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Article history: A surface plasmon resonance based biomolecules sensor using silicon and graphene layers coated over
Received 1 May 2011 the base of the high index prism sputtered with gold has been analyzed. The graphene layer has been used
Received in revised form 2 August 2011 to enhance the adsorption of biomolecules while the addition of silicon layer between gold and graphene
Accepted 17 August 2011
increases the sensitivity. The thicknesses of gold and silicon layers along with the number of graphene
Available online 24 August 2011
layers have been optimized to achieve the best performance of the sensor in terms of sensitivity and
Full Width at Half Maximum (FWHM). To see the effect of wavelength of the light source, simulations
Keywords:
have been carried out for three different wavelengths. The best performance is obtained for 633 nm
Surface plasmon
Sensor
wavelength with optimized thicknesses of gold and silicon layers as 40 nm and 7 nm respectively while
Sensitivity the optimum number of graphene layers is 2. The sensitivity obtained with optimized parameters and
Graphene additional silicon layer, is more than twice the value reported in the literature.
Biomolecules © 2011 Elsevier B.V. All rights reserved.
0925-4005/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2011.08.039
624 R. Verma et al. / Sensors and Actuators B 160 (2011) 623–631
of the prism at an angle greater than the critical angle on the mul-
tilayer structure at the base of the prism. The reflected light is
collected through another face of the prism as shown in Fig. 1. When
the light is incident on an atomic monolayer of graphene it shows
high opacity [19]. A monolayer of graphene absorbs 2.3% of white
light and transmits 97.7% [20]. For L numbers of graphene layers,
the absorption is L × 2.3% of white light. Therefore it is obvious that
transmission decreases as the number of graphene layers increases.
The present SPR sensor is based on angular interrogation method.
In this method, the light source is considered as monochromatic
while the angle of incidence is varied to determine the angle at
which the intensity of the reflected light reaches minimum. The
dispersive behaviours of all the layers for a given wavelength of
the light source have been used for calculation and simulation.
Fig. 1. Schematic diagram of a prism based SPR probe.
the thicknesses of gold (d2 ) and silicon (d3 ) layers and the num-
ber of graphene layers (L) for three different wavelengths (600 nm,
633 nm and 660 nm) of the light source [26]. To optimize, we first
determine the reflectivity as a function of resonance angle using Eq.
(6) and then plot SPR curve to determine the minimum reflectivity
(Rmin ) and the resonance angle ( res ) for a given set of parameters
and the refractive index of the biomolecules layer. We then plot
Rmin and the change in resonance angle for a given change in the
refractive index of the biomolecules layer as a function of number
of graphene layers for different sets of values of gold and silicon
thicknesses for a given wavelength of the light source. For the opti-
mum thicknesses of these layers we focus on the minimum width
of the SPR curve, lowest value of the minimum reflectivity and the
maximum change in the resonance angle.
In the angular interrogation method, the reflectivity, as output
signal, is measured as a function of incident angle and a dip in SPR
curve is obtained at the resonance angle ( res ). The energy conser-
vation requires that the sum of the absorbance (A), transmittance
(T) and the reflectance (R) should be equal to 1. At attenuated total
reflection (ATR) condition, T = 0, and hence A + R = 1. At resonance
angle, ideally reflectance R is also zero (R = 0) which implies A = 1. It
means that the total energy of the incident light is absorbed in the
medium and the sharpest SPR curve is obtained. This occurs when
Fig. 2. Schematic diagram of an N-layer model. the light beam incident on the prism traverses through metal layer
as surface plasmons are generated at the interface which radiates
where light back into the metal film. If the thickness of the metal layer
is small, the backscattered field increases and since backscattered
cos ˇk −i sin ˇk /qk wave is out of phase with incident light wave, these two waves
Mk =
−iqk sin ˇk cos ˇk interfere destructively. Due to this the reflectance reduces to mini-
1/2 mum and for the optimum thicknesses of layers these compensate
qk = (εk − n2 sin2 )
1/2 each other and the reflectance becomes zero or the total absorption
ˇk = dk (2/)(εk − n2 sin2 ) occurs [27]. However, the reflectivity also depends on the wave-
length of the incident light in addition to angle of incidence and
is the angle of incidence of light with the normal to the inter-
the thicknesses of the various layers.
face. The amplitude reflection coefficient (rp ) for p-polarized light
As mentioned earlier, in the present sensor, the prism base is
is
coated with gold, silicon and graphene sequentially and hence it
(M11 + M12 qN )q1 − (M21 + M22 qN ) has three layers over the prism base. When a sensing sample con-
rp = (5)
(M11 + M12 qN )q1 + (M21 + M22 qN ) sisting of biomolecules comes in contact to graphene layer, the
biomolecules from sensing sample get adsorbed on the graphene
The reflection coefficient of N layer model for p-polarized light
layer resulting in the formation of a fourth layer of biomolecules
is
2 with refractive index ns + nbm ; ns is the refractive index of the
R = rp (6) sensing medium or the sample. To optimize parameters, simula-
tions have been carried out for different numbers of graphene layers
To know the resonance angle, reflection coefficient R is plotted for given thicknesses of gold and silicon layers. Figs. 3(a)–(c) show
as a function of incident angle . The angle corresponding to min- the variations of Rmin with number of graphene layers (L) for differ-
imum reflection coefficient (Rmin ), called resonance angle ( res ), is ent thicknesses of gold layer assuming no silicon layer for 600 nm,
determined from the plot. The resonance angle changes with the 633 nm and 660 nm wavelengths respectively. It may be noted that
change in the refractive index of the sensing medium. Larger the the complete transfer of energy of the incident light to surface plas-
change better is the performance. If the change in resonance angle mons (R = 0) for a given thickness of gold layer depends on the value
is res corresponding to the change in refractive index n, then of L. As the thickness of the gold layer decreases the number of
the sensitivity of the sensor is defined as graphene layers required to transfer complete energy increases.
For a given thickness of the gold layer, the number of graphene lay-
res
S= (7) ers required for the complete transfer of energy further depends on
n the wavelength of the light source. As the wavelength of the light
source increases the dip in the reflectivity curve corresponding to
3. Results and discussion a fixed thickness of the gold film shifts towards the higher number
of graphene layers. In the wavelength range studied, no graphene
There are number of design parameters of the sensor that may layer for minimum reflectivity is required for 50 nm thickness of
affect the performance of the sensor considered in the present gold film, a fact reported in the literature for 50 nm as the opti-
study. Some of the critical parameters are thicknesses and refrac- mized thickness for gold film. The decrease in the thickness of the
tive indices of different layers such as gold, silicon, graphene and gold layer is compensated by the addition of graphene layers for
biomolecules in addition to the wavelength of the light source. achieving complete transfer of energy to surface plasmons. Fur-
For the biomolecules layer we have chosen nbm = 0.005 and thermore, the increase in the total graphene layers thickness is
d5 = 100 nm. The values of refractive indices of different layers and lesser than the decrease in the gold film thickness which may be
the thickness of a single layer of graphene have been discussed due to the higher refractive index of the graphene in comparison
in Section 2.1. Using these values, we carried out optimization of to gold.
626 R. Verma et al. / Sensors and Actuators B 160 (2011) 623–631
To check the performance of the sensor, we determine the the thickness of the gold film. In addition, the change in resonance
change in resonance angle ( res ) obtained before and after the angle decreases for fixed values of the thickness of gold film and the
adsorption of biomolecules present in the sensing medium (water) number of graphene layer as the wavelength increases. However,
over the graphene layer. Figs. 4(a)–(c) show the variations of change in all these observations, we have not considered complete transfer
in resonance angle as a function of number of graphene layers for of energy to surface plasmons that is required for the optimization
different thicknesses of gold film and no silicon layer for 600 nm, of film thickness, number of graphene layers and the wavelength
633 nm and 660 nm wavelengths respectively. It is observed that of the light source for best performance.
the change in resonance angle increases with the increase in the The simulations, similar to the above, have also been carried
number of graphene layers. Further, for a fixed number of graphene out for different thicknesses of the silicon layer for the same three
layers, the change in resonance angle increases with the increase in wavelengths. Fig. 5 shows the variation of Rmin with the number
R. Verma et al. / Sensors and Actuators B 160 (2011) 623–631 627
Fig. 6. Same as Fig. 4 except that in this case the thickness of the silicon layer is
5 nm.
Fig. 5. Same as Fig. 3 except that in this case the thickness of the silicon layer is
5 nm.
maximum change in resonance angle towards the higher number
of graphene layers and also results in the decrease in its value. In
of graphene layers (L) for diffrent thicknesses of gold layer and Figs. 7 and 8 we have plotted results similar to Figs. 5 and 6 but for
5 nm thickness of silicon layer. Comparison of results in Fig. 5 with 7 nm thickness of the silicon layer. The interpretation of the results
those in Fig. 3 implies that the addition of silicon layer decreases the is the same as for 5 nm thickness of the silicon layer except that the
number of graphene layers required for zero reflectivity for a given peak corresponding to maximum change in resonance angle shifts
thickness of the gold layer. The correponding plots for the change in towards the lower number of graphene layers.
resonanace angle ( res ) for three wavelengths have been shown The required number of graphene layers for the complete trans-
in Fig. 6. The trends of the plots are different from those obtained fer of energy to surface plasmons under the resonance condition,
without the silicon layer. It is found that res first increases up to R < 0.03, and the corresponding change in resonance angle for each
a certain value and then starts decreasing with the increase in the case are given in Tables 1–3 for wavelengths 600 nm, 633 nm and
number of graphene layers for all the thicknesses of the gold layer. 660 nm respectively. It may be noted that the data presented in
Further, the increase in the wavelength of the light source shifts the these tables correspond to nearly zero reflectivity only and hence
628 R. Verma et al. / Sensors and Actuators B 160 (2011) 623–631
Fig. 7. Same as Fig. 3 except that in this case the thickness of the silicon layer is Fig. 8. Same as Fig. 4 except that in this case the thickness of the silicon layer is
7 nm. 7 nm.
Table 1
Optimized values of thicknesses of gold and silicon and the number of graphene layers with corresponding change in resonance angle and FWHM for zero reflectivity in SPR
curves for 600 nm wavelength.
Gold thickness Silicon Number of Resonance angle without Resonance angle with Change in resonance FWHM
(nm) thickness (nm) graphene biomolecules (degree) biomolecules (degree) angle (degree) (degree)
layers
Table 2
Optimized values of thicknesses of gold and silicon and the number of graphene layers with corresponding change in resonance angle and FWHM for zero reflectivity in SPR
curves for 633 nm wavelength.
Gold thickness Silicon Number of Resonance angle without Resonance angle with Change in resonance FWHM
(nm) thickness (nm) graphene layers biomolecules (degree) biomolecules (degree) angle (degree) (degree)
Table 3
Optimized values of thicknesses of gold and silicon and the number of graphene layers with corresponding change in resonance angle and FWHM for zero reflectivity in SPR
curves for 660 nm wavelength.
Gold thickness Silicon Number of Resonance angle without Resonance angle with Change in resonance FWHM
(nm) thickness (nm) graphene layers biomolecules (degree) biomolecules (degree) angle (degree) (degree)
only those combinations of thicknesses and number of graphene distance in the direction perpendicular to the prism base may be
layers are tabulated. In all the tables we have also tabulated depicted as shown in Fig. 9.
FWHM of SPR curves. The maximum change in resonance angles In the above simulations we have considered nbm = 0.005
obtained are 0.56◦ , 0.673◦ and 0.544◦ for 600 nm, 633 nm and and d4 = 100 nm irrespective of the number of graphene layers. If
660 nm wavelengths, respectively. The corresponding FWHM are the change in the local refractive index due to the adsorption of
20.310◦ , 17.975◦ and 17.418◦ ; the last two are nearly the same. biomolecules on graphene layer increases, then the change in res-
These results imply that the combination of 40 nm gold and 7 nm onance angle ( res ) also increases as shown in Fig. 10. This will
silicon layer thicknesses with optimized number of graphene lay- further increase the change in resonance angle and hence the sen-
ers as 2 and 633 nm as the wavelength of the light source is the sitivity of the sensor. Rather than this consideration, if we suppose,
optimum to achieve the best performance of the sensor. We have that the thickness of the biomolecules layer is more than what we
also carried out simulations for higher thicknesses of silicon layer have considered (100 nm thickness of the biomolecules layer), then
but for higher thicknesses the SPR curves become broad and fur- more change in the thickness of the biomolecules layer increases
ther, in none of the cases, complete transfer of energy takes place. the change in the resonance angle and hence the sensitivity of the
From the tabulated values it can be noted that the change in res- sensor as shown in Fig. 11. Thus, any increase in the thickness of
onance angle is lowest when the sensor has only gold layer (no the biomolecules layer will increase the change in the resonance
silicon and no graphene layer). If graphene layers are coated over angle and hence the sensitivity of the sensor.
gold (no silicon layer) then it marginally increases the change in res-
onance angle. If silicon layer is coated over gold layer (no graphene
layer) then the change in resonance angle becomes twice of that
of the gold layer only. Moreover, the addition of graphene layer
over silicon further increases the change in resonance angle. The
change in resonance angle is more than twice of that reported in
the literature [9]. According to these simulations the optimum val-
ues of the parameters for sensitivity and FWHM for biomolecules
SPR sensor are the following: gold layer thickness = 40 nm, sili-
con layer thickness = 7 nm, the number of graphene layers = 2 and
= 633 nm.
It may be noted that the addition of silicon layer enhances the
maximum value of the change in resonance angle for a particu-
lar number of graphene layers. The reason of enhancement of the
change in resonance angle or the sensitivity is the high refractive
index of the silicon layer which increases the field intensity at the
interface and hence the field penetrates strongly in the analyte
[17,28]. Based on the studies reported in the literature on the addi- Fig. 9. Schematic diagram of the field intensity along the direction perpendicular
tion of silicon layer, the schematic of the field intensity with the to the prism base.
630 R. Verma et al. / Sensors and Actuators B 160 (2011) 623–631
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Biographies
latest fabrication and characterization techniques to design a highly
sensitive and accurate biosensor.
Roli Verma received her M.Sc. degree in Physics (2006) and B.Ed. (2007) from C.S.J.M.
University Kanpur (India). Since January 2010, Ms. Verma is a full time Ph.D. student
Acknowledgements at the Physics Department, Indian Institute of Technology Delhi. Ms. Verma is a
student member of Optical Society of America and holds the position of treasurer of
IIT Delhi student chapter of OSA.
The present work is partially supported by the Department of
Science and Technology (DST), India. Roli Verma is thankful to B.D. Gupta received his M.Sc. degree in Physics (1975) from Aligarh Muslim Uni-
versity (India) and a Ph.D. degree in Physics (1979) from the Indian Institute of
Council of Scientific and Industrial Research (CSIR), India for pro- Technology, New Delhi. In 1978 he joined the Indian Institute of Technology, New
viding research fellowship. Delhi, where he is currently a Professor in Physics. In addition, Prof. Gupta has
R. Verma et al. / Sensors and Actuators B 160 (2011) 623–631 631
worked at the University of Guelph (Canada) in 1982–1983, the University of Toronto of America and life member of the Optical Society of India and the Indian Chapter
(Canada) in 1985, the Florida State University (USA) in 1988, the University of Strath- of ICTP.
clyde (UK) in 1993 and the University of Birmingham (UK) in 2010. In 1992, he was
awarded the ICTP Associateship by the International Centre for Theoretical Physics, Rajan Jha received his M.Sc. and Ph.D. degrees from Indian Institute of Technology
Trieste (Italy), which he held for 8 consecutive years. In this capacity, he visited ICTP Delhi, India in 2001 and 2007, respectively. From early 2008 to July 2009, he was
(Italy) in 1994 and 1996. Prof. Gupta is a recipient of the 1991 Gowri Memorial Award a post doctoral researcher at ICFO – The Institute of Photonics Sciences, Barcelona,
of the Institution of Electronics and Telecommunication Engineers (India). He has Spain. He was awarded JSPS (Japanese Society for Promotion of Science) fellowship
published more than 80 research papers including 5 review articles in International in 2009. He is currently working as Assistant Professor in Physics in School of Basic
Journal of Repute. Prof. Gupta authored a book entitled Fiber Optic Sensors: Princi- Sciences at Indian Institute of Technology Bhubaneswar, India. He is a regular mem-
ples and Applications (NIPA New Delhi, 2006) and is the co-editor of the Proceedings ber of Optical Society of America (OSA) and is a life member of Optical Society of India
of SPIE (USA), vol. 3666 (1998) and Advances in Contemporary Physics and Energy (OSI). His areas of research are optical sensors, nano- & bio-photonics, spectroscopy
(supplement volume) (Allied Publishers, New Delhi). His current areas of interest and imaging, solar cell, waveguide & interferometer. He has published more than
are plasmonics and fiber optic sensors. He is a regular member of the Optical Society 20 research articles including a review article in International Journal of Repute.