Journal of Fluorine Chemistry 122 (2003) 113–119

Perfluoroelastomer and fluoroelastomer seals for semiconductor

wafer processing equipment
Shuhong Wang*, John M. Legare
DuPont Dow Elastomers L.L.C., Delaware Technology Park, One Innovation Way, Suite 400, Newark, DE 19711, USA

Abstract

Parts made from fluorinated elastomers, e.g., Kalrez1 perfluoroelastomer parts, parts made from Viton1 fluoroelastomer, are widely used as
seals on semiconductor wafer processing equipment. Many of these seals are required to function in harsh chemical environments and at process
temperatures ranging from 25 to 300 8C. Fluoroelastomers, including those of the perfluoroelastomer type, have extraordinary resistance to
chemicals and heat, enabling them to withstand virtually any process media, including reactive plasmas, at temperatures as high as 316 8C.
This paper is a review of perfluoroelastomers and fluoroelastomers used in semiconductor wafer processing. These seals offer cleanliness
and lack of contamination while maintaining sealing functionality in aggressive media. Applications requiring resistance to both ‘‘wet’’ and
‘‘dry’’ process chemistry include etching, ashing, stripping, copper plating and chemical vapor deposition. Applications requiring thermal
resistance include LPCVD, diffusion furnace and rapid thermal processing (RTP). A relative comparison of the various types of
perfluoroelastomers used as well as a comparison to other elastomeric materials will also be discussed.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Perfluoroelastomers; Fluoroelastomers; Semiconductor wafer processing equipment; Seals

1. Introduction This paper is designed to be a review of the chemistry of

fluorinated elastomers and their use in semiconductor wafer
Semiconductor wafer processing involves many aggres- processing. Perfluoroelastomers and fluoroelastomers offer
sive chemicals and operates under very severe environments. the cleanliness and lack of contamination that are crucial to
Fluoroelastomers, including perfluoroelastomers, are widely this industry while maintaining sealing functionality in
used as seals on semiconductor wafer processing equipment aggressive media. Applications requiring resistance to
due to their extraordinary resistance to chemicals and heat. ‘‘wet’’ process chemistry (i.e., acids, bases, amine-based
Their outstanding chemical resistance and thermal stability strippers, etc.) include etching, rinsing, cleaning, stripping
enable them to withstand virtually any process media, and copper plating. Applications requiring resistance to
including reactive plasmas, at temperatures as high as ‘‘dry’’ process chemistry (e.g., gases, reactive plasmas, plas-
316 8C. A relative comparison of fluorinated elastomers mas used for chamber cleaning, etc.) include etching, ashing,
to other elastomers in terms of thermal stability and che- chemical vapor deposition, high density plasma chemical
mical compatibility can be see in Figs. 1 and 2. vapor deposition and plasma enhanced chemical vapor
The first commercial fluoroelastomer was Viton1 A pro- deposition. Applications requiring thermal resistance include
duced by E.I. du Pont de Nemours in 1957. The first perfluor- low-pressure chemical vapor deposition (LPCVD), oxidation,
oelastomer was invented in 1968 by E.I. du Pont de Nemours. diffusion furnace, lamp annealing and rapid thermal proces-
It was used in parts sold under the trade name Kalrez1. sing (RTP). A relative comparison of the various types of
From this early beginning, the use of perfluoroelastomers perfluoroelastomers used as well as a comparison to other
and fluoroelastomers has increased steadily. Today there are elastomeric materials is also presented and discussed.
four major global manufacturers of fluoroelastomer and per-
fluoroelastomer polymers: DuPont Dow Elastomers, Dyneon,
Ausimont, and Daikin. Fluoroelastomer and perfluoroelasto- 2. Structure and properties of perfluoroelastomers
mer seals are manufactured by companies worldwide. and fluoroelastomers

*
Corresponding author. Tel.: þ1-302-733-8847; fax: þ1-302-733-8844. Fluorinated elastomers contain elastomeric networks
E-mail address: [email protected] (S. Wang). made from amorphous flexible and long polymer chains.

0022-1139/03/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-1139(03)00102-7
114 S. Wang, J.M. Legare / Journal of Fluorine Chemistry 122 (2003) 113–119

Fig. 1. Relative heat and oil resistance of elastomers (ASTM D2000).

The long randomly coiled flexible macromolecules allow the retain its shape after swelling. To accomplish this, polymers
polymer to undergo large deformation upon stretching or with long flexible chains having a three-dimensional net-
compression, and cross-linking between the chains gives a work structure are essential. Randomly incorporating other
permanent three-dimensional network that ensures recovery. monomers into homopolymers breaks the regularity and
Fluorinated elastomers may contain a completely fluori- forms amorphous polymers consisting of randomly coiled
nated or a partially fluorinated backbone. The carbon–fluor- flexible chains. These have flexibility and mobility and can
ine bond is the most stable single bond and the high bond deform when acted upon by an external force. These poly-
dissociation energy of the C–F bond is the main reason for mers needs to be cross-linked to form a three-dimensional
fluoroelastomer thermal, oxidative and chemical stability. network structure to ensure recoverability. Cross-linking
Table 1 lists typical bond dissociation energies of single involves reaction with the cure site monomer (CSM). They
bonds. Homo-polytetrafluoroethylene (PTFE) contains all can be either at the end of the polymer chain or distributed
C–F substitution, which makes it the most thermally and within the polymer chain. The structure and properties of the
chemically stable polymer. However, PTFE has very high resulting network depend largely on cure site functionality
crystallinity. As a result, it is a rigid thermoplastic, not an and curing chemistry.
elastomer. In order for a material to be rubber-like, it has to
be capable of very high deformation. It must also be able to 2.1. Perfluoroelastomers
maintain retractive force when external stress is applied,
recover to its original dimension after removal of an external Perfluoromethylvinyl ether (PMVE) and other perfluoro
stress or retain the retractive force under external force and (alkoxy/alkyl) vinyl ethers are copolymerized with TFE
monomer in most commercial perfluoroelastomers. Per-
fluoro (alkoxy/alkyl) vinyl ethers form the most stable bonds
after those of PTFE. The glass transition temperature (Tg)
and the degree of crystallinity depend on the type and
amount of these monomers incorporated [1,2]. The typical
Tg of a TFE/PMVE copolymer ranges from 25 to 25 8C.
Compared with other elastomers, the Tg of perfluoroelasto-
mers is relatively high. Care must be taken in applications

Table 1
Typical bond dissociation energies for aliphatic bonds (kJ/mol)

C–C 284–368
C–H 381–410
C–Cl 326
C–F 452
C–O 350–389
C–N 293–343
Fig. 2. ASTM D2000 list of abbreviations.
S. Wang, J.M. Legare / Journal of Fluorine Chemistry 122 (2003) 113–119 115

Fig. 3. Mechanism of peroxide cured perfluoroelastomer.

where perfluoroelastomers are used at service temperatures

close to or at the Tg and in temperature cycling applications
near the Tg or below. Recovery at these temperatures can be
very slow.
A wide variety of methods have been developed for cross-
linking perfluoroelastomers. Functionalization is frequently
achieved by incorporating a monomer that contains a reac-
tive site into the backbone of the polymer at relatively low
levels, typically less than 5 mol%. Another approach com-
monly practiced is to terminate chain ends with functional
groups by use of an appropriate chain transfer agent during
Fig. 4. Triazine cross-link structure.
polymerization.
The most commonly used CSMs contain halogens, such
as iodine and bromine, as the reactive site. Examples of pendent group, or vinylidene fluoride. Commercially, the
halogenated monomers described in the literature are [3–5]: most significant of these are the cyano-functional vinyl
ethers. Several types of these have been described in the
CF2 ¼CFOðCF2 Þ3 Br; CH2 ¼CHCF2 CF2 Br;
literature, for example [7–9]:
CH2 ¼CHðCF2 Þ3 CH2 CH2 I
Perfluoroelastomers containing halogenated cure sites are CF2 ¼CFOðCF2 Þ4 CN;
readily cross-linked using peroxide-based curatives. The CF2 ¼CFOCF2 CFðCF3 ÞCF2 CFðCF3 ÞCN;
curative system consists of the peroxide itself, which acts CF2 ¼CFOCF2 CFðCF3 ÞOCF2 CF2 CN
as the initiator for the cure reaction, and a so-called coagent
or radical trap. The mechanism of cure by peroxides in The major advantages of using these CSMs are that they can
perfluoroelastomers has been described in detail elsewhere be effectively cured by a variety of curatives, and that the
[6]. This reaction scheme is summarized in Fig. 3. The major cured structures combine good chemical resistance with the
disadvantage of peroxide curing of perfluoroelastomers is excellent resistance to thermal degradation for this class of
the hydrocarbon nature of the cross-link due to the coagent, elastomer. The cyano-groups most commonly result in
which of course is much more susceptible to oxidative and heterocyclic cross-link structures. For example, curing with
thermal degradation than the polymer backbone. tetraphenyl tin or ammonia results in a triazine cross-link
Besides the halogenated CSMs, there are other important structure as in Fig. 4. Use of the di-functional curative
types of functional monomers. Some of these are based on diaminobisphenol AF results in condensation to form a
vinyl ether structures, with the reactive site terminating the benzoxazole cross-link as in Fig. 5. The resulting network

Fig. 5. Benzoxazole cross-link from diaminobisphenol AF.

116 S. Wang, J.M. Legare / Journal of Fluorine Chemistry 122 (2003) 113–119

has low compression set and excellent thermal stability. This TFE in place of VF2, the fluorine level can be increased into
cyano-group can also be cured with peroxide and the the range 68–70%. This increase in fluorine level improves
resulting network has universal chemical resistance. chemical resistance by lowering the total hydrogen content
Perfluoroelastomers containing small amounts of either in the polymer, but at the expense of low temperature
the perfluorophenoxy functionality or hydrogen moiety properties. Another type of terpolymer made replaces some
undergo reaction by nucleophilic attack. Perfluoro-2-phe- HFP with TFE and keeps the fluorine level at 66%. This
noxypropyl vinyl ether is another commercially important terpolymer actually has improved low temperature flexibil-
vinyl ether: ity. A third type of commercial fluoroelastomer is a tetra-
polymer containing a TFE–VF2–HFP backbone with a small
CF2 ¼CFOCF2 CFðCF3 ÞOC6 F5
level of CSM incorporated to impart peroxide curability.
Polymers containing this cure monomer can therefore be Examples of CSMs for such commercial fluoroelastomers
cured with di-nucleophiles, such as the di-potassium salt of include bromine and iodine-containing monomers. These
bisphenol AF, peroxide curable fluoroelastomers exhibit improved resis-
tance to water, acid, and steam. A fourth type of commercial
Kþ OArCðCF3 Þ2 ArO Kþ fluoroelastomer is a low temperature tetrapolymer where
The cross-link results from the displacement at the position PMVE replaces HFP in the backbone. This fluoroelastomer
para to the ether linkage on the aromatic ring. This type of polymer has improved low temperature sealing capability as
cross-linking system has excellent amine resistance. indicated by a lower glass transition temperature.
There are three primary cure systems used for curing
2.2. Fluoroelastomers fluoroelastomers. Diamine and bisphenol are used to cure
fluoroelastomers that contain monomers that react via
The most widely available fluoroelastomers are generally nucleophilic attack, such as VF2 and HFP. The bisphenol
copolymers of two or three monomers, one of which is cure tends to give the best processing compounds and is the
vinylidene fluoride. Fluoroelastomer properties such as heat most popular fluoroelastomer curing system today. Amines
and chemical resistance, low temperature flexibility, resis- are difficult to process, scorchy, and are very seldom used.
tance to steam and acids, and compression set resistance, can Peroxides are used in fluoroelastomers that contain haloge-
vary considerably depending on monomer composition and nated CSMs. This cure system maximizes chemical resis-
concentration, and the cure chemistry employed [10]. The tance and is the only cure system that works with PMVE
building blocks of fluoroelastomers are listed in Table 2. containing low temperature tetrapolymers.
Using these fluoro-monomers, four basic fluorinated elas- As with other elastomers, fluorinated elastomers are
tomer polymer structures can be made as shown in Table 3. normally compounded with fillers, processing aids, cura-
The first widely available fluoroelastomer was a copolymer tives, etc. Mechanical properties of an elastomer compound
of VF2 and HFP. The copolymer is normally 66% fluorine, not only depend on the polymer but also heavily depend on
and it is still the most common fluoroelastomer in use today. the other ingredients. A wide range of mechanical properties
It is possible to make a terpolymer fluoroelastomer by can be achieved by varying polymer structure as well as
incorporation of TFE along with VF2 and HFP. By adding compounding technology.

Table 2 3. Applications for perfluoroelastomers and

Building blocks of fluoroelastomers fluoroelastomers in semiconductor wafer
HFP Hexafluoroproplyene processing equipment
VF2 Vinylidene fluoride
TFE Tetrafluoroethylene Semiconductor wafer processing applications can be
PMVE Perfluoromethylvinyl ether
CSM Cure site monomer
categorized into three types: plasma and gas deposition,
thermal and wet. Elastomer performance considerations can
vary significantly depending on the process type.

Table 3 3.1. Plasma and gas deposition applications

Examples of commercial fluoroelastomer structure

Fluoroelastomer Monomer sequence Example Semiconductor fabricators have found that plasma is a
type very powerful tool for etching, chemical vapor deposition
Copolymer VF2–HFP Fluoroelastomer-A (66%F) and stripping because all materials are consumed in plasma
Terpolymer VF2–HFP–TFE Fluoroelastomer-B (68%F) and plasma can increase reactivity. Seals made from fluori-
Tetrapolymer VF2–HFP–TFE–CSM Fluoroelastomer-GF (70%F) nated elastomers are used in these processes because of their
Tetrapolymer VF2–PMVE–TFE–CSM Fluoroelastomer-GFLT exceptional resistance to aggressive media. Despite this,
(67%F)
prolonged exposure to plasmas can degrade their surface
S. Wang, J.M. Legare / Journal of Fluorine Chemistry 122 (2003) 113–119 117

Fig. 6. Percentage of weight loss of fluorinated elastomers versus silicone rubber in reactive plasmas.

resulting in particulate contamination before sealing func- ber cleaning. Typical applications for fluoroelastomer seals in
tionality is lost. The ideal seal for plasma applications, plasma and gas deposition wafer processing equipment
therefore, would resist surface degradation and maintain include gate valves, door seals, chamber lid seals, electrode
its functionality. seals, lamp seals, exhaust seals, gas inlet/outlet seals, window
Fluoroelastomer seals are designed to withstand chemical seals, seals for centering rings, fittings, etc.
attack and provide extended seal life in plasma. They exhibit
low weight loss and particle generation properties, thus 3.2. Thermal applications
improving wafer yield, increasing process reliability and
reduced frequency of equipment maintenance. High heat and temperature spikes can ‘‘cook’’ elastomeric
Fig. 6 illustrates the low weight loss properties of fluori- seals beyond recognition, causing them to become hard and
nated elastomers compared to silicone rubber in NF3, a 50/50 brittle. When this occurs, it means that their cross-linking
mixture of C2F6/O2, and oxygen plasma. Fluorine plasma is structure, the key to their elasticity, has become irreversibly
the most common process chemical used in semiconductor damaged. This loss of elasticity makes effective sealing
wafer processing. NF3 plasma, due to its high reactivity, is impossible. In addition, elastomers can degrade under high
typically used for etching and chamber cleaning. However, temperatures, causing outgassing to occur, thereby contam-
the plasma resistance of fluorinated elastomers can vary inating the process environment. The result is unscheduled
widely depending upon the plasma chemistry and the process downtime, or even worse, product loss. Fig. 8 shows the
parameters employed, i.e., power (wattage) level, flow rate, extremely low outgassing properties of typical perfluoroe-
etc. The plasma resistance of fluorinated elastomers also lastomer compound from room temperature up to 400 8C.
depends on other ingredients contained in the compound. Thermal processes like RTP, LPCVD, oxidation, diffu-
Bletsos and Legare discuss the impact of fillers on plasma sion, lamp annealing, etc., need seals that resist not only the
resistance [11]. Fig. 7 shows the excellent chemical resis- process chemicals, but also the extreme temperatures
tance exhibited by perfluoelastomers compared to other required. Reliable, in service temperature ratings for sealing
fluoroelastomers in chlorine trifluoride (ClF3) used for cham- materials are best defined by long-term (672 h) testing for

Fig. 7. ClF3 resistance of fluorinated elastomers.

118 S. Wang, J.M. Legare / Journal of Fluorine Chemistry 122 (2003) 113–119

Fig. 8. Outgassing properties of a typical perfluoroelastomer compound.

seal force retention [12]. Fig. 9 shows the excellent long- causing them to swell and degrade or to leach undesirable
term seal force retention properties of fluorinated elastomers metallic and ionic extractables that affect integrated circuit
versus silicone rubber. Applications for fluoroelastomer functionality [13].
seals in thermal processing equipment include quartz cham- Fluoroelastomer seals are used in wafer cleaning wet
ber seals, plenum seals, seals for centering rings, etc. etching, photolithography and copper plating applications.
They feature low metallic, ionic and total organic carbon
3.3. ‘‘Wet’’ process applications (TOC) extractables as well as excellent chemical resistance
and provide superior contamination performance. Tables 4
To transform raw semiconducting materials into useful and 5 show the extractables performance of fluorinated
devices requires hundreds of chemical processing steps. A elastomers in ultrapure deionized water (UPDI) and ‘‘pir-
significant number of these steps involve aggressive acids, anha’’ (H2SO4:H2O2) after 1 month at 80 8C [14]. Applica-
solvents (including amines), and bases used to clean, rinse, tions for fluoroelastomer seals in ‘‘wet’’ chemical wafer
etch or strip unwanted materials and contaminants from the processing equipment include drain seals, seals for chemical
wafer surface. These chemicals can attack elastomeric seals containers, filter seals, door/lid seals, flow meters, etc.

Fig. 9. Seal force retention properties of fluorinated elastomers versus silicone rubber.
S. Wang, J.M. Legare / Journal of Fluorine Chemistry 122 (2003) 113–119 119

Table 4 unwanted sources of process contamination. Chemical and

Extractables performance of fluorinated elastomers in 18 MO UPDI (1 equipment manufacturers go to great lengths to minimize the
month at 80 8C, parts per billion (ppb) ICP-MS/GF-AA/IC/TOC)
potential for contamination that could result in chip defects.
Extractable Perfluoroelastomer Perfluoroelastomer Fluoroelastomer Demand for fluoroelastomer seals is increasing as wafer
detected (black) (brown) (black) process requirements become more stringent.
Aluminum 9.5 – 4.5
Copper 0.9 0.2 0.4
Magnesium 2.7 3.9 61.2 Acknowledgements
Zinc 0.5 0.9 0.2
Barium – – 23.6
Iron 3.6 0.1 0.9 The authors appreciate all the discussions and support
Calcium 15.4 28.0 400.0 from their colleagues at DuPont Dow Elastomers L.L.C.
Potassium – – 8.0 Kalrez1 and Viton1 are registered trademarks of DuPont
Sodium – – 16.5 Dow Elastomers L.L.C.
Fluoride ion 1100.0 17.0 268.0
TOC 1540.0 866.0 2650.0
References

Table 5 [1] M. Tatemoto, T. Amano, US Patent 4,487,903 (1984).

Extractables performance of fluorinated elastomers in ‘‘Piranha’’ (3:1 (v/v) [2] M. Abe, S. Okamoto, A. Naruki, US Patent 4,920,170 (1990).
96% H2SO4:30% H2O2; 1 month at 80 8C, parts per billion (ppb) ICP-MS/ [3] M. Abe, H. Tatsu, US Patent 5,151,492 (1992).
GF-AA) [4] D. Apotheker, P.J. Krusic, US Patent 4,035,565 (1977).
[5] V. Arcella, G. Brinati, M. Albano, V. Tortelli, US Patent 5,674,959
Extractable Perfluoroelastomer Perfluoroelastomer Fluoroelastomer (1997).
detected (black) (brown) (black) [6] Logothetis, Prog. Polym. Sci. 14 (1989) 251.
[7] E.K. Gladding, R. Sullivan, US Patent 3,546,186 (1970).
Aluminum – – 7.8
[8] J.E. Nottke, US Patent 3,933,767 (1976).
Copper – 2.0 –
[9] F. Breazeale, US Patent 4,281,092 (1981).
Magnesium 17.0 20.0 195.7
[10] R. Stevens, A review of fluoroelastomers—properties, chemistry,
Zinc – 2.0 –
compounding and applications, in: Proceedings of the ACS Rubber
Barium – – 33.7
Meeting, April 13, 1999.
Iodine – – 53.0
[11] Bletsos, J. Legare, The role of additives in perfluoroelastomer
Tin 234.0 – –
sealing parts exposed to reactive plasmas, in: Proceedings of the
Chromium – – 2.4
Microcontamination’93 Conference, Canon Communications, Santa
Iron – – 30.5
Monica, CA, USA, 1993, p. 625.
Calcium – 17.0 572.0
[12] M. Heller, J. Legare, S. Wang, S. Fukuhara, J. Vac. Sci. Technol. A
Sodium – – 10.1
17 (1999) 2119.
Potassium – – 2.9
[13] DuPont Dow Elastomers Technical Bulletin KZE-H90137-00-
A0601.
[14] J. Legare, E. Thomas, K. Fulford, J. Cargo, Characterization of
elemental extractables in perfluoroelastomer and fluoroelastomer
The trend towards larger wafers, smaller feature size and sealing parts, in: Proceedings of the Microcontamination’93
decreasing thickness of deposited layers has placed Conference, vol. 36, Canon Communications, Santa Monica, CA,
increased emphasis on the need to minimize or eliminate USA, 1993, p. 36.