Whiddington's law leads to a
primary range which is proportional
to the square of the primary energy.
The production of secondaries as
o ,2 .4 .6 .8 1.0
function of depth is governed by
(17-3), so that by making use of(17-5),
Fig. 17-6. The function (xp - X)-1I2 A)1/2 1
as function of x/xp which determines the . n(x) = ( 2" . fEe(x" _ X)1/2 (17-6)
production of secondaries as function
of depth according to equa.tion (17-6).The function (x" - x)-1/2 versus xIx"
has been plotted in Fig. 17-6. It is
evident from (17-6) that most of the secondaries are produced at the end
of the primary path.
For the moment we shall confine our attention to showing that the
yield curve exhibits a maximum. For this purpose, let us first consider
the case of very low primary energies such that x" ~ 1/a. = x •. In that
case, the probability for escape for all secondaries produced may be taken
equal to 1(0), Hence, in accordance with (17-l) and (17-3),
." E '~---------- -
t5 = 1(0) f n(x) dx = 1(0) ~ for x" ~ X. (17-7)
fEr

Thus, for low primary energies the secondary yield should rise propor-
tionally to E pO' The other extreme case to be considered corresponds to
a primary range very large compared with the range of the secondaries.
Under these circumstances one is essentially interested in the function
n(x) for very small values of x/x", because the function I(x) in (17-1)
decreases strongly for values of x> x" = 1/a.. From Fig. 17-6 it is
evident that the production of secondaries as a function of depth may then
be considered as approximately constant over the range of x-values of
Sec. 17-3] SECONDARY ELECTRON EMISSION 425
interest. J n fact one may then employ in 3ccordance with (17-5) and
(17-6),
A
\ n(x) ~ n(O) = _._-
€,E)o
Hence, from 07-1) it follows that

(17-8)

Thus, for high primary energies, (J decreases in inverse proportion to

E"o' From the above discussion it is clear that the yield curve should
exhibit a maximum for primary energies at x" ~ x". It is of interest to
note that the conclusions 1" f~ :

(J proportional to E" for x"<{x,, I

I"
(J proportional to E)-I for x,,}>x s (
are independent of the particular mathematical form assumed for j(x),
as long as it decreases monotonically with x. This follows immediately
from (17-8), because for a given solid under given external conditions,
J fix) dx is a constant.
Unhwsal yield CUYl'es. Up to here we have considered only the extreme
regions of low and high primary energies. We shall now show that the
assumptions made above lead to the following interesting result. If one
plots (J/(J", as function of E"o/E.pln , where (J", represents the maximum
yield and E pm the corresponding primary energy, a universal curve is
obtained which should be valid for all materials. This was first pointed
out by Baroody, and can be shown in the following manner. IO Sub-
stitution of (17-4) and (17-6) into (17-1) gives for the yield,

A)l/:!. I .
. ~ j(O) J:p (xp ~ X)1/2 dx
-'X.t

b ="2
( {I 7-9)

Introducing a new variable y such that

y2 = lJ(x" - x)

expression (I 7-9) may be rewritten in the form,

2A)I/21 v=.
(J = ( -.IJ( - j(O)€-=,' (, ell" dl'
€, 0

10 E. M. Baroody, Phys. Rev., 78, 780 (1950).

426 SECONDAR Y ELECTRON EMISSION [Chap. 17

Writing ctX p = E!oct/2A = Z2, the last expression gives for the yield as
function of the primary energy.

/) = (2A) 1/2 • .!._ J(O)F(z) with F(z) = e-,2 (.z ey2 dy (17-10)
IX €. .0

The maximum yield can be obtained by putting db/dE vo equal to zero;

it is fouJ;J.d that this maximum occurs for z = 0.92, so that
2A)1/2
Evm = 0.92 ( --; (17-11)

It thus follows that the ratio b/b m may be written

tJ F(z)
om = F(O.92) =
[J 2A
1.85F Evo
IX ]
= 1.85F
[O.92E po ]
Evm ( 17-12)

This expression is independent of the constants A and IX which characterize

the solid. The result is illustrated by the full curve in Fig. 17-7. It may
be noted that for z< I, the function F(z) ~ z; this is in agreement
with the conclusion drawn previously that the yield increases proportionally
with E,)o for low primary energies. Similarly, for z ~ I, F(z) ~ 1/2z, Le.,
for high primary energies /) varies as E/-:o', again in agreement with what
has been said above.
A somewhat different universal curve has been obtained by JonkerY
In the theory given above, it was assumed that a secondary electron
produced at a distance x below the surface had a probability e-:Xx of
arriving at the. surface. Instead, Jonker employs the following model:
he assumes that the secondaries move in straight lines from their point
of origin toward the surface. Thus, if for an electron moving in a given
direction, the distance between its point of origin and (he surface, as mea-
sured along the direction of flight, is equal to I, he takes e- :xl as the pro-
bability for the electron to arrive at the surface. On the further assumption
of an isotropic distribution of the directions of flight, he is then able to
find an expression for b as function of Epo. Again, /)//)m as function of
E"o/E pm is independent of the material. The broken curve in Fig. 17-7
represents the universal curve obtained by Jonker.

17-4. Comparison of the elementary theory with experiment

From the discussion in the preceding section it is evident that the
general shape of the yield curve can be explained on the basis of some
simple assumptions. It is further of interest to note that if one plots
b/b m versus Epo/Evm for a number of different metals, one obtains indeed
a single curve which fits the metals investigated; experimental points are
11
.
J. L. H. Jonker, Philips Research Rep's., 7, 1 (1952).
Sec. 17-4] SECONDARY ELECTRON EMISSION 427

represented in Fig. 17-7 by dots. It is observed that in the low primary

energy region, Jonker's curve fits the experiments better than does
Baroody's curve. On the other hand, it must be admitted that, physically
speaking, JOllker's theory is not founded any better than the one due to
Bruining-Baroody; this will become clear from our later discussions
of the escape mechanism. ,;'
1.2...-------,.------r------,

o 1 2 3

Fig. 17-7. Universal yield curves representing %m versus £.0/£',,;

the full curve represents equation (17-12), given by Baroody (ref. 10);
the dashed line is according to Jonker, (ref. II); 'the dots represent
, measured data for metals (see ref. 10).

Both'theoretical curves show considerable deviation from the experi-

mental one for primary energies> Epm. In this connection it is interesting
to note that for magnesium oxide, which is an insulator, the yield decreases
as E;;oI, in agreement with the theoretically predicted behavior (Fig.
17_3).12 Germanium (Fig. 17-4), on the other hand, shows deviations
similar to those for metals. It has been suggested that the deviations
from the Epr.,t law for high primary energies result from the presence of
inelastically reflected primaries. The influence of such primaries on the
yield is twofold:
(i) They increase the yield simply because they are collected as
emitted electrons.
(ii) They may increase the yield because they may produce more
secondaries over a depth equal to the range of the secondaries"
than does a primary that penetrates deeply into the solid. The
reason is that their path may pass twice or more through the
same region of the solid close to the surfa,ce.
I' A. J. Dekker, Phys. Rev., 94, 1179 (1954).
428 SECONDARY ELECTRON EMISSION [Chap. 17

Neither of these effects explains the observed deviations unless one

assumes that inelastic scattering becomes more probable with increasing
values of Epo beyond Ept(l.' That this is indeed the case for primary ener-
gies of the order of many kev is evident from the experiments of Trump
and van de Graaff. 4 However, the energies involved here are only of the
order of I kev. A difficulty in this explanation arises as a result of the fact
that MgO actually follows the E;;r/ law, because it is not evident why
Rutherford scattering would not occur in this case. However, the yield
of MgO is relatively large, and if (i) were the main cause of the deviations,
one might argue that this effect would be relatively unimportant in the
case of MgO. It would clearly be of interest to obtain more experimental
information about yield curves of other insulators, extending to suffici-
ently high primary energies.
In the elementary theory, we introduced two constants to characterize
the material: the constant A appearing in the Whiddington law describing
the energy loss of the primaries, and the absorption constant rx for the
secondaries. Experimental information about A is available for high-
energy electrons. For example, Terrill found A = 4.5 X 1012 volt2
cm- 1 for electrons of 25-50 kev penetrating through gold; other materials
give values of the same order of magnitude.l3 For the moment let us
assume that these values are applicable to primaries with an energy of the
order of I kev. For a material with Epm = I kev, one then obtains,
according to (I7-11), for the absorption constant, ex ~ 106 cm- I . In
other words, this leads to a range of the secondaries of about 100
Angstroms. It should be noted that one expects A to decrease with de-
creasing E po , because slow primaries can excite only electrons from the
outer electronic shells in the atoms. This would have the effect of lowering
the value of rx.

17-5. Variation of the secondary yield with angle of incidence

A large number of experiments show that if the primary beam is

incident at an oblique angle with the surface, the yield is larger than
for perpendicular incidence. For low primary energies, however, the
effect is very small. As an example we give in Fig. 17-8 some results
obtained by Bruining for a smooth (S) surface of nickel carbide. 14 The
reason for the increase is that the secondaries are produced at smaller
depths, and in terms of the elementary theory, are not so strongly absorbed
before they reach the surface. That the effect for a rough surface would
be much less pronounced is also evident and is illustrated, by the curves
R in Fig. 17-8, referring to soot. Bruining has interpreted his data in the
following strongly simplified manner. Suppose n electrons are liberated
13H. M. Terrill, Phys. Rev., 22,161 (1922).
" H. Bruining, Physico, 3, 1046 (1936).
Sec. 17-5) SECONDAR Y ELECTRON EMISSION 429
per primary electron inside the material. Then, if x", is the mean depth
of origin and exp (-~xm) is the probability for escape, the yield for
perpendicular incidence (B = 0) is
given by'", 70·8
1.25
V \ro·8
For an angle of incidence B with the
normal, the yield should be equal to

a
1.00

.75
~V
W
~V
[/

-- ,
40· 8 .........

~
...........

Hence
In (rJ o/t5 o)
t I
~xm = I _ cos B (17-13)
.50
I 60· .Ii

He finds that ~x'" as calculated

~

I lIP'b ~ o· R

from the experimental data is nearly

.25
I
independent of B, indicating that 7
the result may have significance.
<\ssuming ~ = 1.5 X 106 cm-I one
finds xm ~ 30 A.I5 o 200 400 600
It is of interest to mention some -Epo
results obtained by Jonker.I6 We
Fig. 17-8. Secondary yield aas function
have seen in Sec. 3 of this chapter of primary energy for different angles of
that he employed a somewhat dif- incidence of the primary electrons.
ferent model to calculate the escape The S curves refer to a smooth surface
probability. In the same paper he of nickel carbide; the R curves to a
investigated the influence of the angle rough surface of soot. The angle is
measured relative to the normal. [After
of incidence on the secondary yield Bruining, ref. 14]
by simply replacing x by x cos O.
Without repeating his calculations here, he finds that

I.OIA)1/2
E1Jm cos B = ( -~- = constant

where A and ~ are the material constants introduced in Sec. 17-3: This
relationship is in very good agreement with his measurements on nickel,
nickel carbide, and lithium. Similarly, his theory permits establishment
of a relation between the maximum yield 15 m ~nd the angle of incidence,
leading to
rJ m (cos B)ItZ = constant
1. This value was found for nickel by A. Becker, Ann. Physik, 2, 249 (1929).
16 J. L. H. Jonker, Philips Research Repts., 6, 372 (1951). ,,'
430 SECONDAR Y ELECTRON EMISSION [Chap. 17
This relation is in reasonable agreement with his results for the materials
mentioned above. Finally, it is interesting that, according to his calcu-
lations, a universal yield curve is obtained by plotting b versus const.
£1)0 cos (), whereby the constant is chosen in such a manner that the
maxima of"the curves for different values of () coincide. His experiments
bear out the fact that such a universal curve for different ()'s indeed exists.
However, there is the same discrepancy between the experimental and
the theoretical curves as discussed in the preceding section. On the other
hand, it seems that Jonker has established an important experimental fact.

17-6. Baroody's theory of secondary emission for metals

Although the elementary theories provide a certain amount of insight

into the phenomenon of secondary emission, it does not allow one to
discuss many details. For example, one simply speaks about numbers of
secondaries without paying attention to their energies. Also, the ex-
ponential absorption law for secondaries actually hides a very complicated
mechanism by which the secondaries lose energy on their way to the surface.
,Baroody in employing a Fermi model for the conduction electrons
in metals, improved the situation considerably for this group ofmaterialsP
His theory shows, among other things, that the secondary yield for
metals with high work function is larger than for those of low work
function. This had been found experimentally but could not be explained
by the elementary theory. In fact, one would expect metals of high work
function to have a low yield because it is difficult for secondaries to
escape in that case. It may be noted that Kadyschewitsch used a similar
model as Baroody, but his calculations are complicated. The essential
points of Baroody's theory will now be discussed.
It is assumed that the metal is at absolute zero so that in the momentum
space all electrons lie within a sphere of radius PF about the origin;
all higher states are empty. This assumption does not restrict the appli-
cation of the results, because no temperature effect of the yield has
been detected for metals. The velocity of the primary electrons is assumed
to be very high relative to that of the conduction electrons. Consider
then, as represented in Fig. 17-9, the collision between a primary and a
conduction electron. The instant at which the distance between the two
electrons is b will be denoted by t = o. Assuming the conduction electron
to be at rest and the primary to move along a straight line, the component
of the Coulomb force between the two particles perpendicular to the
primary path is at any instant t given by

(17-16)

17 E. M. Baroody, Phys. Rev., 78, 780 (1950).

Sec. 17-6] SECONDAR Y ELECTRON EMISSION 431

where v is the velocity of the primary. The assumption of a simple

Coulomb force in the case of metals is probably incorrect. The reason is
that the highly mobile conduction electrons tend to prevent the field
around the e\tra primary electron from penetrating far into space. Thus
an exponentially decreasing screened
potential would give a better represen-
V.__!----!t=~--~~3~
tation of the interaction. Is This point -
will be discussed further in Sec. (17-7),
and for the moment (17-16) will be
....
-_ --
.
pnmary

e,
assumed to hold. The momentum
transferred from the primary to the -~I!_.-
conduction electron perpendicular to Fig. 17-9. To illustrate the collision
the primary path is then equal to between a primary and a conduction
electron; the momentum f::1p trans-
ferred to the conduction electron is
~. = J+oo
2
Fdt = 2e (17-17) perpendicular to the path of the
p - 00 bu primary,

Thus, for all conduction electrons at a distance b, the eenter of the

occupied momentum sphere will be displaced by an amount ~P' From
this, it is possible to calculate the number of secondaries N(fl) produced
per unit primary path length for which the momentum is larger than flPF,
where fl is a factor which we may choose. Obviously, for the secondary
emission process one is interested in fl > 1. As long as the velocity of
the primary satisfies the relation mv?> (fl + I)PF' Baroody's calculation
gives
(17-18)

where B is a constant, Ep is the primary energy, and EF is the Fermi energy.

We note that the number of secondaries produced with energies very close
to the Fermi energy (fl"'_' I) becomes very large, and for fl = 1, expression
(17-18) becomes infinite. This is a consequence of the Coulomb law
assumption, because- the interaction with electrons far away from the
primary, corresponding to large b values, leads to small energy losses.
In a screened potential, such interactions would not occur and the
difficulty would be removed. The derivative of (17-18), ~dN/dfl, gives
the momentum distribution of the internal secondaries measured in terms
of the Fermi momentum PF' Both N(fl) and its derivative decrease
rapidly with increasing fl. We also note that the number of secondaries
18 R, Kronig and], Korringa, Physica, 10,406,800 (1943); H. A, Kramers, Physica.

13,401 (1947); D, Bohm and E, p, Gross, Phys. Rep,. 75,1851,1864 (1949); D. Bohm
and D. Pines, Phys. Rev,. 80, 903 (1950); 8~, 625 (1951); D, Pines and D, Bohm, Phys.
Rev" 85, 338 (1952); D, Pines, Phys, Ret'" 85, 931 (1952); A, van der Ziel, Phys, Ret·"
92, 35 (1953), ;:1" ' f. :, ,\, .:1',(;'

"
432 SECONDAR Y ELECTRON EMISSION [Chap. 17

produced per unit primary path length with a momentum> PPF varies
inversely as the primary energy. The assumption of a Whiddington law
for the primaries, as used in the elementary theory discussed previously,
is in agreement with this result.
Equation (17-18) gives the production of secondaries for a particular
value Ep of the primary. Now Ep is a function of the path length covered
by the primary inside the solid. Denoting the depth below the surface by
x. Baroody employs the same relationship as that used in the older theories,
E;(x) = E;o - ax (17-19)
The constant a here is equal to Aj2 used in the preceding sections. From
(17-19) and by differentiating (17-18) one thus obtains for the number of
secondaries produced per primary in a slab dx and with a momentum
between f-lPF and {f-l + df-l)PF,
2BE,Y/f-l df-l dx \ (17-20)

To describe the escape mechanism of the secondaries, Baroody introduces

two mean free path lengths, A, and Aa; As refers to scattering of the
secondaries by the lattice vibrations, and Aa refers to "absorption," i.e.,
to inelastic collisions with other electrons. In the latter process the
secondaries may lose appreciable amounts of energy in a single collision.
It must be emphasized that because the secondaries have gained their
momentum from the primary in a direction perpendicular to the primary
path, i.e., parallel to the surface, a secondary must be scattered at least
once before it can escape. Baroody discusses two extreme cases: A, ~ Aa
and As ~ Aa, of which only the latter will be given attention here. When
As ~ Aa, the secondaries carry out a large number of elastic collisions
with the lattice before arriving at the surface. The escape mechanism
may then be described as a diffusion process with absorption. As shown
in elementary diffusion theory19 the fraction of secondaries produced at a
depth x which arrive at the surface is equal to e-x/L, where L is the
diffusion length defined by
L2 = Dra = Aa As/3
~ ,
,---------
(17-21)
Here, D = As vj3 is the diffusion coefficient of the secondaries and
r a = Aa/V is the lifetime associated with the absorption process (v is the
velocity of the secondary). Note that the exponential absorption law used
in the older theory is obtained here on the basis of an admittedly in-
complete physical model. Now suppose ftoPF is the minimum momentum
perpendicular to the surface required for an electron to escape from the
surface. Evidently, if cp is the work function of the metal,
ft5P~j2m = EF + cp or ft~ = 1 + CPjEF (17-22)
10 See, for example, P. R. Wallace, Nucleonics, February 1949, p. 30.
Sec. 17-6] SECONDARY ELECTRON EMISSION 433
Hence an electron at the surface with a momentum PP F will escape only if
the cosine of the angle with the normal is larger than 1-'0/1-'. For an
isotropic velocity distribution, an electron at the surface with momentum
\.
I
1.6
Jb Pt

~
Ag
-~

"1' ° Au
W °
1.4 _-
T~O,:Mo- Pd
'lou
im 1.2
~- Cd,Zr
Co
°
t 1.0

~
:AI

.8 !i}.; Ba
°Ca,K )
.6
oLi

3 5
2
_ "
Work function (ev)
6

Fig. 17-10. Correlation between maximum yield and work function

for various metals. The solid line is drawn to show the trend of
experimental points. The dashed line is a plot of <5.. = (0.35</»1/1,
accordin~ to Baroody. ref. 15.

I-'PF has on the average a probability {fJ - 1-'0)/1-' to escape from the
surface (see Problem 17-7). One thus obtains finally for the secondary yield,
-x/Ld ( )
d= 2BE1I2 rx"
e x roo fJ - fJo d
F Jo (E;o _ ax)I/2 Jl'o (fJ2 _ 1)2 fJ

The integral over x is the same as that in (17-9), so that

d= 2BE1)2 F ['(E;o) 1/2] roo (fJ - 1-'0) dl-' (17-23)
a1 / 2 aL ./1'0 (1-'2 - 1)2
where the function F is defined by (17-10). We note that the dependence
of d on the primary energy is exactly the same as that obtained in Sec.
17-3, and that it follows the full curve in Fig. 17-7. The dependence ofd
on the work function may be obtained as follows. According to (17-23), d
is proportional to E}!2 times a function of fJo. Furthermore, from (17-22)
it follows that EF = cf>1(1-'~ - 1). Therefore, if one makes the reasonable ~
assumption that 1-'0 and the other quantities in (17-23) do not depend on
the work function in any systematic fashion, one concludes that the yield
should be proportional to the root of the work function. In Fig. 17-10 we
represent a number of data c911ected by McKay for the maximum yield of
,
434 SECONDAR Y ELECTRON EMISSION [Chap. 17

several metals. 20 The solid line is the one drawn by McKay, the dashed one
represents (0.354»112 and is matched at thorium. We emphasize that the
dependence on 4> does not enter through the escape mechanism but
rather through the expression for the production of secondaries (17-20),
which contains the factor E}J2. We must also remark that if for a given
metal the work function is lowered, for example, by a monolayer on the
surface, the yield, of course, increases.
Space does not permit discussion of this model any further, but
it may be noted that from (17-23) the energy distribution of the secon-
daries may also be obtained; the agreement with experiment is good.

17-7. Wave-mechanical theory of the production of secondaries

Wave-mechanical treatments of the production of secondaries in

solids have been presented by several authors and some of the essential
points of such theories will be discussed briefly here. 21 In the absence
of a beam of primary electrons, the electrons in the solid are represented
by Bloch functions "P1z(r) where k denotes the wave vector. It is convenient
to consider a crystal of unit volume; it will be assumed that the Bloch
functions are normalized per unit volume. The beam of primary electrons
acts as a perturbation on the lattice electrons and induces transitions of the
latter to higher energy states. The wave vector and positional coordinates
of a primary electron will be represented, respectively, by K and R.
The basic problem in the theory of production consists in calculating the
number of transitions pl!r Jlh~t time P( K,k -+ K' ,k') dQ', for which the
primary electron is.scattered ,ihto a. solid angle dQ' around the vector K'
and the lattice electron is excited into a new s~ate k'., It is generally assumed
that the primary electrons may be descril?ed by plane waves of the type
exp i(K. R), the reason being that thejr energy is large enough that they
can be considered free. Such a'n!presentation, however, does not permit
one to take into account Rutherford scattering, and the problem of
elastic and inelastic reflection of primaries must therefore be .investigated
separately.
The next problem which arises is to decide on a law of interaction
between a primary electron and a lattice electron. In insulators and
semiconductors with relatively small densities of conduction electrons,
it would seem that a simple Coulomb law would be suitable. In that case
e2 I
V(R,r) = -,-,.- (17-24)
R - r E
20 H. G. McKay, Advances in Electronics, 1,66 (1948).
21 H. Frohlich, Ann. PhYSik, 13, 229 (1932); D. A. Wooldridge, Phys. Rev., 56, 562,
(1939); E. RlIdberg and J. C. Slater, Phys. Rev., 50, 150 (1936); A. J. Dekker and
A. van der Ziel, Phys. Rev., 86, 755 (1952); A. van der Ziel, Phys. Rev., 92, 35 (1953);
J. F. Marshall, Phys. Rev., 88, 416 (1952); E. M. Baroody, Phys. Rev., 89, 910 (1953).
Sec. 17-7] SECONDAR Y ELECTRON EMISSION 435
where E is an effective dielectric constant. In metals and, in general for
high densities of conduction electrons, the situation is different. The
presence of the "extra" primary electron has the tendency to push the
conduction e~ctrons away from it. This results in the setting up of local
space charges, because the positive ion cores are virtually at rest. Con-
sequently, the field of the primary dies out over distances of the order of
a few Angstroms. Without going into detail, it may suffice to say that the
effect of the piasma I6 (conduction electrons plus positive ion cores)
on the interaction between two electrons may be in"cluded by using instead
of (17-24) a screened potential of the type,

~'C'~~2;)
2
V(R,r) = IR e rl exp [ - IR A rl] 'tw

where ;. ~ 108 cm-I . Because of its simplicity we shall assume (17-24)

to be valid and quote the results for metals based on (17-25).
If there is no interaction, a primary electron plus a lattice electron can
be represented by the wave function

(17-26)

where the total energy E is equal to

Let us suppose that at the instant t = 0, the interaction between the

primary and lattice electron is "switched on." The wave function of the
system at the instant t may then be expanded as follows:

(17-27)
with

According to the usual procedure of time dependent perturbation theory,

the coefficients are given by
I ,}Ih Hl n; f!il Ii
a,
Il K
,(t) = - ftf
iii JoJr
f
R
e-i(K"R)w
Til
,(r)
E IR _ rl
.
ei(K'R)w
"

Til
(r) e-i(E-E')I'h dr dR dt

(I 7-28)

where the notations dr and dR refer to integrations over the volume of,
the crystal. The integration over R becomes .
436 SECONDAR Y ELECTRON EMlSS[ON [Chap. 17

where q = K - K'. If (17-28) is furthermore illtegrated over time, one

obtains for the transition probabilities, ( !

Ia". .(1)1
2 4
2 = 167T e • 2[1 - cos (E' - E)I/IiJ 1 12 ( 17-29)
K €2q4 (E' _ E)2 I
\
where the integral I is defined by
""-',

07-30)

To obtain an expression for P(K,k -+ K',k') dO', defined at the beginning

of this section, one proceeds as follows: Expression (17-29) is multiplied
by the number of states in the range dK' within a solid angle dO' about
K', i .. e, by K'2 dK' dO' = mK' dE' dO'/1i2, and integrated over dE';
the time derivative of the resulting expression then gives the rate at which
these transitions occur. Furthermore, if we consider a bejlm of primaries
with a particle density m/hK, so that one primary crosses unit area per
unit time, we finally obtain
2
y.
' k' d 1v 4m e4K'1 12 £'\1
P(K, k -+ K, ) u = €21i4q4K J d:.l. (17-31)

As far as the selection rules for possible transitions are concerned,

we note that the time function in (17-29) has a strong maximum for
E' - E = 0, i.e., only transitions for which energy is conserved will
occur with relatively high probability. The selection rule governing
the momenta of the primary and lattice electron is deduced from the
integral I defined by (17-30). In fact, if one writes out the Bloch functions,

tp,,(r) = ei(h)u,,(r) .

where u,,(r) has the periodicity of the lattice, i.e.,

u,,(r) = L cb(k)eib' r
.•! blb.b.

with b representing 2 1T times a vector in the reciprocal lattice, one .gets

1= Lcb(k) Sexp [i(q + k - k' + b). rJ dr (17-32)

b

The integral vanishes unless

q +k - k' +b = 0 or K +k +b = K' + k' (17-33)

This expresses the conservation of momentum before and after collision;

the momentum lib is contributed by the lattice.
Sec. 17-7] SECONDARY ELECTRON EMISSION 437
Production of secondaries in metals. For metals, as mentioned above,
a screened potential of the type 07-25) IfIay be expected to give more
accurate results than a simple Coulomb interaction. If the same calcul-
ation as givsn above is carried through with (17-25), van der Ziel has
shown that one obtains instead of(17-31),22
4m 2e4 K'
= + .1.2)2 1'1
2
P(K k -? K' k') dD.' dO' (17-34)
, , K;,4(q2

so that essentially q4 is now replaced by (q2 + .1.2)2, and of course., the

dielectric constant E must be left out. The basic problem has thus been
solved and a number of quantities of interest may now be calculated from
it. For metals, it may be shown that transitions for which b in (17-33)
is different from zero contribute very little to the production of secondaries.
Apart from other deficiencies, this indicates that the free electron model
llsed by Baroody is probably justified. The number of secondaries pro-
duced per second in an energy range between E' and E' +
dE' is of parti-
cular interest. If N is the number of conduction electrons per unit volume,
van der Ziel's calculations give
. , , 7TNe4 dE'
peE ) dE c:::' ----e;'
(E' + E).)2 07-35)

where Ep is the primary energy and £). = ;,2A2j2m c:::' 40 ev for A c:::' 108
em-I. Note that the production increases as Ep decreases, in accordance
with the ideas employed in the elementary theory. We also observe that
(17-35) remains finite even for E' equal to the Fermi energy E F; this is a
consequence of the screened potential. Another quantity of interest
is the energy loss of the primaries per unit path length. It turns out that
in first approximation this quantity is given by a Bethe-type law,

dE
p 7TM.e (Ep) 4
--c:::'--log - (17-36)
dx Ep eE).

where the factor e in the logarithm is the base of natural logarithms.

It is evident that, because the logarithm varies slowly with E P' Whidding-
ton's law is a good approximation, at least over not too large intervals
of E1)' ,;

Production of secondaries in insulators. In insulators and intrinsic

semiconductors, secondaries are produced by excitation of electrons in the·
occupied bands. The situation here is much more difficult than for metals
for the following reasons. In the first place, if one assumes a Sommerfeld,
model for the conduction electrons, one knows the energy values as
well as the wave vectors for the occupied states. For filled bands, on the
other hand, the relation between energy and momentum is complicated
22 See A. van der Ziel, Phys. Rev., 92,35 (1953).
438 SECONDARY ELECTRON EMISSION [Chap. 17 ,

and not simply given by E = /i 2 k 2 /2m. Furthermore, for electrons in the

occupied bands one knows little about the periodic functions u~.(r)
occurring in the Bloch functions, whereas for the conduction electrons
in a metal it is a good approximation to consider uk(r) a constant. Con-
sequently, there is little or no information about the value of 1 112 in (17-31)
and hence about the energy distribution of the secondaries produced in
insulators and semiconductors. For the general theory we refer to the
Iiterature. 23 It may be of interest to note that the energy losses of the
primaries again lead to a law of the form given by (I7-36), i.e., the energy
loss per unit path length is proportional to E;1 log (E11/Eo), where Eo
is an excitation energy, which varies with the primary energy as a result
of the fact that only high-energy primaries are able to excite the deeper-
lying electronic levels.

17-8. Interactions to be considered in the escape mechanism; factors

determining high and low yields

As we have mentioned before, the description of the escape mechanism

by a simple exponential absorption law is unsatisfactory in the sense that
it does not give insight into the actual processes that determine the
probability of escape. Recently, however, some attempts have been made
to set up a theory for the escape mechanism based -on our knowledge of the
behavior of electrons in crystals. In general, a secondary produced at
a certain depth x with a given energy Eo may be expected to carry out a
Brownian motion during which it may undergo the following types of
interactions:
(i) Interaction with lattice electrons ,Aj
(ii) Interaction with lattice vibrations
(iii) Interaction with electron traps
(iv) Interaction with occupied donor levels, if present
Consequently, the energy of a secondary gradually decreases, and as
soon as it drops below a minimum value E min required to escape from the
surface, it is no longer of importance for the secondary emission process.
In other words, for a secondary to have a nonvanishing escape probability
it must have lost less than (Eo - E min ) during the period required to
drift from its point of origin to the surface. For metals E min = EF 4> +
,...__ IO ev, where Ep is the Fermi energy and 4> is the work function.
In insulators E min is equal to the electron affinity of the crystal
l""__ 1 ev.
For metals, (i) refers essentially to interaction with the conduction
electrons and may be expected to be practically independent of temperature.
23 See, for example, A. 1. Dekker and A. van del' Ziel, Phys. ReI'., 86. 755 (1952).
Sec. 17-8] SECONDARY ELECTRON EMISSION 439

Any temperature effect of the secondary emission may be expected to

result from (ii) because the mean free path fer lattice scattering is tempera-
ture-dependent. However, for metals no temperature effect has been
observed, imJicating that (i) essentially determines the escape probability
in this case. Interactions (iii) and (iv) are irrelevant in the case of metals.
As a result of the strong interaction between second.aries and the con-
duction electrons in metals, and the relatively high average energy loss
suffered by the secondaries in such collisions, the secondary yield of metals
is in general small.
In insulators the density of electrons in the conduction band is so
small that their presence may be neglected. This leaves, as far as (i)
is concerned, only the possibility of energy losses due to excitation of
electrons from the filled band. For such excitation processes, energies
of the order of several ev are required. Thus if Ee is the minimum exci-
tation energy involved, interactions of type (i) do not occur for secondaries
of energies below E.. Furthermore, because E, for a good insulator is in
general appreciably larger than the electron affinity X of the crystal,
secondaries in insulators have on the average a good chance of escaping
from the surface, unless any of the other type of interaction would lead
to relatively high energy losses. Neglecting for the moment (iii) and (iv),
the escape mechanism for insulators is then essentially determined by the
interaction with lattice vibrations. This leads to a temperature-dependence
of the yield, as will be discussed in Sec. (J 7-9). The possible influence of
traps and donor levels will be discussed briefly in Sec. (J 7-10). From these
qualitative remarks and from the fact that in a collision with the lattice
an electron of several ev energy loses on the average about O. I ev or less,
it will be evident that relatively high yields may be expected for insulators.
This is in agreement with the experimental data.
In intrinsic semiconductors such as germanium and silicon, the
upper filled band is separated from the conduction band by only about
1 ev. Thus, electrons with energies> 1 ev are likely to lose appreciable
amounts of energy by exciting lattice electrons from the .filled band into
the conduction band. This, combined with the fact that X ~ 1 ev, leads
one to the conclusion that the secondary yield for such materials should
be relatively small and of the same order as for metals. This is in agree-
ment with the observations. On the other hand, a small temperature
effect of the yield is observed in germanium (Fig. (17-4», showing
its position to be intermediate between metals and insulators in this
respect.
Before discussing some of the processes mentioned above, we may
call attention to the following general formula for the probability of
escape of electrons at the surface of a solid. Let E min be the minimum
energy required in the direction perpendicular to the surface for an
electron to escape. For electrons of a total energy E and assuming an
.~.
440 SECONDAR Y ELECTRON EMJSS[ON [Chap. 17

isotropic velocity distribution, the probability peE) of escape is then

given by
E ) 1/2

\
peE) = 1.,- ( ; " (17-37)

as can readily be verified by the reader.

17-9. The temperature effect of the secondary yield in insulators

Although the production of secondaries in metals is well in hand

according to the discussion of Sec. (17-7), the escape problem for metals
is rather complicated because of the interaction of secondaries with con-
duction electrons. 24 The situation for insulators is just the reverse. The
theory of the production of secondaries is too general to give quantitative
results in specific cases, but certain aspects of the escape mechanism may
be discussed by means of relatively simple concepts. We shall therefore
discuss here the escape mechanism for insulators and in particular the
influence of temperature on the secondary yield. 25 To begin with, the
influence of temperature on the range of the secondaries will be calculated
and from it one may then predict how the temperature should influence
the secondary yield.
For simplicity let us for the moment consider only those secondaries
which are produced with an initial energy Eo and let us assume that the
secondaries interact only with lattice vibrations, thus neglecting traps
and donor levels. From the theory of the interaction between electrons
and lattice vibrations it follows that the average energy lost by an electron
of some ev per collision is independent of the energy of the electron and
only a function of temperature. 26 Denoting the average energy loss per
collision by oc(T), the energy of a secondary as function of the number of
collisions N it has suffered since it was produced is given by

E(N) = Eo - Noc(T) (17-38)

Also, the mean free path for collisions with lattice vibrations for electrons
of several ev of energy is proportional to the energy times a function of
temperature. We may therefore write for the mean free path,

A(E,T) = AoEf(T) (17-39)

where ).0 is a constant. According to (17-38) the energy decreases linearly

with N, and therefore, so does A. Now, we have seen in the preceding
section that a certain minimum energy EmiIl is required for escape. Hence,
24For a discussion of this problem, see P. A. Wolff, Phys. Rev., 95, 56 (1954).
25A. J. Dekker, Phys. Rev., 94,1179 (1954).
,. See, for example, F. Seitz, Phys. Rev., 73, 549 (1948); 76, 1376 (1949).
Sec. 17-9] SECONDARY ELECTRON EMISSION 441
the "life" of a secondary is limited to a maximum number of collisions
N", such that
(17-40)

If the moti~ of the secondaries is considered a Brownian motion in

one dimension, the mean square displacement of a secondary during its
"life" of N", collisions is given by

(x2)av = N m ().2)av = N",),M/(T)]2(E2)av .. ,,-, - 07-41)

where the averages must be taken over the N", collisions. Now, according
to (17-38) we may write

(E2)av = Eg + a.2(N2)av - 2a.Eo(N)av

The average value of N is simply N m /2, and if N",?> I, which we shall

assume to be the case, .
2 __ fN m N2 dN _ I 2
(N )av -)0 ~ - "jN,,,
m

Making use of 07-40), one readily finds that (E2)av is independent of

temperature and only determined by the constants Eo and E min • Hence
the temperature-dependence of the mean square displacement may be
expressed by
[f(T)J2
<x2 )av = const. N m [f(T)]2 = const. - ( -
ocT)
(17-42)

Clearly, the square root of this expression may be considered a measure

for the range of the secondaries. Although the range increases with
increasing values of Eo, the temperature-dependence for any value of
Eo is evidently determined by (17-42). Let us now consider the case for
which the primary energy is large, i.e., the range of the primaries is large
compared with' the range of the secondaries. From the discussion in
Sec. 17-3 it follows that in this case the production of secondaries is
nearly constant over a depth equal to the range of the secondaries. Thus
to a first approximation, one expects the secondary yield to be propor-
tional to the range of the secondaries. The ratio of the yields at two
different temperatures T1 and T2 would then be given by
151 /(T1 ) [a.(T2 )] 1/2 l'
-,...., - - - -
?>
lor x:::? X (17-43)
15 2 - /(T2 ) OC(T1) 1'"

For ionic crystals, the mean free path for lattice scattering is given bY~,5
I
(17-44)
or /<T) = (2n" + I)

where n" = [exp (hv/kT) - 1]-1 and l' is the frequency of the optical
442 SECONDARY ELECTRON EMISSION [Chap. 17

longitudinal vibrations of the lattice. Furthermore, the average energy

loss per collision suffered by a secondary is given by

~(T) = - -dE A = :-----:-

hv \ (17-45)
dx 2n,. + I ,
Thus for ionic crystals, expression (17-43) may be written in the form
61
T ~
[2n"2 + 1] 1/2 for
~
xp:;>- Xs ( 17-46)
{}2 2nvl +1
This result has been applied to explain the variation in yield as function
of temperature for magnesium oxide single crystals. 2 ,i For Tl = 1013°K
and T2 = 298°K, Johnson and McKay observed an average ratio ()1/()2
= 0.78 for primary energies above 2 kev. 5 Now, from optical absorption
measurements it follows that for MgO, hv = 1300 k. 25 Employing this
value, one obtains from (17-46) for the same ratio, 01 /6 2 = 0.76, in
good agreement with the experimental value. It thus seems that the simple
model used above gives a satisfactory explanation of the temperature
effect in MgO. For nonpolar crystals a similar calculation may be carried
out, starting from (17-43). However, no experimental data are available
to check the theory further. It may be noted that a more general theory 27
based on the Boltzmann transport equation leads to the same result as
obtained here.
It must be emphasized that as the temperature is raised the average
energy loss suffered by the secondary per collision decreases. For MgO,
for example,
~ (298°K) = 0.108 ev IX (I0l3°K) = 0.063 ev
The decrease of the yield with increasing temperature is thus a conse-
quence of the reduction in the mean free path and of the fact that the
path of the secondaries is curled up. In fact, if the secondaries moved
in straight lines toward the surface, there would be no temperature effect,
because dEldx is temperature-independent for electrons of a few ev
energy. (For thermal electrons this is not true).
For low primary energies, corresponding to the rising part of the
yield curve, the influence of temperature on the yield is very slight,
because most secondaries are then produced close to the surface and the
energy losses resulting from scattering become less important.

17-10. The possible influence of donor levels on the secondary yield of

insulators

The question may be raised as to whether it would be possible to

increase the secondary yield of an insulator by introducing donor levels.
27 A. J. Dekker, Physica, 21, 29 (1955).
Sec. 17-10] SECONDARY ELECTRON EMISSION 443
In principle, such donor levels may Influence the production of secondary
electrons as well as the escape mechanism of the secondaries. Let us
first consider the possible influence of a certain concentration of donor
levels on t1'le escape mechanism. Qualitatively, one might argue that
secondaries on their way to the surface may ionize the donors, thus
leading to electron multiplication and an increase in the secondary yield.
Quantitatively, however, it seems that the probability for this process to
occur is very small, except if the donor concentration near the surface is
extremely high. The reasons for this are the following. [n the preceding
section we have seen that as a result of the interaction with lattice vibrations
the secondaries are slowed down gradually. Thus the escape mechanism
can be influenced by imperfections only if the interaction with these
imperfections takes place within the period required for a secondary to
be slowed down to the minimum energy Emil) required for escape. Thus,
consider a secondary produced with an initial energy of Eo = 6 ev,
and let E min = 1 ev. If the secondary loses on the average 0.05 ev per
collision with the lattice, its slowing-down life extends over about 100
collisions. For a mean free path for scattering of, say, 10 A, the actual
path length covered by the secondary during life is then approximately
1000 A. Let there be 1018 donors per cm 3 ; if a is the cross section for
ionization of a donor by a secondary, the minimum value for the cross
section in order to obtain a measurable change in the yield must then be
of the order of 10-14 cm2. Although such cross sections are not impossible,
they are very large indeed, and it seems that considerably higher donor
concentrations would be required to produce an observable effect on the
escape mechanism. Similar arguments hold for other lattice defects.
As far as the possible influence of donor levels on the production of
secondaries in insulators is concerned, the following remarks may be mape.
First of all, the donor concentration is always small compared with that
of the host atoms in the lattice. It seems, therefore. that any increase in
the production of secondaries resulting from the direct interaction between
the incident primaries and the donor levels would be very small. On the
other hand, the incident primaries probably produce a considerable
number of excitons in their wake; these excitons may diffuse about in the
crystal and ultimately give up their energy by ionizing a donor electron
as in the case of the photoelectric phenomena discussed in Sec. 15-9.
The possible enhancement of the secondary emission resulting from ioni-
zation of donors by excitons has been discussed by the author.28

REFERENCES
H. Bruining, Physics and Applications of Secondary Electron Emission.
McGraw-Hili, New York, 1954.
I
28 A . .I. Dekker, Physica, 22, 361 (1956).
444 SECONDARY ELECTRON EMISSION [Chap. 17

O. Hachenberg and W. Brauer, Fortschr. Physik, 1,439 (1954).

K. G. McKay, Adwnces in Electronics, 1,66 (1948).
R. Kollath, Encyclopedia of Physics, Springer, Berlin, vol. 21, 232-291,
(1956).
L. R. Koller, Gm. Elec. Rev., 51, 33, 50 (1948). \
D. A. Wright, Semi-Conductors, Methuen, London, 1950, Chap. 5.

PROBLEMS

17-1. At first sight it may seem strange that the "range" of a primary
electron may be smaller than that of a secondary, because the energy of
the former is always larger than that of the latter. From the definitions of
x and Xs used in the theory of secondary emission, explain that this
J)

difficulty actually does not exist.

17-2. Assuming A = 1012 volt2 cm- 1 in the Whiddington law (17-2),
calculate the penetration depth of primaries of 500, 2000, and 5000 ev.
17-3. Plot dEp/dx versus Ep for the range Ej} = 200 ev to 5000 ev
according to 'equation (17-36), assuming N = 1022 cm-3 and E). = 40 ev.
Approximate the high primary energy region by a Whiddington law and
compare the value of A obtained in this way with the value given by
H. M. Terrill, Phys. Rev., 22, 161 (1922).
17-4. Give a complete derivation of(17-12), filling in the steps omitted
Sec. 17-3.
17-5. Explain why in Fig. 17-8 the primary energy for which the yield
is a maximum shifts to larger values with increasing angles of incidence
with the normal.
17-6. Give a derivation of equation (17-18).
17-7. Derive equation (17-37) for the escape probability; note that
this equation is identical with the statement in Baroody's theory that
(p, - po)/p, is the probability of escape for an electron at the surface.
17-8. Calculate the mean square displacement for a secondary electron
in MgO at room temperature, assuming it is slowed down by lattice
vibrations from an energy of 5 ev to 2 ev. Employ the data for the mean'
free path given in A. J. Dekker, Phys. Rev., 94, 179 (1954). Carry out
the same calculation for a temperature of 600o K.
17-9. Employing the data of A. J. Dekker, loc. cit., calculate the
diffusion coefficient for electrons with an energy of 4 ev in MgO. From
it, calculate the mobility of such electrons by means of the Einstein
relation.

•
Chap. 17] SECONDARY ELECTRON EMISSION 445
17-10. According to recent measurements by J. R. Young, Phys. Rev.,
103, 292 (I956) the range of primary electrons up to 5 kev in Al 2 0 3 is given
by R = <r.ol 15 E1.35, where R is expressed in mg/cm 2 and Ein kev. Calcu-
late the pehetration depth of an electron of I kev, Show that -dE/dx is
proportional to E -O.:~5; compare this result with Whiddington's law.
Develop an elementary theory of secondary emission based on these new
developments, assuming for simplicity that the primary range is propor-
tional to E1' J/:l.
,

Chapter 18

DIAMAGNETISM AND PARAMAGNETISM

18-1. Introductory remarks

It is convenient to group the magnetic properties of solids under the

following headings:
(i) diamagnetism \
(ii) paramagnetism \
(iii) ferromagnetism, antiferromagnetism, ferrimagnetism
I n the present chapter we shall consider the dia- and paramagnetic
behavior of solids for static applied fields; the properties corresponding
to group (iii) will be discussed in the next chapter. Magnetic properties
depending on the frequency of an alternating applied magnetic field are
discussed in Chapter 20.
When a substance is placed in a magnetic field H, a magnetic moment
M per unit volume results; M is called the magnetization. For isotropic
materials, M and H are parallel vectors and the susceptibility.X defined by

M=X H I.. (18-1 )

is then a scalar quantity. In anisotropic substances, X is a tensor. In case

M refers to a gram molecule, one may introduce the molar susceptibility
Xm' All atoms or ions produce a diamagnetic contribution to the total
susceptibility, although it may be masked by the other types; it is a
consequence of the magnetic moment induced in the atoms by an external
field. In this respect, diamagnetism may be compared with the electronic
polarization in an electric field. Both are essentially independent of
temperature. There exists, however, an essential difference: in the electrical
case the induced moment lies along the direction of an applied field,
leading to a positive electrical susceptibility; in the magnetic case the
induced moment produces a negative susceptibility.
Paramagnetism requires the existence of permanent magnetic dipoles,
and the paramagnetic susceptibility is the analogue of the orientational
susceptibility associated with permanent electric dipoles. In both cases the
susceptibility is positive and temperature-dependent. The properties
corresponding to group (iii) above also require the existence of permanent
magnetic dipoles, and moreover, a relatively strong interaction between
446
Sec. 18-1] DIAMAGNETISM AND PARAMAGNETISM 447
them. These properties are "cooperative" in the same sense as those
encountered in ferroelectricity and order-disorder transitions in alloys.

,
The magnetic induction B may be defined as

B = H + 47T M = ftH (18-2)

where ft is called the permeability; it should not be confused with the

same symbol used below for the magnetic dipole moment of an atom.
Unless stated otherwise, we shall assume H, M, and B to be parallel
vectors, so that ft is a scalar. For para- and diamagnetic materials, the
permeability is a constant, unless saturation conditions are approached
(see below). For the properties mentioned under (iii) the relation between
Band H is much more complicated and shows hysteresis, as will be
further discussed in Chapter 19.
From (18-1) and (18-2) it follows that
ft = I + 47TX Jlf:;mom !}l()Qt (18-3)

This relation is the analogue of the expression for the dielectric constant
€ when X represents the ratio of the electric moment per unit volume and

the applied electric field.

It is convenient to normalize the potential energy of a dipole fJ. in a
magnetic field H in such a way that

(18-4)

In connection with the potential energyl of a substance in a magnetic

field and its importance in experimental determinations of the suscepti-
bility,2 the reader is reminded that the proper thermodynamic formulas
for magnetized materials can be obtained from the "normal" thermo-
dynamic expressions for a gas by replacing

the pressure p by M

the volume V by H

Thus, for an adiabatic process in which the magnetic field to which a

substance is subjected is varied from 0 to H. the change in energy per
unit volume is given by

fdE = -- f: M dH = - f~l XH d~ = -hH2 (18-5)

1 For a discussion of energy relations, see E. A. Guggenheim, "Proc. Roy. Soc.

(London), A155, 49 (1936).

2 For experimental methods, see L. F. Bates, Modern Magnetism, 3d ed., Cambridge,
London, 1951; also P. W. Selwood, Magnetochemistry, Interscience, New York, 1943.
,
448 DIAMAGNETISM AND PARAMAGNETISM (Chap. 18

18-2. The origin of permanent magnetic dipoles

As stated in the hypothesis of Ampere, magnetic dipoles have their

origin in the flow of electric currents. From electricity theory it is well
known, for example, that a stationary loop current flowing in a plane
produces a magnetic field which at large distances may be described as
resulting from a magnetic. dipole3 . '. ,

ft = IS/e (18-6)'

where I is the current and S is the area of the loop. The dipole direction
is perpendicular to the plane of the loop. Employing this relation, let us
consider the magnetic dipole moment associated with an electron describing
a circular orbit of radius r, the angular velocity of the electron being Woo
The loop current in this case is4 -ew o/27T so that, according to (18-6),
the magnetic dipole moment associated with the electron orbit is

(18-7)

It is of interest to relate the magnetic dipole moment to the angular

momentum of the electron, which in this case is m(l)or2 • According to
(18-7) we have
ft = -(e/2mc) X angular momentum "I (18-8)
The minus sign indicates that the dipole moment points in a direction
opposite to the vector representing the angular momentum. Relation
(18-8) is valid for any electron orbit, as will be shown in Sec. 18-7; it is
not valid, however, for the spin of an electron or nucleus, as we shall
see below.

The use of quantum numbers.5 A few remarks may be made here to

refresh the reader's memory on the use of quantum numbers in the theory
of atoms. r," I

(a) The principal quantum number n determines the energy of the

orbit; it can accept only the integer values n = 1, 2, 3, .... The corre-
sponding electronic shells are called the K, L, M, N, .,. shells.
(b) The angular momentum of the orbit is determined by the quantum
number '. which is restricted to the set of values

I = 0, 1, 2, '" , (n - 1) (18-9)
3 For a general proof. see, for example, R. Becker, Theorie del' Elektrizitiit, Teubner,

Leipzig, 1933, Vol. 2, p. 96. See also Problem 18-1 for a particularly simple example.
• Unless otherwise specified, the electronic charge will be represented by -e.
o A clear account may be found in G. Herzberg, Atomic Spectra and Atomic Structure,
Dover, New York, 1944.
Sec. 18-2] DIAMAGNETISM AND PARAMAGNETISM 449
The total angular momentum associated with a given value of 1 is
1i[1(I + 1)]112 (18- 10)

Electrons as~ciated with states 1 = 0, I, 2, 3, '" are called, respectively,

s, p, d, f, g, ... electrons. Note that electrons in an s state always have
zero angular momentum and thus a vanishing magnetic moment.
(c) The possible components of the angular momentum along any
specified direction (such as the direction of an external magnetic field H)

~----- hVI(I+ 1)
1-1
------~,.
'//E
,, g~BH
S
=+1/2

s= -1/2
i ' d .~
Fig. 18-1. Illustrating the three Fig. 18-2. Illustrating the splitting
possible orientations of an angular of an energy level for an electron
momentum defined by the quantum with a spin ! and zero orbital
number I = 1 in an external mag- momentum in a magnetic field. For
netic field. s = + t, the magnetic moment of
f 1 Bohr magneton is antiparallel; for
s ~~ -! parallel to the field, in
accordance with (18-12).

are determined by the magnetic quantum number m, where m is restricted

to the set of values
m l = I, (1- I), ... 0, '" -1(1- 1), -I (18-11 )

F or example, a p electron has the possible components of angular momen-

tum along the direction of a magnetic field Ii, 0, -Ii. Consequently, the
possible magnetic moment components along the direction of an applied
magnetic field are (see Fig. 18-1)
-eli/2mc, 0, +eli/2mc
20
The quantity eli/2mc = 0.927 X 10- erg/oersted is called the Bohr
magneton; it will be denoted by !lB'
(d) So far we have described an electron simply as a particle of char&e
e and mass m. However, the electron itself has an angular 'momentum
known as the spin. The possible angular momentum components of the.
spin along an external field direction are ±1i/2. This has led to the
introduction of the spin quantum number s = ±l .
.;'
450 DIAMAGNETISM AND PARAMAGNETISM [Chap. 18

On the basis of (18-8) one thus expects that the electron spin will give
rise to a component of half a Bohr magneton. It must be emphasized,
however, that for the spin, relation (18-8) is not valid. In fact the magnetic
moment component fl ... of the spin along an external field is given by
flu = g(e/2mc)(1i/2) (18-12)
where g is called the spectroscopic splitting factor, or the gyromagnetic
ratio (actually, it is the inverse of the latter). For the electron spin
g = 2.0023, i.e., the electron spin gives rise to very nearly one Bohr
magneton in the direction (or opposite) of an external field H. The r.:ason
for the name "splitting factor" is the following. Consider an electron
with a spin 1 and without orbital angular momentum, under influence of
a magnetic field H. As illustrated in Fig. 18-2, this gives rise to two
energy levels separated by an energy

" (18-13)
where we used (18-4) and (18-12). Thus g determines the amount by
which the original level is split up. !

(e) The orbital angular momentum and the spin may be combined
vectorially to give the total angular momentum; the latter is determined
by the quantum number j. Thus, for an electron with a certain I and a
spin of t,j can accept the values 1 ± i. Tn atoms containing a number of
electrons, the I vectors may be combined to form a resultant L, and the
s vectors are combined to form a resultant S. This type of combini-tion is
called Russell-Saunders coupling; it is the only type of coupling that we
shall consider. The resultants Land S then combine to form the total
angular momentum J of the whole electron system of the atom. For such
atoms, the spectroscopic splitting factor is given by the Lande formula,6
J(J + I) + S(S + 1) - L(L + I) (18-14)
g= I + 2J(J + 1) ,

Hund's rules. In order to predict the magnetic dipole moment associated

with the electronic system of a given atom, the above considerations must
be combined with the Pauli principle and Hund's rules. According to the
Pauli principle, only one electron can occupy a state defined by the set of
quantum numbers n, I, m l , and s. We leave it up to the reader to show
that this leads immediately to the conclusion that filled electron shells do
not contribute to the magnetic moment of an atom. Thus the magnetic
moment in atoms must result from incompletely filled shells. With regard
to the latter, Hund's rules state that for the ground state of such atoms:
(i) The electron spins add to give the maximum possible S consistent
with the Pauli principle.
• For a derivation see G. Herzberg, op. cit., p. 109.
Sec. 18-2) DIAMAGNETISM AND PARAMAGNETISM 451
(ii) The orbital momenta combine to give the maximum value for L
that is consistent with (i). -
(iii) For an incompletely filled shell, we have
"J = L - S for a shell less than half occupied,

J= L + S for a shell more than half occupied.

For example, consider the Cr2+ ion, with an electron configuration
Is2; 2S2, 2p 6, 3s 2, 3p 6, 3d4 • 7 All shells are filled except the 3d shell, which
contains four electrons. For a d shell, 1= 2, so that according to (18-11)
m l has 2/ + I = 5 possible values. Each of these can accommodate 2
electrons (s = ±l), so that the maximum number of electrons in the 3d
level is 10. In the Cr2+ ion, the 3d shell is therefore less than half occupied.
According to Hund's rule (i), we have S = 2. The possible m 1 values are
+2, +1, 0, -1, and -2. If we place the four electrons all with a spin
of +t in the first four of these, one obtains L = 2, which is the maximum
value consistent with the spin distribution. Hence, according to (iii), we
have in this case J = O.
Other atoms or ions may be treated in a similar way and from the S,
L, and J values, the magnetic moment may be calculated from (18-14)
and (18-12).

Nuclear magnetic moments. So far we have mentioned only the orbital

motion and the spin of the electrons as possible contributors to the
magnetic moment of atoms. Another contribution may arise from the
nuclear magnetic moment. The latter is expressed in nuclear magnetons,
in analogy with the Bohr magneton defined by

It" = eli/2M '[Ic = 5.05 X 10-24 erg/oersted (18-15)

where M p represents the mass of a proton. Thus nuclear magnetic

moments are smaller than those associated with the electrons by a factor
,.._, 103 . The nuclear magnetic moments are a result of'the nuclear angular
momentum (nuclear spin).
Summarizing, we see that atomic magnetic dipoles originate from:
(a) the orbital motion of the electrons; (b) the electron spin; (c) the
nuclear spin.

18-3. Diamagnetism and the Larmor precession 'f

The basic principle of diamagnetic behavior may be illustrated readily

with reference to the well-known law of Lenz in electricity theory.
, Is' means: two electrons in the Is state (n = I, I = 0), etc. ·Iqq£:
452 DIAMAGNETISM AND PARAMAGNETISM [Chap. I
Consider a loop current with its associated magnetic field. When one
attempts to change the magnetic flux enclosed by the loop by applying
an external field H, a current is induced in such a direction that the
magnetic field resulting from the induced current counteracts the field H.
Suppose now that the electrical resistance of the loop is zero; the induced
current will then persist as long as the external field is present. Such a
situation is realized in the loop current associ-
Hand WL ated with the motion of an electron in an
atom. It is also approached in supercon-
ductors. Consequently, any atomic orbit
will produce a negative contribution to the
magnetic susceptibility.

The Larmor precession. Let us now con-

sider the influence of a magnetic field on the
motion of an electron in an atom quanti-
tatively. With reference to Fig. 18-3, we shall
assume an arbitrary direction for the angular
momentum vector Ma relative to the magnetic
Fig. 18-3. The angular mo- field H.
mentum vector Ma precesses The magnetic dipole moment is in accord-
about H with the Larmor ance with (18-8)
frequency (ilL as a conse-
quence of the torque exerted (18-16)
by the magnetic field on the
magnetic dipole moment The magnetic field produces a torquefJ.X H
associated with Ma. on the dipole, so that, according to Newtonian
mechanics, we may write
(dJdt)M" = fJ. X H = -(eJ2mc)M" X H I (18-17)
This is the equation of motion of a vector Ma precessing about H with
an angular frequency
WL = eHJ2mc (18-18)
where WL is called the Larmor frequency. That this is so can be seen
from Fig. 18-3, from which it follows that for a precession of the type
(18-18),
dMa = W L X Ma dt = (eJ2mc:)H X Ma
in agreement with (18-17). We note that eJ2mc = 1.40 X 106 sec-I gauss-I,
so that even for a field of 10 5 gausses the Larmor frequency WL is much
smaller than the angular frequency of the electron in its orbit (~IO I4 to
1015 radians sec-I). It should be realized that the derivation of (I8-18) is
based on the assumption that Ma is independent of H, i.e., it is assumed
that the orbit is not deformed under influence of the magnetic field. To a
first approximation this is correct.
Sec. 18-3] DIAMAGNETISM AND PARAMAGNETISM 453
From what has been said above, it follows that under the influence of
an external field, the plane of the orbit is nut stationary, but precesses
about H. As a result of the charge of the electron, the precession produces
an induced m&gnetic moment with a component opposite to that of H.
In fact, in accordance with (18-8), this component is equal to

(18-19)

where (p)2 is the mean square radius of the projection of the orbit on a
plane perpendicular to H. When this treatment is extended to a solid
containing N atoms per cm3 , each atom containing Z electrons, one
obtains for the diamagnetic susceptibility defined as the induced moment
per cm3 per gauss,
(18-20)
l
Here it has been assumed that the charge distribution of the atoms is
spherically symmetric, so that (r2) = i(pj2 represents the mean square
distance of the electrons from the nucleus. 8 The diamagnetic susceptibility
is thus determined essentially by the charge distribution in the atoms.
Note that X is negative. With (r2) ~ 10-16 cm2 and with N ~ 5.1022 cm-3 ,
one obtains X ~ 1O- 7Z ~ 10-6 •
Experimental values for the molar diamagnetic susceptibility of a
number of ions in solids are given in Table 18-1. 9 It should be emphasized
that the susceptibility of ions is determined to some extent by their
environment and the values are therefore approximate. Note the increase
in the absolute magnitude of X.u with the number of electrons per ion.
The reader may compare this table with that for the polarizabilities of
these ions (Table 6-1). ,(

Table 18-1. The Molar Diamagnetic Susceptibility x 10' for a

Number of Ions

Li+ -0.7 Mg2+ -4.3 F- -9.4

Na+ -6.1 Ca H -10.7 Cl- -24.2
K+ -14.6 8rH -18.0 Br- -34.5
Rb+ -22.0 BaH -29.0 1- -50.6
Cs+ -35.0

8 For a spherical charge distribution

(x 2) = (y") = (Z2); ,
furthermore
(r2) = (x') + (y') + (z') and (p)" = (x') + (yO).
• G. W. Brindley and F. E. Hoare, Trans. Faraday Soc., 33, 268 (1937); Proc. Phys.
Soc. (Londoll), 49, 619 (1937).
454 DIAMAGNETISM AND PARAMAGNETISM [Chap. 18
For a discussion of the diamagnetism associated with the free electrons
in metals, we refer the reader to the literature. 1o For a simple semI-
classical theory of the diamagnetism of organic ring molecules, using
electric circuit theory, see Pauling.ll
.\
18-4. The static paramagnetic susceptibility

The classical theory of paramagnetism; Consider a medium containing

N magnetic dipole moments fL per unit volume. Suppose the interaction
between the dipoles is weak, so that the field in which a given dipole finds
itself is equal to the applied field H. We shall assume in this section that
the magnetic field is constant or varies very slowly with time. In the
classical theory, the dipoles are assumed to be freely rotating. Hence the
resulting magnetic moment M per unit volume can be calculated in
exactly the same way as the polarization P for a dipolar gas. Thus,
according to the Langevin-Debye theory (see Sec. 6-3) we find
M = N p..L(pH/kT) (18-21)
where L(x) is the Langevin function. As long as pH <{ kT this reduces to
the simple expression
(18-22)
Note that p is of the order of one Bohr magneton c:::: 10-20
erg/gauss, so
that for a field of 104 gausses, pH c:::: 10-16 erg. At room temperature
kT/3 c:::: 10-14 erg, so that the condition pH <{ kT is satisfied ex<.!ept for
very low temperatures. The relation X = const.IT is known as the
Curie law.

The quantum theory of paramagnetism. According to the quantum

theory, the permanent magnetic moment of a given atom or ion is not
freely rotating, bVt restricted to a finite set of orientations relative to the
applied field. Let us thus consider a medium containing N atoms per
unit volume, the total angular momentum quantum number of each
atom being J (this combines the total orbital angular momentum Land
the total spin S of the electronic system per atom). According to the
discussion of Sec. 18-2, this gives rise to the possible components of the
magnetic moment,
MJgPn where MJ = J, (J - I), .,. , -(J - I), -J (18-23)
Here M J is the magnetic quantum number associated with J. The
potential energy of a magnetic dipole with a component MJgPn along H
10 See, for example, F. Seitz, Modern Theory of Solids, McGraw-Hill, New York,
1940, p. 583.
11 L. Pa uling, J. Chem. Phys., 4, 673 (1936). . , q; I' I
Sec. 18-4] DIAMAGNETISM AND PARAMAGNETISM 455
is - M Jg P uH, so that, according to statistical mechanics, the magnetiza-
tion is given by -
+J
'", 2 MJgPB exp (MJgPB H /kT )
M = N --...:.J-..,.+-:J;---------- (18-24)
2 exp (MJgPBH/kT)
-J
The coefficient of N on the right-hand side is the statistical average of
the magnetic moment component per atom along H.
We may distinguish again between two cases:
(i) MJgPBH/kT~ I. Under these circumstances the exponentials in
(18-24) may be approximated by (I +
MJgpBH/kT), and by writing out
the sums, one readily finds for the paramagnetic susceptibility,
x= M/H = Ng2J(J + 1)p~/3kT {I 8-25)
This result is identical with the classical result (l8-22) because the total
, pi
magnetic moment PJ associated with J is given by
= g2J(J + l)p~ (18-26)
See, for example, expression (l8-1O). We note that from susceptibility
measurements in the range where the Curie law holds, it is possible to
determine the effective number of Bohr magnetons.
Pelf = g[J(J + 1)11/2 (18-27)
(ii) At low temperatures and strong magnetic fields the condition
imposed under (i) may not be satisfied, and (18-24) must be calculated
without approximating the exponentials. After some algebraic manipula-
tion12 one obtains the expression
{I 8-28)

where x = gJpBHjkT and BAx) is the Brillouin function defined by

2J + 1 [(2J + 1)x]
B J (x) = -----u- coth 2J -
1 ( x)
2J coth 2J (18-29)

Physically speaking, this result implies saturation of the magnetization at

low temperatures, i.e., all dipoles ultimately will be directed along H. In
this respect (18-28) is the analogue of the Langevin expression (l8-21),
the difference being that the latter holds for freely rotating dipoles only.
In fact, if J -";>- CI) (infinite number of possible orientations), the Brillouin,
expression (I8-28) becomes identical with (18-21).
The order of magnitude of the paramagnetic susceptibility of a solid
per cm3 may be estimated from (18-25). With N,-oJ 1022 and a dipole
12 See, for example, L. F. Bates, 0p. cit., p. 43.
456 DIAMAGNETISM AND PARAMAGNETISM [Chap. 18

moment of one Bohr magneton, one obtains X ~ 1/300T. At room

temperature X ~ 10- 5 ; at lOK, X ~ 10-3 - 10-2 • These values are of
importance in connection with the following question which may arise:
in the theory of the dielectric polarization of a solid it was necessary to
introduce the internal electric field, i.e., the actual field acting on a given
.. . \ .

12
Dy

10

.8
Pefl'

t 6

Pr Nd

Cp

Fig. 184. The effective moment in Bohr magnetons as function.

of the number of electrons for the trivalent positive rare earth ions.
The full curve represents the values calculated from (18-27); the
vertical lines represent the range of experimental values. [After
Bates, Modern Magnetism, Cambridge, 1951, p. 148]

atom was represented by the sum of the applied field and the field due to
the polarization of the surroundings. On the other hand, in the derivation
of the magnetic susceptibility above, the field acting on a dipole in a
paramagnetic solid was assumed to be equal to the applied field H. The
justification for this is the following: the order of magnitude of the internal
field is given by H + y M = H(l + YX), where y ~ 4. Hence the fractional
error made in neglecting the internal field correction is of the order of X.
As we have seen above, this is small for paramagnetic materials. For the
electrical case, the susceptibility is PIE = (€ - 1)/47T, and the internal
field cannot be neglected in solids or liquids, since (€ - 1) is not small
compared with unity.
It should finally be mentioned that there exists also a temperature-
independent paramagnetic contribution to the susceptibility at low
temperatures. This is called van Vleck paramagnetism. 'For its theoretical
treatment we refer to van Vleck, Theory oj Electric and MagnetiC
Susceptibilities, Oxford, New York, 1932.
Sec. 18-5] DIAMAGNETISM AND PARAMAGNETISM 457

18-5. Comparison of theory and experiment for paramagnetic salts

It was noted in Sec. 18-2 that paramagnetism requires the existence of

partly filled el~ctronic shells. Thus paramagnetic compounds are essentially
those containing transition group elements. Of these, the rare earth group
(incomplete 4f shell) and the iron group (incomplete 3d shell) have been
investigated most extensively. The palladium group (4d), the platinum
group (5d), and the uranium group
(5f-6d) have received relatively little
attention. 6
","'--',,
\
\
\
The rare earth ions. The theory \
4 \
outlined in the preceding section \
\
\
describes the behavior of most of the \
\
rare earth salts quite well. This may 2 \
be seen from Fig. 18-4, where the full \
\
curve represents the effective number
20 22 24 26
of Bohr magnetons calculated by van -z
Vleck from expression (18-27); the
J values and g were obtained from Fig. 18-5. The effective moment in
Hund's rules and from Lande's Bohr magnetons for the iron group as
function of the number of electrons Z
formula, as outlined in Sec. 18-2. in the ions. The dashed curve repre-
. The vertical lines correspond to ob- sents the values calculated from (18-27);
served values of Perr, obtained from the full curve refers to the "spin-only"
measurements of the temperature formula (18-30). The vertical lines
dependence of X (see equation 18-25). represent the ranges of experimental
values. (After Bates, Modern Magnetism,
The ions Sm3+ and Eu3+ evidently Cambridge, 1951, p. 152]
do not obey the simple theory.
However, it has been shown by van Vleck and Frank13 that these' dis-
crepancies can be explained satisfactorily if one considers the special
situation with regard to the energy levels of these ions.

The iron group ions. If one calculates the effective number of Bohr
magnetons for the ions of the iron group from expression (18-27), the
results do not agree at all with the experimental values obtained from the
Curie law. This may be seen from Fig. 18-5 where the vertical lines
r·epresent experimental values and the dashed curve represents (18-27).
However, if one assumes that only the electron spins contribute to the
magnetization, i.e., if one replaces (18-27) by
,
Peff = 2[S(S + 1W/ 2 . (18-30)
one obtains quite good agreement with experiment (full curve in Fig.
18-5). Thus the iron group ions behave as if the orbital magnetic moment
,3 A. Frank, Phys. Rev., 39, 119 (1932).
458 DIAMAGNETISM AND PARAMAGNETISM [Chap. 18
does not contribute at all. One speaks in this case of quenching of the
orbital momentum. The quenching is not necessarily complete; it may be
partial. Stoner suggested the following explanation for the different
behavior of the rare earth and iron groups in this respect:14 In the solid
state, the paramagnetic ions find themselves in strong electric fields
produced by neighboring diamagnetic ions. In the iron group, the para-
magnetic 3d electrons are the outermost electrons and these are therefore
fully exposed to the crystalline field. Consequently, the orbital motion is
locked into the field of the neighbors and cannot orient itself in an external
magnetic fieldP The electron spin has no direct interaction with the
electrostatic field and thus orients itself freely in an external magnetic field.
In the rare earth group, on the other hand, the paramagnetic 4f electrons
lie relatively deep inside the ions, because the outer electrons occupy 5s
and 5p levels. The screening of the 4f electrons from the crystalline field thus
leaves the orbits of the 4f electrons practically the same as in the free ion.
Further experimental evidence for the idea of quenchi.ng of the orbital
momentum in the iron group salts has been obtained from studies of the
anisotropy of the susceptibility in single crystals. The crystalline fields
distort the orbits in particular directions and thus the magnetic field
associated with these orbits has directional properties. The spin magnetic
moment orients itself along the resultant of the external field plus the
field associated with the orbits, and anisotropy results.
]n connection with expression (18-28) it may be noted that at low
temperatures saturation effects are observed which are described accurately
by the Brillouin function ;16 for the iron salts one must, of cou~, use S
rather than J in expression (18-28).

]8-6. Nuclear paramagnetism

At the end of Sec. 18-2 it was mentioned that nuclear magnetic

moments are smaller than the magnetic moments associated with electrons
by a factor,.._, 103 . In paramagnetic substances, therefore, the static nuclear
paramagnetism is masked by the electronic paramagnetism. Nuclear
paramagnetism has been observed, however, in solid hydrogen,17 which is
diamagnetic as far as the electronic system is concerned. The magnetic
moment obtained from ihese measurements is in agreement with the
known proton magnetic moment of 2.793 nuclear magnetons. Nuclear
magnetic moments are presently determined mainly by nuclear resonance
methods, to be discussed in Chapter 20.
14 E. C. Stoner, Phil. Mag., 8, 250 (1929).
I·;J. H. van Vleck, Theory of Electric ulld MagnetiC SII5,Ceptihifities, Oxford, New
York, 1932, p. 287.
'" See, for example, W. E. Henry, Phy,1'. Rev., 88, 559 (1952).
If B. Lasarew and L. Schubnikow, Phys. Z. Sowjetllllioll, 11,445 (1937).
Sec. 18-7) DJAMAGNETISM AND PARAMAGNETISM 459

18-7. The Hamiltonian for an electron in a I1\ilgnetic field

It is of some interest to consider the problem of para- and diamagnetism

from a some~hat different angle, starting from the Lorentz equation for
the force on an electron moving in a combined electric and magnetic field.

F = -eE - (e/c)v X H (l8-31)

The spin of the electron will be neglected in this section. Introducing the
vector potential A by means of the relation H = curl A, it can be shown
that (18-31) is equivalent with the following expression for the total energy
(the Hamiltonian) :18
1 ( p+-A
.Ye=- e)2 +V ( 18-32)
2m c

where V is the potential energy. Thus if we take

A;r = -k.vH; A~ = ixH; Az = 0

then H", = Hy = 0 and H = Hz. Thus for a magnetic field In the
z-direction, (18-32) becomes

From this we may draw two important conclusions. First, if the electron
motion were associated with a permanent magnetic dipole moment (.L.
this should give rise to a term -(.L' H = -- J.1. z H in the Hamiltonian, in
accordance with (18-4). Thus the second term on the right may be
identified with - J.1. z H, so that

fl. = --(e/2mc)(xp" -- yp,.) (18-34)

However, it follows from the definition of the angular momentum

M,,=rXp ( 18-35)

that (18-34) is related to the z-component of the angular momentum.

(18-36)

Hence relation (18-8) between the permanent dipole moment and the
angular orbital momentum follows immediately in a general fashion from
the Hamiltonian.

" See, for example, F. Seitz, The Modem Theory olSolids, McGraw-Hili, New York.
1940, p. 214; or N. F. Mott and I. N. Sneddon.. WavemechanicJ and Its Applicatioll~,
Oxford. New York. 1948, p. 39. , )"".~,
460 DIAMAGNETISM AND PARAMAGNETISM [Chap. 18

Secondly, let us consider the term in H2 in expression (18-33). Suppose

we had written down the Hamiltonian for the electrons associated with a
unit volume of a substance containing N atoms, each atom containing Z
electrons. The term in H2 would then read
z ,
N(e 2/8mc 2)H2 L (x~ + yf) = NZ(e 2/8mc 2)H2(p2) (18-37)
i=1

where (p2) represents the mean of the squares of the radii of the projections

s
t

Fig. 18-6. Curves OAB and HC represent the entropy versus T

without and with magnetic field, respectively. BC and C A are
the first two steps in the cooling process employing adiabatic
demagnetization.

of the orbits on a plane perpendicular to H. Now if the magrtetic field

induces a dipole moment in the material, the corresponding energy term
should be quadratic in H. Thus (18-37) may be considered the energy
term associated with the diamagnetism of the solid. Comparison of(18-37)
and (18-5) thus yields
Xdia = -NZ(e2 /4mc2)(p2) = -NZ(e2/6mc2)(r2)
where (r2) represents the mean square distance of the electrons relative to
the nucleus. It is observed that this result is identical with (18-20).

18--8. The principle of adiabatic demagnetization19

Because of its importance in obtaining temperatures below I°K, we

may briefly indicate the principle of adiabatic demagnetization. The
working substance in this process is a paramagnetic salt. In Fig. 18-6, let
the curve OAB represent the entropy of the system as function of T, in
the absence of an external field. Suppose now that at the temperature T H
T
.~ ,9 This method ,was (irst suggested by P. Debye, Ann. Physik, 81, 1154 (1926) and by
W. F. Giaugue, J. Am. Chern. Soc., ~9, 1864 (1927).
Sec. 18-8] DIAMAGNETISM AND PARAMAGNETISM 461
a magnetic field H is applied isothermally (good thermal contact with a
surrounding reservoir). Since the magnetic aipoles will tend to line up in
parallel with the field, the spin system becomes more ordered, and hence
the entropy decreases, say, from .B to C. If now the specimen is isolated
from its surroundings and the field is taken away, we move in Fig. 18-6
from C to A along an adiabatic (dS = 0). By successive steps of this kind,
temperatures of 10-3 degree absolute have been obtained.
Thermodynamically, the problem may be treated as follows.
According to the second law (see remarks in Sec. 18-1)

TdS=dE+MdH=(::)H dT + [(;!)7,+M]dH,

Because dS is a total differential, it follows that

where the last equality follows from one of the Maxwell relations. For
an isothermal process (B to C) one may thus write

dS=(aa~)HdH ,or S=SH~O+JoH(~~)HdH (18-38)

. In the Curie region we have, according to (18-25) and 08-27),

M = N ft~p:tfH/3kT
so that then
S = S}/~o - Nft1p;tfH2/6kT~ (18-39)
For further details of this process we refer to the literature. 2o
\

REFERENCES

L. F. Bates, Modern Magnetism. 3d ed., Cambridge, London, 1951.

P. W. Selwood, Magnetochemistry, Interscience, New York, 1943.
E. C. Stoner, Magnetism and Matter, Methuen, London, 1934.
J. van den Handel, "Paramagnetism," Adl'ances in Electronics and Electwn
Physics, 6, 463 (1954).
J. H. van Vleck, Theory of Electric and MagnetiC Susceptibilities, Oxford,
New York, 1932. ,
J. H. van Vleck, "Landmarks in the Theory of Magnetism," Amer. J. Phys.,
18, 495 (1950).
20 See, for example, N. Kiirti and F, Simon. Proc. Roy. Soc. (Londoll), A149, 152
( 1935).
462 DIAMAGNETISM AND PARAMAGNETISM [Chap. 18
"- ,
PROBLEMS l
\
18-1. Consider a rectangular loop of wire carrying a current I. From
the torque produced by a homogeneous magnetic field perpendicular to
one pair of sides, show that the current is equivalent to a magnetic dipole
moment f-' = IS/c, where S is the area of the loop. Do the same for a
circular current.
18-2. Consider an electron moving in a circular orbit of radius r under
influence of a nuclear charge Ze. From the equilibrium condition, find
the angular frequency Woo Applying a magnetic field H perpendicular to
the orbit and assuming' that in first approximation r remains unaltered,
show that the new angular frequency is

OJ = ±wo + eH/2mc = ±OJo + (I)L '

when the Larmor frequency w L ~ Wo'

18-3. Discuss the Gouy balance as an instrument for measuring the

static susceptibility of a solid (see L. F. Bates or P. W. Selwood, op. cit.).
18-4. From the rules governing the use of quantum numbers, show
that the K, L, and M shells in an atom can accommodate at most,
respectively, 2, 8, and 18 electrons.
18-5. Consider a spinning spherical shell of charge e and mass m
uniformly distributed ove. its surface. Show that the ratio of the magnetic
moment to the angular momentum is e/2mc (i.e., the g factor is nnity).
18-6. Consider a system of N electron spins in an external field H.
For H = 104 gausses and T = 300o K, calculate the excess number of spins
oriented parallel to the field. Do the same for liquid helium temperature.
18-7. Discuss the diamagnetism of the conduction electrons in a metal
on the assumption that they are free. (See for example F. Seitz, Modern
Theory of Solids, McGraw-Hili, New York, 1940, p.583.)
18-8. Consider a system of N noninteracting spins of t in a magnetic
field H; the system is in equilibrium with a temperature bath T. Set up
an expression for the free energy F of the system in terms of the excess
number of aligned spins n, where n is for the moment undetermined.
From the fact that F should be a minimum, rederive the proper expression
for the susceptibility of the system.
18-9. When CH and C M represent, respectively, the specific heats at
constant field and at constant magnetization, show from thermodynamics
that for a substance which satisfies the Curie law, M = CH/T,
Chap. 18] DIAMAGNETlSM AND PARAMAGNETlSM 463
18-10. Suppose a sphere of magnetic material finds itself in a magnetic
field H. Show that when H is suddenly increased by an amount /);.H and
when the energy absorbed by the sphere cannot leak away, the increase
in temperatu'r,e is given by

/);.T = - _!'_ (OM(H,T») /);.H

CH oT

This is known as the magnetocaloric effect.

.
H,

18-11. Suppose a beam of atoms is passed through an inhomogeneous

magnetic field. Let fl-z be the component of the magnetic moment of a
certain atom along the field direction. Show that the force on the atom
is F z = fl-.{dH/dz). This formula forms the basis of the Stern-Gerlach
experiment in which an atomic beam is split up into a number of separate
beams; this number is equal to the number of possible fl-z values.

;1 nl

I
~
t
Chapter 19 \
\
I \

FERROMAGNETISM,
ANTIFERROMAGNETISM, AND
FERRIMAGNETISM

Ferromagnetism

19-1. Introductory remarks

In ferromagnetic materials the magnetization versus magnetic field

relationship exhibits hysteresis similar to that encountered in Chapter 8
for the relationship between P and E in ferroelectric materials. Of the
elements, only Fe. Ni, Co, Gd, and Dy are ferromagnetic, although there
are a relatively large number of ferromagnetic alloys and oxides (see Table
19-2). Above a critical temperature Of' ksown as the ferromagnetic Curie
temperature. the spontaneous magnetization vanishes and the material
becomes paramagnetic. Well above the Curie temperature the suscepti-
bility follows the Curie-Weiss law,

x= C/(T - 0) (19-1 )

where C is the Curie constant; the temperature 0 is called the paramagnetic

Curie temperature and is usually some degrees higher than Of (see Fig. 19-4).
The theory of ferromagnetism is centered about the following two
hypotheses put forward in 1907 by Weiss. 1
(i) A ferromagnetic specimen of macroscopic dimensions contains, in
general, a number of small regions (domains) which are spontaneously
magnetized; the magnitude of the spontaneous magnetization of the
specimen is determined by the vector sum of the magnetic moments of
the individual domains.
(ii) Within each domain the spontaneous magnetization is due to the
existence of a "molecular field" which tends to produce a parallel alignment
of the atomic dipoles. r
The occurrence of hysteresis in the magnetization versus field relation-
ship can be explained on the basis of these hypotheses in a similar way as the
hysteresis loop for P versus E in Sec. 8-1. The reader is reminded that
I P. Weiss, J. Phys., 6, 667 (1907).
464
Sec. J9-1] FERROMAGNETISM 465
the spontaneous magnetization refers to a single domain, whereas the
remanent magnetization (for H = 0) refers-to the specimen as a whole
(see Sec. 8-1).
As a parti"ular example of a hysteresis curve we give in Fig. 19-1 the
magnetization curve for a single crystal of silicon-iron.2 It is observed
20 xl()3 gauss

12r---+---+---+-~~-4~---+---+--~

4
B
0
t
-4

-8

-12

-16

-20
-.08 -.04 0 .04 .08
- H(gaU88)

Fig. 19-1. The magnetization curve for a single crystal of silicon

iron; the B scale is approximate. [After Williams and Shockley,
ref. 2]

that for this particular case a very weak field (of the order of 10-2 gauss)
is sufficient to produce a magnetization M = B/47T = 103 gausses. It
should be mentioned that the coercive field for bulk materials may be
several orders of magnitude larger than for the example in Fig. 19-1.
Assuming atomic dipoles of the order of one Bohr magneton (,.._,1O-20 cgs
unit) one verifies readily that values of M of the order of 103 gausses
require essentially a parallel alignment of all the atomic dipoles in the
specimen; hence the saturation of the magnetization in that region. By
way of contrast this may be compared with a paramagnetic solid which in
the same field of 10-2 gauss would give a magnetization M ~ N f-t~H/kT ~
10-6 gauss at room temperature; this is smaller by a factor of 10 9 . Note
2 H. J. Williams and W. Shockley, Phys. Rev., 75,155 eI949).

"
466 FERROMAGNETISM [Chap. 19
that in a paramagnetic salt only one in 10 9 atomic dipoles is, on the
average, lined up along the external field direction for the conditions
specified above.

19-2. The Weiss molecular field

Spontaneous magnetization implies cooperation between the atomic

dipoles within a single domain, i.e., there must be some kind of interaction
between the atoms which produces the tendency for parallel alignment of
the atomic magnetic dipoles. In order to obtain a phenomenological
description of spontaneous magnetization, Weiss assumed that the mole-
cular field H", acting on a given dipole may be written in the form 3

Hm= H+ yM (19-2)

where H is the applied field, M is the magnetization and y is the molecular

field or Weiss constant. Clearly, the term yM provides the cooperative
effect. Without giving a physical interpretation of the constant y, we shall
show in this section that a field of the type (19-2) indeed leads to spon-
taneous magnetization, to the existence of a ferromagnetic Curie point,
and to the Curie-Weiss law (19-1). We shall use the quantum theory of
magnetization rather than the classical Langevin theory used by Weiss in
his originai article.
Consider a solid containing N atoms per unit volume, each with a total
angular momentum quantum number J (which includes the total orbital
contribution L and the total spin contribution S). According to the results
of Sec. 18-4 one may then write for the magnetization t

M = Ngp,nlBAx) \ (19-3)

where for paramagnetic solids x = gP,BHJjkT. For ferromagnetic

materials we should replace H by H m' in accordance with assumption
(19-2), because Hm is the actual field seen by any given atomic dipole.
Thus, in the present case ~ __

(19-4)

As long as we are interested in spontaneous magnetization, H = 0 and

we may write
M = xkT/yg fl BJ (I9-5)

Since M must satisfy both (19-3) and (19-5), its value at a given temperature
may be obtained from the point of intersection of the two corresponding

• Note that in the dipole theory offerroelectricity. Sec. 8-3, a field of exactly the same
_,
form is assumed. . ." "" iof ~H'~'"

...
Sec. 19-2] FERROMAGNETISM 467

M versus x curves, as indicated schematically in Fig. 19-2. Note that

09-5) represents a straight line, the slope-of the line being proportional
to T. From Fig. 19-2 it follows that for T < 0" one obtains a nonvanishing
value for A(, although the external field H = 0. 4 Hence for T < 0,.
spontaneous magnetization results. For T = Of' the slope of the straight
line represented by (19-5) is equal to that of the tangent of curve (19-3)
at the origin. Thus, for T ~ 8f the spontaneous magnetization vanishes.

M T>8r
t

o _x I
Fig. 19-2. Schematic representation of the method for finding the
spontaneous magnetization at a temperature T. A point of inter-
section such as P determines M(T).

Jt will be evident that there must exist a relation between the Curie
temperature 8/ and the molecular field constant y; in fact, one expects
Of to increase with y because the tendency for parallel alignment increases
as y becomes larger. In order to establish this relationship, we make use
of the fact that for x ~ I (near the origin in Fig. 19-2), the Brillouin
function is approximately given by

BAx) ~ (J + l)x/3J (19-6)

Hence, the tangent of curve (19-3) at the origin has a slope equal to
NgflB(J +
1)/3. Putting this equal to the slope of curve (19-5) for T = Of'
one obtains
(19-7)

where fl is the total magnetic moment per atom. Hence 8f is proportional

to the molecular field constant.
Let us now consider the susceptibility in the region well above the
ferromagnetic Curie temperatl\re. In this region magnetization occurs
is
only when an external field H applied because there is no spontaneous
magnetization. Thus, for fields low enough so that we are far away from

, Although the origin in Fig. 19-2 is also a point of intersection, it can be shown that
the free energy of the state with nonvanishing M value is smaller than that for M = 0,
i.e., the latter is unstable.
468 FERROMAGNETJSM [Chap. 19

saturation, we may employ the approximation (19-6) for BAx), and (19-3)
becomes
M = NgP,B(J + 1)xf3 (19-8)

where x is given by (19-4). Solving for M/H after substituting x into

(19-8) one obtains readily the Curie-Weiss law

x= M/H= Cf(T- 0) (19-9)

where C = N p,2/3k and 0 = yN p,2/3k = yc. Note that the value obtained
here for 0 is identical with that obtained for Of from expression (19-7).
In other words, the Weiss theory does not distinguish between the para-
and ferromagnetic Curie temperatures.

19-3. Comparison of the Weiss theory with experiment

Temperature dependence of the spontaneous magnetization. The

maximum component of an atomic dipole associated with a quantum
number J in any given direction is g~P,B. Hence the maximum value of
the spontaneous magnetization is given by Ngp,BJ, where N is the number
of atoms per unit volume. This also follows from (19-3) because for x ~ 00
the Brillouin function BAx) ~ 1. In accordance with Fig. 19-2, the
maximum spontaneous magnetization occurs for T = 0, and we shall
therefore write NgP,BJ = M(O). In order to describe the temperature
dependence of the spontaneous magnetization in a convenient manner,
we rewrite (19-3) in the form

M(n/M(O) = BAx) (19-10)

where M(T) is the magnetization at a temperature T. Similarly, we may

write (19-5) in the form

M(T)/M(O) = xkT/yNg2p,jP = xT(J + 1)/3JO, (19-11)

where the last equality is obtained by substituting for y in terms of 0,

by employing (19-7). The quantity M(T)/ M(O) must satisfy both (I9-1O)
and (I 9-11); hence it can be obtained by the intersection method indicated
in Fig. 19-2. It is important to note that for a given value of J, this
procedure leads to a universal curve when M(T)IM(O) is plotted as function
of TIO" as will be evident from (19-10) and (19-11). In Fig. 19-3 we have
represented such curves for J = t, J = 1 and J = 00; the latter case
corresponds to classical freely rotating dipoles. In the same figure one
finds experimental points for Fe, Ni, and Co. It is observed that the
curve for J = t fits the data best, indicating that the magnetization is
essentially associated with the electron spins rather than with the orbital
momentum of the electrons. That this is indeed the case has been confirmed
Sec. 19-3] FERROMAGNETISM 469
by gyromagnetic experiments. 5 In such experiments one either reverses
the magnetization of a freely suspended' specimen and observes the
resulting rotation, or one rotates the specimen and observes the resulting
magnetizati~; the former is called the Einstein-de Haas method, the
latter the Barnett method. From such experiments one obtains the g value,

1.0

.8

0
~
......
.6
~
~ • Fe
'"
t .4 °Ni
xCo

f ,,'''_
.2

o .4 .6 .8 1.0
- T/9{

Fig. 19-3. The spontaneous magnetization for Fe, Ni, and Co as

function of temperature. The curves for J = t, J = 1 and J = 00
are those obtained from equation (19-10) and (19-11).

i.e., the ratio between the magnetic moment and the angular momentum;
for the electron spin g = 2, for the orbital motion g = I. Results of such
experime~ts are given in Table 19-1; they show that the magnetization is
largely due to the electron spins. 5 __ _
Table 19-1. The Magnetomechanical Ratio g for Some Ferromagnetics"
g u
"
Fe 1.93 FeaO. (magnetite) 1.93
Co 1.87 Cu.MnAI (Heusler alloy) 2.00
Ni 1.92 78~'-;; Ni, 22 % Fe (permalloy) 1.91
a For references to the original literature, see c. KITTEL. Introduction 10
Solid Slale PhysiCS. Wiley. New York. 1953. p. 168.

As in other order-disorder phenomena, the decrease of the spontaneou~

magnetization with temperature is associated with an anomalous specific
heat; because of lack of space, this problem will not be discussed here.
:> See, for example, S. J. Barnett, Proc. Am. A cad. Arts Sci., 75, 109 (1944); G. G.
Scott, Phys. Rev., 82,542 (IY51); 87,697 (1952).
470 FERROMAGNETISM [Chap. 19

The effective number of Bohr magnetons per atom. From the saturation
magnetization at T = 0 and the number of atoms per unit volume, one
can calculate the effective number of Bohr magnetons neff per atom.
Values of neff obtained in this way are given in Table 19-2, together with
the ferromagnetic Curie temperature ()f and the spontaneous magnetization.
It is observed that although each atom has an integral number of electrons,
the values of neff are all nonintegral. The reader may at this point be
reminded that for the single ions the number of unpaired 3d electrons is
determined by the total number of 3d electrons in accordance with Hund's
rules as follows: 6
Total number of 3d electrons: 0 I 2 3 4 5 6 7 8 9 10
Number of unpaired 3d electrons: 0 I 2 3 4 5 4 3 2 I 0

Thus for iron, which has 6 electrons in the 3d shell in the ionic state;
one expects on this basis four Bohr magnetons (5 with an "up" spin and
I with a "down" spin). We see from Table 19-2, however, that neff is 2.2.
Table 19-2. Saturation Magnetization, Ferromagnetic Curie Point, and the
Effective Number of Bohr Magnetons per Atom. a For the mixed oxides nerr
is calculated per molecule MOFe 20 3• where M is the divalent metal ion.
, '.
Msat (cgs) Msat (cgs)
Solid OaK 0, CK) "e1! (OCK)
room temp.

Fe 1707 1752 1043 2.221

Co 1400 1446 1400 1.716
Ni 485 510 631 0.606
Gd ... 1980 289 7.10
Dy ... . .. 105 ...
MnBi 600 675 630 3.52
Cu 2MnAI 430 (580) 603 (4.0)
CU2Mnin 500 (600) 506 (4.0)
MnAs 670 870 318 3.40
MnB 147 ... 533 . ..
Mn,N 183 ... 745 0.24
MnSb 710 ... 587 3.53
CrTe 240 ... 336 2.39
CrO, ... ... .. 2.07
MnOFe~03 358 ... 783
,

5.0 I
FeOFe.O. 458 ... 848 4.2
CoOFe 20 3 .. , ... 793 3.3
NiOFe.O. 240 ... 863 2.3
CuOFe.O. 290 ... 728 1.3
MgOFe 2O. 143 ... 583 1.1

a Reprinted with permission from C. KlTTEL~Introduction to Solid Slale Physics~ Wiley. New York.
19S3. p. 166.

• See SeC. 18-2.

Sec. 19-3] FERROMAGNETISM 471
This discrepancy is not surprising if one recognizes that in the solid the
atomic levels are broadened into bands and that the simple atomic picture
cannot be valid.
Thus M04.t7 and SlaterS explain the nonintegral values for neff on the
basis of a wide 4s band overlapping with a narrow 3d band (Fig. 10-16).
In general, there is on the average a certain fraction of the total number
of 3d and 4s electrons in each band.
l/x --~-
For example, the fact that iron has
ncH'= 2.2 indicates that in the 3dband t
there are 5 electron spins parallel and
2.8 antiparallel. Hence, of the total
of 8 electrons, 7.8 reside on the
average in the 3d band and 0.2 in
the 4s band.

The paramagnetic region. Com- . 1, -T

prehensive experimental studies of
the behavior of Fe, Co, and Ni
above the Curie points have been Fig. 19-4. Schematic representation of
made by Sucksmith and Pearce 9 the behavior of the ferromagnetic metals
above the Curie point; the slight
and by Fallot.lO According to the curvature leads to the distinction
Curie-Weiss law (19-9), a plot of between the ferromagnetic and para-
I/x versus T should yield a straight magnetic Curie points.
line, the intercept along the T-axis
being equal to O. The experiments show that this law is indeed
satisfied with considerable accuracy except in the region close to
the Curie point. In fact, for all three metals there occurs a concave
upward curvature near the Curie point, which leads to the distinction
between the ferrom:lgnetic and paramagnetic Curie temperatures Of and
0, respectively. This behavior is indicated schematically in Fig 19-4. To
illustrate this point, we give here Of and 0 in degrees Kelvin for these
metals. According to Stoner the observed curvature near the Curie point
is consistent with his theory of ferromagnetism based on the collective
electron treatment.n
Fe Co Ni
0, 1043 1393 631
(j 1093 1428 650

'; N. F. Mott. Proc. Phys. Soc. (London), 47, 571 (1935). '"
• J. C. Slater. J. Appl. Phys., 8, 385 (1937); see also E. C. Stoner, Proc. Roy. Soc.
(LOlldoll), A165, 372 (1938); A169, 339 (1939); for an alternative explanation. see C:'
Zener, Phys. Rev., 81, 440 (1951); 83,299 (1951); 85,324 (1952).
9 W. Sucksmith and R. R. Pearce, Proc. Roy. Soc. (Lolldoll). A167, 189 (1938).

10 M. Fallot. Alln. Physik, 10,291 (1938); J. phys. radium, 5, 153 (1944).

11 E. C. Stoner, Proc. Leeds Phil. Lit. Soc., 3, 457 (1938).

472 FERROMAGNETISM [Chap. 19

19-4. The interpretation of the Weiss field.

From what has been said in the preceding section one may conclude
that, apart from certain details, the Weiss field describes the observations
satisfactorily. So far, however, we have not touched upon the problem
of the origin of this field. We shall limit the discussion here to one inter-
pretation, viz., that given by Heisenberg; references to other interpretations
are given below.
First of all, a rough estimate of the required molecular field Hm may
be made as follows. The energy of a given atomic dipole in this field
should be of the order of k8, i.e.,

(19-12)

For a Curie temperature f) ~ 1000 0 K this gives Hut ~ 10 7 gausses. From

this one concludes immediately that the internal field is not due to a
simple dipole-dipole interaction between neighbors, because such fields
would be of the order IlH/a 3 ~ 103 gausses. It may be pointed out here
that in the case of ferroelectric materials the situation is quite different,
because atomic electric dipoles are larger than magnetic ones by a factor
of about 100;12 thus, at least in principle, the molecular field in ferro-
electrics may be due to dipole-dipole interaction. We may also point out
that in the ferromagnetic solids the molecular field constant y = Hm/M ~
10 7/103 ~ 104 , which is orders of magnitudes larger than the Lorentz
factor 417/3 which one might expect for a simple model based on dipole-
dipole interaction.
In 1928 Heisenberg showed that the large molecular field may be
explained in terms of the so-called exchange interaction between. the
electrons_l3 The principle of this explanation may be illustrated by
considering the hydrogen molecule. Let the nuclei be denoted by
a and b, the atomic wave functions by "PI! and "Pb' the electrons by
I and 2. The interaction potential between the two atoms is then,
in a self-explanatory notation, ~ ....

(19-13)

The reader familiar with the elementary Heitler-London theory of

chemical binding knows that the energy of the system may be written
in the form
E=K±Je (I9-14)

12 I Debye unit is 10- 18 cgs unit. whereas fiB = 0.92 X 10- 20 cgs unit.
13 W. Heisenberg. Z. Physik. 49, 619 (1928).
Sec. 19-4] FERROMAGNETISM 473
when~ K is the Coulomb interaction energx, which does not concern us
here, and Ie is the exchange integral,
" (19-15)
The plus sign in (19-14) refers to the nonmagnetic state of the molecule
in which the two electronic spins are antiparalleJ. The minus sign corre-
sponds to the case in which the two spins are parallel, i.e., to the magnetic
state. It is evident from (19-14) that the
magnetic state is stable only if Ie is posi- - .~,'~- --
tive, because then (K - Ie) < (K + Ie).
It can be shownl4 that (19-14) may
be written in a more convenient form
which contains the relative orientation
of the two spins, viz., ",

E = const. - 21eSI • S2 (19-16)

In other words, the exchange energy
appears in the total energy as if there
exists a direct coupling between the two
spins. It must be emphasized, however, Fig. 19-5. Schematic representa-
that the exchange interaction is funda- tion of the behavior of the exchange
mentally electrostatic and that the spin integral as function of interatomic
distance.
enters into the energy expression as a con-
sequence of the Pauli exclusion principle.
Making use of what has been said above, we shall thus assume from
now on that for two atoms i and j the effective coupling between the spins
due to exchange interaction is equivalent with a term
(19-17)
in the energy expression; Iii is the exchange integral for the two atoms.
In general, the exchange integral is negative, i.e., in general the non-
ferromagnetic state is favored. However, according to a qualitative
analysis by Bethe, Ie is likely to be positive when the distance fa/I between
the nuclei is fairly large compared with the orbital radii of the electrons
invo!ved; the behavior of Ie as function of fab is indicated in Fig. 19-5. 15
According to Slater, the ratio fab/fO where fo is the orbital radius, should
be larger than 3 but not much larger. 16 Some pertinent data in this respect
are given below.
Fe Co Ni Cr Mn Gd
3.26 3.64 3.94 2.60 2.94 3.1
,. See, for example, F. Seitz, The Modern Theory of Solids, McGraw-Hili, New York,
1940, p. 612.
,. H. Bethe, Handbuch der Physik, Vol. 24/2.
,. J. C. Slater, Phys. Rev., 36, 57 (1930).
474 FERROMAGNET]SM [Chap. 19
Note that Cr and Mn are not ferromagnetic. One might raise the question
here whether an element with uncompensated spins, which itself is not
ferromagnetic because the rablro value is not favorable, may be combined
with another nonferromagnetic element to form a compound for which
the r"blro value is suitable for ferromagnetism. That this seems indeed
possible is illustrated by the fact that for example MnAs and MnSb are
both ferromagnetic; the lattice constants of these compounds are, respec-
tively, 2.85 and 2.89 A, as compared with 2.58 A for pure Mn. The ferro-
magnetism of the other alloys given in Table 19-2 can presumably be
explained in a similar manner. We may also mention here that the Curie
point may be shifted by applying high pressures. l7
Because of the importance of the exchange integral, one would like
to relate it to the Weiss constant y and to the ferromagnetic Curie tempera-
ture. Although this is a very complicated problem, an approximate
relationship between Ie and y may be found by a simplified procedure
suggested by Stoner. IS We shall assume that the exchange integral is
negligible except for nearest neighbors and that its value is Ie for all
neighboring pairs. In accordance with (19-17) we may then write for the
exchange energy of a given atom i with its neighbors,

V = -2Ie ~ Si' Sj (19-18)

j

where the summation is over the nearest neighbors of atom i. The essential
assumption of Stoner is that the instantaneous values of the neighboring
spins may be replaced by their time averages. Thus, if there are z nearest
neighbors, we have I
'--(,'; '"" /

(19-19)

Assuming that the magnetization M is along the z-direction, we may write

(19-20)

According to (19-19) and (19-20),

V = -2zIeSziMjgNflB (19-21)

Now, this expression should be equal to the potential energy of spin i in

the Weiss field yM, i.e.,
(19-22)

From the last two equations we obtain the following relation between y
and Ie:
- (19-23)
)7 L. Patrick, Phys. Rev., 93, 384 (1954).
18 E. C. Stoner, Magnetism alld Matter, Methuen, London, 1934, p. 358.
Sec. 19-4] FERROMAGNETISM 475
Making use of (19-7), we obtain for the rel~tion between Of and Je ,

_: __,. Of = 2zJe S(S + 1)/3k (19-24)

Thus for a s'i'mple cubic lattice with z = 6 and with S = 1, one finds
(19-25)

More exact calculations by Opechowski 19 and P. R. Weiss20 (not to be

confused with Pierre Weiss) give, respectively, 0.518 and 0.540 for the
ratio Jf/kOf for a simple cubic lattice.
Another method of calculating the magnetization in terms of the
exchange integral was introduced by Bloch. 21 His so-called spin-wave
method is applicable only in the low-temperature region, and leads to
the result
M(T) = M(O) [ I - A(kT/lr)3/2] for T <!( Of (19-26)

where A is a numerical constant equal to O. I 174 for the simple cubic

lattice. This result is known as the Bloch T3/2 law and is in good agreement
with low-temperature data. For further discussions of exchange inter-
actions and objections against the Heisenberg theory of ferromagnetism
we refer the reader to the literature. 22

19-5. Qualitative remarks about domains

We mentioned in Sec. 19-1 that in order to explain the fact that a piece
of ferromagnetic material may exist in the nonmagnetized state, whereas a
weak magnetic field may produce saturation magnetization in the same
specimen, Weiss introduced the domain hypothesis. Each domain is
spontaneously magnetized, the magnetization being appropriate to the
temperature T of the specimen. The over-all magnetization is given by the
sum "Of the domain vector.s, and thus may vanish under certain circum-
stances; an example is given in Fig. 19-6a. Magnetization of a specimen
may occur either by the growth of one domain at the expense of another,
i.e., by the motion of domain walls (Fig. 19-6b), or by rotation of domains
(Fig. 19-6c). A representative magnetization curve is given in Fig. 19-7,
indicating the predominant processes in the different regions. We may
note here that originally it was thought that the well-known Barkhausen
jumps were due to the rotation of a complete domain and that the size
of the Barkhausen discontinuities was a measure of the size of the domains.
19 W. Opechowski, Physica, 4,181 (1937); 6,1112 (1939). ..
20 P. R. Weiss, Phys. Rel'., 74, 1493 (1948).
21 F. Bloch, Z. Physik, 61, 206 (1930).

22 See the papers by C. Kittel, C. Zener and R. R. Heikes, J. C. Slater, E. P.

Wohlfarth, and J. H. van Vleck held at the Washingt6n Conference on Magnetism,

Revs. Mod. Phys., 25 (1953); see also J. H. van Vleck, Ret's. Mod. Phys., 17, 27 (1945) .
.~.
476 FERROMAGNETISM
'--.
[Chap. 19
Howevj::r, experiments by Williams and Shockley show that the Barkhausen
jumps are mainly associated with irregular fluctuations in the motion of
the domain walls rather than with domain rotation. 23
\ H
-H
Y
....------71
"Hard"
/'directWn

-
/
/

Non·magnetized Wall motion Domain rotation

(a) leI
Fig. 19-6. The domain structure (a) corresponds to the non-
magnetized state; (b) represents magnetization due to wall motion;
in (c) the magnetization is due to rotation of the domain vectors
from an \'easy" to a "hard" direction (see Sec. 19-6).

The most direct experimental evidence for the existence of domains is

provided by the so-called "Bitter powder patterns."24 A drop of a colloidal
suspension of ferromagnetic particles is placed on the carefully prepared

B
j I
c II
I
r

Irreversible wall displacements

- A---------
Reversible wall displacements
-He ·0 --H

Fig. 19-7. Typical magnetization curve of a virgin specimen,

indicating the predominant processes taking place in the different
regions. When the field is reversed at C, the dashed curve is
obtained; H, is called the coercive jorce. [After C. Kittel, Revs. Mod.
Phys., 21,541 (l949)J

surface of the specimen; since there are strong local magnetic fields near
the domain boundaries, the particles collect there and the domains may
be observed under a microscope.
23 H. J. Williams and W. Shockley. Phys. Rev., 75, 178 (1949).

2. F. Bitter, Phys. Rev., 38, 1903 (1931) .

. '
Sec. 19-5] FERROMAGNETISM 477
The physical origin of domains may be llnderstood from the general
thermodynamic principle that tjle free energy E - TS of a solid tends to
reach a minimum value. As a result of the high degree of order in the
magnetic sysi~m, except in the vicinity of the Curie temperature, the
entropy term may be neglected for our purpose; thus, minimizing the
energy E of the system should be sufficient to understand the existence of
domains. To illustrate the essential features of this point of view, we refer
to Fig. 19-8, representing a cross section through a ferromagnetic single

~~~
N S N S
I I I
I I I
I I I , I
I I I I I I I
t t I, ~ I, t I, ~ t'I tI II t II t, ,'t
I I I
I I , ," I I
, I , I I
I : :
S..._.,..._.,..._....
N S N

(al (el

Fig. 19-8. The origin of domains (see text). [After C. Kittel, Revs:
Mod. Phys., 17, 541 (1949)]

crystal. In (a) we have a single domain, i.e., saturation magnetization of the

specimen. Because of the free magnetic poles at the ends of the specimen,
the expression for the energy will contain a term (I J87T) SH2 dV associated
with the field outside the crystal. In a configuration such as in Fig. 19-8b
on the other hand, the field energy is strongly reduced because the spatial
extension of the field is much smaller. Now, as we shall see below, there
is a certain amount of energy involved in producing a domain wall.
Hence, one ultimately arrives at an equilibrium situation with a number
of domains such that the energy required to produce one more domain
boundary is equal to the resulting reduction of the field energy. The energy
involved in building a domain wall is discussed in Sec. 19-7.
A domain structure such as in Fig. 19-8c has zero magnetic field energy.
This is achieved by introducing the triangular prism domains at top and
bottom of the crystal; such domains are called closure domains. Note
that the wall between a closure domain and a vertical domain in Fig. 19-8c'
makes an angle of 45° with the magnetization directions in both types of
domains. Hence the normal component of the magnetization in crossing
such a wall is continuous, i.e., there are no free poles and there is no field
energy. The energy required to produ 7e a closure domain is essentially

._
478 FERROMAGNETISM [Chap. 19

determined by the anisotropy of the crystal, i.e., by the fact that ferro-
magnetic materials have "easy" and "hard" directions of magnetization.
For example, from the magnetization curves represented in Fig. 19-9 one
sees that in iron, which is cubic, the easy directions of magnetization are
the cube edges. 25 In 'nickel, which is also cubic, the easy directions of
magnetization are the body diagonals. In cobalt the hexagonal axis of the
crystal is the only preferred direction; thus in a cobalt crystal with
prominent domains magnetized along the hexagonal axis, the closure

-
18

15
v [1001
~
~

:5 ~/
.....
i 12 L L
t
9
V [1111

Iron
IS·C
6
o 1 2 3 4 5 .6
- Hjloo
Fig. 19-9. Magnetization curves at 18°e for a single crystal of iron
for different directions of the field relative to the crystal axes.
[After Piety, ref. 25]

domains are necessarily magnetized along a hard direction. In iron and

nickel, on the other hand, it is possible to have both the closure domains
and the dominant domains magnetized along easy directions.
Summarizing the ideas discussed above we may say that domain
structure has its origin in the principle of minimum energy. It will be
evident that the number of domains and the domain structure will depend
to a large extent on the shape and size of the crystal under consideration.
The size of the domains for a particular domain structure may also be
obtained from the principle of minimum energy. The volume of domains
may vary between, say, 10-2 to 10- 6 cm3 •

19-6. The anisotropy energy

Since ferromagnetic crystals have easy and hard directions of mag-

netization, the energy associated with the magnetization depends on
direction. In order to obtain the so-called anisotropy energy in terms of
the direction of magnetization, one makes use of the crystal symmetry.
_, R. G. Piety, Phys. Rev., 50, 1173 (1936).
Sec. 19-6J FERROMAGNETISM 479
Thus, for a cubic crystal, let Cl I , oc 2 , and OC 3 represent the direction cosines
of the magnetization referred to the cubic crystal axes. Because of the
cubic symmetry, the anisotropy energy should be an even power of each
Cl; furtherdrore, it should be invariant for interchange between the oc's.
The lowest-order combination satisfying these conditions is (oci + oc~ + ocn
but since this is identically equal to unity, it does not enter in the anisotropy'
effects. The next order combination is (ociocI + ocioc~ + oc~ocn; although
this term by itself represents the experimental results for iron and nickel
reasonably well, one usually adds one more term, viz., ocioc~oc~. Thus for
cubic crystals the anisotropy energy may be written as

( 19-27)

when higher terms are neglected. The constants KI and K2 can be deter-
mined from experiment; for iron at room temperature, )

K2 = 1.5 >( 10'; ergs/cm 3 (19-28)

For crystals with a single preferred axis, such as cobalt, the anisotropy
energy may be written in the form

(19-29)

where 4> is the angle between the magnetization and the easy axis; higher
order terms are usually neglected. For cobalt at room temperature,

K2 = 1.0 X 10 6 ergs/cm 3 (19-30)

It should be stated that the anisotropy constants depend strongly on

temperature. The origin of the anisotropy is not immediately obvious.
For example, the exchange interaction between the spins, given by (19-17),
is completely independent of the geometrical anisotropy of the crystal,
and hence does not lead to anisotropy effects. Furthermore, the anisotropy
which arises from the interaction between the magnetic dipoles associated
with the spins turns out to be much smaller than the observed anisotropy.
It is believed at present that the origin of the anisotropy must be
sought along the following lines. We have seen before that the orbital '
angular momentum of the electrons is partially quenched as a result of
inhomogeneous electric fields produced by neighboring atoms. On the
other hand, because the quenching is incomplete, the electron spin will
interact with the orbital momentum. Thus the electron spins are aware of
the crystal lattice and its geometry as a result of the spin-orbit coupling.
For further details, see a review paper by van Vleck. 26 .

2" J, H. van Vleck, AliI/ales de I'insfifllf Hell/'i Poinca/'e, 10, 57 (1947).

"
480 FERROMAGNETISM [Chap. 19

19-7. The thickness and energy of the Bloch wall 1,

_ Although we have introduced the concept of a domain boundary

before, we shall now consider this in some more detail. According to
Bloch, the spin direction in going from one domain to another does not
change abruptly, but gradually as indicated in the now classical Fig. 19-10;
the domain walls are called Bloch walls. 27 The reason for the gradual
rather than abrupt change in spin direction may be understood from the

Fig. 19-10. Schematic representation of a 1800 Bloch wall.

following argument. Consider two electrons with parallel spins; according

to (19-18) the exchange energy is then-2Je S 2. If we interpret the spin
vectors in (19-18) as classical vectors 28 the exchange energy, when the two
spins make a small angle 1>, is equal to -2JeS 2 cos 1> c::::::_ _2Je S2(I - 1>2/2).
Thus in the process of changing the angle between the spins from zero to
1>, the energy is increased by an amount J,S21>2. Consider now a row of
(N + I) spins within a Bloch wall separating two domains of which the
magnetization directions make an angle 1>0' Let the angle between
successive spins be 1> = 1>0/N. The exchange energy of the row of spins,
taking into account only nearest neighbor interaction, is then

I (19-31)

Hence the energy decreases when N increases. This raises the question:
Why does not the wall become infinitely thick? It is at this point that
the influence of the anisotropy energy must be considered. Since the spins
within the wall are nearly all directed away from the easy axes, one expects
an anisotropy energy which is approximately proportional to the thickness
of the wall. This has the effect of limiting the wall thickness, as may be
seen from the following arguments. Let us consider a wall of 1 cm 2 area,
the thickness being Na, where a is the lattice constant. The total wall
energy per cm z may then be written in the form

a = aeJ: + aau (19-32)

2' F. Bloch, Z. Physik. 61, 206 (1932).
,i
2" According to Kittel this is permitted as long as ¢ is smarl.

.(. ...
Sec. 19-7] FERROMAGNETISM 481

The exchange energy a ex is obtained by multiplying (19-31) by the number

of rows of spins per cm 2 , i.e., by l/a2 . ""The anisotropy energy aan is
approximately equal to the anisotropy constant K times the volume Na of
the wall. I-htnce (19-32) becomes

(l9-33)

The equilibrium value of N may be obtained by minimizing a with respect

to N. Hence, putting da/dN = 0, one obtains

As an example we may consider the case of iron; taking J e ~ kOf /3 in

accordance with (19-25),4>0 = 'IT, K ~ 10 5 ergs/cm3 , S = i, one obtains

N c::::' 300 or t c::::' 1000 A

where t is the thickness of the wall. We may note that the domain walls
in ferroelectric materials are only a few Angstroms thick, as we have seen
in Chapter 8.
The total energy per cm2 of a Bloch wall may be estimated by sub-
stituting for N from (19-34) into (19-33). This gives

a = 2S4>o(J,Xja)1/2 (19-35)

which for iron turns out to be of the order of I erg per cm 2 • We should
emphasize that the above treatment is rather crude; for example, due to
the anisotropy, tile angle between successive spins is not constant
throughout the Bloch wall.
We may mention here that there exists a critical size of ferromagnetic
particles below which the single domain configuration is more stable than
a multidomain structure; the critical size is determined by the anisotropy,
the shape of the particles and the intensity of the magnetization. For
spherical iron particles the critical radius is of the order of 10-6 cm.
The calculations are given in C. Kittel, Revs. Mod. Phys., 21, 541 (1949).
Similar calculations have been carried out for the critical single domain
size offerrites by Morrish and YU. 29 For a more detailed and mo~ecomplete
treatment of the energy considerations entering in the discussion of domain
formation we must refer the reader to Kittel's paper,

19-8. Coercive force and hysteresis

,
The coercive force He is the magnetic field required to produce iero
magnetization in an initially saturated specimen (see Fig. 19-7). Its value
varies widely from material to material and is of great practical importance.
'" A. H. Morrish and S. P. Yu, J. Appl. Phys., 26, 1049 (:955).
482 FERRor..iAG NETISM [Chap. 19

In a good permanent magnet the coercive force may be of the order of

J04 gausses (FePt), whereas a ltommercial power transformer may have a
coercive force of 0.5 gauss. Note that the energy. dissipated in going
around the hysteresis loop is of the order of BsatHr , where B sat is the
saturation value of the magnetic inducton; hence the coercive force
determines to a large extent the hysteresis losses.
We know that experimenta,lly the part OA in. the virgin curve of Fig.
19-7 is reversible, i.e., this mu!)t correspond to reversible motions of the

~ A
\
!
;;

Position of wall
\ . \

Fig. 19-11. Schematic representation of the energy of a ferro-

magnetic specimen as function of the position of a domain
wall.

Bloch wall. Such motions may be vizualized with the aid of a potential
curve, as indicated in Fig. 19-11; the curve represents the energy of a
Bloch wall as function of its position in the crystal. The variations in
energy are a consequence of local strains, impurities, lattice defects, etc.
In the absence of an external field, the wall will be in a position corre-
sponding to an energy minimum, say in A. Application of the field will
modify this curve and unless the field is large enough to help the wall
climb across a maximum such as B, only a small reversible wall displace-
ment will result. For larger fields, the wall displacement may be large,
but irreversible; this corresponds to the region A B in Fig. 19-7. The
domain rotations occurring in the region Be of Fig. 19-7 take place when
the applied magnetic field does not coincide with an easy direction of
magnetization, i.e., work must be done against the anisotropy forces.
The above qualitative picture explains the fact that the coercive force
increases with an increased intensity of local internal strains. The
observation that alloys containing a precipitated phase are magnetically
hard (high He) is also consistent with this picture. The quantitative
aspects are, however, quite complicated. 30
.0 For details, see R. Becker, Physik. z., 33, 905 (1932); M. Kersten, Grundlagen
einer Theorie der ferromagnetischen Hysteresis lind Koerzitivkraft, Edwards, Ann Arbor,
(1943) L. Neel, Ann. univ. Grenoble, 22, 299 (1946); E. C. Stoner and E. P. Wohlfarth,
Phil. Trans., A240, 599 (1948).
..
Sec. 19-9] A NTI FER RO M,.....G N ETISM 483

AntiferromagnL tIsm
\
19-9. Introdud'ory remarks

In Sec. 19-4, we have seen that the Heisenberg theory of ferromagnetism

is based on the assumption that the exchallge integral is positive. When
the exchan~e integral is negative, favoring an antiparallel orientation of
neighboring spins, one has an . ", ...
antiferromagnetic substance. Such 25
systems were first investigated theo-
retically by Neel31 and Bitter32 ; the
theory was later extended by van
Vleck,33 and his formulation is usually t 15
regarded as the basic theory of
antiferromagnetism. Experimentally,
anti ferromagnetism was first dis-
covered as a property of MnO by
Bizette, Squire, and Tsai in 1938. 34 _T(tK)
The most characteristic property Fig. 19-12. The molar susceptibility
of a polycrystalline antiferromagnetic 1.~1 of MnF 2 as function of temperature.
is that its susceptibility shows a maxi- At low temperatures 1..11 depends
mum as function of temperature; slightly on the field strength; the
an example of this behavior is upper branch corresponds to 2 x 10·
given in Fig. 19-12. This character- gausses, the lower one to 400 gausses.
[After de Haas, Schultz and Koolhaas,
istic feature may be explained quali- Physico, 7, 57 (1940»)
tatively on the hasis of the following
model. Consider a crystal containing two types of atoms A and B
distributed over two interlocking lattices; for example, let the A atoms
occupy the corner points of an elementary cube, the B atoms being
located at the centers of these cubes. Furthermore, let the interaction
between the atoms be such that the A spins tend to line up antiparallel
to the B spins. At low temperatures this interaction is very effective and
in an external field the resulting magnetization will be small. As the
temperature is raised, the efficiency of the interaction becomes less
pronounced and the susceptibility increases. Finally, a critical temperature
TN (the Nee I temperature) will be reached above which the spins are "free"
and above this temperature the antiferromagnetic material becomes
paramagnetic, i.e., X decreases wit.h further increase in T. This model will
be further discussed below.
'fl...•..
31 L. Neel, Ann. phys., 18, 5 (1932); 5,232 (1936).
32 F. Bitter, Phys. Rev., 54, 79 (1937).

33 J. H. van Vleck, J. Chern. Phys., 9, 85 (1941).

3. H. Bizette, C. F. Squire, and B. Tsai, Comp!. rend., 207,449 (1938) .

.v
'_
484 ANTIFERROMAGNETISM [Chap. 19

The most direct experimental evidence for the basic picture of anti-
ferromagnetism has been obtained from neutron diffraction experiments. 35
When neutrons are incident on a crystal they are scattered by the atomic
nuclei but also by the interaction between the neutron spin and para-
magnetic ions which may be present. Consequently, the ordered anti-
ferromagnetic state gives rise to "extra" diffraction lines just as one
observes extra X-ray diffraction lines for ordered alloys. The intensity of
these extra lines decreases as the temperature increases because the anti-
ferromagnetic order diminishes. Above the antiferromagnetic temperature
the extra lines disappear. An example has been given already in Fig. 1-17
for MnO.
i
. l
19-10. The two-sublattice model

Let us now pursue the two-sublattice model somewhat further and in

a slightly more general fashion than outlined above. As in the preceding
section, we shall assume that all nearest neighbors of an A atom are
B atoms and vice versa. However, we shall assume that, besides an
antiferromagnetic AB interaction, there are also antiferromagnetic AA
and BB interactions. Thus let the molecular field at an A and a B site be
given, respectively, by
Hma = H - rxMa - f3Mb
(19-36)
Hmb = H - f3 M a - rxMb

where H is the applied field, and M" and Mb represent the magnetization
of the A and B lattices; rx and f3 are positive Weiss constants. We shall
consider two temperature regions:
(i) T > TN' When the temperature is above the Neel temperature, we
are far away from saturation, and the magnetization of the A lattice may
be written
M" = (NfJ,2f3kT)H" with /-,2 = /-,}Jg2J(J + I) (19-37)

where N is the number of A atoms per unit volume. If we assume that

the dipoles on the B sites are identical with those of the A sites and that
there are equal numbers of A and B sites, we may write similarly,

(19-38)

Substituting equations (19-36) into the last two equations leads, upon
addition, to
(19-39)

3', C G. Shull and J. S. Smart. Phys. Rev., 76, 1256 (1949).

Sec. 19-10] ANTI FERROMAGNETISM 485
This equation becomes a scalar equation if we assume that M and Hare
parallel. On this assumption we can solve for the susceptibility, leading to

c (19-40)
T+O

This may be compared with expression (19-9) for the susceptibility of a

ferromagnetic material above the critical temperature. It is observed that

l/X

• -9 o o _T

Fig. 19-13. The reciprocal susceptibility versus temperature for

a para-, ferro- and antiferromagnetic material above the critical
temperature.

the antiferromagnetic case contains T + () rather than T -- 0; moreover,

the Curie constant C is twice the Curie constant of the individual A or
B lattice. In order to illustrate the difference between the paramagnetic,
the ferromagnetic, and the antiferromagnetic behavior in the high-
temperature region, we have plotted in Fig. 19-13 I/X versus T. For the
three cases one obtains

para ferro alltilerro

I/X = TIC I/x = (T-(J)/C I-Ix = (T + (J)/C (19-41)

(ii) The region be/ow the Neel temperature. At the NeeI temperature TN
itself, one is still sufficiently far away from saturation effects to employ the
equations given above for Ma and M b • Thus in the absence of an applied
magnetic field we may write for T = TN in accordance with (19-37),

or
[(I+ N fl2J3kTfI')rx]M + (Nfl2J3kT.'I.)f3M = 0
II b ( 19-42)
Similarly,
(Nfl2/3kTN )fJM" + [I + (Nfl2/3k-T_y)rx]Mb = 0 (19-43)
486 ANTIFERROMAGNETlS~ [Chap. 19
•
The last two equations have a nonvanishing solution for Ma and Mb only
if the determinant of their coefficients vanishes. Making use of the fact
that 2N fl2/3k = C one finds that

TN = C(P -_ oc)/2
\ (19-44)

Note that the Neel temperature increases as the antiferromagnetic AB

interaction (P) becomes stronger, whereas it decreases with increasing
antiferromagnetic AA and BB interaction (oc); this, of course, is what one
would expect on the basis of qualitative arguments.
In the model employed here, the Nee I temperature is not identical
with e, appearing in the high-temperature susceptibility. In fact, one can
readily set up a relation between Ts and e. It follows from (19-40) that
+
() = Nfl2(OC {J)/3k = CCoc P)/2. Hence +
\
TN/ e = ({J - oc)/({J + oc) (19-45)

It is of interest to compare this result with the observed values of TN and

(j given in Table 19-3. It is noted that experimentally TN < () in all cases,
indicating that oc must be positive; this in turn seems to indicate that in
so far as the present model is applicable, there is indeed an anti ferro-
magnetic AA and BB interaction. j I
Table 19-3. Some Parameters of Selected Antiferromagnetics." (After
A. B. Lidiard, Rep/s. Progr. Phys., 17,201 (1954)

Crystal Cation lattice

Compound TN ("K) ()CK) X.tx T N
structure structure

MnF2 rutile b.c. tetragonal 72 113 0.76

FeF2 rutile b.c. tetragonal 79 117 0.72
CoF2 rutile b.c. tetragonal 38' 53 ...
NiF. rutile b.c. tetragonal 73 116 ...
MnO, rutile b.c. tetragonal 84 316 0.94
MnO NaCl f.c.c. 122 610 0.67
MnS NaCl f.c.c. 165 528 0.82
FeO NaCl f.c.c. 198 570 0.79
CoO NaCI f.c.c. 292 280 ...

a Reproduced with kind permission of the Physical Society.

Let us now consider the susceptibility of an antiferromagnetic material

below the Neei temperature; for simplicity we' shall assume only AB
interaction, i.e., we shall assume IX = O. First, as a result of crystalline
anisotropy, there will be one or' more "natural" spin directions along
Sec. 19-10] ANTlFERROMAGNETISM 487
which the spins will tend to align thems~lves. There are therefore two
cases of special interest;
(a) An a,pplied magnetic field perpendicular to the natural spin direction.
(b) An applied field parallel to the natural spin direction.
Case (a) has been represented schematically in Fig. 19-14q ; the
calculation of the susceptibility in this case is analogous to the calculation
of the polarizability of an elastically bound charge, in which the equilibrium
is determined by the balance of the external force and a restoring force.

l.

(bl

Fig. 19-14. Illustrating the calculation of Xi' as described in the

text, for an antiferromagnetic arrangement of dipoles.

In the present case, the field tends to line up the dipoles along the field
direction, but as a result of the tendency for the A and B dipoles to remain
antiparallel, a compromise is obtained in which the dipoles make a certain
angle cp with the original spin direction. To calculate the susceptibility
Xi for this case, we proceed as follows. Consider one of the dipoles B as
made up of two unit poles, as indicated in Fig. 19-14b. The forces on the
positive pole are Hand -f3M,,, as indicated; the forces on the negative
pole are equal but of opposite sign. In equilibrium, the resultant forces
should lie along the line joining the poles, so that for small angles cp we
must have , t
2f3Ma cp = H
I

Since Mil = M,), the total magnetization along the external field direction
is equal to

so that '
Xi = liP (19-46)

Thus for the model under discussion, Xi is independent of temperature:

It can readily be shown that X.l is equal to the susceptibility at the Neel
temperature when approached from the high-temperature region. We
may note that (19-46) is still obtained, even if IX
Problem 19-8.
*
0, as shown in
488 ANTIFERROMAGNETISM "- \ [Chap. 19

The reader will have noticed that nowhere in the above derivation for
X.1 did we introduce an argument that explicitly referred to the existence
of a natural spin direction; we considered only the balance between the
force produced by the external field and the
exchange force between nearest neighbors.
A simple way in.which the existence of a
natural spin direction might be introduced
is indicated in Fig. 19-15 for one of the B
dipoles. It is assumed that there exists a
constant field Han which by itself tends to
keep the dipole in the "natural" spin
Fig. 19-15. The resultant of the
three forces shown should coin- direction, i.e., Han is an anisotropy field.
cide with the line joining the two If one then considers the equilibrium of
poles, as described in the text. forces in the presence of an external field
H l_ Han' one must require that the
resultant of H, Han> and the exchange force -f3Ma lie in the dipole
direction. We leave it as a problem for the reader to show that, as long
as the angle cp is small, one finds in this case
1
X ------ (19-47)
.L - f3 +
Han/2Ma
Since Ma increases as T decreases, this model leads to an increasing value
of X.1 with decreasing temperature; this is indeed observed on single
crystals of MnF2.36
(b) The calculation of the susceptibility XII corresponding to an applied •
field along the natural spin direction is much more complicated, since
statistical methods involving Brillouin functions must be employed.
Calculations by van Vleck give the curves as represented in Fig. 19-16
for different J values: the susceptibility rises smoothly from zero to X(TN)
as the temperature increases. That XII = 0 for T = 0 can be understood
qualitatively on the basis of the discussion of Sec. 19-9. The measurements
by Stout and Griffel on MnFz indicate that the theory is at least qualitatively
correct. ~---:_
The susceptibility below the Neel temperature in polycrystaIIine
materials is given by an average value lying between X.1 and XII; as a
result, one obtains in such cases a susceptibility versus temperature curve
of the type ind;cated in Fig. 19-12. '

19-11. Superexchange interaction

A few remarks may be made here about the nature of the interaction
in antiferromagnetics of the NaCl structure, such as MnO. From the
neutron diffraction experiments by Shull and Smart35 on MnO one
3. J. W. Stout and M. Griffel, J. Chem. Phys., 18, 1455 (1950).
Sec. 19-11] ANTIFERROMAGNETISM 489

concludes (see Fig. 19-17) that the stronges~ negative interaction for a
given Mn2+ ion does not come from its nearest Mn2+ neighbors but from
those Mn2+ ions which are at a distance y2 times as far. In fact, the
lot.

x
t

Fig. 19-16. The susceptibility of an antiferromagnetic substance as

function of temperature, for spin values of t, i, and!. [After van
Vleck, ref. 33]

negative interaction takes place between those Mn2+ ions which are
separated by an 0 2- ion such that the angle Mn2+ - 0 2- - Mn2 + is 180°.
Since the overlap between the 3d electrons of these Mn2+ ions is negligible

o Mn2+
0 02 -

Fig. 19-17. The antiferromagnetic arrangement of spins in MnO;

note that the spins in {Ill} planes are parallel to each other.

one concludes that the antiferromagnetism of MnO is not due to a direct

exchange interaction. Neel suggested that Kramers' theory of super
exchange may provide an answer for the interaction between the Mn2+ ions
through an intermediate 0 2- ion. 37 This theory has been discussed by
" H. A. Kramers, Physica, 1, 182 (1934) .
...
490 ANTIFERROMAGNETIS~ [Chap. 19
'>
Anderson38 and van Vleck ;39 in simple terms, the nature of this type of
interaction may be understood qualitatively as follows: the description of
manganese oxide as a completely divalent ionic compound of the type
Mn2+02- is inadequate in the sense that one should include in the wave
functions terms corresponding to Mn+ and 0- ions; we may call Mn+O-
an excited state of Mn2+02-. The electron configuration of the ground
state (Mn2+02-) for the two types of ions involved may be represented by

In the excited state, one of the 2p electrons of the 0 2- ion is transferred

to the Mn2+ ion, leading to the configuration

\
The 0- ion has evidently a resulting spin which has the same direction as
that of the Mn+ ion to which the electron has been added. Suppose now
that on the right-hand side of the 0- ion another Mn2+ ion is located; as
a result of the spin of the 0- ion the magnetic moment of this Mn2+ ion
will have a tendency to be lined up antiparallel to that of the 0- ion if
the interaction between these ions is antiferromagnetic (negative exchange
integral, i.e., not too large separation between the ions). Hence, on this
assumption one obtains an antiparallel alignment between the two Mn2+
ions as a result of the presence of the 0 2- ion between them. The angle
0
of 180 is particularly suitable for this type of interaction because of the
dumbbell shape of the 2p wave function involved. This type of interaction
may also play an important role in the antiferromagnetic interactions in
ferrites, as we shall see below. I

I·

Ferrimagnetism !I

Probably the oldest ferromagnetic material known to mankind is

magnetite, which corresponds to the chemical formula Fe 3 0 4 or, more
specifically, to Fe2+Fe~+04' When one replaces the divalent ferrous ion
by another divalent metal such as Mn, Co, Ni, Cu, Mg, Zn, or Cd, one
obtains a feHite of the general composition Me2+Fe~+04 where Me2+ is
the divalent metal ion. In mixed ferrites the Fe21- ion is replaced by a
mixture of ions. In searching for ferromagnetic materials for use at high
frequencies, Snoek, Verwey, and others at the Philips Research Laboratories
in Holland developed a number of such ferrites which are known under
3' P. W. Anderson, Phys. Rev., 79, 350 (1950).
39 J. H. van Vleck, J. phys. radium, 12, 262 (1951).
Sec. 19-11] FERRIMAGNETISM 491

the trade name Ferroxcube. 40 The most important of these are the MnZn
ferrites (Ferroxcube IV). The doc resistivity of ferrites is 104 to 1011 times
as large as that of iron. Thus in transformer cores they can be used up
to much hi~her frequencies than iron.

19-12. The structure of ferrites 41

The physical properlies offerrites are intimately related to the structure

of these solids. They belong to the large class of compounds which have
the spinel structure (after the mineral spinel, MgAI204). The oxygen ions,
with a radius of 1.32 A form, to a good approximation, a close-packed
cubic structure. The unit cell contains 32 oxygen ions, 16 Fe3 + ions, and
8 divalent metal ions. The total of 24 metal ions, ranging in radius
between 0.4 and I A, are distributed amongst eight tetrahedral interstices
(surrounded by four 0 2- ions) and sixteen octahedral interstices (sur-
rounded by six 0 2- ions). The distribution of the metal ions is very
important for an understanding of the magnetic properties of these
materials; the following distributions may occur.
(i) In the "normal" spinel structure of a ferrite the 8 divalent metal
ions occupy tetrahedral positions; the 16 trivalent iron ions occupy
octahedral positions. We shall follow a usual notation for this structure:
Me2+[Fe~+]04 the brackets around the Fe3+ ions indicating that they
occupy octahedral sites.
(ii) In the "inverse" spinel structure of a ferrite, the divalent Me2+
ions occupy octahedral sites; the Fe3+ ions are distributed in equal
numbers over the tetrahedral and octahedral sites. The arrangement may
thus be represented by Fe3+[Fe3+Me2+J04.
(iii) In the intermediate case we have arrangements of the type

19-13. The saturation magnetization

The importance of the distribution of the metallic ions over the

tetrahedral and octahedral sites may be illustrated with reference to the
,saturation magnetization for simple and mixed ferrites; data for the
saturation magnetization obtained by Gorter are given in Fig. 19-18 for
various mixed crystals of the type Me2+Fe~+04-ZnFe~+04.42
.0 See J. J. Went and E. W. Gorter, Philips Tech. Rev., 13, 181 (1952); J. J. Went,
G. W. Rathenau, E. W. Gorter, and G:W. Oosterhout, Philips Tech. Rev., 13, 194 (1952) .
., For a comprehensive review, see E. W. Gorter, Philips Research Repts., 9, 295
(1954); also F. C. Romeyn, "Physical and Crystallographic Properties of Some Spinels,"
Thesis, Leiden, 1953 .
.. E. W. Gorter, Philips Research Repts., 9, 321 (1954). • ',. . ,' .
.v
492 FERRI MAGNETISM [Chap. 19
'I
Since the ferrites are essentially ionic compounds, one would expect
that the saturation magnetization may be calculated from the number of
unpaired spins of the. ions. For example, in magnetite (Fe2+Fe~+04) the
Fe2+ and Fe3+ ions have, respectively, six and five 3d electrons. Thus,
according to the discussion on page 470 these ions have, respectively, four
and five unpaired spins. For normal ferromagnetic behavior one thus
expects a saturation magnetic moment of 4 + 2 X 5 = 14 Bohr magnetons
per molecule Fe 3 0 4. However, experiments by Weiss and Forrer give
4.08,uB; it looks as if only the Fe 2+ ions contribute to the magnetization.
It is worth while to point out here that Fe 30 4 is an inverse spinel.

10

6
iJ.B
Mn 5
t
Fe 4
Co 3
Lio,5 + FeO,5 I
I
Ni 2

Mg 1

.2 .4 ,6 .8 1.0
Composition ZnFe204

Fig. 19-18. Saturation magnetization in Bohr magnetons of various

mixed series of MeFe.O. and ZnFe.O.. [After E, W. Gorter,
ref, 421 "

Zinc ferrite and cadmium ferrite, which are known to have the normal
spinel structure, are paramagnetic, All other known simple ferrites which
are ferromagnetic have the inverted spinel structure, and it thus seems
that ferromagnetism is associated with the inverted structure, The rather
peculiar magnetic properties may further be illustrated by noting that
according to Fig. 19-18 the replacement of paramagnetic ions such as
Fe2+, C02+, Mn'H by the diamagnetic Zn'l.+ ions leads to an increase in
the saturation magnetization, at least for small zinc concentrations.
We may also mention that when one plots the reciprocal of the
susceptibility versus temperature above the Curie point, one frequently
obtains a concave curvature towards the T-axis, rather than a straight line
predicted by the normal ~urie-Weiss law.
Sec. 19-14] FERRIMAGNETISM 493

19-14. Elements of Neel's theory

In order to explain the magnetic properties of ferrites, Neel in 1948

put forward'''the hypothesis that there exists a "negative" interaction
between the ions on the tetrahedral sites (A sites) and the octahedral sites
(B sites) which tends to promote an antiparallel spin alignment of the
A and B ions. 43 Thus, in magnetite, which may be represented by
Fe3+[Fe2 +Fe3+J04' the saturation magnetization per molecule Fe 30 4 should
be (4 + 5) - 5 = 4PB, in close agreement with the experimental value
quoted above. Besides the negative AB interaction just mentioned, on'e
must take into account an AA and a BB interaction. These turn out (see
below) to be negative as well, but are considerably weaker than the AB
interaction. One thlis arrives at the rather remarkable situation in which
ferromagnetic behavior is explained in terms of three antiferromagnetic
interactions. Neel coined the term "ferrimagnetism" for this type of
behavior.
In order to give the essential features of Neel's theory, we shall consider
the relatively simple case of a ferrite represented by the formula
(19-48)

where Me2+ is a diamagnetic ion. We shall assume, to begin with, a

negative AB interaction; the AA and BB interactions will be repre-
sented by a factor -ex and -{3, respectively, giving the sign and strength
of these interactions relative to the AB interaction. Thus, when ex turns
out to be negative, it indicates that the AA interaction is antiferromagnetic.
It is convenient for the problem at hand to introduce the magnetizations
Ma and Mb associated with the A and B sites per gram ion rather than
per cm3 • The total magnetization per mole is then

M = xMa + (2 - X)Mb (19-49)

Consider now the molecular field Ha acting on an ion occupying an A

site; according to Neel this m~y be written in the form
(19-50)

where H is the applied field, -y(2 - X)Mb is due to the negative AB

interaction, and yexxMa is due to the AA interaction. Thus Neel assumes
a molecular field linear in the magnetization, as did Weiss in the theory
of ferromagnetism. Similarly, the molecular field acting on a B atom is
given by
(19-51)
We shall first consider the paramagnetic region above the Curie point.
.3 L. NeeJ, Ann. phys., 3, 137 (1948). ,} :,
494 FERRI MAGNETISM rChap. 19
Under these circumstances the partial magnetizations may be assumed to
follow a Curie-Weiss law, i.e.,

(19-52)
where C m is the Curie constant per mole; the Cm's are the same for the A
and B lattices, because for the example chosen here, the Fe3+ ions are the
only magnetic ions. Substituting Ha and Hb from (19-50) and (19-51) into
the two equations (19-52) one obtains for the paramagnetic behavior

HIT 1 (J
-=-=-+---- (19-53)
M Xmole Cm XO T- ()
where
1
- = (y/4)[2x(2 - x) - ax2 - fJ(2 - xy>']
Xo
(J = l-6y2Cm x(2 - x)[x(1 + a) - (2 - x)(1 + fJ)]2
() = tyC m x(2 - x)(2 + a + fJ)

Note that according to (19-53) there exists a concave curvature toward

the T-axis when I/Xmole is plotted versus T, in agreement with experiment.
From the shape of the experimental curves one can find Xo' (J, and ();
hence x, a, fJ, and y can also be obtained, at least qualitatively. Neel
found for several ferrites that both a and fJ are negative (i.e., the AA and
BB interactions are also antiferromagnetic). Furthermore, lal
and IfJl are
both ~I, indicating that the AB interaction predominates.
In order to obtain the spontaneous magnetization in the region below
the Neel point, we put H = 0 in (19-50) and (19-51). Since there are
saturation effects, we cannot emplOy the Curie-Weiss law, and we therefore
must replace equations (19-52) by the general expressions (see 19-3).

(19-54)
I
Mb = NgSflBBS(gSflBHb/ kT ) l (19-55)
, '------..-

where now N is the number of Avogadro, since Ma and Mb refer to a ~ole.

From these expressions together with (19-50) and (19-51) (with H = 0)
one can obtain Ma and M b , i.e., the total magnetization

M = (2 - X)Mb - xlvfa

as function of T. The solutions depend of course on x and are given in

Fig. 19-19. Thus, even for the relatively simple example given here, the
situation is quite complicated. For further details of the theory we refer
the reader to the literature. Apart from certain details, it seems that Neel's
theory describes the observations quite well.
Sec. 19-14] FERRI MAGNETISM 495
For the possible explanation of the nature of the antiferromagnetic
interaction in terms of superexchange v;re refer to Gorter. 44 In certain
cases one observes a weakly positive BB interaction; this has been
explained b¥ Zener in terms of a "double exchange" mechanism. 45
We may make here some further remarks on the curves given in Fig.
19-18. From X-ray diffraction data it follows that in the mixed zinc
ferrites the Zn2+ ions occupy tetrahedral (A) sites, as they do in the pure

------~-~.

Fig. 19-19. The theoretical spontaneous magnetization as function

of temperature for varying ratio of ferric ions in A and B sites,
according to NeeJ's theory. [After E. W. Gorter, ref. 42]

zinc ferrite (which has the normal spinel structure). The other divalent
ions Mn 2+, Ni 2+, etc. occupy octahedral sites, and the Fe3+ ions are
distributed over the remaining tetrahedral and octahedral sites. Thus the
mixed zinc ferrites satisfy the representation

For low zinc concentration there are a sufficient number of Fe3 + ions in the
A sites to Cause all the magnetic moments in the B sites to remain paraIleI
(due to AB interaction). Hence for low zinc concentrations the saturation
magnetization will increase with increasing Zn2+ concentration (because
M A decreases relative to Mb)' In fact, the slope of the magnetization
versus composition (x) should be such that for x = I the intercept should
give 10,uB' This is represented by the dashed straight lines in the figure.
The fact that the actual magnetization falls below these curves is a result
of the continually reduced AB interaction; the BB interactions then take
over, favoring an antiparallel alignment of the B atoms. Finally, for x = I,
we have the pure zinc ferrite with vanishing saturation moment.
.. E. W. Gorter, Philips Research Repts., 9, 321 (1954).
4. C. Zener, Phys. Rev., 81, 440 (1951); 82,403 (1951).
~.
to
496 FERRI MAGNETISM [Chap. 19

REFERENCES

L. F. Bates, Modern Magnetism, 3d ed., Cambridge, London, 1951.

R. Becker and W. Doring, Ferromagnetismus, Springer, Berlin, 1939.
R. M. Bozorth, Ferromagnetism, Van Nostrand, New York, 1951.
A. Fairweather, F. F. Roberts, and A. J. E. Welch, "Ferrites," Repts.
Progr. Phys., 15, 142 (1952).
E. W. Gorter, "Saturation Magnetization and Crystal Chemistry of
Ferrimagnetic Oxides," Philips Research Repts. 9, 295,321,403 (1954).
See also Proc. IRE, 43, 1945 (1955).
C. Kittel, "Physical Theory of Ferromagnetic Domains," Revs. Mod.
Phys., 21, 541 (1949).
A. B. Lidiard, "Antiferromagnetism," Repts. Progr. Phys., 17,201 (1954).
J. L. Snoek, New Developments in Ferromagnetic Materials, EI~evier,
New York, 1947.
E. C. Stoner, "Ferromagnetism," Repts.Progr. Phys., 11,43 (1948); 13,
83 (1950).
J. H. van Vleck, "A Survey of the Theory of Ferromagnetism," Revs.
Mod. Phys., 17, 27 (1945).
"Report on Washington Conference on Magnetism," Revs. Mod. Phys.,
January 1953.
"Report on Grenoble Conference on Magnetism," J. phys. rad., March
1951.
PROBLEMS

19-1. Consider a system of classical freely rotating magnetic dipoles,

all of the same magnitude fl; there are N dipoles per cm3 • Assume that
+
the local field acting on a given dipole is equal to Happlied y M, where
M is the magnetization. Show that this leads to ferromagnetic behavior
below a critical temperature () = yNfl2/3k. Show that above this tempera-
ture the susceptibility is given by X = «()/y)/(T - (). Compare these
results with those obtained in Sec. 19-2.
19-2. A system consists of N freely rotating dipoles of magnitude fll
and an equal number of dipoles fl2. Suppose the dipoles interact in such
a way that the local field at the position of any given dipole is equal to
Happlied+ yM, where M is the total magnetization per cm3 . Discuss the
behavior of this system.
19-3. Show that equation (19-14) can actually be written in the form
(19-16). See for example F. Seitz, Modern Theory of Solids, McGraw-Hill,
New York, 1940, p. 612.
Chap. 19] FERRI MAGNETISM 497
19-4. Give a discussion of the collective electron theory of ferro-
magnetism. See, for example, J. C. Slater, Quantum Theory of Matter,
N

McGraw-Hill, New York, 1951, Chap. 14, Appendix 22.

,
19-5. Magllt~tostriction may be thought of as resulting from the
dependence of the anisotropy energy on the state of strain in a crystal;
discuss magnetostriction on this basis. See C. Kittel, Revs. Mod. Phys ..
, 21, 541 (1949).
19-6. Show that for iron the critical size for spherical single-domain
particles is of the order of 10- 6 cm. See C. Kittel, Revs. Mod. Phys., 21,
541 (1949).
19-7. For a ferromagnetic crystal let Ms(T) be the spontaneous
magnetization at a temperature T; let y be the Weiss constant. Show
that the extra specific heat is given by ~C = -(y/2)(dM;/dT). Make a
qualitative plot of ~C versus temperature.
19-8. Consider a two sublattice model of A and B sites, the dipoles
on the two types of sites being equal. Assuming that the local field at an
A site is given by Hma = HapPlied - 13Mb - IXMa, with a similar expression
for H mb , show that the susceptibility Xi is equal to 1/13 and independent
of IX. Compare Sec. 19-10.

( :.

-,
Chapter 20
I \
\
MAGNETIC RELAXATION AND
RESONANCE PHENOMENA

There are numerous frequency-dependent effects associated with the

magnetic properties of solids. Since it is impossible to deal with all of these
within the scope of this volume, we have chosen paramagnetic relaxation
and nuclear magnetic resonance as particular examples in order to illustrate
. certain aspects of these phenomena. Other frequency-dependent effects are
mentioned briefly. Cyclotron resonance has been mentioned already in Sec.
13-6 in connection with the determination of the effective mass of electrons
in semiconductors; it will therefore not be discussed here.

Paramagnetic Relaxation
j ,
20-1. Phenomenological description I

In Chapter 18 the discussion of paramagnetic substances was limited

to static magnetic fields. Presently we shall be concerned with phenomena
occurring in oscillating magnetic fields. Consider a paramagnetic material
in the absence of an external field. The magnetic dipoles are then oriented
at random and there is no resultant magnetization. Suppose now that
suddenly a magnetic field H is applied. One then expects that a certain
period will elapse before the magnetization has reached its equilibrium
value Me. In analogy with the time effects in dielectrics it is found experi-
mentally that the build-up of the magnetization may be described by one
or more relaxation times T such that the equation
dM/dt = (Me - M)/T (20-1)
determines the rate of growth of M.l
From this it follows that if one applies instead of a constant magnetic
field He a field of the type
H(t) = He + Ho cos wi (20-2)
the magnetization M per unit volume will in general lag behind in phase, i.e.,
M(t) = Me + Mo cos (wt - 9') (20-3)
I It is useful to compare what follows with Sees. 6-7 and 6-8.
498
Sec.lO-J] MAGNETIC RELAXATION AND RESONANCE 499

This phenomenon is called paramagnetic relaxation and was first observed

by Gorter. 2 Usually the constant field "' is parallel to the oscillating
field, but it may also be perpendicular to it. Unless stated otherwise, the
two fields will be assumed parallel.
Denoting the static susceptibility by X.' one may write (20-3) in the form

M(t) = 'l..8He + X' Ho cos wI + X" Ho sin wt (20-4)

where X"/X' = tan cpo For low frequencies X" = 0 and x' =--' Xs' The
frequency-dependence of X' is called dispersion, in analogy with the optical
case; X' is referred to as the high-frequency susceptibility, for obvious
reasons. The quantity X" determines the absorption of energy by the
specimen. In fact, making use of (20-2) and (20-3), one finds for the
absorption per second per unit volume,3
A = (W/27T) cp M dH = (w/2)X" H~ (20-5)

It is usually convenient to employ complex notatiqn. Thus if one writes

(20-6)
it follows that
(20-7)
where x* = X' - iX"
is the complex susceptibility. We may note in passing that x' and X" are
related to each other by the so called Kramers-Kronig relations 4 (see
Problem 20-3). Also, both x' and X" are functions of H, as well as of
frequency.
So far, the description has been completely phenomenological. The
task of the theory of paramagnetic relaxation is twofold:
(a) The quantities '/ and X" should be related to the relaxation times
mentioned above.
(b) The relaxation times must find an interpretation based on
the properties of the magnetic atoms and the lattice in which they are
incorporated.

20-2. Relaxation mechanisms

In order to get an insight into the problem, consider a system of free

magnetic dipoles, oriented at random. Suppose the dipoles have no
2 C. 1. Gorter, Physica, 3,503 (1936). .,
3 The reader is reminded that by replacing in the "normal" thermodynamic expres-
sions the pressure by M and the volume by H, one obtains expressions appropriate to
the magnetic case.
, H. A. Kramers, AlIi cOI(f{r.fis., Como. 545 (1927); R. Kronig. J. Opl. Soc. Amer.
12,547 (1926).

. •~> ;".:.
500 MAGNETIC RELAXATION AND RESONANCE [Chap. 20

interaction with each other, nor with their surroundings. When an

external field H is applied, the dipoles will precess about the field direction,
as explained in Sec. 18-3. In fact, this is the only influence that can be
attributed to the field. Thus the component of a given dipole along the
field direction will remain unaltered, and no magnetization will result.
If magnetization is to occur, there must be a mechanism by which the
dipoles can exchange energy with their surroundings, because only then
does it become possible for them to orient themselves along the field
direction. For example, if a dipole ftH shifts from an antiparallel to a
parallel position in the external field H, the system must dispose of an
energy 2ft nH. It is illustrative at this point to note that it requires several
hours for the magnetic moments of the protons in ice, at liquid air
temperature, to orient themselves in a magnetic field. 5 This is simply a
consequence of the fact that the nuclei are in very poor energy contact
w\th each other and with their surroundings. If the ice is melted, the
relaxation time reduces to a few seconds. In substances where the para-
magnetism is due to electrons, the relaxation times vary between 10-11 to
10- 6 second at room temperature. It is essentially with these substances
that we are concerned here.
In 1932, before paramagnetic relaxation had been observed, Waller
wrote a remarkable theoretical paper on the subject. 6 He came to the
conclusion that a distinction should be made between two relaxation
mechanisms:
(i) The spin-lattice relaxation, corresponding to applied fields which
are large compared with the internal magnetic field (see below).
(ii) The spin-spin relaxation, corresponding to applied fields small
compared with the internal magnetic field.
Before discussing these mechanisms we may emphasize the essential
difference between them. 7 In any paramagnetic material, each spin finds
itself in a fluctuating magnetic field due to neighboring dipoles. This
internal field Hi is of the order of ftB/a3, where a is a few Angstroms, i.e.,
Hi ~ 1000 gausses. For example, in iron alum, Hi is 450 gausses. s Suppose
now that an external field <Z,Hi is applied to the system. The effect of the
applied field is then to change slightly the direction of the field seen by a
dipole, but the magnitude remains essentially unaltered. The dipoles wiII
thus precess about a slightly different direction, and as a result a net mag-
netization in the direction of the applied field occurs. The magnetization
in this case does not require any energy exchange between the spins and the
lattice. There is, however, an energy exchange between the spin system
and the field. The mechanism described here corresponds to (ii) above .
.; E. A. Turner, A. M. Sachs, and E. M. Purcell, Phys. Rev., 76, 465 (1949).
6 I. Waller, Z. Physik, 79, 370 (1932).

, Sec also A. H. Cooke, Repts. Progr. Phys., 13, 276 (1950), footnote, p. 279.
8 J. Volger, F. W. de Vrijer, and C. J. Gorter, Physica, 13, 621 (1947).
Sec. 20-2] MAGNETIC RELAXATION AND RESONANCE 501

When, on the other hand; a constant fi.eld He}> Hi is applied and He

is increased by a small amount, the direction of the field seen by the dipoles
remains unaltered whereas the magnitude varies. In this case an increase
of the magnetization can occur only if the number of dipoles parallel to
the field increases. Thus some dipoles must flip over from the antiparallel
to the parallel orientation. This requires a change in energy, which is
brought about by an energy exchange with the lattice.
Experiments on paramagnetic relaxation are interpreted in terms of the
sum of mechanisms (i) and (ii). It is fortunate that they can be separated
readily: spin-spin relaxation is measured in small magnetic fields; the
relaxation times are of the order of 10-10 sec and measurements are made
with frequencies of many megacycles. Spin-lattice relaxation is measured
in strong fields at frequencies low enough so that spin-spin relaxation can
be neglected. The spin-lattice relaxation times are strongly temperature
dependent, increasing with decreasing T, whereas the spin-spin relaxation
times are temperature independent. (

20-3. Spin-lattice relaxation

The first theory of spin-lattice relaxation, based on a model in which

the magnetic interaction between the spins is neglected, was developed by
Gorter and Kronig. 9 They obtained the well-known Debye relaxation
equations (see Problem 20-4)
'.
(20-9)

Although these equations describe the observations qualitatively, better

agreement is obtained with a thermodynamic theory developed by Casimir
and DuPre.l° The basis of this theory is that the relaxation time associated
with the spin-lattice interaction is so long compared to the spin-spin
relaxation time that the spin system can be considered to be always in
thermodynamic equilibrium. Thus the spin system is treated as a thermo-
dynamic system, separate from but in energy contact with the lattice.
The spin system has its own specific heat, temperature, etc. In contrast
with this, the previous theories mentioned above considered the individual
spins in energy contact with the lattice. That the temperature Ts of the
spin system is not necessarily the same as that of the lattice may be seen
as follows. Consider a system of spins of t in thermal equilibrium with
the lattice in an external field H at a temperature T. According to
Boltzmann statistics we then have Np/Na = exp (2P B H/kT), where Nil and
Na refer, respectively, to the number of spins parallel and antiparallel to H.
9 C. J. Gorter and R. Kronig, Physica, 3, 1009 (1936); R. Kronig, Physica. 5, 65

(1938).
10 H. B. G. Casimir and F. K. DuPre, Physica, 5, 507 (1938).
502 MAGNETIC RELAXAnON AND RESONANCE [Chap. 20

When H is suddenly increased to H', the temperature of the lattice remain-

ing T, it takes some time for the ratio Np/Na to adjust itself to the new
field. However, substituting H' for H in the Boltzmann distribution above,
one can define a certain temperature T. such that the instantaneous
populations satisfy the Boltzmann expression; in this case, Ts would be
the spin temperature. In the above example Ts > T immediately after the
increase of the field; as time goes on, Ts approaches T. In an oscillating
field, the difference () = Ts - T will also oscillate, the amplitude of the
oscillation becoming smaller as the heat contact between the spin system
and the lattice becomes better. As long as () is not too large, the heat
transferred from the lattice to the spin system during a short time interval
dt may be written
dQ = -oc() dt . (20-10)
where the quantity oc may be called the coefficient of heat contact between
the spin system and the lattice. On the other hand, the first law of thermo-
dynamics for the spin system may be written in the form
(20-1 I)
where ClI and C111 are the specific heats at constant Hand M, respectively.
For a field of the type (20-6) we may write
H(t) = H, + Hoe iw1

M(t) = Me + Moiw'
() ",co () oeiWI
so that
(20-12)

On the other hand, " ...: " ':,,' i, : '.

(20-13)
By eliminating 00 from the last two equations one obtains for the complex
susceptibility,
x* = Mo = (OM) I + (iw/oc)C lIl (20-14)
• Ho oH, l' 1 + (iwjoc)Cf[
Recognizing that (oM/oHh is the static susceptibility x." one may write
the real and imaginary parts as

(20-15)

x" (20-16)
x. ].1X )l"h{J;"'-

where the relaxation time 7 = Cf[/oc is determined by the coefficient of

Sec. 20-3] MAGNETIC RELAXAnON AND RESONANCE 503
heat contact between the spin system and the lattice. Note that the high-
frequency susceptibility X' contains, besides the Debye function (20-9), a
constant part equal to C JIICII' A typical example of a set of dispersion

2
~ .6~----+---~~~~---+---=~~~==~
-><

t
1 H=800 4
2 H=1600
.2 3 H=2400
4 H=3200
O~----~-- ______ ~ ______L -____ ~ ________ ~

. .1 .2 .5 1.0 2.0 5.0XI06

- Frequency (cps)
Fig. 20-1. Paramagnetic dispersion of Gd2(SO.)a·8H,O at 7rK.
The numbers refer to the constant parallel field H,.. [After Broer
and Gorter, ref. III

measurements is given in Fig. 20-1 for the octahydrate of gadolinium

sulfate at 77°K.ll The dots are measured points, the curves correspond to
equation (20-15); there is thus good agreement with the Casimir-DuPre
A
3
t 1 H=4OO
2 H=1600
3 H=3200
_.-'"
2

1 _.-- --
.2 .5, 1.0 2.0 5.0 lOX 106
- Frequency (cps)

Fig. 20-2. Paramagnetic absorption in Gd.(SO.k8H.O at nOK,

in arbitrary units for various values of the constant parallel field H,.
The dashed part of the curve is interpreted as spin-spin relaxation.
[After Broer and Gorter, ref. HI

theory. The absorption (equation 20-16) of the same material is given in

Fig. 20-2, and again good agreement is obtained. The deviations at high
frequencies (dashed curve) are due to the onset of spin-spin relaxation.
We note here that recent experiments at liquid helium temperatures
11 L. J. F. Broer and C. J. Gorter, Physica, 10, 621 (1943).
,.'
"':-'",.
504 MAGNETIC RELAXATION AND RESONANCE [Chap. 20
indicate that the relaxation effects at such temperatures cannot be
described by a single relaxation time. 12
Without going into details, it is evident from equations (20-15) and
(20-16) that relaxation measurements also provide information about the
specific heat of the spin system. 13
The interpretation of the spin-lattice relaxation time is based on the
interaction between the spins and lattice vibrations. According to Waller
there are two possible mechanisms; (i) absorption and emission of phonons
by the spin system, (ii) inelastic scattering of phonons by the spin
system may occur in which a phonon is absorbed and another phonon
of different energy is emitted. The latter type of process is analo-
gous to the Raman effect in optics. For a discussion of the details of
the various ways in which the lattice vibrations may interact with the
spin system we must refer to the literature cited at the end of this chapter.
We may remark that the theory can account satisfactorily for the relaxation
times observed at liquid air temperatures; in the region of liquid helium
temperatures, however, certain aspects are as yet unexplained.

20-4. Spin-spin relaxation

We have seen in Fig. 20-2 that at high frequencies absorption is

observed (dashed curve) over and above the spin-lattice absorption. This
absorption is interpreted as due to spin-spin relaxation and can be
described by the formula I
I
ASPill = 1(1)27"sXse111 / e II r (20-17)

for the great majority of experimental results obtained so far. In contrast

with the lattice relaxation time 7" s is independent of temperature; it is of
the order of 10-10 second.
It follows from (20-17) that 7"s can be determined only from absolute
absorption measurements, whereas the spin-lattice relaxation time may be
obtained from relative measurements. Also, because 7"" is small, measure-
ments at high frequencies are required.
The interpretation of 7"s is quite complicated, and for the theory we
must refer the reader to the literature. 14 It may suffice here to give a rough
estimate of its value. Let Hi be the rms value of the internal magnetic
field at the position of any dipole due to the other dipoles. If the dipoles
are free spins, the Larmor precession frequency associated with Hi is
equal to WL = (ejmc)Hi' One thus expects that the time required for the
12 H. C. Kramers, D. Bijl, and C. J. Gorter, Physica, ]6, 65 (1950).
13 R. J. Benzie and A. H. Cooke, Proc. Phys. Soc. (London), A63, 201 (1950).
"See, for example, L. J. F. Broer, Physica, 10, 801 (1943); A. Wright, Phys. ReP.,
76, 1826 (1949); J. H. van Vleck, Phys. Rev., 74, 1168 (1948).
,
",
Sec. 20-4] MAGNETIC RELAXATION AND RESONANCE 505
spin to change its axis of precession will be of the order of T .. ~ l/(J) I.' That
this gives indeed the order of magnitude cim be seen from the table below.

Table 20-1. Some Spin-Spin Relaxation Times and Internal Fields"

Solid' H, (gausses) ! 'T~ exp l/wL c.. lc

I
I
(in 10- 10 sec) (in 10~lO sec)

Fe(NH,)(SO')2' 12H 2 0 450 1.1 1.2

Gd 2(SO,) .. 8H 2 O 1380 0.57 0.4
Cu(NH,).(SO')2·6H20 200 9.1 2.7
CuSO .. 5H 2 O 370 6.7 1.5

a'Reproduced with kind permission of the Physical Society. London. from A. H. Cooke. Nepts. Progr.
Ph),s .. 13. 276 (1950).
_........--.-'~ /' -

Nuclear Magnetic Resonance

20-5. Nuclear magnetic moments

In general, atomic nuclei have an angular momentum and associated

with it a magnetic moment. When one speaks of the "nuclear spin" J,
one refers to the largest observable value of the component of the angular
momentum in units of Ii along any specified direction. This direction may
be that of an applied magnetic field; in general, we shall refer to the
specified direction as the z-direction. The total angular momentum is in
analogy with (18-10) given by

M" = Ii[l(l + 1»)1/2 (20-18)

The possible components along the z-direction are again determined by a

magnetic quantum number mb which can accept the values

m[ = I, (I - 1), ... , -(1- 1), - / (20-19)

(compare 18-11).
The magnetic moment fA. associated with Ma is given by
(20-20)

in analogy with (18-12). Here M'IJ is the proton mass and g is the inverse
of the gyromagnetic ratio. The maximum component of fL along an
applied field H is thus equal to
(20-21)
506 MAGNETIC RELAXATION AND RESONANCE [Chap. 20
where /-In = 5.049 X 10-24 erg/gauss is called the nuclear magneton. It
serves a purpose similar to the Bohr magneton in the magnetic moments
associated with electrons.
In an external field H, the magnetic moment will precess with the
Larmor frequency,
(20-22)

~
-rr------
1=3/2

gJln H
-3/2

- - ' - - - - - - - -1/2
The proof is essentially the same as that given
in Sec. 18-3 for the precession of an electron
orbit, and will not be repeated here. Note the
minus sign, indicating that the precession
,::: vector has a direction opposite to H.
J:>;l
An applied magnetic field also produces a
t -------1/2 splitting of the energy levels. Consider for
example the isotope Na23 with 1 = l The
------3/2 possible components of lL along the field
direction are then, in units of g/-ln'
Fig. 20-3. The four Zeeman
levels for 1 = ~ in a magnetic
field H; transitions are pos-
sible only between successive
Since the energy of a dipole lL in a magnetic
levels, leading to the resonance field is equal to - /-lzH, we obtain four levels,
condition (20-23). as indicated in Fig. 20-3.

20-6. Conditions required for resonance absorption

Transitions between these levels are, for magnetic dipole radiation,

governed by the selection rule !:l.m I = ± 1; hence transitions are possible
only between successive levels. From what has been said above, it thus
follows that resonance may be observed in an alternating magnetic field
of angular frequency w, such that .,
(20-23)

It follows immediately from (20-22) and (20-23) that the required frequency
is identical with the Larmor frequency. For a field of 104 gausses, the
nuclear resonance frequencies w L/27T lie in the radio frequency range
between I and 50 megacycles (see Table 20-2). Resonance of this type
was first observed by Purcell's group15 and, independently, by Bloch and
collaborators. 16
The experiments are carried out by applying a variable static magnetic
field He in the z-direction and a radio frequency field of amplitude Ho <{ He
15 Purcell, Torrey, and Pound, Phys. Rev., 69, 37 (1946); Bloembergen, Purcell,

and Pound, Phys. Rev., 73,679 (1948).

1. Bloch, Hansen, and Packard, Phys. Rev., 69, 127 (1946); 70, 474 (1946); F.
Bloch, Phys. Rev., 70, 460 (1946).
Sec. 20-6] MAGNETIC RELAXATION AND RESONANCE 507 !
perpendicular to He. One then pbserves absorption of radio frequency i
energy by the spin system when the resonance condition (20·23) is satisfied.
The reason for the perpendicular field arrangement may be explained
wtfh reference to Fig. 20-4. For simplicity, consider a spin 1= 1, leading:
to two energy levels in the constant field He. In the lower level, the
orientation of the dipole is as indi-
cated in the figure. At the same He

--'1-'-
time, the dipole precesses with the
Larmor frequency about He' Clearly,
when absorption is observed, tran-
sitions between the lower and upper : ................
level must occur, i.e., the radio
frequency field must have a chance
to tip the dipoles from the parallel
to the anti parallel position and vice i
versa. That this is indeed achieved III:;:---'J----x l
by employing the oscillating field
perpendicular to He may be seen as
follows. Let the oscillating field be Fig. 20-4. Illustrating the constant
represented by torque acting on a precessing dipole due'
to a field rotating with the Larmor i
H., = 2Ho cos wt; Hy == Hz = 0 frequency.
(20-24)
For our purpose it is convenient to consider this oscillating field as the!
sum of two rotating fields, one rotating to the right, the other to the left: i

right H.,= Hocoswt; H y = Hosinwt; Hz=O

(20-25)
left Hx = Ho cos wI; HII = -Ho sin wI; Hz = 0
If OJ = OJ L' one of these rotating components will follow the precessing j

dipole and the dipole will eventually tip over as a result of the constant!
torque exerted on itY The other rotating component is evidently of littlej
consequence. The reader can convince himself readily that the probability:
for tipping from the parallel to the antiparallel position is equal to that!
for tipping in the opposite direction. Hence, in order to observe absorption i
of radio frequency energy by the spin system it is essential that the lower!
level be more heavily populated than the upper one. In thermal equilibriumi
this is indeed the case, because according to Boltzmann, for the case 1= !.
we have for the ratio of the number of parallel to anti parallel spins,

It must be realized that the excess number in the lower level is usuallYI
i
For the transition probabilities, see N. Bloembergen, E. M. Purcell, and R. V,'
17

Pound, Phys. Rev., 73, 679 (1948). 1

508 MAGNETIC RELAXATION AND RESONANCE [Chap. 20
very small indeed; for protons for example g = 5.58 and one finds with
+
H -:::: 104 gausses at room temperature, Np/Na -:::: 1 7 X 10- 6 •

20-7. The Bloch equations and the complex susceptibility

The Bloch equations 16 to be discussed below occupy a central position

in the interpretation of nuclear resonance experiments. They provide
a semiclassical theory of the frequency dependence of the complex
susceptibility,
x* = X' - iX" (20-26)

Let us consider a sample containing magnetic nuclei under influence of a

constant magnetic field Ho in the z-direction plus an oscillating field
2Ho cos wt of small amplitude along the x-direction. For reasons explained
above, we shall consider only one of the rotating components of the
oscillating field, say the left-rotating component in (20-25). Hence
Hx = Ho cos wt; Hy = -Ho sin wt; Hz = He; Ho < He (20-27)

Consider first the influence of a field H alone, on a single nuclear dipole tL.
In accordance with (18-17) we may write
(20-28)
, I
i.e., the field alone simply leads to a Larmor precession of tL about H.
Adding the effect of all dipoles per unit volume, we may write for the
rate of change of M due to the field alone,
(aM/at)fic1d = g(e/2M p c)M X H == yM X H (20-29)
For the field defined by (20-27) we have "':f'

y = g(e/2Mp c) -:::: wL/He ,I (20-30)

Besides the influence of the field, two other sources contribute to the
rate of change of M, viz.,
(i) The spin-lattice interaction
(ii) The spin-spin interaction
Their influence will now be considered. Suppose that Me represents the
magnetization along the z-direction if the system is in thermal equilibrium
when only the constant field If.e is applied. When this field is suddenly
switched off, the magnetization will gradua!ly approach zero. Similarly,
when the field is suddenly switched on, a certain time interval is required
to obtain the equilibrium value Me. During this build-up, a certain
fraction of the dipoles must flip over from an antiparallel to a parallel
orientation relative to the field. Since this process requires a change in
energy of the spin syste~? the build-up time is determined by the heat
Sec. 20-7] MAGNETIC RELAXATION AND RESONANCE 509
contact between the spin system' and tht:_ lattice. Thus, as a result of the
spin-lattice interaction the rate of change of the z-componem of M is
assumed to be given by
... (oMZ/ot)'1 = -(Mz - Mc)h (20-31)
where the subscripts sf refer to the spin-lattice interaction; the character-
istic time Tl is the spin-lattice relaxation time. Combining (20-31) with the
z-component of equation (20-29) we obtain for the total rate of change
of M.,
dMz/dl = y[-M",Ho sin wI - MyHo cos wI] + (Me - Mz)h (20-32)
This is one of the Bloch equations; the two others provide expressions
for the rate of change of the transverse components M", and My. In order
to set up the expressions for Mx and My, it is important to realize that if
there were a completely random distribution of the x and y components
of the nuclear dipoles, M x and M" would be zero. In other words, one is
interested in the lifetime associated with a certain Mx or My value in the
absence of an applied oscillating field. Now, consider two neighboring
identical dipoles i and j. Since both are precessing about He' then j will
produce an oscillating field of the Larmor frequency at the position of i
and vice versa. Consequently, transitions may take place in which i and j
simultaneously reverse their orientation (spin exchange), thus limiting the
lifetime of each state. Since the interaction energy !}.E is of the order of
~;'/r3, the lifetime T2 as given by the Heisenberg uncertainty principle is
T2 ~ Il/!}.E = Ilr 3 / ~;.. The characteristic time T2 was introduced by Bloch
as the spin-spin relaxation time. ·He thus assumed that the rate of change
of M", and My as determined by the spin-spin interaction is given by
(oMx/ot)ss = -M,JT2 and (oMy/ot)ss = -My /T2 (20-33)
From a different point of view, one may argue that a given dipole sees,
besides the applied field, an internal field Hi""'" ~n/r3 produced by its
neighbors. Thus one expects a spread in the precession frequencies !}.wL
where, according to the res~nance condition (20-23),
!}.wL ~ g~nHdll ~ g~~/Ily3 (20-34)
Thus the width of the absorption band corresponds to a characteristic
time 21T/!}.wL which is essentially the same as T2 introduced above. It must
be noted, however, that the two effects mentioned here in connection with
T2 are not identical; for example, spin exchange is possible only between
identical nuclei, whereas the internal field point of view is always valid.
When we add to the equations (20-33) the con:esponding component
equc.lions of (20-29), we obtain the following two Bloch equations
I

+
dMx/dt = y(MyHc MzHo sin wI) - Mx/T2 (20-35)
dMy/dt = y(MzHo cos wt - M.,Hc) - M y/T2 (20-36)
,,".
510 MAGNETIC RELAXATION AND RESONANCE [Chap. 20

Since the constant field and the oscillating field are applied, respectively,
in the z and x-directions, one is particularly interested in solutions of the
Bloch equations (20-32), (20-35), and (20-36) for M z and M.,. Without
giving the mathematical details here, one ob!ains 18 \

(20-37)

(20-38)

where Xe is the static susceptibility given by the Curie law. From the
definition of the complex susceptibility it follows (see 20-4) that

M.,(t) = X'(2Ho cos WI) + X"(2Ho sin wI) (20-39)

Comparison of (20-39) and (20-38) thus leads to the expressions

(20-40)

(20-41)

The reader is reminded that the absorption of radio frequency energy is

determined by X", as expressed by formula (20-5).
In discussing the results obtained, one may distinguish between two
cases;
(i) The amplitude Ho of the oscillating field is so small that y2R~'Tl'T2 ~ 1.
In this case M z is simply equal to XeRe, i.e., equal to the static equili-
brium value. This means that the spin-lattice relaxation is rapid enough to
maintain a Boltzmann distribution of the population in the various energy
levels, notwithstanding the fact that, because of radio frequency absorption,
an excess is thrown from lower to higher levels. For this case, the frequency-
dependence of x' and X" is represented in Fig. 20·5. Note that the half
width of the absorption line under these circumstances is determined by
the spin-spin relaxation time 7 2 ; it is, in fact, equal to 1/72 in terms of an'
angular frequency.
(ii) When y2HJ71'T 2 is not negligible compared to unity, M z < XeHe
and both X' and X" are reduced'in magnitude. In this case one speaks of
saturation of the spin system; the spin-lattice relaxation is not able to
maintain a Boltzmann distribution of the populations in the energy levels
under these circumstances. In other words, the spin temperature increases
beyond the lattice temperature as a result of the rapid rate of absorption
18 See F. Bloch, Phys. Rev., 70, ..460 (1946); G. E. Pake, Am. J. Phys., 18,438 (1950).

" .
iV,,,
Sec. 20-7] MAGNETIC RELAXATION AND RESONANCE 511

of radio frequency energy. Also, the absorption line becomes weaker

and broader.
The Bloch equations given above were obtained from macroscopic
consideratio~. However, somewhat more complex but essentially similar
relations may be derived from a microscopic viewpoint, employing
statistical mechanics. l9

I ,

-4 -3 -2 -1 0 1 2 3 4
_(wL-wl1"2

Fig. '20-5. The real (X') and imaginary (X") part of the complex
susceptibility as function Of(WL - WP2, pertaining to the case of
negligible saturation.

20-8. The influence of molecular motion on the relaxation times

Several methods have been described in the literature for measuring

the relaxation times Tl and T2. 20 Measurements of Tl are based on the
competition between resonance absorption (which tends to equalize the
populations in the different levels) and spin-lattice interaction (which
tends to maintain a Boltzmann distribution). The values of T} obtained
experimentally vary between }O-5 and 104 seconds, the latter value being
19 R. K. Wangsness and F. Bloch, Phys. Rev., 89,728 (1953).
20 See, for example, N. Bloembergen, E. M. Purcell, and R. V. Pound, Phys. Re~.,
73,679 (1948); M. Soutif and R. Gabillard, Physica, 17,319 (1951); R. L. Conger and
P. W. Selwood,J. Chern. Phys., 20, 383 (1952); H. C. Torrey, Phys. Rev., 76,1059 (1949);
E. E. Salpeter, Proc. Phys. Soc. (London), A63, 337 (1949); E. L. Hahn, Phys. Rev.,
80,580 (1950).
512 MAGNETIC RELAXATION AND RESONANCE [Chap. 20

obtained for ice at low temperatures. 5 I n order to interpret experimental

results it is important to realize that both Tl and T2 are strongly influenced
by the migration or motion of atoms. Consider for example the build-up
of the magnetization of a system of nuclear dipoles which is suddenly
exposed to a static field He. The build-up requires dipolar transitions, and
for these to occur, oscillating magnetic fields of a frequency equal to the
Larmor frequency a.re required. Lattice vibrations contribute very little
in this respect, since their frequencies are too high ('""10 13 sec l). However,
at least in gases and liquids, the atoms or molecules are in rapid motion
and the intensity of the Fourier component at the Larmor frequency will
thus determine Tlo In viscous media one may introduce a "correlation
time" which, for spherical molecules, is defined by'll

(20-42)

where l/ is the viscosity and a is the radius of the molecules; Tc measures

the time required for the surroundinss of a given molecule to change
appreciably. For water at 20°C, Tc ~ 3 X 10-12 sec. The relaxation time
T} is related to Tc and to the resonance frequency (I) L by

(20-43)

where C is a constant which includes factors which are independent of

temperature and frequency.2l Note that for (l)LTc <'{ I, liT} ~ 3CT c, and
for (I) LT c?> I, then I/TI 3Cf2wiT c; in the intermediate region TI exhibits
,-.J

a minimum value given by (Tl)min = 3(1) LI23/2C, occurring forw LTc = I/V2.
For a particular model concerning the molecular or atomic motion, C
can be calculated; C can also be determined experimentally from the
minimum value of TI' An example of TI as function of Tc is given in Fig.
20-6. Experimental verification of expression (20-43) has been obtained
for liquids as well as for solids over a wide range of Tl and Tc values. In
the case of solids, Tr is determined by the diffusion of atoms or vacancies;
this makes it possible to determine diffusion coefficients from nuclear
resonance experiments. We shall return to this point below.
As an example of the influence of molecular motion on TI we may
mention that for water at 20°C, TI = 3.6 ± 0.2 seconds2'l (the calculated
value,2l on the basis of a diffusion mechanism is 3.4 seconds); on the
other hand, for ice at 80 0 K one obtains TI ~ 2.5 hours, and the line
becomes much broader and weaker (compare 20-41).23 It should be stated
that TI may be strongly reduced if paramagnetic ions are present; these
ions have an effective moment which is 103 times as large as the nuclear
21 See Bloembergen, Purcell, and Pound, loco cit.
22 G. Chiarotti and L. Giulotto, Phys. Rev., 93, 1241 (1954).
23 E. A. Turner, A. M. Sachs, and E. M. Purcell, Phys. Rev., 76, 465 (1949).
,;"_
Sec. 20-8] MAGNETIC RELAXATION AND RESONANCE 513

moments, and are a very efficient medium for establishing heat contact
between the nuclear spins and their surrou-ndings.
The spin-spin relaxation time also depends on T e , as is illustrated in
Fig. 20-6. L-et us consider a solid at very low temperature where T e is long
because atomic jumps are rare. The spin-spin relaxation time will then
have some small limiting value, say
10-6 sec. As the temperature is raised, 10- 3 . . . - - - - - - - - - - - - . . , .
T2 wi!! remain constant, and so will
the line width in accordance with
(20-41), until Te has been reduced to 10-1
a value of the same order as T2' As
the temperature is increased further,
the number of spin exchanges per
10- 5
unit time decreases, since atoms are
nearest neighbors for a time T c' which
is smaller than the lifetime of the
spin states. Hence T2 begins to in- 10- 15 10- 11 10-3
crease and will continue to do so as Te
decreases; in the region of To values
Fig. 20-6. 7"1 and 7"2 as function of the
where both T1 and T2 increase with correlation time 7",; 7"1 is given by
decreasing T c , the values of T1 and T2 (20-43). [After Bloembergen, Purcell,
are approximately equal. and Pound, ref. 17)

20-9. Some applications to solid state physics

Nuclear magnetic resonance experiments have become a powerful tool

in studying the physical properties of solids. Although it is not possible
to go into details here, a few examples may be given here to illustrate this.

(i) Structural studies.24 The width and structure of a resonance

absorption line are influenced by the magnetic interaction between the
dipoles. Since. this interaction is determined by the relative positions of
the nuclei, the width and shape of the lines provide information about
the structure of solids. The simplest case is encountered in solids where
the nuclei occur in single pairs, so that the effective magnetic field at the
position of a given nucleus is determined by the applied magnetic field He
plus the internal field produced by its partner. With reference to Fig. 20-7
let the vector r, joining two such nuclei, make an angle () with the applied
field He in the z-direction. In order to calculate the effective magnetic
field at the site of nucleus b we shall start from the classical formula for
the field produced by a dipole !Joa at a point r:
(20-44)

.< Gutowski, Kistiakowski, Pake, and Purcell, J. Chern. Phys., 17,972 (1949).
514 MAGNETIC RELAXATION AND RESONANCE [Chap. 20

Since Ha ~ He the effective field seen by nucleus b is still essentially

parallel to He' i.e"., we are interested only in the z-component of Ha
produced at b. Furthermore, let the spins be t so that Pa can be taken
as tgPm its direction being either parallel or antiparallel to He. The
reader will convince himself readily that the effective field at b is then
given by
Heff = He ± (g Pn/2r)(3 cos~ e - I) (20-45)

I where the ± sign is due to the two possible

I orientations of spin a. Thus, for a given direc-
I tion of He relative to the crystal axes, the field
I .b
at b has two possible values, leading to two

P.a
a
V "

Fig. 20-7. Illustrating the

possible resonance frequencies. In fact, according
to (20·45), the splitting corresponds to (gPn/r)
13 cos 2 e - 11 gausses. We must note here that
in the quantum mechanical theory the separation
is l times as large. 25
Simple two-spin systems of the type just
mentioned occur to a good approximation for
configuration of a simple
two-spin syswm in an the protons in hydrates, such as CaS0 4 ·2H 20,
external field Hr. CuCl 2·2H 20 etc., and in solid 1,2-dichloro-
ethane. As an example, we give in Fig. 20"8
the resonance line for the latter compound in the solid state, measured
at 90 o K. The full curve represents the observed absorption line; the
open circles represent the smoothed-out absorption line for r = 1.70 A,
taking into account additional broadening due to other neighboring nuclei
and field inhomogeneity. The dots on the right-hand side are for r= l.nA.
For more complicated cases we refer to the literature cited in the biblio-
graphy. We may mention here that nuclei with / > t have electric
quadrupole moments which give rise to a quadrupole energy term in the
expression for the total energy when electric field gradients occur at the
nucleus. In solids this gives rise to splitting of the resonance lines from
which information about the symmetry of the crystalline electric field
gradients may be obtained. 26
(ii) Molecular rotation in solids. 27 In the liquid and gaseous states one
usually deals with narrow absorption lines, which are generally well
resolved; this is a result of the fact that in these cases 'T e is small, resulting
in a large value of'T2 (and 7 1 ), In solids on the other hand, 'Te is large,
'T2 is small and therefore the bands are broad. In certain solids, however,

•• G. E. Pake, J. Chern. Phys., 16, 327 (1948) .

•• H. E. Petch, D. W. L. Smellie and G. M. Volkotf, Phys. Rev., 84, 602 (1951);
Can.J. Phys., 30, 270(1952); G. M. Volkotf, Can.J. Phys.,31, 820(1953); H. E. Petch,
N. G. Crana, and G. M. Volkotf, Can. J. Phys., 31,837 (1953).
27 H. S. Gutowski and G. E. Pake, J. Chern. Phys., 18, 162 (1950).

'" .~
.\

{ ',.,
Sec. 20-9] MAGNETIC RELAXATION AND RESONANCE 515

molecular groups may carry out rotations when the temperature is

sufficiently high. It is thus possible by measuring the narrowing of the
line width as function of temperature to observe the onset of such rotations.
'"
aba.

J
:!
1
l __

.------.

-10 -5 o 5 10 gauss

Fig. 20-8. The proton magnetic resonance absorption' for solid

Q
1,2-dichloroethane (CH 2CI-CH.CI) at 90 K. The solid line
represents the experimental data. The open circles are computed
for r = 1.70 A, the dots for r = 1.72 A. [After Gutowski, e/ al.,
ref. 24] ,

(iii) Nuclear resonance in metals. In Fig. 20-9 we have represented the

width of the resonance line of Na 23 in metallic sodium. The width at high
temperatures is 0.05 gauss and is presumably due to field inhomogeneity.
The transition at 190 0 K is interpreted to be associated with the diffusion

2
oH
t
..
..
1
_.
0
100 200
-T(OK)

Fig. 20-9. The N a 23 nuclear resonance line width as function

of T in metallic sodium. [After Gutowski, ref. 27]

of vacancies in the sqdium lattice for reasons explained above. From the
transition temperature and the slope of the curve, Gutowski arrives at an
activation energy for the self-diffusion of 9.5 ± 1.5 kca1. 28 According to
an analysis by Norberg and Slichter, the diffusion coefficient and its
temperature dependence determined from nuclear resonance experiments

•.
2. H. S. Gutowski, Phys. Rev., 83, 1073 (1951).
,
516 MAGNETIC RELAXATION AND RESONANCE [Chap. 20
are in good agreement with direct diffusion measurements. 29 A detailed
theory of diffusion effects has been given by Torrey.3o
We may mention here that Knight discovered that the resonance
frequency in metals is higher than for nuclei of the same isotope in chemical
compounds in the same magnetic field. 31 This effect is due to the local
field produced at the position of the nuclei by the paramagnetism of the
conduction electrons. 32
For the application of nuclear resonance to order-disorder phenomena
in alloys, we refer to a paper by Bloembergen and Rowland. 33

20-10. Determination of nuclear magnetic moments

By determining the resonance frequency associated with a field Hone

essentially determines the g-value of the nuclei under study; this follows
immediately from (20-23). Thus, when the nuclear spin I is known, one
can calculate the maximum component of the magnetic dipole moment
from the relation (f.lz}max = gflnl; this component is usually referred to
as the nuclear magnetic moment when expressed in units of the nuclear
magnetion !In' (Actually, the magnetic moment is equal tog!ln[l(J + 1)]1/2.)
Magnetic moments for a number of nuclei are given in Table 20-2, together
with the resonance frequency V L in megacycles/sec for a field of 1()4 gausses.
Presently, the resonance method is the most accurate one for determining
magnetic moments.

Table 20-2. Nuclear Magnetic Moments in Units of the Nuclear Magneton

lin = 5.049 X 10- 24 erg/gauss

Magnetic Resonant frequency

Nucleus I moment for H = 10' gausses
gl in megacycles/sec.

neutron 1/2 ~1.9135 29.1

HI 1/2 2.7935 42.6
LF 3/2 3.2571 16.5 ~ -- .

Na 23 3/2 2.2178 11.3

AP7 5/2 3.6419 11.1
Cu· 3 3/2 2.2266 11.3
Cu" 3/2 2.3850 12.1
CI35 3/2 0.8222 4.2

29 R. E. Norberg and C. P. Slichter, Phys. Rev., 83, 1074 (1951); see also R. E.

Norberg, Phys. Rev., 86, 745 (1952).

30 H. C. Torrey, Phys. Rev., 92, 962 (1953).

31 W. D. Knight, Phys. Rev., 76,1259 (1949).

32 Townes, Herring and Knight, Phys. Rev., 77,852 (1950).

33 N. Bloembergen and T. J. Rowland, Acta Metallurgica, 1, 731 (1953).
Sec. 20-11] MAGNETIC RELAXATION AND RESONANCE 517

,
Other Resonance and Relaxation Effects

20-11. Paramagnetic resonance

Paramagnetic or electron spin resonance is the analogue of nuclear

spin resonance. The resonance condition is obtained by replacing M p in
expression (20-23) by the electron mass, so that

WL = g(e/2mc)Hc (20-46)

Since the electron mass is ,....._, I 03 times smaller than M p' the resonance
frequencies for the same field are ,....._,103 higher than for nuclear resonance.
For a free electron g = 2.0023, and in that case WL = 2.8026H megacycles
per second when H is expressed in gausses. Paramagnetic resonance was
first observed by Zavoisky on the paramagnetic salt CuCi 2 ·2H 20.34
Studies of paramagnetic resonance in crystalline solids have provided a
great deal of accurate information about the crystalline electric fields.
A summary of this has been given in a paper by Bleany and Stevens. 3S
Other investigations have been concerned with free radicals, trapped
electrons, conduction electrons in metals, and excited molecules. We shall
confine ourselves to some remarks iIi connection with color centers and
donor levels.
We have seen in Sec. 15-6 that an F center in an alkali halide crystal
is considered an electron trapped at a negative ion vacancy, the electron
being shared by the six surrounding positive ions. Such electrons may be
expected to exhibit the electron spin resonance phenomenon and this is
indeed the case. The absorption lines are quite broad. For example, in
KCI colored additively with excess potassium, one observes a resonance
line of 54 gausses wide (one usually employs a fixed frequency of the
transverse a-c field and sweeps the constant part He slowly through
resonance) and a g factor 0(1.995. 36 Now, when one calculates the width
of the line on the basis of dipolar interaction between randomly distributed
F centers, the width would be only 0.1 gauss. However, attempts to ascribe
the observed line width to the interaction between the F center electron
and the surrounding nuclei K39 and K41 have been successful. For example,
from the fact that K39 has a nuclear magnetic moment of 0.391O,un and
K41 of -0.2145, one would expect on the basis of this notion that replacing
K39 by K41 should produce a narrower line. One finds for K41CI (containing
3. E. Zavoisky, J. Phys. U.S.S.R., 9, 211, 245, 447 (1945).
35 B. Bleany and K. W. H. Stevens, Repts. Progr. Phys., 16,108 (1953).
36 A. F. Kip, C. Kittel, R. A. Levy, and A. M. Portis, Phys. Rev., 9],1066 (1953);

. ,
.
see also C. A. Hutchinson, Jr., Phys. Rev., 75,1769 (1949) .
518 MAGNETIC RELAXATION AND RESONANCE [Chap. 20

99.2 per cent K41) irradiated with X-rays, a line width of 36 gausses. If
only the immediately neighboring K ions were the source of interaction,
the line width would have been 31 gausses; presumably the interaction
with the next shell of chlorine ions also contributes to some extent to
the line width.
We also mentioned in Sec. 15-6 that from the observed g factor and
line width one has concluded that the F center electron is not accurately
described by a pure s-state wave function; the wave function also contains
components with non vanishing orbital momentum.
Electron spin resonance lines have also been observed in n- and p-type
silicon. 37 The lines exhibit a hyperfine structure resulting from the inter-
action between the electron spin and the nuclear spin of the atom to
which it belongs. In general, for a nuclear spin I, one obtains (21 + 1)
lines; the number of lines observed is in agreement with this rule. At high
donor concentrations the lines become narrow and the splitting disappears;
this is a result of the ionization of the donor levels, the remaining line
being attributed to the conduction electrons.

20-12. Ferromagnetic resonance and relaxation

In principle, ferromagnetic resonance experiments are very similar to

nuclear and electron spin resonance experiments. A specimen of the
material, usually in the form of the thin disk, is placed in a microwave
cavity so that the specimen is acted upon by an oscillating magnetic field
of angular frequency wand small amplitude H Q• At the same time, a
relatively strong d-c field He is applied parallel to the disk, so that the
magnetization is saturated. The magnetization vector M .. may be con-
sidered as precessing about He' and for a fixed frequency w, He may be
varied such that the precession frequency equals w; energy is then
absorbed from the microwave field.
Ferromagnetic resonance was first observed by Griffiths.3s At first sight
one is tempted to interpret the results on the basis of the resonance
condition (20-46) for paramagnetic resonance. However, one then obtains
values for g which are much larger than the free electron value g ,__ 2.
It was shown by KitteP9 that for a sample in the form of a disk with He
parallel to the disk, the resonance condition is given by

(20-47)

(8= magnetic induction). When this formula is used, the g values obtained

31 See, for example, A. M. Portis, A. F. Kip, C. Kittel, and W. H. Brattain, Phy.l.

Rev., 90, 988 (1953). .
3' J. H. E. Griffiths, Nature, 158,670 (1946).

3. C. Kittel, Phys. Rev., 71, 270 (1947): 73,155 (1948).

Sec.20-121 MAGNETIC RELAXATION AND RESONANCE 519
are close to the free electron value. As an example, we give in Fig. 20- 10
the ferromagnetic absorption line for nicKel ferrite, measured at 24,000
megacycles/sec.
Jn gene~l, the theory of ferro-
magnetic resonance is in good agree-
ment with experiments; however, the
explanation for the very large line widths
(,.._,100 gausses) which are observed is
still in doubt. 40 Since the line width
is determined by relaxation effects
(compare 20-41 ),' this difficulty has
stimulated studies of ferromagnetic
relaxation; references on this topic
may be found in E. Abrahams,
Advances in Electronics and Electron
PhysiCS, 7, 47 (1955).
For antiferromagnetic solids, the
resonance frequencies lie just beyond 6.8 7.2 7.6
the limit of the experimentally accessible ... H (kilogauss)

region. The reason for this may be Fig. 20-10. The ferromagnetic reso-
found in Kittel's theory of antiferro- nance line in Ni-ferrite at 24,000
magnetic resonance. 41 On the basis of megacycles/sec. {After Yager, Galt,
a two sublattice model, he finds that Merrit, and Wood, Phys. Rev., 80,
744 (1950»)
below the Curie point the resonance
frequency is a doublet determined by
(20-48)

where (' = g(e/2mc), H is the applied field, He! is the anisotropy field for
one sublattice, and Hrnf is the molecular field. Thus for MnF 2 for which
H A ':::: 9000 gausses and Hmf ~ 10 6 gausses, one obtains Wo ':::: 10 cm-l.42
The anti ferromagnetic doublet has, however, been observed for
CuCI 2 '2H 20, which has an antiferromagnetic Curie point of 4'3°K and
thus a relatively weak molecular field. 43

20-13. Frequency-dependence of the initial permeability in ferrites

Because of the great interest in ferromagnetic insulators, such as the

ferrites, for high-frequency applications, extensive investigations are being
made of the high-frequency behavior of these materials. In particular, one
,
'" C. Kittel, J. phys. rud., 12, 291 (1951); J. H. Van Vleck, Physica. 17, 234 (1951).
<I C. Kittel, Phys. Rev., 82, 565 (1951) .

.
.. F. Keffer, Phys. Rev., 87, 608 (1952) .
• 3 Ubbink, Poulis, Gerritsen, and Gorter, Physica, 18, 361 (1952); for the theory.

see J. Ubbink, Physica. 19.9 (1953) .

"
520 MAGNETIC RELAXATION AND RESONANCE [Chap. 20

is interested in the frequency-dependence of the initial permeability

because the latter"determines essentially the propagation of electromagnetic
waves in the material. In such experiments there is no applied static
magnetic field, in contrast with the ferromagnetic resonance experiments;
one measures for a demagnetized sample the complex permeability
(2049)
in an alternating field. 'We note that the complex permeabili.ty is related to

24

20 ,,'-I

16
\
12

0
-2
1 2 5 10 100 1000 10,000 !mc/sec~..

Fig. 20-11. The frequency dependence of (P' - I) and /t" for

ferramic A in the demagnetized state. [After Rado, Wright, and
Emerson, ref. 47}

the complex susceptibility X* by the relation X* = (,u* - 1)/41T. The

frequencies of interest range between zero and 104 megacycles per second.
In such measurements on sintered Ni-Zn and Mn-Zn ferrites, Snoek
found that the losses of these materials above a frequency of the order of
5-100 megacycles/sec become very high.44 The shape of the curves for fl'
versus frequency are similar to those given in Fig. 20-11, except that he
found only one maximum. The fact that fl' first increases indicates a
resonance phenomenon, although the fact that the fl' -values did not
become < I (i.e., X' < 0), indicates a relaxation effect at the same time.
The resonance was explained by Snack in the following way. According
to Landau and Lifshitz the crystalline anisotropy field is equivalent with
.. J. L. Snoek, New Delielopments in Ferromaglletic Materials, Elsevier, New York,
1947.
Sec. 20-13] MAGNETIC RELAXATION AND RESONANCE 521
an internal field Hi. 45 Thus the electron_spins precess about Hi with the
Larmor frequency within each crystallite of the polycrystalline material.
When an alternating magnetic field of the Larmor frequency is applied,
ferromagri~tic resonance occurs when this field has a component perpen-
dicular to Hi' This has been called "natural" resonance, in contrast with
the "induced" resonance obtained with an applied static magnetic field. 46
More recently, Rado et al. carried out some interesting experiments
of the same type on "ferramic A," which is a sintered mixture of several
oxides, but containing mainly magnesium ferrite.47 The curves obtained
for (/1/ - I) and fl" are given in Fig. 20-11. It is observed that in this case
two resonances occur, one at about 50 megacycles/sec and another in the
vicinity of 1000 megacycles/sec. When they carried out the same experi-
ment with small particles ('"'-'0.5 fl) embedded in wax, they observed that
the 50-megacycle resonance was absent. Also, they had shown previously
that particles of this size behave essentially as single-domain particles.
They conclude from these results that the 50-megacycle resonance is
associated with domain-wall displacements, and that the 100-megacycle
resonance is due to domain rotations. The theory of these phenomena is
still in a state of flux and will not be discussed here. 48

,
REFERENCES

E. Abrahams, "Relaxation Processes in Ferromagnetism," Admnces in

Electronics and Electron PhYSiCS, 7, 47 (1955).
A. H. Cooke, "Paramagnetic Relaxation Effects," Rep/s. Progr. Phys.,
13, 276 (1950).
K. K. Darrow, "Magnetic Resonance," Bell System Tech. J., 32, 74,
384 (1953).
C. J. Gorter, Paramagnetic Relaxation, Elsevier, New York, 1947.
H. S. Gutowski, "Nuclear magnetic resonance," Ann. Revs. Phys. Chem.,
5,333 (1954).
J. Van den Handel, "Paramagnetism," Advances in Electronics and
Electron PhysiCS, 6, 463 (1954).
W. D. Knight, "Electron Paramagnetism and Nuclear Magnetic Reso-
nance in Metals," in Solid State PhYSiCS, Academic Press, New York,
vol. 2, 1956.
~.; L. Landau and E. Lifshitz, Phys. Z. Sowjetunioll, 8, 153 (1935) .
•• G. T. Rado, Revs. Mod. Phys., 25, 81 (1953) .
• 7 G. T. Rado, R. W. Wright, and W. H. Emerson, Phys. Rev., 80,273 (1950) .

•• The present situation has been reviewed by E. Abrahams, Advances in Electronics

alld Electron PhysiCS, 7, 47 (1955).
•
522 MAGNETIC RELAXATION AND RESONANCE [Chap. 20

G. E. Pake, "Nuclear Magnetic Resonance Absorption," I and II, Am. J.

Phys., 18, 438, 473 (1950).
G. E Pake, "Nuclear Magnetic Resonance," in Solid State Physics,
Academic Press, New York, vol. 2, 1956.
G. T. Rado, "Ferromagnetic Phenomena at Microwave Frequencies,"
Advances in Electronics, 2,251 (1950).
J. Smit and H. P. J. Wijn, "Physical Properties of Ferrites," Advances in
Electronics and Electron Physics, 6, 70 (1954).
J. L. Snoek, New Developments in Ferromagnetic Materials, Elsevier,
New York, 1947.
"International Conference on Spectroscopy at Radiofrequencies," Physica,
17, 169-484 (1951).
"Washington Conference on Magnetism," Revs. Mod. Phys., January 1953.
Conference on Defects in Crystalline Solids, held at the H. H. Wills
Physical Laboratory, University of Bristol, July 1954.

PROBLEMS

20-1. Consider a series arrangement of a self-inductance L and a

resistance R; show that the conductance G of the system as function of
frequency is given by I.
G(w) = G(O) _ i G(O)wT /1

1 + 2
W T2 1 + 2
W T2

with T = L/R. Note that this expression is similar to that for X according
to the Debye equations (20-9).
20-2. Show that at low frequencies the paramagnetic absorption is
one order of magnitude more sensitive than the dispersion.
20-3. As mentioned in Sec. 20-1, X' and X" are not independent of each
other; in fact if one of them is known for all angular frequencies w, the
other may be calculated from one of the Kramers relations:
.' w __ 2 (C/O wX"(w) dw " 2 ~oo woX'(w) dw
X ( 0) - -)0 (2 i) and X (w o) = - - (2 2)
7T W - Wo 1T' 0 W - Wo

(a) Show that the Debye equations (20-9) satisfy these relations; do
the same for the Casimir-Dupre equations (20-15) and (20-16).
(b) Give a proof of the Kramers relations by following these hints:
Apply a magnetic field in the form of a delta function

H(t) = bet) = .!_ I'

7T .0
00 cos wt dw
Chap. 20] MAGNETIC RELAXATION AND RESONANCE 523
The corresponding magnetization is then

M(t) = .!_ ex; (x' cos wI

7T • ()
+- x" sin WI) dw
Now, for t < 0 we must have M(t) = 0; also cos wI is an even and sin w(
is an odd function of I. Hence, we must require for I > 0 that

rco x' cos wI dw ==0 .0(CO X" sin wI dw =

.10
f{l)

From this information, derive the Kramers relations by inversion of the

Fourier integrals.
20-4. This problem refers to the theory of Gorter and Kronig of
paramagnetic relaxation, leading to the Oebye equations. Consider N
noninteracting spins of t. Apply a constant field Hr. In equilibrium
N"P"p = NpP pa where Na is the number of spins parallel to He and P"'P
is the probability for a transition from the antiparallel to the parallel
orientation. First show that if IllJHc ~ kT

(Note that the P's depend on He.) Next assume that

~(t) = He + Hoe iw
, and PUP = (P"p)Ho=O + (O:ap)
,uH l'
Hoe i ,"'

where Ho ~ He' Set up the equations for (oNplot) and (?N,Jot) ap-
propriate to the field H(t). Calculate the magnetization Mo corresponding
to the a-c field and show that

X = MolHo = Xstatic(l + iWt)-l with T = liP

This expression gives tHe Oebye equations (20-9).

APPENDIX

A. Thermodynamic conditions for equilibrium

When a physical system is not in thermal equilibrium, it will in time

proceed to equilibrium by means of a number of irreversible processes.
The second law of thermodynamics in its general form reads

T dS ?:o dE + p dV (A-I)
where p dV represents the work done by the system. If the work is of a
mechanical nature, p and V stand for pressure and volume, but in other
types of work they may represent other quantities, such as polarization
and field strength, etc. The equality sign in (A-I) holds only in the state
of equilibrium. From (A-I) one may derive conditions for equilibrium,
depending on the external quantities one choses to keep constant. It
should be emphasized that the first law of thermodynamics, which
expresses the conservation of energy, holds for reversible as well as for
irreversible processes, i.e.,
bQ = dE+ pdV (A-2)
The following cases arise:
(a) c5Q = O. This refers to systems which are isolated from the rest of
the universe so that no heat exchange with the surroundings is possible.
This gives.
T dS ?:o 0 for bQ = 0 (A-3)

Thus, for such a system the entropy can only increase or remain constant;
i.e., in equilibrium the entropy of such a system reaches its maximum value.
(b) Systems held at constant volume and temperature. Under these
conditions one concludes from (A-I) that T dS - dE ?:o 0, or

,dF= deE - TS) ~ 0 for constant V,T (A-4)

Here F is called the Helmholtz free energy or, as in this book, simply the
free energy. Note that in this case F must be a minimum when equilibrium
has been reached.
(c) Systems held at constant pressure and temperature. In the physics
of solids this is the most frequently occurring case. It follows from
(A-I) that
+
dG = deE p V - TS) ~ 0 for constant p, T (A-5)
525
526 APPENDIX
\,
Here G is called the Gibbs free energy, or the thermodynamic potential.
The reason that in so many of the problems discussed in this book F is
minimized rather than G, is that when p is the atmospheric pressure, the
term p dV is usually negligible compared with dE and T dS. In other
words, this procedure is justified as long as the pressure is low enough
as to have no influence on the properties of the crystal. In fact, for p = 0,
conditions (A-4) and (A-5) become identical. .

B. Particle in a box according to wave mechanics

Consider a particle allowed to move in one dimension. Let the potential

energy of the particle be zero for 0 < x < L and let it be infinite for
x ~ 0 and x ?: L. The SchrOdinger equation is
\

\ (B-1)

where E is the total energy of the particle, i.e., in our case the kinetic
energy. The general solution is

'P(x) = Aeil.:x + Be- ib with k2 = (2m/1i2)E

The boundary conditions require

'P = 0 for x = 0 and for x = L

The first condition yields A = -B; this leaves only solutions of the type
sin kx. Applying the second boundary condition, one singles out only
those solutions for which l'
sin kL = 0 or kn = mr/L with n = 1,2,3, ...
The solutions
'If'n = C sin (mTx/L) (B-2)

are standing waves. For each value of n there IS a wave function 'Pn
corresponding to an energy

(B-3)

Note that lik n represents the momentum of the particle. The energy
spectrum evidently consists of discrete levels, the separation depending
on L2 and n 2 • The constant C in (B-2) may be obtained from the require-
ment that for a particle known to be in the state 'P", the probability to
be found anywhere between x = 0 and x = L must be equal to unity, i.e.,

(B-4)

..
.r' .
-~
APPENDIX 527
For a particle in a 3-dimensional cubic potential box of edge L, the
solutions are again standing waves; -

.... v{x,y,z) = C sin (n",7Tx/L) sin (ny7Ty/L) sin (n z7Tz/L) (B-5)

where n x , ny, n z are integers? 1. The energy levels are

E ",".", -- - (tz2 7T 2/2 m L2)(nx2 + n2 + nz2)

ll
(B-6)

A particle described by one of the wave functions (B-5) is said to be in a

given "state." Note that one energy level may correspond to various
states; for example, the integer values (112), (I21), (211) all correspond
to the same energy level, although they represent different wave functions.
The energy level is then said to be 3-fold degenerate.
What is the number of possible wave functions corresponding to a
momentum between p and p + dp? This may be found by realizing that
(B-6) represents p2/2m. We may then write (B-6) as

p2L2j1i 27T2 = n; + n; + 11; _ R2

The number of different sets of integers corresponding to a range between

Rand R dR is+
(B-7)

where the factor t arises from the fact that the integers are positive. For
each set of integers n x , ny, n z there is one wave function, i.e., one state;
the spin is not included in this case. Note that (B-7) may be interpreted
as follows; divide the momentum space into cells of h3 ; each cell then
corresponds to a possible wave function per unit volume.
, j
C. Indistinguishable particles and the Pauli principle

Consider two weakly interacting particles in a I-dimensional potential

box and let the potential energy inside the box be taken as zero. For a
single particle in the box, the Schrodinger equation is
(C-I)

Let the solutions of this equation be Vl,,, Vlb' Vlc' ... , corresponding to the
energies Etl , E b , E e ,.... For the system of two particles we have
,)2 02 2m)
( Gxi + ox~ + Ii'!. E Vl(X I ,X 2 ) ~= 0 (C-2)

We leave it to the reader to show that possible solutions of this equation

are the product of the single particle solutions;
Vlixl)V'b(X2) and Vlb(X 1)Vla(X 2 ) (C-3)
~.

,
528 APPENDIX

The former describes the situation in which particle I is in state 'Pa and
particle 2 is in state 'Pb; the latter corresponds to particle 1 in 'Pb and
particle 2 in 'Pa' Note that both solutions correspond to the same energy
E = £" + Eb • From the mathematical point of view any linear combina-
tion of the solutions (C-3) is a satisfactory solution of (C-2). From the
point of view of physics, however, there are only two acceptable linear
combinations, viz.,
\.- ---
'1Ps y m = 'Pixl )'Pb(X 2) + 'Pb(Xl )'1pix 2) (C-4)

and 'Panti = 'Pa(X1)'Pb(X2) - "I'b(Xl )lpix 2) (C-5)

In (C-4) an interchange of the coordinates of the particles leaves the wave

function unaltered and one speaks of the symmetric wave function. In the
antisymmetric wave function (C-5) an interchange of the coordinates Xl
and x 2 produces a change of sign. The physical reason for selecting only
(C-4) and (C-5) from an infinite number of possible mathematical solutions
is based on the principle of indistinguishability of the two particles. In
other words, from a physical experiment we may ascertain that one of
the particles is in state 'Pa and the other in state 'Ph; but it is impossible
to distinguish experimentally between the possible solutions "I',,(xl)"I'ix2)
and 'Pb(Xl )'Pa(X 2), The principle thus rejects the possibility of "painting"
numbers on the particles. Mathematically, the principle may be expressed
as follows: let 'Pl,2 represent a wave function describing the system of
two particles, and let "1'2,1 be obtained from "1'1,2 by interchanging the
coordinates Xl and x 2 • We then require that

1"1'1,21 2 dX1 dx z = l'Pd 2 dX1 dX 2 { (C-6)

because each of these expressions gives us the probability of finding one

particle in the range dX1 and the other in the range dx 2 • The principle of
indistinguishability thus imposes the following symmetry conditions on
the two-particle wave functions:
1/
either 'P1,2 = "1'2,1 \:~ (C-7)
or "1'1,2 = -"1'2,1 (C-8)

Note that (C-4) and (C-5) satisfy, respectively, (C-7) and (C-8); it can be
shown that (C-4) and (C-5) are the only solutions with these properties.
In nature there are two types of particles: those for which the two-
particle wave function is always symmetric and those for which the two-
particle wave function is always antisymmetric. To which group a
particular type of particles belongs must be decided from experiment.
Electrons, protons, and neutrons require antisymmetric wave functions.
Particles described by antisymmetric wave functions have the following
fundamental peculiarity: from (C-5) it follows that if 'Pil =--= 'Ph' i.e., if both
APPENDIX 529
particles are in the same state, 1fJ,,"ti vanishes, i.e., such a situation does
not exist. By extending the above treatment to many particles, one
arrives at the following conclusion:
In a s¥stem of particles described by antisymmetric wave functions,
such as electrons, only one particle can occupy anyone "state." This is
the Pauli exclusion principle.
The word "state" must be amended here in the following sense; the
complete wave function of an electron does not contain only the spatial
coordinates x,y,z but also the spin, which can accept two possible values.
Thus if the spin is included in the wave functions 1fJa and 1fJb' the wording
of the conclusion is correct. If a state is considered to be described by its
spacial coordinates only, the Pauli principle should read that no more
than two electrons can occupy a given state. Particles obeying the Pauli
exclusion principle give rise to Fermi-Dirac statistics. Particles described
by symmetric wave functions give rise to Bose-Einstein statistics, and for
them no limitation exists on the number of particles occupying a given state.

D. Fer.mi statistics

Consider a system of particles for which the possible wave functions

(states) and energy levels are known. Let the energy levels be denoted by
€1' €2, ... , €i ••• and let the number of possible states (including the spin)
corresponding to these energy levels be denoted by Zl' Z2' ... ,Zi' ....
The interaction between the particles is assumed to be weak, so that the
total energy of the system E is equal to the sum of the separate energies
of the particles. The fundamental problem of statistical mechanics is this:
given the total number of particles N and the total energy E, what is the
most probable population n1 , n 2 , .•• , ni , ... of the energy levels? Evidently,
1: n,
1
= N and ~ nif. i
,
= E (D-1)
Also, the levels of interest for the problem are only those below the value
E; this limits the total number of possible states involved to

ZtOI"1 = Zl + Z2 + ... + Z; + ... + Z R (0-2)

where ZE is the number of possible states of the level E.

To solve the problem just stated, it is necessary to decide upon the
probability for a single particle to be in a given state. We shall accept
the postulate of "equal a priori probabilities," in which it is assumed that
there is no preference for any of the Ztotal possible states. In other words,
the probability for anyone particle to be in a given state is simply
p = l/Ztotal (0-3)
Furthermore, we shall restrict the discussion to particles for which the
Pauli exclusion principle holds, i.e., to Fermi-Dirac statistics.
530 APPENDIX ""'1
What is the probability P(n1' n 2 , ... ) that the populations in the energy
levels are nl , n 2 , ... ? Consider Zi boxes and n i indistinguishable balls and
assume that each box can con tam either one or no ball (Zi ~ n i). The
probability for a specific distribution (say box 1 empty, box 2 filled, box 3
filled etc.) is evidently p7l,. However, there are in general many ways Wi
in which the balls can be distributed, viz., just as many ways as there are
possible arrangements of n i occupied and (Zi - n;) empty boxes. Hence

Wi = Zil![nil(Zi - ni )!]

Thus the probability of finding ni particles in €oi is

P(ni) = p"'W; = p"'Zil![n;l(Z; - n;)l]

For the other levels, similar arguments hold, so that

P(n 1, n 2 , ... ) = p N W 1W 2 ••• pNW (D-4)

Note that r" is a constant and that the most probable state of affairs is
determined by the maximum value of W. One thus has to find that set
of values nl' n 2 , n 3 , .. , for which W obtains its maximum value. It is more
convenient, however, to maximize log W. By applying Stirling's theorem,
assuming all quantities involved to be ;?> 1, one may write

log W = b log W; = ~ [Z; log Z; - n i log n i - (Zi - n;) log (Z; - n;)]
1. 1.

(D-5)

When W is a maximum, we must have for small variations On; in the

numbers n i , 1
b log W = l: [-log n i
I
+ log (Z; - n i)] On; = 0 (D-6)

However, the variations on i are not independent of each other, but should
satisfy the following auxiliary conditions derived from (D-I):

oN = l: on i = 0 and oE = L €o; On; = 0 (D-7)

I ,

Using the method of undetermined multipliers of Lagrange, we may write

from (D-6) and (D-7),

olog W - (X L• On"1. -
•
f./ L. "
P
1
€o. On·1 = 0 (D-8)

where (X and (3 are undetermined constants. Suppose now we choose (X

and {J such that of the sum (D-8) the coefficients of onk and on j are zero, i.e.,

log [(Z~ - nk)!nk] - (X - (3€ok = 0

log [(Zj - n j )/IlJ - (X - {J€oj = 0

'4 ,;
APPENDIX 531
This is always possible, because we have two equations from which fJ and
IX may be found. Now the variations r5"'i are independent except for two
of them (because there are two auxiliary conditions). If we consider bn k
and bn j as the dependent ones, it is evident that (0-8) can be satisfied
only if for all values of i,

log [(Z; - ni)/n,] - Q( - fJfi = 0 (D-9)

Hence ;' ni = Z;/(e HfJ€; + I) =~ ZiF(fi) (D-IO)

As shown in appendix E, fJ must be identified with IjkT, where k is

Boltzmann's constant. Expression (0-10) is the Fermi-Dirac distribution.
The value of IX is determined by the condition ~, n i = N.

Note that if e~ ~ I, then the term of unity in the denominator of (0-10)

may be neglected for all values of fl' and the Fermi distribution reduces
to the Boltzmann distribution; in this case one speaks of a nondegenerate
gas. If 0 < e'1. < I, i.e., for Q( negative, the gas is degenerate and the
term of unity in the denominator must be retained at least for the low
energy range; this is the case for the conduction electrons in a metal.

E. The Boltzmann relation

It will be shown that the number of possible arrangements W intro-

duced in appendix D is related to the entropy of the system. Suppose a
small amount of heat r5Q is added to a system. According to the first
law of thermodynamics, this will produce a change in the energy of the
system equal to
bE= oQ - p oV (E-1)

where p 0 V is the work done by the system. On the other hand, if the
total energy is E, we may write

oE = :E
"
fj i'Jn i + :E, n i r5fi (E-2)

It must be emphasized that any changes Ofi in the energy levels are
possible only if the volume changes; this follows from the discussion in
appendix B. Hence the last term in (E-2) may be written
: OE.
1: n, bE·
i"
= 1: n· _' b V = - P i'J V
; ' oV
(E-3)

because p ,-" -oEjoV. We thus conclude that

oQ = ~, Ei On; (E-4)
532 APPENDIX .~

Consider this question: When a small amourit of heat t5Q is added

reversibly to a system, what is the corresponding change in log W? The
term "reversibly" means that the system is continuously in thermal
equilibrium, i.e., during the whole process of adding bQ, W is a maximum.
Employing (0-8), while keeping the total number of particles constant,
we obtain
b log W = in:,, E; t5n; = {3 bQ

There evidently exists a simple relation between a small amount of heat

added to the system and the resulting change in log W. Now t5log W is
a complete differential, i.e.,
. a l i
r
_

b log W = 7 an 1
(log W) bn i

Hence, {3 bQ must also be a complete differential. We know from thermo-

dynamics that bQ itself is not a complete differential, but that liT is an
integrating factor. Therefore {3 = IjkT, where k is a constant, and instead
of (E-5) we may write

k b log W = oS or S = k log W + const. (E-6)

This is the famous Boltzmann relation between the entropy S and log W.
The value of k must be obtained by comparison with experiment, and
turns out to be Boltzmann's constant k = 1.38 X 10- 16 erg degree-I.
The above Wand entropy are associated with the distribution of
energy and in this volume are written W(h and Sth' The subscripts stand
for "thermal" and distinguish them from Wrf and Srf, which refer to con-
figurational or mixing entropy which results from possible arrangements
of particles in space.
I ..

'I
INDEX

a-band, 377 Antiferroelectrics, ]96, 210

Absorption, infrared, 56 Antiferromagnetism, 483 ff.
theory, 154 f{. table, 486
Acceptor levels, 310, 323 Atomic polyhedron, 269
Acoustical branch, 55 Atomic radii, metals, 60
Activation energy, diffusion, 70, 152, 172 Atomic scattering factor, 14, 20
Activators, luminescence, 399, 409 Attractive forces, interatomic, 23 ff.,
Adiabatic demagnetization, 460 118 ff., 128
Adsorption, 228 Axes, crystal, 6
Alkali halides, bandstructure, 369 rotation-inversion, 6
dielectric constant, 145 Axis, rotation, 6
diffusion, 168, 171
electron mobility, 393 BAND theory, 238 ff.
F centers, 377 ff. Band to band transitions, 415
index of refraction, 145, 158 Band width, insulators, 371
infrared absorption, 147 Bardeen-Shockley formula, mobility, 329
ionic conductivity, 175 ff. Barium titanate, 191, 198 ff.
ionic radii, 126 internal field, 143
lattice energy, 122 Barkhausen julpps, 475
molecules, J31 Baroody's theory, secondary emission,
optical absorption, 366 ff. 430 ff.
photoconductivity, 386 ff. Barrier layer, metal-metal, 348
photoelectric effect, 390 ff. metal-semiconductor, 349
thallium activated, 406 ff. Binary alloys, 104
transport numbers, 181 Bitter powder patterns, 476
vacancies, 160", 167, 173 Black-body radiation, 43, 59
Alkali metals, band structure, 267 Bloch equations, nuclear resonance, 508 ff.
overlapping bands, 265, 268 Bloch functions, 240 ff.
photoemission, 234 Bloch T3/2 law, 475
Alkaline earth oxides, diffusion, 169 Bloch theorem, 240 ff.
lattice energy, 122 Bloch theory, electrical resistivity, 289,
Allotropy, 62 292
Alloys, band theory, 108 Bloch wall, 480
electrical resistivity, 288 Body-centered cubic lattice, 5
Hume Rothery phases, 107 Bohr magneton, 449
interstitial, 104 effective number of, 456, 457, 470, 492
Jones' theory, 272 Boltzmann relation, entropy, 53]
neutron diffraction, 21 Boltzmann transport equation, 278 ff.
ordered, 109 ff. Born cut-off wavelength, 45
phase diagrams, 116 Born-Haber cycle, 122
substitutional, ]04 Born theory, ionic crystals, 117
Amorphous, 2 Boundary conditions, periodic, 247, 255
Anisotropy, 27, 31, 82 Boundary scattering, phonons, 297
magnetization, 478 Bragg reflection, X-rays, 13

533
534 INDEX

Brass, 109 Curie temperature, antiferromagnetic, 22,

Bravais lattices, 4, 6, 7 , 486
Brillouin function, magnetism, 455, 467 ferroelectric, 185
Brillouin zones, 48, 246, 255, 263 ferromagnetic, 464, 470
Burgers vector, 85 Curie-Weiss law, ferroelectric, 186, 194,
197
CARRIER injection, 341, 415 magnetic, 464, 471
Casimire-DuPre' theory, spin-lattice, 501 Cyclotron resonance, 334 ff.
Cathodoluminescence, 398, 417
Cavity field, 159, 196 DEBYE equations, relaxation, 151, 159,
Center of symmetry, 185 501
Cesium chloride structure, 123, 127 Debye frequency, 42
Charge compensation, principle of, 410 ff. Debye function, specific heat, 38
Classification of solids, 23, 25, 27 Debye temperature, 42; table, 44
Clausius-Mosotti formula, 144, 197 metals, 294
Closure domains, magnetism, 477 Debye unit, electric dipole, 319
Coactivators, luminescence, 411 Degenerate electron gas, 214, 236, 313,
Coercive force, 185, 476, 481 316
Cohesive energy, metals, 269 ff. Density of states, 256, 264, 265, 268
ionic crystals, 117 copper, 267
Collisions, electron-phonon, 289 insulators, 308
phonon-phonOn, 296 Destrieau effect, electroluminescence, 414
Colloids, F centers, 392 Diamagnetism, 451 ff., 460
Color centers, 377 ff. free electrons, 219
magnetic resonance, 51 7 Diamond, energy gap, 251
models, 394 physical constants, 321
X-rays, 394 structure, 8, 30, 321
Compound unit cell,S Dielectric constant, 133, 186
Compressibility, 31, 33, 120 alkali halides, 145, 159
Conduction band, 251 complex, 148
Conductivity, see Electrical or Thermal gases, 140
conductivity; Dielectric losses, 149 ff.
ionic, 160 ff. Diffraction, electron, 20
Configurational, coordinate, 408 neutron, 21
entropy, 63, 106, 161 X-ray, 10
Constant energy surfaces, 262, 334 Diode theory, rectification, 353
Contact potential, 230 Dipolar solids, 147 ff.
Conwell-Weisskopf scatteri ng formula, Dipole layer, 229
330 Dipole moment. electrical, 129, 134, 158
Coordination number, 60 magnetic, 448 ff.
Covalent bands, 320 Dipole radiation, 398
Creep, metals, 83 Dipole theory, ferroelectrics, 192, 195
Crystals, directions, 9 Direct lattice vectors, 253
growth, 31, 210, 324 Dislocations, 82, 85 ff.
planes, 9 configurational entropy, 93
Cubic, body-centered, 5, 7, 30, 60 density, 87, 96
face-centered, 5, 7, 30, 60 edge, 88
simple, 7, 8 energy of formation, 92, 1D3
system, 8 etch pits, 98
Cubic lattice, band theory, 260 Frank-Read source, 99
Curie constant, 186, 193 interaction, 93
Curie law, paramagnetic, 455 jogs, 90
I Dislocations (cont.):
recombination of, 90
INDEX

Electrons (cont.):
mean free path, metals, 283
535

j screw, 90
stress fieldSl 91 ff.
mobilities, 333
range in solids, 428, 445
Dispersion, 155 relaxation time, 276, 284, 328
Dissociation energy, 24, 123, 124 transverse mass, 336
Domains, ferroelectric, 184, 207 Electron scattering, ions, 330
ferromagnetic, 475 ff. neutral impurities, 331
Donor levels, 310, 322 phonons, 289, 329
Double hysteresis loop, ferroelectrics, 206 Electrostriction, 186
Drift velocity, 276 Energy bands, allowed and forbidden,
Dushman-Richardson equation, 221 239 ff., 245
overlapping of, 265
EASY direction of magnetization, 476 silicon, 336
Edge dislocation, 89 sodium, 261
Effective mass, 248 ff., 261, 316,334, Energy levels, metals, 213
336 Entropy, 525, 532
Einstein-de Haas method, 469 configurational, 63, 106, 161
Einstein frequency, 36 thermal, 63, 161
function, specific heat, 38 Etch pits, dislocations, 98
relation, mobility, 177, 342 Exchange integral, 473
temperature, 38 Expansion coefficient, 33, 197
Elastic, constants, 78 Extinction coefficient, 156
moduli,81
strain components, 81 FACE-centered cubic lattice, 5, 7, 30, t>l
stresses, 78 F centers, 377 ff.
waves, 39 ff. coagulation, 392
Electrical conductivity, alloys, 110 photoconductivity, 388
meta Is, 27 5 ff. F' centers, 383 ff.
semiconductors, 326 ff. Fermi-Dirac statistics, 214, 529
Sommerfeld theory, 281 ff. Fermi energy, 214, 215, 224, 231
Electric double layer, 229 Fermi level, insulator, 306, 309
Electric field, cavity, 159, 196 Fermi temperature, 219
internal, 141, 194, 195, 199 Ferrimagnetism, 490 ff.
reaction, 144, 159, 195 NceJ's theory, 493 ff.
Electroluminescence, 413 Ferrites, 491
Electronic polarizability, 134 ff. initial permeability, 519
theory of, 154 Ferroelectric domains, 207
Electron affinity, 123, 124,315,369 F crroelectrics, ]84 ff.
Electron diffraction, 20, 212 thermodynamic theory, 20]
Electron distribution, insulators, 306 ff. Ferromagnetism, anisotropy energy, 478
metals, 213 ff. Curie temperature, 464, 470
semiconductors, 308 ff. Curie-Weiss law, 464, 471
Electron emission, thermionic, 220 fr. domains, 464, 475 ff.
field enhanced, 225, 227 g-factor, 469
secondary, 418 ff. Heisenberg theory, 472 ff.
Electron pair bonds, 320 paramagnetic Curie point, 471
Electrons, effective mass, 248 fr., 261, resonance, 518
316,334,336 Ferroxcube, 491
exchange interaction, 472 Fick's law, 70, 169
Hamiltonian in magnetic field, 459 Field emission, 227
lattice mobility, 329 First-order transition, 186, 204, 206
longitudinal mass, 336 Floquet's theorem, 240
536 INDEX

Fluorescence, 398 "; Homopolar bonds, 26

Flux density, 133 Hume-Rothery alloy phases, 107
Forbidden transitions, 398 Hund's rules, 450, 470
Franck-Condon principle, 367, 401 Hydration energy, 164
Frank-Read source, dislocations, 99 Hydrogen bonds, 187, 189
Free electrons, 211 Hysteresis, 184,465,481
diamagnetism, 219, 462 double loop, 206
effective number of, 250
energy distribution, 213 IMAGE force, dislocation, 95
paramagnetism, 217 electrons, 225
specific heat, 216 ions, 228
Frenkel defects, 67, 163 Impurity semiconductors, 310 ff., 319
Fundamenta! ,absorption, ionic crystals, Index of refraction, alkali halides, 145
373 complex, 156
metals, 237
GALVANOMAGNETIC effects, 304 Indistinguishability of particles, 527
Germanium, constant energy surfaces, 334 Infrared absorption, ionic crystals, 56,
crystal growth, 324 147
electrical properties, 331 ff. germanium, silicon, 339
infrared absorption, 339 Initial permeability, 519
lattice properties, 320 ff. Injection of carriers, 341, 415
lifetime of carriers, 343 Insulators, band scheme, 251
physical constants, 311 dielectric properties, 133
secondary emission, 421 electron distribution, 305 ff.
Gibbs' free energy, 526 secondary emission, 440
Glow curve, luminescence, 405, 407 thermal conductivity, 295 ff.
'Goldschmidt radii, ions, 126 Interaction, dislocations, 93
Gorter-Kronig theory, paramagnetic re- exchange, 472
laxation, 523 super exchange, 488
GOllY balance, 462 Interatomic forces, 23 ff., 119, 121, 128
Grain boundaries, 1,98 Intermetallic compounds, 344 ff.
Grey tin, 320 Internal field, 141, 194, 195, 199
Gruneisen constant, 33 Interstitial atoms, 63, 67
Gudden-Pohl effect, luminescence, 413 Intrinsic semiconductors, 308 ff., 319
Gyromagnetic ratio, 450 Inverse spinel, 491
Barnett method, 469 Inversion center, 6
Einstein-de Haas method, 469 Ionic conductivity, 160, 175
Ionic crystals, 25 ff.
HALL effect, alkali halides, 393 defects, 160
metals, 301 infrared absorption, 56, 147
semiconductors, 326 ff. lattice energy, 117, 122
Hall mobility, 328, 333 Ionic polarizability, 134, 137
Hamiltonian, electrons, 459 Ionic radii, 124, 126, 127
Harmonic oscillator, 34 ff., 51, 101 Ionization energy, 123, 128,229
Helmholtz free energy, 525 Ion mobility, 180, 183
Hexagonal close-packed structure, 61 Isotropic, 27
Hexagonal system, 8
Hole, 252 JUNCTION, rectifier, 357 ff.
density, 309 transistor, 361
effective mass, 337
lifetime, 343
mobility, 333 . ,,.
K-band, color centers, 381
Killers, luminescence, 399, 417
INDEX 537

Kirkendall effect, 76 Magnetization (cont.):

Knight shift, nuclear resonance, 516 easy and hard directions, 476, 478
Kronig-Kramers relations, 499, 522 Magnetization curve, ferromagnetic, 465
Kronig-Penney. model, 243 ff. Magnetocaloric effect, 463
Magnetoresistance, 304
LAGRANGE, undetermined multipliers, Matthiessen's rule, 275, 287
530 Metals, atomic radii, 60
Landau diamagnetism, free electrons, 219 band structure, 251
Lande formula, 450 cohesive energy. 26, 269 ff.
Langevin function, 139, 193 electrical conductivity, 275 ff.
Larmor precession, 452 electron mean free path, 284
Lattice defects, ionic crystals, 160, 166, free electron theory, 211 ff.
375 Hall effect, 301
metals, 62, 85 mutual solubility, 105
Lattice, direct, 253 photoelectric emission, 232
reciprocal, 254 rectifying properties, 348
Lattice energy, ionic crystals, 117, 122, secondary emission, 422, 430 ff.
130 structure, 60
Lattice vibrations, 32 ff.; see also Vibra- thermal conductivity, 299 ff.
tional modes thermionic emission, 220
Debye model, 41 Metastable levels, 403, 408
Einstein model, 36, 65, 161 Miller indices, 8
LCAO method, 257 Minority carriers, 341
Lenz's law, 451 Mobility, electrons, 307, 329
Lifetime, carriers, 341 ionic, 180. 183
Liquid crystals, 2 Molecular field, ferromagnetism, 466 ff.
Long-distance order, 3, III Molecular rotation, 514
Longitudinal mass, 336 Monoclinic system, 8
Lorentz field, 142, 199 Mosaic structure, 97
Lorentz force equations. 280, 302 Mott-Schottky theory of rectification, 351
Lorenz number, 300
NEARLY free electron approximation,
Loss factor, 149
260,262
Luminescence, 398 ff.
Neel temperature, 483
carrier injection, 415
Neutron diffraction, 21, J87, J 89; 20 J, 488
coactivators, 411
Nondegenerate level, 257
decay mechanisms, 402 ff.
Nonstochiometric composition, 26, 377 ff.
F centers, 382
n-type conductivity, 311
glow curves, 405
Nuclear magnetic moments, 516
killers, 399, 417
Nuclear magnetic resonance, 505 ff.
quenching, 409
Nuclear magnet on, 451
sulfide phosphors, 410
thallium-activated KCI, 406 ff. OHM'S law, 177,275
One-electron approximation, 238
MADELUNG constant, 118, 131 Optical absorption, 154
Magnetic, induction, 447 alkali halides, 366 ff.
permanent dipoles, 448 thallium-activated KCI, 406
permeability, 447 Optical branch, 55
susceptibility, 446 Optical transitions, band scheme, 337
Magnetism, '!ee Dia-, Para-, Ferro-, Order-disorder transitions, 109 ff.
Anti/erro- and Ferrimagnetism Bragg-Williams theory, III
Magnetite, 491) Ordered alloys, electrical conductivity,
Magnetization, 446 11. 288
538 INDEX
J
Order, long-range, 3, .111 ",. '"":" Powder pattern, X-ray, 19, 30
of reflection, 14 Primitive translations, 253
short-range, 3, 114 Pyroelectricity, 185
Orientational polarization, 138 ff.
Orthorhombic system, 8 QUADRIPOLE radiation, 398
Oscillator strength, 378 Quantum numbers, 448
Overlapping, energy bands, 265 "~ , Quenching, luminescence, 409
wave functions, 258, 370 orbital momentum, 458

PARAMAGNETISM, Curie law, 455 RADIATION damage, 325

dispersion and absorption, 503 Radiationless transition, 402
free electrons, 217 Radioactive tracers, 168
iron group ions, 457 Random walk, 71,102
nuclear, 458 R-bands, optical absorption, 392
rare earth ions, 456 Reaction field, 144, 159, 195
relaxation, 498 ff. Reciprocal lattice, 254, 263
resonance, 517 Recombination of carriers, 341,344, 358
Particle in a box, wave mechanics, 526 Rectification, p-n junction, 357 ff.
Pauli exclusion principle, 217, 527 theory, 351 ff. \
Pauling radii, ions, 126 Rectifiers, 348 ff.
Peierls' Umklapp processes, 291, 297, 298 Reduced zone, 255-
Peltier effect, 304 Reflection coefficient, electrons, 220
Periodic boundary conditions, 50, 247, metals, 237
255 Relaxation time, dielectrics, 150
Periodic functions, 253 ff. electrons, 276, 284, 328
Permanent electric dipole moment, 137 Remanent polarization, 185
Perovskites, 190 Repulsive forces, interatomic, 23, 119,
Phase diagrams, 115, 116 121, 128
Phonon, 289 Resistivity, metals, 275 ff.
boundary scattering, 297 alloys, 288
drag, 292 Bloch-Gruneisen formula, 293
impurity scattering, 297 minimum, 294
Phonon-phonon collisions, 296 pressure dependence, 289
Phosphorescence, 398 temperature dependence, 285, 292
Photoconductivity, 372, 386 ff. Resonance absorption, optical, 155
Photoelectric effect, metals, 232 Rhombic system, 8
alkali halides, 390 ff. Rhombohedral system, 8
Photoluminescence, 398 Richardson plot, thermionic emission, 222
Piezoelectricity, 185 Rochelle salt, 186, 201
Plane of symmetry, 6 Rotation axis, n-fold, 6, 8
Plasma, 435 Rotation inversion axis, 6
Plastic deformation, 81 Rotation, molecular, 2
Point-contact rectifier, 351 Rotator, energy levels, 58
Poisson ratio, 79 Rutherford scattering, 330
Polarizability, 128 ff.; table, 159 A
Polarization, 134, 157 SATURATION magnetization, 470
energy of, 167 ferrites, 492
orientational, 138 Saturation polarization, 158
remanent, 185 Scattering cross section, 286
spontaneous, 184 Scattering factor, atolTlic, 14
Polyhedron, atomic, 269 Scattering of electrons, 329 ff.
Potassium dihydroph~sphate, 189, 201 Schottky, barrier, 349

.{ '",
INDEX 539

Schottky, (COlli,): Specific heat (COl/f.):

defects, 65, 163 Ei!)l;tein theory, 36
effect, thermionic emission, 226 ferroclectrics, 194
Scintillation c~nter. 417 free electrons, 216
Screened potential, 435 I,: ordered alloys, 110, 114
Screw dislocation, 90 row of atoms, 53, 59
Secondary electrons, 418 square lattice, 59
Secondary emission, 418 ff. . ", 3-dimensional lattice, 57
escape mechanism, 438 Spectroscopic splitting factor, 450
, temperature effect, 440 Spinel structure, 491
theory, 423 ff. Spin-lattice relaxation, 501 ff" 509, 513
universal yield curves, 425 Spin-orbit coupling, 479
Second-order transition, 186, 202, 206 Spin-spin relaxation, 500 ff" 509, 513
Seebeck effect, 304 Spin temperature, 501
Segregation coefficient, 324 Spontaneous, magnetization, 468
Seignette salt, 187 polarization, 184, 194
Semiconductors, electron distribution, Stern-Gerlach experiment, 463
305 ff, Strain components, 81
electronic degeneracy, 316 Stress components, 80
energy gap, 337 ff, Structure, CsCI, 123, 127
Hall effect, 326 ff. diamond,8
impurity, 3 to ff. factor, 17, 18
intrinsic, 251, 308 mosaic, 97
nonpolar, 319 ff, NaCl,118
II-type, 311 Stability, ionic crystals, 124
p-type; 311 transformation, 62
surface states, 354 ff. ZnS, 123, 127
thermionic emission, 314 [[, Sublimation energy, 68, 123,272
work function, 315 Sulfide phosphors, 410
Shear modulus, 79 Superconductivity, 276
Shear stress, 79 Super exchange interaction, 488
critical resolved, 82 Super lattices, 109
Short-distance order, 3, 114 Surface, adsorption, 228
Silicon, constant energy surfaces. 337 charge, 142
crystal growth, 324 states, 354, ff.
electrical properties, 331 ff. Susceptibility, antiferromagnetics, 483,485
energy bands, 336 diamagnetic, 453
infrared absorption, 339 electric, 186, 204
lattice properties, 320 ff, ferro magnetics, 464, 485
physical constants, 321 paramagnetic, 218, 446, 454, 485
secondary emission, 422 Symmetry elements, 8
Silver halides, 129 System of crystal axes, 6, 8
Simple cubic lattice, 8
Slip, 82, 83 TETRAGONAL system, 8
Smakula's formula, color centers, 378 Thermal conductivity, insulators, 295 ff.
Sommerfeld, model of metals, 212 metals, 299 fe,
theory of conductivity. 281 Thermal entropy, 63
Space lattices, 6, 7 Thermionic emission, metals, 220 ff.
Specific heat, 32 ff. semiconductors, 314 fe,
Born cut-off, 45 Thermodynamic potential, 231, 526
Debye theory, 41, 57 Thermoelectric effects, 304
.f
Dulong and Petit, 34 I Thermoluminescence, 405, 407

"
540 INDEX

Thomson effect, 304 Vibrational modes (cont.):

Tightly bound electron approximation, equivalence with harmonic oscillator,
257 fL 51
Transistors, 361 ff. longitudinal, 41, 46
equivalent circuit, 363 optical branch, 55
junction, 361 row of identical atoms, 46, 49
point contact, 363 transverse, 41, 46
Transition elements, 457 Vibrational spectrum, NaCl, 57
Transition, ferroelectric, 185
first-order, 186, 204, 206 WAVE functions, symmetric and anti-
induced, 206 symmetric, 528
order-disorder, 109 Wave vector, 47
second-order, 186, 202, 206 Weiss domains, 207
Transport numbers, 176, 178, 181 Weiss field, 192
Transverse mass, 336 Weiss hypotheses, 464
Trapping, zinc sulfide, 412 Weiss molecular field, 466 ff., 472, 474
Triclinic system, 8 Whiddington's law, 423
Trigonal system, 8 Wiedemann-Franz law, 276, 300, 303
Tunneling, 227, ~51 Wigner-Seitz approximation, 269 ff.
Work function, metals, 212, 215, 224
ULTRAVIOLET absorption, alkali hal- semiconductors, 315
ides, 371 ff. Wronskian, 242
Umklapp processes, 291, 297 X-RA Y diffraction, 10 ff.
Unit cell, 4 binary alloys, 1I0
Bragg, 13
VACANCIES, 63, 65 dislocation density, 97
formation in metals, 68 experimental methods, 19
in ionic crystals, 160, 166 line broadening, 30
pairs, 69, 174 von Laue, 10
Vacuum level, electrons, 212 X-ray emission, 268 \
Valence band, 306 X-rays, production of color centers, 394
Valence crystals, 25
van der Waals, crystals, 26 YOUNG'S modulus, 79
forces, 128, 132
V bands, Ge and Si, 337 ZEROPOINT energy, 37, 128
V centers, alkali halides, 376, 393 ff. Zincblende structure (sphalerite), 123,
Vegard's law, 104 127
Vibrational modes, acoustical branch, 55 Zinc sulfide, electfonic levels, 412
continuous medium, 39 Zone boundaries, 264
diatomic linear lattice, 54 Zone refining, 324