Novel hydrofluorocarbon polymers for use as pellicles in 157 nm semiconductor photolithography: Fundamentals of transparency

Article abstract of DOI:10.1016/S0022-1139(03)00081-2

With the advent of 157 nm as the next photolithographic wavelength, there has been a need to find transparent and radiation durable polymers for use as soft pellicles. Pellicles are ～1 μm thick polymer membranes used in the photolithographic reproduction of semiconductor integrated circuits to prevent dust particles on the surface of the photomask from imaging into the photoresist coated wafer. Practical pellicle films must transmit at least 98% of incident light and have sufficient radiation durability to withstand kilojoules of optical irradiation at the lithographic wavelength. As exposure wavelengths have become shorter the electronics industry has been able to achieve adequate transparency only by moving from nitrocellulose polymers to perfluorinated polymers as, for example, Teflon AF 1600 and Cytop for use in 193 nm photolithography. Unfortunately, the transparency advantages of perfluorinated polymers fail spectacularly at 157 nm; 1 μm thick films of Teflon AF 1600 and Cytop have 157 nm transparency of no more than 38 and 2%, respectively, with 157 nm pellicle lifetimes measured in millijoules. Polymers such as -[(CH₂CHF)_xC(CF₃) ₂CH₂]_y-, or -CH₂ CF₂)_x[2,2-bis(trifluoromethyl)-4,5-difluoro-1, 3-dioxole]_y- with chains that alternate fluorocarbon segments with either oxygen or hydrocarbon segments frequently show >98% transparency at 157 nm, if amorphous. These polymers are made from monomers, such as vinylidene fluoride (VF₂) and hexafluoroisobutylene, which themselves exhibit good alternation of CH₂ and CF₂ in their structures. In addition, we find that ether linkages also can serve to force alternation. In addition, we find that fluorocarbon segments shorter than six carbons, and hydrocarbon segments less than two carbons or less than three carbons if partially fluorinated also promote 157 nm transparency. We also find that even with these design principles, it is advantageous to avoid small rings, as arise in the cyclobutanes. These results suggest a steric component to transparency in addition to the importance of alternation.Upon irradiation these polymers undergo photochemical darkening and therefore none has demonstrated the kilojoule radiation durability lifetimes required to be commercially attractive. This is likely because these exposure lifetimes require every bond to absorb ～10 photons, each photon having an energy roughly twice common bond energies. We have studied intrinsic (composition, molecular weight) and extrinsic (trace metals, impurities, environmental contaminants, oxygen, water) contributions to optical absorption and photochemical darkening in these polymers. Studies of photochemical darkening in model molecules illustrate the dynamics of photochemical darkening and that appreciable lifetimes can be achieved in fluorocarbons. To a first approximation the polymers that have lower 157 nm optical absorbance also tend to show the longest lifetimes. These results imply that quantum yield, or the extent to which the polymer structure can harmlessly dissipate the energy, can be important as well.

Full text of DOI:10.1016/S0022-1139(03)00081-2

Journal of Fluorine Chemistry 122 (2003) 63–80
Novel hydrofluorocarbon polymers for use as pellicles in 157 nm
semiconductor photolithography: fundamentals of transparency
Roger H. Frencha,*, Robert C. Whelanda, Weiming Qiua, M.F. Lemona, Edward Zhangb,
Joseph Gordonb, Viacheslav A. Petrova, Victor F. Cherstkovc, Nina I. Delayginac
aDuPont Central Research & Development, Experimental Station E356-384, Wilmington, DE 19880-0356, USA
bDuPont Photomasks Inc., 4 Finance Dr., Danbury, CT 06810, USA
cINEOS, Russian Academy of Sciences, Vavilova 28, Moscow 117813, Russia
Abstract
With the advent of 157 nm as the next photolithographic wavelength, there has been a need to find transparent and radiation durable
polymers for use as soft pellicles. Pellicles are ꢀ1 mm thick polymer membranes used in the photolithographic reproduction of semiconductor
integrated circuits to prevent dust particles on the surface of the photomask from imaging into the photoresist coated wafer. Practical pellicle
films must transmit at least 98% of incident light and have sufficient radiation durability to withstand kilojoules of optical irradiation at the
lithographic wavelength. As exposure wavelengths have become shorter the electronics industry has been able to achieve adequate
transparency only by moving from nitrocellulose polymers to perfluorinated polymers as, for example, Teflon1 AF 1600 and CytopTM for use
in 193 nm photolithography. Unfortunately, the transparency advantages of perfluorinated polymers fail spectacularly at 157 nm; 1 mm thick
films of Teflon1 AF 1600 and CytopTM have 157 nm transparency of no more than 38 and 2%, respectively, with 157 nm pellicle lifetimes
measured in millijoules.
Polymers such as –[(CH2CHF)xC(CF3)2CH2]y–, or –(CH2CF2)x[2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole]y– with chains that
alternate fluorocarbon segments with either oxygen or hydrocarbon segments frequently show >98% transparency at 157 nm, if amorphous.
These polymers are made from monomers, such as vinylidene fluoride (VF2) and hexafluoroisobutylene, which themselves exhibit good
alternation of CH2 and CF2 in their structures. In addition, we find that ether linkages also can serve to force alternation. In addition, we find
that fluorocarbon segments shorter than six carbons, and hydrocarbon segments less than two carbons or less than three carbons if partially
fluorinated also promote 157 nm transparency. We also find that even with these design principles, it is advantageous to avoid small rings, as
arise in the cyclobutanes. These results suggest a steric component to transparency in addition to the importance of alternation.
Upon irradiation these polymers undergo photochemical darkening and therefore none has demonstrated the kilojoule radiation durability
lifetimes required to be commercially attractive. This is likely because these exposure lifetimes require every bond to absorb ꢀ10 photons,
each photon having an energy roughly twice common bond energies. We have studied intrinsic (composition, molecular weight) and extrinsic
(trace metals, impurities, environmental contaminants, oxygen, water) contributions to optical absorption and photochemical darkening in
these polymers. Studies of photochemical darkening in model molecules illustrate the dynamics of photochemical darkening and that
appreciable lifetimes can be achieved in fluorocarbons. To a first approximation the polymers that have lower 157 nm optical absorbance also
tend to show the longest lifetimes. These results imply that quantum yield, or the extent to which the polymer structure can harmlessly
dissipate the energy, can be important as well.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Fluoropolymer; Hydrofluorocarbon; 157 nm; Photolithography; Optical absorbance; Pellicle
1. Introduction
doubled about every 18 months. The main driver behind this
continued miniaturization of chip circuitry is the continuing
advances in photolithography to reduce integrated circuit
feature sizes. The photolithographic process starts with a
circuit pattern etched in chrome metal on glass [1]. Illumi-
nation of the patterned photomask in the optical stepper
projects an image of the circuit pattern that is captured as a
latent image by a photosensitive polymer layer, known as a
photoresist, on the silicon wafer. The shorter the wavelength
The electronics industry continues to make tremendous
gains in miniaturization and circuit complexity. For decades
now, the industry has been able to follow Moore’s Law
whereby the number of transistors on a silicon chip has
* Corresponding author. Tel.: þ1-302-695-1319; fax: þ1-302-479-4803.
E-mail address: roger.h.french@usa.dupont.com (R.H. French).
0022-1139/03/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-1139(03)00081-2

64
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
of light used, the smaller the circuit features that can be
copied. Much commercial production is presently being
done with light having a wavelength of 248 nm using either
a lamp or a KrF excimer laser light source. The use of
193 nm ArF excimer laser light is just entering commercial
practice while photolithography based on 157 nm F2 exci-
mer lasers is now in the development stage.
where T0 is the intensity of the incident light and T the
intensity of the transmitted light. An obvious way to increase
the intensity of the transmitted light is to decrease film
thickness. This is an acceptable strategy down to thicknesses
of about 0.8 mm beyond which polymer films becomes too
fragile to stretch tautly and defect-free across a 5 in: Â 5 in:
pellicle frame. This thickness dependence is accounted for
by reporting a film’s absorbance per micrometer (A/mm),
Organic polymers play several critical roles in the photo-
lithographic process. We have already mentioned photore-
sists, submicrometer thick films of photosensitive polymer
that capture projected circuit patterns. One of the major
issues for resists is that 157 nm light is absorbed so strongly
that the top of a film can be overexposed at the same time the
bottom of the film is underexposed leading to undesirable
photoresist line profiles after development [2]. This is true
even when resist films are only several tenths of a micrometer
thick [1]. For purposes of sharp pattern development, experi-
ence suggeststhat at least 40%ofincident light should makeit
to the bottom of the resist layer. The first polymer to demon-
strate that such transparencies are possible [3] was Teflon1
AF, the copolymer of 2,2-bis(trifluoromethyl)-4,5-difluoro-
1,3-dioxole (PDD) with tetrafluoroethylene (TFE). Teflon1
AF of course cannot function as a resist itself because it lacks
the chemical groups needed for photosensitivity and aqueous
base development. This has lead to development of new
fluoropolymers for use as photoresists at 157 nm [4].
Another critical role for polymers in photolithography is
that of the pellicle, a transparent dust cover for the photo-
mask [5]. The chrome photomask, which serves as the
master image of the circuit layout, has circuit features down
to tenths of a micrometer. Dust particles that lodge on the
photomask will print as a defect each time the master is
copied to a chip, thereby dropping the yield of functional
chips immediately to 0%. To prevent this, an ꢀ0.8 mm thick
film called a pellicle is held several millimeters above the
photomask on a frame. Now when a dust particle deposits, it
attaches to the pellicle film where the particle is held up and
out of the focal plane so that it no longer copies. The two
most chemically challenging specifications the electronics
industry has placed on pellicle films are that they transmit
most of the incident light and that they can be used repeat-
edly without showing significant changes in their optical
characteristics [6,7]. This is the challenge we have under-
taken in the present work, to produce a polymeric pellicle
membrane with sufficient transparency and radiation dur-
ability for use with 157 nm F2 excimer laser irradiation.
ꢀ
ꢁ
T0=T
A=mm ¼ log10
(2)
t
where t is the thickness of the film measured in micrometers.
A/mm measurements are convenient for ranking transpar-
ency differences between films, keeping in mind that such
comparisons include not only the effects of polymer struc-
ture but also of polymer purity and processing. A 98%
transparent film 0.8 mm thick would have an A/mm of
0.011. Were the same material as thick as a piece of paper
(ꢀ76 mm), it would transmit only 20% of incident light. So,
even though a pellicle candidate may set records with
respect to the transmission of 157 nm light, all such poly-
mers presently absorb significant quantities of light. The
radiation durability problems discussed later should thus
come as no surprise.
When working with 0.8 mm thick films, the best pellicles
all too soon become so transparent that they can no longer be
meaningfully distinguished with conventional transmission
based absorbance measurements of thin films with micro-
meter scale thickness. This occurs for A/mm values <0.01.
Much of the uncertainty comes from the anti-reflective effect
of thin polymer when coated on CaF2. That is, the small
amount of light absorbed by a highly transparent film is lost
in comparison to the transmission increase resulting from
decreased reflectivity from the anti-reflective effect. In the
worst of such cases, Tsample is greater than Tsubstrate and the
calculated absorbance goes negative. These aspects of the
characterization of thin polymer films are discussed in
greater detail in reference [5].
1.2. Additional property requirements for soft pellicles
The pellicle consists of a precisely designed membrane,
which acts as a tuned etalon [8], on a pellicle frame that is
adhesively mounted to the reticle or photomask. Beyond the
optics of the pellicle, pellicles also have a large number of
ancillary properties that are essential. The multiple property
requirements embodied in pellicles require a materials
design approach. Currently, no materials are known to meet
the optical transparency performance requirements at the
157 nm lithography wavelength. The use of new materials
requires that careful attention be given to design of the tuned
etalon to control the pellicle reflectance and transmission. To
achieve the desired pellicle lifetimes, new radiation tolerant
materials will need to be developed that meet stringent
radiation durability requirements. To produce unsupported
pellicle membranes, the polymer must also be designed to
1.1. Optical requirements of pellicles
The electronics industry has specified that a pellicle film
should pass at least 98% of incident 157 nm light. For
measurements on pellicle films this can be expressed as
an optical absorbance A,
ꢀ
ꢁ
T0
T
A ¼ log10
(1)

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
65
achieve the required spinning, film formation, and mechan-
ical properties, and have minimal outgassing in use.
and (4), respectively. The A/mm is then determined by
dividing the optical density by the film thickness, as shown
in Eq. (5). The optical A/mm reported here are base 10:
1.3. Novel polymers for 157 nm soft pellicles
Tsample
Tfilm ¼ 100 Â
ODfilm ¼ log10
(3)
(4)
(5)
Tsubstrate
ꢀ
Previously, it has been believed that perfluorinated
polymers have the shortest wavelength cutoffs, highest
transparencies and lowest absorbances [2,3]. What we report
here is that higher transparencies and lower absorbances can
be achieved at 157 nm using hydrofluorocarbon polymers
which minimize hydrocarbon and fluorocarbon run lengths
and force a regular alternation of fluorocarbon and hydro-
carbon segments down the polymer chain.
ꢁ
100
Tfilm
log10ðTsubstrate=Tsample
Þ
Afilm ðmmÀ1Þ ¼ Afilm=mm ¼
tfilm
The transmission measurement of liquid samples was
made in a Harrick Scientific Corp. Demountable Liquid
Cell model DLC-M13. Teflon1 AF spacers of 6 or 25 mm
thickness were used in order to establish the desired path
lengths and sandwiched between two 2 mm thick 0.5 in.
diameter CaF2 windows. Care was taken to avoid bubbles in
the 8 mm diameter window aperture.
2. Experimental
2.1. Optical spectroscopy and characterization
2.1.1. Optical absorbance determined using vacuum
ultraviolet spectroscopy
2.1.2. Measurement of photochemical darkening
The 157 nm exposure was performed in a nitrogen purged
environment. The energy in the incident and transmitted
beams were monitored using pyroelectric detectors and a
Ratiometer was used to measure the in situ variation of the
relative sample transmission with increasing laser radiation
dose. The details of these methods and measurements have
been discussed previously [7].
VUV spectroscopy including both transmission and
reflectance measurements has become an established tech-
nique for electronic structure studies of large band-gap,
insulating materials such as polysilanes [9] and fluoropoly-
mers. The details of the VUV-laser plasma light source
(LPLS) spectrophotometer have been discussed previously
[10]. The spectrophotometer utilizes a LPLS [11], and a 1 m
monochromator with Al/MgF2 and iridium coated optics.
The energy range of this windowless instrument is 1.7–
44 eV (700–28 nm), which extends beyond the air-cutoff of
6 eV and the window-cutoff of 10 eV. The resolution of the
instrument is 0.2–0.6 nm, which corresponds to 16 meV
resolution at 10 eV and 200 meV resolution at 35 eV.
A Perkin-Elmer Lambda 9 spectrophotometer, with
transmission and reflectance attachments and using xenon
and deuterium lamps, was used to cover the UV-Vis/NIR
spectral regions. The wavelength (energy) resolution is
2 nm (40 meV) at 5.0 eV. Transmission was measured over
the complete energy range of the instrument to check the
accuracy of the VUV transmission spectra. The results
agreed well with the data from the VUV spectrophot-
ometers. Data were spliced together in the overlapping
wavelength region using a multiplicative scaling factor on
the VUV transmission to bring it into agreement with the
UV-Vis results.
2.1.3. Accuracy of transmission based optical
measurements
As in all experimental measurements, the accuracy of
the measured values is a function of the sample and mea-
surement apparatus. The inherent sensitivity of spectral
transmission and absorbance measurements is affected by
the optical path length of the sample, and the transmission
drop that occurs as light transmits through the sample in
the measurement. As the transmission drop decreases, the
accuracy of the absorbance measurement decreases. A
transmission difference of ꢀ0.1% is near the limit of the
measurement method. In such a case, a thicker sample, with
a longer path length, is required to keep the measured
transmission drop larger than the instrument’s sensitivity.
2.2. Synthesis
The polymers synthesized, and their compositional analy-
sis, are summarized in Table 1. Differential scanning calori-
metry (DSC) measurements were performed under nitrogen,
heating twice at 10 8C/min using a TA Instruments Model
2910. Unless mentioned otherwise, glass transition (Tg) and
melting point (Tg) temperatures are taken from the second
heats. Inherent viscosities (IV) were determined on 0.5 wt.%
solutions at 25 8C by automated glass capillary viscometry
using a Cannon Autovisc1. Polymer compositions were
determined either by elemental analysis or by NMR
spectra run on polymer solutions. Unless specified otherwise,
In addition, the use of VUV spectroscopic ellipsometry is
useful as an independent technique for characterization
of materials in this spectral range [5]. The VUV spectro-
scopic ellipsometer uses a deuterium and a xenon lamp,
and can also be used to measure the transmission spectrum
of polymer films on a substrate, or a pellicle membrane
directly.
Once the transmission spectra of the substrate and the film
coated on that substrate are determined, the film transmis-
sion and optical density can be determined using Eqs. (3)

66
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
Table 1
Fluoropolymers: synthesis and compositional analysis
Vinylidene fluoride copolymers
Poly(vinylidene fluoride/hexafluoropropylene) (1): VF2/HFP
Poly(vinylidene fluoride/chlorotrifluoroethylene) (5): VF2/CTFE
21:79 VF2:HFP, NMR,
acetone-d6, Tg ¼ À22.5 8C,
IV ¼ 0.753 dl/g, acetone
Calc. (C2F2H2)5(C2F3Cl)4:
27.50% C, 1.28% H, 18.04% Cl.
Found: 27.26% C, 1.41% H,
17.91% Cl. Tg ¼ 99 8C,
IV ¼ 0.546 dl/g, acetone
Poly(vinylidene fluoride/perfluoromethylvinylether) (4): VF2/PMVE
Calc. (C2H2F2)13(C3F6O)10:
26.98% C, 1.05% H. Found:
27.21% C, 0.88% H.
Tg ¼ À29 8C, IV ¼ 0.166 dl/g,
2-heptanone
Poly(vinylidene fluoride/perfluoropropylvinyl ether) (6): VF2/PPVE
Calc. (C2F2H2)7(C5F10O)5:
26.34% C, 0.79% H.
Found: 26.17% C, 0.88% H.
Tg ¼ À32 8C, IV ¼ 0.169 dl/g,
hexafluorobenzene
Poly(vinylidene fluoride/perfluorodimethyldioxole) (2): VF2/PDD
Calc. (C5F8O2)1(C2H2F2)1:
29.05% C, 1.08% H. Found:
28.99% C, 1.11% H. Tg ¼ 56 8C
(first heat), Tg not detected
on second heat
Poly(vinylidene fluoride/2-(difluoromethylene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane (10):
Calc. (C5F8O2)1(C2H2F2)2:
29.05% C, 1.08% H.
Found: 28.71% C, 1.38% H.
Tg ¼ 100 8C (first heat),
Tm ¼ 165 8C (second heat),
IV ¼ 0.287 dl/g,
VF2/PMD
hexafluorobenzene
Poly(CH2¼CF2/CF2¼CHOCF2CF3) (7): VF2/PEDVE, VF2 analogue
Calc. (C4F7OH)10(C2H2F2)11
:
27.74% C, 1.20% H. Found:
27.89% C, 0.91% H. Tg ¼ À5 8C
Poly(CH2¼CF2/CF2¼CHOCF2CF2H) (3): VF2/TEDVE, VF2 analogue
Calc. (C2H2F2)3(C4H2F6O)2:
30.45% C, 1.83% H. Found:
30.65% C, 1.41% H. Tg ¼ À11 8C,
IV ¼ 0.122 dl/g, acetone
Poly[CH2¼CF2/(CH2¼C(CF3)CF2OCF(CF3)2] (8): VF2/DHB,
HFIB analogue
49:51 VF2:DHB, NMR,
hexafluorobenzene. Neither Tg nor
Tm detected, IV ¼ 0.083 dl/g,
hexafluorobenzene
Poly[CH2¼CF2/(CH2¼C(CF3)CF2OCH(CF3)2] (9): VF2/THB,
HFIB analogue
47:53 VF2:THB, NMR,
hexafluorobenzene, Tg ¼ 47 8C,
IV ¼ 0.116 dl/g,
hexafluorobenzene

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
67
Table 1 (Continued )
Hexafluoroisobutylene containing polymers
Poly(hexafluoroisobutylene/vinyl fluoride) (11): HFIB/VF
Calc. (C4F6H2)47(C2H3F)53
34.79% C, 2.51% H. Found:
:
34.80% C, 2.57% H. Tg ¼ 70 8C,
IV ¼ 0.379, tetrahydrofuran
Poly(hexafluoroisobutylene:trifluoroethylene) (12): HFIB/TrFE
Poly(hexafluoroisobutylene/vinyl alcohol) (13): HFIB/VOH
54:46 HFIB:TrFE, NMR,
acetone-d6, Tg ¼ 70 8C,
IV ¼ 0.055 dl/g, acetone
Calc. (C4H2F6)1(C2H4O)1:
34.63% C, 2.91% H. Found:
34.34% C, 2.73% H. Tg ¼ 90 8C
Ethylene copolymers
Poly(ethylene/perfluoropropylvinyl ether) (14): E/PPVE
47:53 PPVE:E, 1H NMR and
19F NMR, hexafluorobenzene,
Tg ¼ À15.5 8C, IV ¼ 0.341 dl/g,
hexafluorobenzene
Poly(ethylene/hexafluoropropylene) (15): E/HFP
Calc. (C2H4)57(C3F6)43: 36.26% C,
2.85% H. Found: 36.22% C,
2.82% H. Tg ¼ À15 8C
Perfluorodimethyldioxole copolymers
Poly(ethylene/perfluorodimethyldioxole) (16): E/PDD
51:49 PDD:E, 1H NMR and
19F NMR, hexafluorobenzene,
Tg ¼ 71 8C, IV ¼ 0.318 dl/g,
hexafluorobenzene
Poly(perfluorodimethyldioxole/tetrafluoroethylene) (17, 18 and 19):
PDD/TFE Teflon1 AF
Other
Poly(hexafluoropropylene/tetrafluoroethylene) (23): HFP/TFE
Ratio HFP/TFE ¼ 50:50 HFP:TFE,
NMR, hexafluorobenzene,
IV ¼ 0.407 dl/g, Fluoroinert1
FC-75
Liquid cyclobutanes
1,1,2,2-Tetrafluorocyclobutane (20): TFCB
Propylene/hexafluoropropylene cyclic adduct (21): P/HFP
Hexafluoropropylene cyclic dimer (22): HFP2

68
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
fluorine NMR was used. NMR compositions are reported
in mole percents. Most of polymerizations were initiated
with hexafluoropropylene oxide dimmer peroxide ‘‘DP’’,
CF3CF2CF2OCF(CF3)(C¼O)OO(C¼O)CF(CF3)OCF2CF2-
CF3 [23].
(a) Preparation of 1,1,2,2-tetrafluoroethyl-2-chloro-2,2-
difluoroethyl ether. A mixture of 2-chloro-2,2-difluoro-
ethanol (22.0 g), t-butanol (45 ml), KOH (10.0 g) and
TFE (25 g) was shaken at room temperature for 8 h in a
autoclave. The bottom layer of the reaction mixture
was isolated and washed with water (40 ml) to give a
crude product, 1,1,2,2-tetrafluoroethyl-2-chloro-2,2-di-
fluoroethyl ether, 29.5 g, yield 72% [13]. This product
was used for next step without further purification.
(b) Preparation of 1,1,2,2-tetrafluoroethyl-2,2-difluorovi-
nyl ether. A mixture of 1,1,2,2-tetrafluoroethyl-2-
chloro-2,2-difluoroethyl ether (29.0 g), KOH (10.0 g),
and DMSO (5 ml) was heated to reflux on a spinning
band distillation apparatus. The product was distilled
out to give 9.6 g of 1,1,2,2-tetrafluoroethyl-2,2-difluoro-
vinyl ether, bp 38 8C (39.7 8C [13]), yield 40%.
2.2.1. Vinylidene fluoride copolymers
2.2.1.1. Poly(vinylidene fluoride/hexafluoropropylene) (1):
VF2/HFP. A poly(vinylidene fluoride/hexafluoropropylene)
(VF2:HFP) sample made by the method of [12] was cha-
racterized.
Solutions of VF2:HFP were spin coated at spin speeds of
3000 and 6000 rpm onto CaF2 substrates to produce polymer
˚
films of 69,800 and 1641 A thickness. VUV absorbance
measurements were then used to determine the absorbance
per micrometer.
19F NMR (CDCl3) À92.3 (s, 2F), À92.7 (ddt, J ¼ 57, 14,
3 Hz, 1F), À110.5(dd, J ¼ 54, 3 Hz, 1F), À137.4(dt, J ¼ 52,
5 Hz, 2F) ppm. 1H NMR (CDCl3) 5.84 (tt, J ¼ 52, 3 Hz, 1H),
6.10 (dd, J ¼ 13, 4 Hz, 1H)ppm. 13C NMR(CDCl3) 98.9 (dd,
J ¼ 61, 16 Hz),107.2(tt,J ¼ 252,40 Hz),116.3(tt,J ¼ 273,
40 Hz), 157.0 (dd, J ¼ 293, 281 Hz) ppm.
The 157 nm absorbance per micrometer determined from
the thicker polymer film is 0.015 per micrometer. The
193 nm absorbance per micrometer determined is 0.005 per
micrometer. The 248 nm absorbance per micrometer deter-
mined is 0.003 per micrometer.
2.2.1.2. Poly(vinylidene fluoride/perfluorodimethyldioxole)
(2): VF2/PDD. A 75 ml autoclave was loaded with 25 ml of
CF2ClCCl2F, pre-chilled to less than À20 8C, loaded further
with 0.3 g of PerkadoxTM 16 N [bis(4-t-butylcyclohexyl)-
peroxydicarbonate] and 20 g of perfluorodimethyldioxole
(PDD), evacuated, and 10.4 g of VF2 added. Heating 18 h at
70 8C gave a thick oil. Evaporation in air, drying 22 h under
pump vacuum, and drying 24 h in a 75 8C oven gave 17 g of
hard white foam.
A viscous solution was prepared by rolling 4 g of
poly(PDD/VF2) with 16 g of hexafluorobenzene and filter-
ing through an 0.45 mm glass fiber syringe filter [Whatman,
AutovialTM]. The filtrate was used to spin coat thick films on
optical substrate for absorption measurements. Solutions
of VF2:PDD were spin coated at spin speeds of 6000 rpm
CF2¼CHOCF2CF2H copolymerization with CH2¼CF2. A
75 ml stainless steel autoclave chilled to less than À20 8C
was loaded with 9.4 g of CF2¼CHOCF2CF2H monomer,
10 ml of CF3CFHCFHCF2CF3 solvent, and 5 ml of ꢀ0.17 M
DP in CF3CFHCFHCF2CF3. The autoclave was chilled,
evacuated and further loaded with ꢀ4 g of VF2. The
autoclave was shaken overnight at room temperature. The
resulting hazy fluid was dried under nitrogen, then under
pump vacuum, and finally for 23 h in a 77 8C vacuum oven,
giving 4.6 g of tacky gum.
Solution preparation and spinning. A clear, colorless
solution was made by rolling 2.5 g of polymer with 10 g
of 2-heptanone solvent and passing through a 0.45 mm glass
fiber microfiber syringe filter (Whatman AutovialTM).
Solutions of polymer 3 were spin coated in a conventional
atmosphere spinner at spin speeds of 1000 rpm for 60 s onto
CaF2 substrates with a subsequent post apply bake at 120 8C
˚
onto CaF2 substrates to produce polymer films of 2097 A
thickness. VUVabsorbance measurements were then used to
determine the absorbance per micrometer.
The 157 nm absorbance per micrometer determined from
the thicker polymer film is À0.04 per micrometer. For this
very transparent material, this demonstrates an antireflective
coating effect thereby producing a negative value of the
157 nm absorbance per micrometer. The 193 nm absorbance
per micrometer determined is 0.02 per micrometer. The
248 nm absorbance per micrometer determined is 0.08
per micrometer.
˚
for 2 min to produce polymer films of 9400 A thickness.
VUVabsorbance measurements were then used to determine
the absorbance per micrometer.
Absorption results. The 157 nm absorbance per micrometer
determined is À0.002 per micrometer. The 193 nm absor-
bance per micrometer determined is À0.001 per micrometer.
The 248 nm absorbance per micrometer determined is 0.003
per micrometer.
2.2.1.3. Poly(CH2¼CF2/CF2¼CHOCF2CF2H) (3):
VF2/TEDVE, VF2 analogue
2.2.1.4. Poly(vinylidene fluoride/perfluoromethylvinylether)
(4): VF2/PMVE. A 210 ml autoclave was loaded with 50 ml
of CF2ClCCl2F, chilled to less than À20 8C, and 10 ml of
ꢀ0.2 M DP in CF3CFHCFHCF2CF3 added. The autoclave
1,1,2,2-Tetrafluoroethyl-2,2-difluorovinyl ether, CF2¼
CHOCF2CF2H. Monomer was prepared using modified
literature procedure [13].

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
69
was evacuated and loaded with 33 g perfluoro(methylvinyl
ether) (PMVE) and 13 g VF2. Shaking the autoclave over-
night at room temperature gave solution that was evaporated
down to soft polymer and then further dried for 29 h under
pump vacuum and for 20 h in a 75 8C vacuum oven. This
gave 31 g of soft polymer suitable for use as a glue.
A solution was made by rolling 4 g of this polymer with
16 g of hexafluorobenzene. This solution was passed
through a 0.45 mm glass microfiber syringe filter (Whatman,
AutovialTM) and the filtrate used to spin coat thick films on
optical substrate for absorption measurements. Solutions
of 13:10 VF2:PMVE were spin coated onto CaF2 substrates
through a 0.45 mm glass microfiber syringe filter (Whatman,
AutovialTM) and the filtrate used to spin coat thick films
on optical substrate for absorption measurements. Solutions
of 7:5 VF2:PFPVE were spin coated onto CaF2 substrates
˚
to produce polymer films of 29,874 A thickness. VUV
absorbance measurements were then used to determine
the absorbance per micrometer.
The 157 nm absorbance per micrometer determined is
0.028 per micrometer. The 193 nm absorbance per micro-
meter determined is À0.003 per micrometer. The 248 nm
absorbance per micrometer determined is À0.00074 per
micrometer.
˚
to produce polymer films of 25,970 A thickness. VUV
absorbance measurements were then used to determine
the absorbance per micrometer.
2.2.1.7. Poly(CH2¼CF2/CF2¼CHOCF2CF3) (7): VF2/
PEDVE, VF2 analogue. Preparation of perfluoroethyl-2,
2-difluorovinyl ether, CF2¼CHOCF2CF3 monomer.
The 157 nm absorbance per micrometer determined is
0.034 per micrometer. The 193 nm absorbance per micro-
meter determined is 0.015 per micrometer. The 248 nm
absorbance per micrometer determined is 0.018 per micro-
meter.
(a) Preparation of 2-chloro-2,2-difluoroethyl trifluoroace-
tate. A mixture of 2-chloro-2,2-difluoroethanol (132 g)
and DMF (15 drops) was charged to a 250 ml flask.
Trifluoroacetyl chloride (17 g) was introduced to the
flask via a dry ice condenser at about 50 8C. The resulting
mixture was refluxed for 4 h. The mixture was distilled
2.2.1.5. Poly(vinylidene fluoride/chlorotrifluoroethylene)
(5): VF2/CTFE. A 75 ml autoclave chilled to less than
À20 8C was loaded with 25 ml of CF2ClCCl2F and 5 ml of
ꢀ0.1 M DP in CF3CFHCFHCF2CF3. The autoclave was
evacuated and loaded with 9.6 g of VF2 and 17 g of
chlorotrifluoroethylene (CTFE). Shaking the autoclave
overnight at room temperature gave viscous white fluid that
was evaporated down to stretchy solid and then dried for 1 h
under pump vacuum and for 30 h in a 75 8C vacuum oven.
This gave 19 g of product.
Rolling 3 g poly(VF2/CTFE) with 20 g of 2-heptanone
gave solution that was filtered though an 0.45 mm glass fiber
syringe filter (Whatman, AutovialTM). The filtrate was used
to spin coat thick films on optical substrate for absorption
measurements. Solutions of 5:4 VF2:CTFE were spin coated
onto CaF2 substrates to produce polymer films. VUV absor-
bance measurements were then used to determine the
absorbance per micrometer.
to give 234 g of the acetate, bp 79–81 8C, yield 97%. 19
F
NMR (CDCl3) À62.8 (t, J ¼ 8 Hz, 2F), À75.2 (s, 3F)
ppm. 1H NMR (CDCl3) 4.79 (t, J ¼ 9 Hz) ppm.
(b) Preparation of perfluoroethyl 2-chloro-2,2-difluor-
oethyl ether. A mixture of 2-chloro-2,2-difluoroethyl
trifluoroacetate (20 g), HF (150 g), and SF4 (60 g) was
heated to 150 8C for 21 h. The mixture was poured into
water (300 ml). The bottom layer was isolated to give
crude product (16.1 g), yield 73%. It was relatively
pure based on NMR analysis. Then the crude product
was washed with Na2CO3 until pH ¼ 8, dried over
Na2SO4, and distilled to afford the product, 11 g, bp
54–55 8C, yield 50%. 19F NMR (CDCl3) À63.5 (tt,
J ¼ 9, 3 Hz, 2F), À86.4 (s, 3F), À91.2 (s, 2F) ppm.
(c) Preparation of perfluoroethyl-2,2-difluorovinyl ether A
mixture of perfluoroethyl 2-chloro-2,2-difluoroethyl
ether (69 g), KOH (30.0 g) and DMSO (15 ml) was
heated to reflux on a spinning band distillation
apparatus. The product was distilled out to give 43 g
of perfluoroethyl-2,2-difluorovinyl ether, bp 15 8C,
yield 85%. 19F NMR (CDCl3) À86.5 (s, 3F), À91.8
(dd, J ¼ 18, 4 Hz, 1F), À92.1 (s, 2F), À109.3 (d,
J ¼ 18 Hz, 1F) ppm. 1H NMR (CDCl3) 6.08 (dd,
J ¼ 13, 4 Hz) ppm. 13C NMR (CDCl3) 98.9 (m), (ddt,
J ¼ 62, 16, 5 Hz), 116.2 (qt, J ¼ 284, 45 Hz), 114.3
(tq, J ¼ 275, 42 Hz), 156.3 (d, J 295 Hz) ppm.
The 157 nm absorbance per micrometer determined is 5.6
per micrometer. The 193 nm absorbance per micrometer
determined is 0.27 per micrometer. The 248 nm absorbance
per micrometer determined is 0.12 per micrometer.
2.2.1.6. Poly(vinylidene fluoride/perfluoropropylvinyl
ether) (6): VF2/PPVE. A 210 ml autoclave was loaded
with 50 ml of CF2ClCCl2F, chilled to less than À20 8C,
and 10 ml of ꢀ0.2 M DP in CF3CFHCFHCF2CF3 added.
The autoclave was cooled evacuated and 13 g VF2 and 53 g
PPVE added. After shaking overnight at ambient tempera-
tures (22–26 8C), the autoclave was vented, and solution
recovered. Excess solvent was evaporated under nitrogen and
thepolymerdried72 hundervacuumatroomtemperatureand
then for 28 h at 75 8C, 45 g.
Copolymerization of CF2¼CHOCF2CF3 with CH2¼CF2.
A 75 ml stainless steel autoclave chilled to less than À20 8C
was loaded with 10 ml of CF3CFHCFHCF2CF3 solvent and
5 ml of ꢀ0.17 M DP in CF3CFHCFHCF2CF3. The autoclave
was chilled, evacuated and further loaded with 10 g of
CF2¼CHOCF2CF3 and ꢀ4 g of VF2. The autoclave was
A solution was made by rolling 4 g of this polymer with
16 g of hexafluorobenzene. This solution was passed

70
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
shaken overnight at room temperature. The resulting fluid
was dried under nitrogen, then under pump vacuum, and
finally for 4 days in a 77 8C vacuum oven, giving 2.6 g of
tacky gum.
H GaldenTM ZT 85 solvent and passing through a 0.45 mm
glass fiber microfiber syringe filter (Whatman AutovialTM).
Solutions of polymer 7 were spin coated in a conventional
atmosphere spinner at spin speeds of 90 rpm for 30 s onto
CaF2 substrates with a subsequent post apply bake at 120 8C
for 2 min to produce polymer films of 10,800 A thickness.
VUVabsorbance measurements were then used to determine
the absorbance per micrometer.
˚
Solution preparation and spinning. A solution was made
by rolling 1 g of polymer with 9 g of H GaldenTM ZT 85
solvent and passing through a 0.45 mm PTFE fiber microfiber
syringe filter (Whatman AutovialTM) to remove haze.
Solutions of Polymer 5 were spin coated in a conventional
atmosphere spinner at spin speeds of 1000 rpm for 30 s onto
CaF2 substrates with a subsequent post apply bake at 120 8C
Absorption results. The 157 nm absorbance per micro-
meter determined is 0.0275 per micrometer. The 193 nm
absorbance per micrometer determined is 0.0045 per
micrometer. The 248 nm absorbance per micrometer
determined is 0.0008 per micrometer.
˚
for 2 min to produce polymer films of 10,200 A thickness.
VUVabsorbance measurements were then used to determine
the absorbance per micrometer.
2.2.1.9. Poly[CH2¼CF2/(CH2¼C(CF3)CF2OCH(CF3)2]
(9): VF2/THB, HFIB analogue
Absorption results. The 157 nm absorbance per micro-
meter determined is 0.034 per micrometer. The 193 nm
absorbance per micrometer determined is 0.02 per micro-
meter. The 248 nm absorbance per micrometer determined
is 0.01 per micrometer.
Preparation of 1,1,5-trihydro-2,5-bis(trifluoromethyl)-4-
oxo-perfluoro-1-hexene, CH2¼C(CF3)CF2OCH(CF3)2
monomer. A 100 ml flask was charged with tributylamine
(15 g), diglyme (15 ml), and hexafluoroisopropanol (13.7 g)
in a dry box. HFIB fluorosulfate (see footnote 1) (20.0 g)
was added dropwise at 3–12 8C. The resulting mixture was
stirred at room temperature for 2 h. The mixture was fresh
distilled to give a liquid, which was then spinning band
distilled to afford 21.1 g product, bp 92–93 8C, yield 83%.
(Less pure fractions were not counted.) 19F NMR (CDCl3)
À65.3 (t, J ¼ 7 Hz, 3F), À70.8 (m, 2F), À74.0 (q, J ¼ 5 Hz,
2.2.1.8. Poly[CH2¼CF2/(CH2¼C(CF3)CF2OCF(CF3)2]
(8): VF2/DHB, HFIB analogue
Preparation of 1,1-dihydro-2,5-bis(trifluoromethyl)-4-
oxo-perfluorohex-1-ene, CH2¼C(CF3)CF2OCF(CF3)2
monomer. A 250 ml flask was charged with KF (12 g) and
diglyme (55 ml) in a dry box. Hexafluoroacetone (40.5 g)
was added to the mixture via a dry-ice condenser. The solid
was dissolved completely. The HFIB fluorosulfate1 (49 g)
was added dropwise. The resulting mixture was stirred at
room temperature for 3 h. The mixture was fresh distilled to
give a liquid, which was then spinning band distilled to afford
36.3 g product, bp 84–86 8C, yield 55%. (Less pure fractions
werenotcounted.)19FNMR(CDCl3)À65.3(t,J ¼ 8 Hz,3F),
À66.6(m,2F),À81.0(m,6F),À146.4(t,J ¼ 23 Hz,1F)ppm.
1H NMR (CDCl3) 6.39 (m) ppm. 13C NMR (CDCl3) 101.5
(d and septet, J ¼ 269, 38 Hz), 117.7 (qd, J ¼ 258, 32 Hz),
118.6 (t, J ¼ 274 Hz), 127.4 (m), 131.2 (m) ppm.
1
6F) ppm. H NMR (CDCl3) 4.99 (septet, J ¼ 5 Hz, 1H),
6.37 (m, 2H) ppm. 13C NMR (CDCl3) 69.4 (septet, t, J ¼ 35,
4 Hz), 118.8 (t, J ¼ 269 Hz), 120.2 (q, J ¼ 283 Hz), 120.6
(sextet, J ¼ 5 Hz), 130.9 (sextet, J ¼ 35 Hz) ppm.
CH2¼C(CF3)CF2OCH(CF3)2 copolymerization with
CH2¼CF2. A 75 ml stainless steel autoclave chilled to less
than À20 8C was loaded with 11.6 g of CH2¼C(CF3)CF2-
OCH(CF3)2 monomer, 10 ml of CF3CH2CF2CH3 solvent, and
10 mlofꢀ0.17 MDPinCF3CFHCFHCF2CF3. Theautoclave
was chilled, evacuated and further loaded with ꢀ2 g of VF2.
The autoclave was shaken overnight at room temperature.
The resulting hazy fluid was dried under nitrogen, then under
pump vacuum, and finally for 66 h in a 75 8C vacuum
oven, giving 12.9 g of white polymer. Fluorine NMR in
hexafluorobenzene found 53.4 mol% VF2 and 46.6 mol%
CH2¼C(CF3)CF2OCH(CF3)2. A small sample was purified
for DSC measurements by dissolving 0.5 g of polymer in 3 g
of H Galden ZT 85 solvent [HCF2O(CF2O)m(CF2CF2O)n-
CF2H], filtering the haze off using a 0.45 mm PTFE syringe
filter (Whatman AutovialTM), evaporating off excess solvent,
and drying in a 75 8C vacuum oven for 16 h.
CH2¼C(CF3)CF2OCF(CF3)2 copolymerization with
CH2¼CF2. A 110 ml stainless steel autoclave chilled to
less than À20 8C was loaded with 26 g of CH2¼C(CF3)-
CF2OCF(CF3)2 monomer, 25 ml of CF3CFHCFHCF2CF3
solvent, and 10 ml of ꢀ0.17 M DP in CF3CFHCFHCF2CF3.
The autoclave was chilled, evacuated and further loaded with
ꢀ5 g of VF2. The autoclave was shaken overnight at room
temperature. The resulting viscous fluid was dried under
nitrogen, then under pump vacuum, and finally for 88 h in
a 75 8C vacuum oven, giving 26.7 g of white polymer.
Solution preparation and spinning. A clear, colorless
solution was made by rolling 2 g of polymer with 18 g of
Solution preparation and spinning. A hazy solution was
made by rolling 2 g of polymer with 18 g of H GaldenTM ZT
85 solvent. The haze was removed by filtering first through a
bed of chromatographic silica in a 0.45 mm glass fiber
1 Patent pending.

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
71
microfiber syringe filter (Whatman AutovialTM), centri-
fuging at 15,000 rpm, and finally filtering again through
a 0.2 mm PTFE syringe filter (Gelman Acrodisc CR).
Evaporation of 0.1192 g of this solution on a glass slide
gave a clear film weighing 0.0085 g (solution ꢀ7 wt.% in
solids). Solutions of polymer 9 were spin coated in an
enclosed vapor can spinner at spin speeds of 800 rpm for
30 s, after an initial 10 s vapor equilibration period onto
CaF2 substrates with a subsequent post apply bake at 120 8C
alcohol. Drying for 6 days under pump vacuum gave 30 g of
white powder and lumps.
A solution was made by rolling 10 g of the polymer with
40 g of 2-heptanone and filtering through a 0.45 mm glass
microfiber syringe filter (Whatman, AutovialTM). The fil-
trate was used to spin coat thick films on optical substrate for
absorption measurements. Solutions of HFIB:VF were spin
coated onto CaF2 substrates to produce polymer films of
˚
9239 A thickness. VUV absorbance measurements were
˚
for 2 min to produce polymer films of 11,700 A thickness.
VUVabsorbance measurements were then used to determine
the absorbance per micrometer.
then used to determine the absorbance per micrometer.
The 157 nm absorbance per micrometer determined is
0.005 per micrometer. The 193 nm absorbance per micro-
meter determined is À0.00082 per micrometer. The 248 nm
absorbance per micrometer determined is À0.002 per micro-
meter.
Absorption results. The 157 nm absorbance per micro-
meter determined is 0.011 per micrometer. The 193 nm
absorbance per micrometer determined is À0.002 per
micrometer. The 248 nm absorbance per micrometer deter-
mined is À0.002 per micrometer.
2.2.2.2. Poly(hexafluoroisobutylene:trifluoroethylene) (12):
HFIB/TrFE. A 400 ml stainless steel autoclave chilled to
less than À20 8C was loaded with 10 ml of ꢀ0.17 M DP in
Vertrel1 XF. The autoclave was cooled, evacuated, and
further loaded with 50 g of trifluoroethylene and 100 g
of hexafluoroisobutylene. The reaction mixture was
shaken overnight at ambient, removed from the autoclave,
and evaporated down under nitrogen, then for 3 days under
pump vacuum, and finally for 22 h in a 75 8C vacuum oven.
There was obtained 10.5 g of white solid. A solution was
made by rolling 2 g of this polymer with 8 g of 2-heptanone.
This solution was passed first through a 0.45 mm glass
microfiber syringe filter (Whatman, AutovialTM) and then
through a 0.45 mm PTFE membrane syringe filter (Whatman,
AutovialTM). This solution was used to spin coat thick films
on optical substrate for absorption measurements.
2.2.1.10. Poly(vinylidene fluoride/2-(difluoromethylene)-
2,5,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane (10):
VF2/PMD. A 75 ml autoclave chilled to less than À20 8C
was loaded with 5 ml of ꢀ0.17 M DP in CF3CFHCFHCF2-
CF3, 15 ml of CF3CFHCFHCF2CF3, and 11.6 ml of per-
fluoro(2-methylene-4-methyl-1,3-dioxolane) (PMD). The
autoclave was pressured with 100 psi of nitrogen and eva-
cuated 10 times and then further loaded with 9.6 g of VF2.
Shaking overnight at room temperature gave white solid.
Evaporation under nitrogen, 16 h under pump vacuum, and
32 h in a 77 8C vacuum oven gave 23 g of resin.
Rolling 1 g of polymer with 19 g of hexafluorobenzene
gave partial solution that was passed through a ꢀ0.25 in.
deep pad of chromatographic silica in a 0.45 mm glass fiber
filter (Whatman, AutovialTM). A portion of this solution
was sent for 19F NMR which found the composition of
the dissolved polymer to be 54 mol% PMD and 46 mol%
VF2 suggesting that the insolubles were high in VF2
content. The remaining filtrate was used to spin coat thick
films on optical substrate for absorption measurements.
The 157 nm absorbance per micrometer determined is
0.085 per micrometer. The 193 nm absorbance per micro-
meter determined is 0.002 per micrometer. The 248 nm
absorbance per micrometer determined is 0.002 per micro-
meter.
Solutions of HFIB:TrFE were spin coated onto CaF2 sub-
˚
strates to produce polymer films of 12,146 and 1500 A
thicknesses, respectively. VUV absorbance measurements
were then used to determine the absorbance per micrometer.
The absorbance per micrometer determined from the
thicker polymer film is 0.012 per micrometer. The
193 nm absorbance per micrometer determined is 0.005
per micrometer. The 248 nm absorbance per micrometer
determined is À0.001 per micrometer.
2.2.2.3. Poly(hexafluoroisobutylene/vinyl alcohol) (13):
HFIB/VOH
2.2.2. Hexafluoroisobutylene copolymers
Hexafluoroisobutylene/vinyl acetate copolymer (HFIB/
VOAc). A 400 ml autoclave was loaded with 50 ml of
CF2ClCCl2F, 27 ml of vinyl acetate, and 50 ml of ꢀ0.1 M
DP in CF3CFHCFHCF2CF3. The autoclave was chilled,
evacuated, and further loaded with 49 g of HFIB. Shaking
overnight at room temperature gave a viscous pale yellow
solution. The polymer was precipitated by addition to
400 ml of methyl alcohol. Filtration, drying under pump
vacuum, and drying for 19 h in a 75 8C vacuum oven gave
52 g of poly(HFIB/VOAc) having an inherent viscosity of
0.13 in acetone at 25 8C.
2.2.2.1. Poly(hexafluoroisobutylene/vinyl fluoride) (11):
HFIB/VF. A 400 ml autoclave was loaded with 200 ml
water and 0.05 g of VazoTM 56 WSP initiator. The auto-
clave was cooled and evacuated and then 80 g of hexa-
fluoroisobutylene and 25 g of vinyl fluoride added. After
shaking for ꢀ48 h at 50 8C, the autoclave was vented, and
an opalescent blue emulsion recovered. The emulsion was
broken by vigorous agitationin a Waring blender, filtered, and
washedfourtimesintheWaringblenderwith100 mlofmethyl

72
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
Hexafluoroisobutylene/vinyl alcohol copolymer. Fifty
2.2.3.2. Poly(ethylene/hexafluoropropylene) (15): E/HFP.
A 400 ml stainless steel autoclave chilled to less than
À20 8C was loaded with 20 ml of ꢀ0.17 M DP in Vertrel1
XF.The autoclave was cooled, evacuated, and further loaded
with 150 g of perfluoromethylvinyl ether and 7 g of ethy-
lene. The reaction mixture was shaken overnight at ambient
temperature, removed from the autoclave, evaporated down
under nitrogen, then overnight under pump vacuum, and
finally for 6 days in a 75 8C vacuum oven. There was
obtained 8 g of thick grease.
grams of the poly(HFIB/VOAc) prepared above, 500 ml of
methyl alcohol, and 25 ml of 25 wt.% sodium methoxide in
methyl alcohol were refluxed for 6 h. Over this period, addi-
tional methyl alcohol was added as ꢀ860 ml of methyl
alcohol were distilled off. Addition of resulting polymer
solution to water gave a gummy precipitate. The water
was decanted off and the precipitate taken back into
200 ml of methyl alcohol and reprecipitated with 500 ml
of water in a Waring blender. Vacuum filtration, drying under
pump vacuum and then for 24 h in a 75 8C vacuum oven gave
37 g of poly(HFIB/VOH) as off white granules.
A solution was made by rolling 2 g of this polymer
with 18 g of H Galden ZT 85. This solution was passed
through a 0.45 mm glass microfiber syringe filter (Whatman,
AutovialTM). Solutions of E/HFP were spin coated onto
Solution preparation and spinning. A solution was made
by rolling 3.28 g of this polymer with 35 g of 1-methoxy-
2-propanol acetate. This solution was passed through a
˚
CaF2 substrates to produce polymer films of 9760 A
thicknesses. VUV absorbance measurements were then
used to determine the absorbance per micrometer. The
absorbance per micrometer determined for the film is
0.043 per micrometer. The 193 nm absorbance per micro-
meter determined is 0.031 per micrometer. The 248 nm
absorbance per micrometer determined is <0.01 per micro-
meter.
0.45 mm glass fiber syringe filter (Whatman, AutovialTM
)
giving a slightly hazy pale yellow solution. The solution was
treated with 0.4 g decolorizing carbon and filtered again
and then with 0.58 g of silica gel and filtered a third time.
The solution was still pale yellow but no longer hazy. The
filtrate used to spin coat thick films on optical substrate for
absorption measurements. Solutions of 1:1 HFIB:VA were
spin-coated onto CaF2 substrates to produce polymer films
2.2.4. Perfluorodimethyldioxole copolymers
˚
of 1350 A thickness.
2.2.4.1. Poly(ethylene/perfluorodimethyldioxole) (16): E/
PDD. A ꢀ210 ml stainless steel autoclave chilled to less
than À20 8C was loaded with 10 ml of ꢀ0.17 M DP in
Vertrel1 XF and 73.2 g of perfluorodimethyldioxole. The
autoclave was cooled, evacuated, and further loaded with
6 g of ethylene. The reaction mixture was shaken overnight
at ambient temperature, removed from the autoclave, and
evaporated down under nitrogen, then for 24 h under
pump vacuum, and finally for 31 h in a 72 8C vacuum
oven. There was obtained 59 g of white solid. A solution
was made by rolling 4 g of this polymer with 40 g of H
Galden ZT 85, centrifuging for 5 h at 14,000 rpm, and
filtering through a 0.2 mm PTFE syringe filter (Gelman
Aerodisc1 CR 26 mm). This solution was used to spin coat
thick films on optical substrate for absorption measure-
ments.
Absorption results. VUV absorbance measurements were
then used to determine the absorbance per micrometer. The
157 nm absorbance per micrometer determined is 0.350 per
micrometer. The 193 nm absorbance per micrometer deter-
mined is À0.047 per micrometer. The 248 nm absorbance
per micrometer determined is À0.107 per micrometer.
2.2.3. Ethylene copolymers
2.2.3.1. Poly(ethylene/perfluoropropylvinyl ether) (14):
E/PPVE. A 400 ml stainless steel autoclave chilled to
less than À20 8C was loaded with 10 ml of ꢀ0.17 M DP
in Vertrel1 XF. The autoclave was cooled, evacuated, and
further loaded with 133 g of perfluoromethylvinyl ether and
9 g of ethylene. The reaction mixture was shaken overnight
at ambient temperature, removed from the autoclave, eva-
porated down under nitrogen, then for 24 h under pump
vacuum, and finally for 31 h in a 72 8C vacuum oven. There
was obtained 63 g of white solid.
Solutions of HFIB:TrFE were spin coated onto CaF2
˚
substrates to produce a polymer film of 9900 A. VUV
absorbance measurements were then used to determine
the absorbance per micrometer.
A solution was made by rolling 2 g of this polymer
with 18 g of H Galden ZT 85. This solution was passed
through a 0.45 mm glass microfiber syringe filter (Whatman,
AutovialTM). Solutions of E/PPVE were spin coated onto
The absorbance per micrometer determined for the
film is 0.019 per micrometer. The 193 nm absorbance per
micrometer determined is 0.006 per micrometer. The
248 nm absorbance per micrometer determined is <0.01
per micrometer.
˚
CaF2 substrates to produce a polymer film of 23,000 A
thickness. VUV absorbance measurements were then used
to determine the absorbance per micrometer. The absor-
bance per micrometer determined from the film is 0.016
per micrometer. The 193 nm absorbance per micrometer
determined is 0.008 per micrometer. The 248 nm absorbance
per micrometer determined is <0.01 per micrometer.
2.2.4.2. Poly(perfluorodimethyldioxole/tetrafluoroethylene)
(17, 18 and 19): PDD/TFE Teflon1 AF. Solutions of Teflon1
AF 1200, 1601, and 2400 (12 wt.% in FC-40 solvent) were
spin coated at spin speeds of 6000 rpmonto CaF2 substrates to
˚
produce polymer films of 4066, 3323 and 2133 A thicknesses,

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
73
respectively. VUVabsorbance measurements were then used
to determine the absorbance per micrometer.
micrometer determined is 0.086 per micrometer. The
248 nm absorbance per micrometer determined is
0.073 per micrometer.
For Teflon1 AF 1200, the absorbance 157 nm
absorbance per micrometer determined is 0.64 per
micrometer. The 193 nm absorbance per micrometer
determined is 0.004 per micrometer. The 248 nm
absorbance per micrometer determined is À0.001 per
micrometer.
3. Results and discussion
3.1. Optical transparency at 157 nm
For Teflon1 AF 1601, the 157 nm absorbance per
micrometer determined is 0.42 per micrometer. The
193 nm absorbance per micrometer determined is
0.02 per micrometer. The 248 nm absorbance per
micrometer determined is 0.01 per micrometer.
For Teflon1 AF 2400, the 157 nm absorbance per
micrometer determined is 0.007 per micrometer.
The 193 nm absorbance per micrometer determined
is À0.06 per micrometer. The 248 nm absorbance
per micrometer determined is À0.06 per micrometer.
Through an extensive program of synthesis and optical
characterization of new hydrofluorocarbon polymers we
have established structural design principles to guide the
development of novel fluoropolymers with reduced optical
absorbance and therefore greater 157 nm transparency.
3.1.1. Absorbance of current polymeric materials
At the start of this work, the published literature offered
very little encouragement that 0.8 mm thick organic films
would even be able to show 98% transparency to 157 nm
light. For example, the optical absorbance of Teflon1 AF
and CytopTM is shown in Fig. 1. Teflon1 AF [14] was cited
earlier as an breakthrough lead for 157 nm resists because it
showed A=mm ¼ ꢀ0.5 [1]. An A/mm of 0.5 is ꢀ40Â too
absorbing for pellicles. CytopTM [5], another cyclic per-
fluoroether polymer, is still more absorbing at 157 nm with
an A=mm ¼ 1:9. Lest one think that the problem is the ether
2.2.5. Other polymers
2.2.5.1. Liquid cyclobutanes (20, 21 and 22). For 1,1,2,2-
tetrafluorocyclobutane (TFCB) (20), the absorbance 157 nm
absorbance per micrometer determined is >0.2 per micro-
meter. The 193 nm absorbance per micrometer determined
is 0.019 per micrometer. The 248 nm absorbance per
micrometer determined is 0.0003 per micrometer.
functionalities present in both Teflon1 AF and CytopTM
,
the purely perfluorocarbon polymer 1:1 poly(HFP:TFE)
[15] shows a markedly larger A/mm of 3.9. Perfluorinated
polymers are nonetheless better than purely hydrocarbon
polymers. For example, poly(acrylic acid), poly(styrene),
poly(methylmethacrylate), and poly(vinyl alcohol) all have
A/mm values falling between 4.5 and 11 [3].
For the propylene/hexafluoropropylene (P/HFP) cyclic
adduct mixture 21, the 157 nm absorbance per
micrometer determined is >0.2 per micrometer. The
193 nm absorbance per micrometer determined is 0.07
per micrometer. The 248 nm absorbance per micro-
meter determined is 0.002 per micrometer.
3.1.2. Absorbance of normal and perfluoro paraffins
Optical absorption data have been reported for short chain
paraffin hydrocarbons H(CH2)nH [16], for fluorocarbons
F(CF2)nF [17], and for oligomeric TFE [18]. As shown in
Fig. 2, these data demonstrate that the fundamental absorp-
tions moves to longer wavelengths with increasing chain
lengths such that 157 nm absorption may set in as early as
n ¼ 6–10 [17,18] for linear fluorocarbons and as early as
n ¼ 1–2 for linear hydrocarbons. The higher energy and
shorter wavelength of the fundamental fluorocarbon absorp-
tions mean that fluorocarbon chains are more resistant than
hydrocarbon chains to UV absorption and not surprisingly
the industry has been moving increasingly towards per-
fluorination when seeking high UV transmission. Yet, at
the same time, we see from this data that long (CH2)n or
(CF2)n chains may also, by their very nature, absorb at
157 nm, making transparent polymers seem at first glance
an unlikely proposition.
For hexafluoropropylene/hexafluoropropylene cyclic
adduct mixture (HFP2) (22), the 157 nm absorbance
per micrometer determined is 0.1 per micrometer.
The 193 nm absorbance per micrometer determined
is 0.0001 per micrometer. The 248 nm absorbance
per micrometer determined is 0.0003 per micrometer.
2.2.5.2. Poly(hexafluoropropylene/tetrafluoroethylene)
(23): HFP/TFE. HFP/TFE copolymer was prepared by the
method of [15].
Rolling 31.6 g of HFP/TFE copolymer with 986 g of
PF-5080 (performance fluid manufactured by 3 M,
believed to be largely perfluorooctanes) gave solution.
Vacuum filtration through a 0.45 mm filter gave clear
solution.
Solutions of 1:1 HFP:TFE were spin coated onto CaF2
˚
substrates to produce polymer films of 1850 A
thickness. VUV absorbance measurements were then
used to determine the absorbance per micrometer.
The 157 nm absorbance per micrometer determined is
3.9 per micrometer. The 193 nm absorbance per
3.1.3. Vinylidene fluoride copolymers
Four out of 10 pellicle candidates having ꢁ46 mol% of
VF2 (CF2¼CH2) gave highly transparent polymers having

74
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
Fig. 1. Optical absorbance in units of 1 per micrometer vs. wavelength for Teflon1 AF 1601 and CytopTM. At wavelengths below 150 and 157 nm, the
absorbance spectra show saturation due to the very low transmission of the samples at shorter wavelengths.
an A=mm < 0:01 at 157 nm. The optical absorbance spectra
for these polymers are shown in Fig. 3 and the absorbances
and VF2 contents are summarized in Table 2. The one VF2
polymer here showing a major absorption at 157 nm con-
tained chlorine, a likely chromophore, that had been intro-
duced by a comonomer.
absorbances and HFIB contents are summarized in Table 3.
Two out of three candidates containing ꢀ50 mol% of hexa-
fluoroisobutylene [(CF3)2C¼CH2] gave highly transparent
polymers having A=mm < 0:01 at 157 nm. The one HFIB
copolymer showing significant absorption was copolymer-
ized with a monomer containing –OH, a likely chromophore.
Even with the –OH chromophore, the HFIB/vinyl alcohol
copolymer is ꢀ10,000Â less absorbing (A=mm ¼ 0:3) than
the wholly hydrocarbon analog polyvinylalcohol (A=mm ¼
ꢀ4.5 [3]).
3.1.4. Hexafluoroisobutylene copolymers
Hexafluoroisobutylene copolymers present a similar pic-
ture. Optical absorbances are presented in Figs. 4 and 5 the
3.1.5. Intrinsically alternating monomers: CX2¼CY2
VF2 (CF2¼CH2) and HFIB [(CF3)2C¼CH2] have one
structural feature in common. Both can be structurally
classified as CX2¼CY2 monomers that force a regular alter-
nation between fluorinated and hydrocarbon chain segments.
That is, even though long (CF2)n and (CH2)n sequences are
absorbing [2–4] as discussed in [1], regularly alternating
sequences such as [(CH2)1(CF2)1]n are not. Perhaps the
photochemically excited states involve conjugated sigma
bonds and it is easier to mix together bonds of equal energies
(all C–F bonds or all C–H bonds) than bonds of different
energy (C–H with C–F bonds). This localization of the
electrons in the polymer backbone in different CH2 or CF2
bonds serves to raise the transition energy for the excitation
and thereby shift the fundamental absorption to shorter
wavelengths. In any event, the empirical observation is
that the fundamental absorption edge shifts to higher
energy and shorter wavelengths and the 157 nm transparency
Fig. 2. Literature values [16–18] for the wavelength of the absorbance
peak for the weak first absorption shoulder (a, dashed line) and the first
strong absorbance peak (b, solid symbols) about the fundamental
absorption edge in normal [CnH2nþ2] and perfluoro [CnF2nþ2] paraffins
showing the shift of the absorption to longer wavelengths with increasing
chain length for chain lengths from 1 to 8.

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
75
Fig. 3. Optical absorbance in units of 1 per micrometer vs. wavelength for VF2 copolymers. The effects of saturation of the transmission measurement can be
seen as a plateau at higher absorbance values and shorter wavelengths due to the low transmission of the samples at these wavelengths.
often increases as the number of identical adjacent bonds is
minimized.
family of copolymers between PDD and TFE. Increasing
TFE content increases the (CF2CF2)n run length with a
noticeable increase in 157 nm absorption. Published run
lengths [14] are shown in Table 5 and the optical absor-
bances are shown Fig. 6.
3.1.6. Effect of run lengths on transparency:
ethylene and TFE copolymers
Given that forced alternation as in [(CH2)1(CF2)1]n favors
high transparency, it is reasonable to ask the extent to which
run lengths x and y in [(CH2)x(CF2)y]n can be increased
without damagingtransparency. Table 4 andFig. 5show A/mm
results for three ethylene copolymers. All three copolymers
have high transparencies and approximate a [(CH2)x(CF2)y]n
structure for which x ¼ y ¼ 2.
Only Teflon1 AF 2400 with few (CF2CF2)n runs longer
than n ¼ 3 gave a low absorbing polymer. This is consistent
with the earlier observation that fluoroalkanes F(CF2)nF may
remain transparent up to about only 6–10 carbons atoms
[17,18].
Apparently PDD interferes with the absorptive effect of
long runs of adjacent (CF2)n groups. Looking at the structure
of PDD it can be seen that the PDD monomer unit adds two
adjacent C–F bonds to a polymer chain as shown in Fig. 7.
Transparencies for [(CH2)x(CF2)y]n when x > 2 and y > 2
can be probed only indirectly. For example, Teflon1 AF is a
Table 2
Absorbance at 157 nm for vinylidene fluoride (VF2) copolymers listed in approximate order of decreasing VF2 content
Compound no.
Monomer copolymerized with (CF2¼CH2): VF2
VF2 (%)
A=mm
1
2
CF2¼CFCF3: HFP
79
60
60
56
55
58
52
52
47
46
<0.01
<0.01
<0.01
0.02
2,2-bis(Trifluoromethyl)-4,5-difluoro-1,3-dioxole: PDD
CF2¼CHOCF2CF2H: TEDVE
3
4
CF2¼CFOCF3: PMVE
5
CF2¼CFCl: CTFE
5.9
6
CF2¼CFOCF2CF2CF2: PPVE
0.028
0.35
7
CF2¼CHOC2F5: PEDVE
8
CH2¼C(CF3)CF2OCF(CF3)2: DHB
CH2¼C(CF3)CF2OCH(CF3)2: THB
2-(Difluoromethylene)-2,5,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane: PMD
0.026
<0.01
0.085
9
10

76
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
Fig. 4. Optical absorbance in units of 1 per micrometer vs. wavelength for HFIB copolymers. The effects of saturation of the transmission measurement can
be seen as a plateau at higher absorbance values and shorter wavelengths due to the low transmission of the samples at these wavelengths.
Fig. 5. Optical absorbance in units of 1 per micrometer vs. wavelength for ethylene copolymers.

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
77
Table 3
Absorbance at 157 nm for hexafluoroisobutylene (HFIB) copolymers
Table 4
Absorbance at 157 nm for ethylene (E) copolymers
Compound no.
Monomer copolymerized
HFIB (%)
A=mm
Compound
no.
Perfluorinated monomer
E (%)
A=mm
with HFIB, (CF3)2C¼CH2
copolymerized with ethylene
11
12
13
CH2¼CHF: VF
50
54
50
<0.01
<0.01
0.3
14
15
16
CF2¼CFOCF2CF2CF3: PPVE
CF2¼CFCF3: HFP
52
57
<0.01
0.043
0.021,
CF2¼CFH: TrFE
CH2¼CH(OH): VOH
2,2-bis(Trifluoromethyl)-4,
5-difluoro-1,3-dioxole: PDD
<0.022 [20]
In a chain that alternates PDD with TFE as in Teflon1 AF,
this makes for an uninterrupted sequence of C–F bonds
down the chain, something we have just argued is bad for
absorption. Nonetheless, Teflon1 AF 2400 is highly trans-
parent. Teflon1 AF 2400 has a stiff and sterically congested
chain as evidenced by its high glass transition temperature
(240 8C) [19]. We speculate that the absorption of adjacent
C–F bonds is highly dependent upon rotational angle and
that the PDD monomer forces conformations unfavorable
for 157 nm absorption.
3.1.7. Beyond alternation: rotational effects on absorbance
Data for simple fluorocarbon fluids can be interpre-
ted as supporting a rotational dependence for absorption.
Table 5
Absorbance at 157 nm vs. TFE run length in Teflon1 AF
Compound no.
Teflon1 AF grade
TFE in polymer (mol%)
(CF2CF2)n runs having n value shown (%) [7]
A=mm
n ¼ 3
n ¼ 4
n ¼ 5
17
18
19
1200
1600
2400
ꢀ52
ꢀ35
ꢀ11
ꢀ18
ꢀ15
ꢀ5
ꢀ14
ꢀ10
ꢀ0
ꢀ10
ꢀ5
0.64
0.42
ꢀ0
<0.01
Fig. 6. Optical absorbance in units of 1 per micrometer vs. wavelength for Teflon1 AF TFE:PDD copolymers as a function of composition. The effects of
saturation of the transmission measurement can be seen as a plateau at higher absorbance values and shorter wavelengths due to the low transmission of the
samples at these wavelengths.

78
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
Table 6
The 157 nm absorbances of cyclobutanes
Compound no.Compound
A=mm
20
21
1,1,2,2-Tetrafluorocyclobutane [21]: TFCB
>0.2
>0.2
Propylene/hexafluoropropylene cyclic
adduct mixture [22]: P/HFP
22
Hexafluoropropylene/hexafluoropropylene
cyclic adduct mixture [21]: HFP2
0.1
Fig. 7. Comparison of PDD monomer and Teflon1 AF.
The cyclobutanes of Table 6 are much more strongly absorb-
ing as shown in Fig. 8, than would have been predicted from
the ethylene copolymers of Table 4 or sequence length
effects of Table 5. Possibly this is because the four-mem-
bered rings force eclipsed conformations that are favorable
for 157 nm absorption. Other factors may be as important
or more important. Cyclobutane rings may, for example,
change s and p orbital hybridization around the chain
carbons atoms and thereby absorption.
Unacceptable optical changes include a 10% loss in overall
transparency, warping, or, in extreme instances, perforation.
Viewed as a cumulative energy dose, 7.5 kJ/cm2 is equiva-
lent to several days of Florida sunlight which does not sound
very impressive. Focusing instead on individual photon
energy, 157 nm light has an energy of 182 kcal/mole, an
energy roughly twice that of C–C, C–H, and C–F bond
strengths. Hitting a 1 mm thick film of poly(TFE) with a
cumulative dose of 7.5 kJ/cm2 of 157 nm light would expose
each C–C and C–F bond in the polymer to an average of 740
photons. Even were the poly(TFE) film 98% transparent,
each bond in the polymer would still absorb 15 photons. Not
surprisingly, none of our pellicle candidates have shown a
lifetime anywhere near 7.5 kJ/cm2.
3.2. 157 nm lifetime and photochemical degradation
Many of the hydrofluorocarbon polymers in Tables 2–4
meetthetransparencyspecification(A=mm < 0:01at157 nm)
for pellicles. A second critical requirement for pellicle can-
didates is that they experience little change in optical char-
acteristics after 75 million exposures to 157 nm light, each
exposure having an incident energy of 0.1 mJ/cm2 (Fig. 9).
When a pellicle candidate is irradiated with 157 nm light,
there is first a loss of transparency which at much higher
doses is sometimes accompanied by slight visible discolora-
tion. Our primary screen for pellicle lifetime has thus been to
Fig. 8. Optical absorbance in units of 1 per micrometer vs. wavelength for three cyclobutane compounds. The effects of saturation of the transmission
measurement can be seen as a plateau at higher absorbance values and shorter wavelengths due to the low transmission of the samples at these wavelengths.

R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
79
Fig. 9. Induced absorbance of TAFx46P and TAFx4P polymers on CaF2.
measure the exposure in J/cm2 needed to produce a 10% loss
in transparency at 157 nm. Results [7] for some of the
polymers discussed here are shown in Fig. 9 and summar-
ized in Table 7. The best of our pellicle candidates lose 10%
of their transparency after a dose of only 2–6 J/cm2 versus
the industry goal of 7.5 kJ/cm2.
To a first approximation, the polymers that have lower
157 nm optical absorbance also tend to show the longest
lifetimes. But there is the occasional exception as for
example polymer 8 (VF2/DHB) which has a relatively high
A/mm of 0.026 and yet one of the longest lifetimes observed
(6 J/cm2). It is interesting to compare the 10% PCD lifetime
and optical absorbance of VF2/DHB, to that of VF2/THB.
There is only one atom difference between the DHB and
THB monomers, and this change leads to apparently better
alternation in the THB monomer. The optical absorbance of
the VF2/THB polymer is substantially smaller than that of
VF2/DHB as shown in Table 2, yet the lifetime of VF2/THB
is not increased due to this lower optical absorbance.
Instead, VF2/THB has a substantially reduced lifetime when
compared to VF2/DHB. These results imply that quantum
yield, or the extent to which the polymer structure can
harmlessly dissipate the energy, can be important as well.
To make further progress, a better understanding is needed
of what are the chromophores, how the energy is dissipated,
what bonds are broken, and what if any role adventitious
impurities or structural irregularities play.
4. Conclusions
For application as pellicles for 157 nm photolithography,
membrane forming polymers with low optical absorbance
and high radiation durability are required. It has been
found that polymers such as –[(CH2CHF)xC(CF3)2CH2]y–,
or –(CH2CF2)x[2,2-bis(trifluoromethyl)-4,5-difluoro-1,
3-dioxole]y– with chains that alternate fluorocarbon seg-
ments with either oxygen or hydrocarbon segments fre-
quently show >98% transparency at 157 nm, if amorphous.
These polymers are made from monomers, such as VF2
and hexafluoroisobutylene, which themselves exhibit good
alternation of CH2 and CF2 in their structures. Ether linkages
also can serve to force alternation. In addition we find that
fluorocarbon segments shorter than six carbons, and hydro-
carbon segments less than two carbons or less than three
carbons if partially fluorinated, also promote 157 nm trans-
parency. Even with these design principles, it is advanta-
geous to avoid small rings, as arise in the cyclobutanes.
These results suggest a steric component to transparency in
addition to the importance of alternation.
Table 7
10% PCD lifetime: exposure dose required to reduce 157 nm transparency
of a 0.8 mm thick membrane by 10%
Compound Polymer
no.
Dose
(mJ/cm2)
1
2
Poly(vinylidene fluoride/hexafluoropropylene): 4.8
VF2/HFP
Poly(vinylidene fluoride/
perfluorodimethyldioxole): VF2/PDD
Poly(CH2¼CF2/CF2¼CHOCF2CF3):
VF2/PEDVE
3.3
2.0
3
8
Poly[CH2¼CF2/(CH2¼C(CF3)CF2OCF(CF3)2]: 5.2
VF2/DHB
Poly[CH2¼CF2/(CH2¼C(CF3)CF2OCH(CF3)2]: 1.8
9
VF2/THB
10
Poly(hexafluoroisobutylene/vinyl fluoride):
HFIB/VF
3.5

80
R.H. French et al. / Journal of Fluorine Chemistry 122 (2003) 63–80
Microlithography XV, Anthony Yen (Ed.), SPIE 57 (2002) 4691,
However, upon irradiation these polymers undergo photo-
576–583.
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the kilojoule radiation durability lifetimes required to be
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each photon having an energy roughly twice common bond
energies.
To a first approximation, the polymers that have lower
157 nm optical absorbance also tend to show the longest
lifetimes. These results imply that quantum yield, or the
extent to which the polymer structure can harmlessly dis-
sipate the energy, can be important as well.
[7] V. Liberman, M. Rothschild, J.H.C. Sedlacek, A. Grenville, R.H.
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