JP2003514956A - Ultraviolet and vacuum ultraviolet permeable polymer compositions and their use - Google Patents

Abstract

  (57) [Summary] Disclosed are partially fluorinated and fully fluorinated polymers that are substantially transparent to ultraviolet radiation at wavelengths between 140 and 186 nanometers.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to partially fluorinated and fully fluorinated polymers that are substantially transparent to ultraviolet radiation at wavelengths of about 140 nanometers to 186 nanometers.

BACKGROUND OF THE INVENTION The semiconductor industry is the foundation of the $ 1 trillion electronics industry. In the semiconductor industry, Mo is constantly
The density of integrated circuits is doubling every 18 months in an attempt to satisfy the requirements of ore's law, most of which is due to optical lithographic printing.
There is a constant need for improvements in the ability to reduce the features when printing features on silicon in a graph. The circuit pattern is included in the photomask and the optical stepper (s)
The pattern of the mask is projected onto the photoresist layer on the silicon wafer using a stepper). Present lithographic printing is done using 248 nm light,
Lithographic printing using 3 nm light is just in the early stages of production. Alternatives to lithographic printing using neither visible light nor UV light, i.e. the next generation of lithographic printing using X-rays, e-beams or EUV radiation, are not ripe enough for production. The industry has concluded through the International Association of SEMATECH that lithographic printing based on 157 nm light will be the next technological step. 157 nm is located in the spectral region called vacuum ultraviolet (VUV) and this range extends from 186 nm to less than 50 nm. When using such VUV lithographic printing, it is necessary to use a material that is transparent in such a range. Specifically, the standardization of new lithographic printing using light at 157 nm results in the need for new polymeric materials based on the transmission requirements at 157 nm. With the ongoing use of new technologies, there is a continuing need for improved materials useful at shorter wavelengths.

Certain fluoropolymers have already been identified as useful in optical applications such as light guides, antireflective coatings and layers, skins and glues, and the like. Most of this work has been done at wavelengths above 200 nm, and there is little interest in the absorbance of perfluoropolymers at such wavelengths.

WO 9836324 (August 20, 1998, Mitsui Chemical)
al Inc. ), A resin consisting of only C and F, optionally in combination with a silicon polymer having a siloxane backbone, from 140 to 200 nm.
It is disclosed to be used as a thin film having an absorbance / micrometer of 0.1 to 1.0 at the ultraviolet wavelength of. In addition to the data presented in this document, measurements made by the applicant on fluoropolymers (see Table I below) show that the absorbances of the C and F fluoropolymers at least at 157 nm are WO 98363
It is shown to be much larger than A / μ = 0.1-1 as claimed in 24.

WO 9822851 (May 28, 1998, Mitsui Chemical)
al Inc. ) Claims the use of a tacky photo-degradable polymer which, when coated on the inside of a pellicle frame, fixes the particles of dust. The composition of such a pressure-sensitive adhesive material predominantly low molecular weight - (CF ₂ -CXR
) It consists of a copolymer, wherein, X is halogen and R is -Cl or -CF _3. For the purpose of improving creep resistance, a polymer having a higher molecular weight such as poly (perfluorobutenyl vinyl ether), poly [(tetrafluoroethylene / perfluoro- (
2,2-Dimethyl-1,3-dioxole)], poly (tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride), poly (hexafluoropropylene / vinylidene fluoride) or poly (chlorotolylfluoroethylene / vinylidene fluoride) ) Is added as a small component. Examples of such techniques have all been made using poly (chlorotrifluoroethylene) as a low molecular weight adhesive, poly (chlorotrifluoroethylene) strongly absorbing and claiming light at 157 nm. The advantage shown as a benefit of the formulation is the tackiness after long-term exposure to UV degradation (UV degradation shown is only at 248 nm).
It should be noted that it is only a retention (not permeable).

Japanese Patent 07295207 (November 10, 1995, Shinetsu C
hem. Ind Co. ) For the purpose of increasing the strength of Cytop (trademark) CT
XS (poly (CF ₂ ═CFOCF ₂ CF ₂ CF═CF ₂ )) was added to Teflon ™.
A bilayer skin in combination with AF 1600 is claimed. Both Teflon ™ AF 1600 and Cytop ™ exhibit strong absorption at 157 nm (see Table 2).

US Pat. No. 5,286,567 (February 15, 1994, Shin-Etsu)
Chemical Co. , Ltd. ), A copolymer made of tetrafluoroethylene and a 5-membered cyclic perfluoroether monomer, which is made hydrophilic by plasma treatment and thus has antistatic properties, is used as a thin skin. Is being billed. The presence of 5-membered ring monomer and tetrafluoroethylene is not always A / μ.
It is shown in Table 2 that the criteria are not sufficient to yield <0.1, and of the five such polymers shown in Table 2, only one polymer satisfies the above goal. Only.

European Patent No. 416528 [March 13, 1991, DuPont (DuP
ont)] has a refractive index of 1.24-1.41 at a wavelength of 190-820 nm.
It is claimed to use the amorphous fluoropolymers of the above as a skin.

Japanese Patent 01241557 (Bando Chemical Industr
ies, Ltd. , September 26, 1989), vinylidene fluoride (VF ₂ )
, Tetrafluoroethylene / hexafluoropropylene (TFE / HFP), ethylene / tetrafluoroethylene (E / TFE), TFE / CF ₂ = CFORf
, TFE / HFP / CF ₂ = CFORf, chlorotrifluoroethylene (CTF
E), E / CTFE, CTFE / VF 2 and made from vinyl fluoride (VF) (co) polymers have been used can be used at the 280-360nm thin skin is claimed.

Japanese Patent 59048766 (March 21, 1984, Mitsui Toat
su Chemicals, Inc. ), It is claimed that a stretched film of poly (vinylidene fluoride) is used as a film having a good transmittance at 200 to 400 nm.

Many of the fluoropolymers cited in the references cited above are fairly cloudy to the eye, because they are crystalline and therefore have high light transmission and circuit patterning. This is because it seems to scatter light to a degree that is not desirable for accurate reproduction. Poly (vinylidene fluoride), Poly (chlorotrifluoroethylene)
, Poly (tetrafluoroethylene / ethylene), commercial poly (tetrafluoroethylene / hexafluoropropylene) compositions and poly (ethylene / chlorotrifluoroethylene) all exhibit such crystallinity and are optically hazy materials. Is. Therefore, more recent references include Cytop (TM) and Teflon (TM) A.
In the direction of F, it is because they are completely fluorine-substituted, combined with excellent optical clarity, solubility and no crystallinity. Because it is. However, as shown in the discussion below, Cytop ™ and Teflon ™
Most grades of AF do not show the required transmission at 157 nm.

It is an object of the present invention by providing partially fluorinated and fully fluorinated polymers which are substantially transparent to UV radiation in the wavelength range from 140 to 186 nanometers, especially 157 nanometers. Overcoming the challenges associated with technology.

[0013]     (Summary of Invention)   The present invention provides the absorbance / micron shown at wavelengths of 140 to 186 nanometers.
Vacuum ultraviolet (VUV) transparency (transpar) of (A / micrometer) ≦ 1
ent) material, which is a perfluoro-2,2-dimme
Chill-1,3-dioxole or CX₂= CY₂[Where X = -F or -C
F₃And Y = -H] amorphous vinyl homopolymer or perfluoro-2,2-
Dimethyl-1,3-dioxole and CX₂= CY₂Containing amorphous vinyl copolymer
And, in some cases, one or more monomers CR in the homopolymer or copolymer.^a
R^b= CR^cR^d{Where each R^a, R^bAnd R^cAre each independently H or F
Selected, and R^dIs -F, -CF₃, -OR_f[Where R_fIs C_nF_{2n + 1}
(Where n = 1 to 3)] and -OH (R^c= H))
May be contained in an amount of 0 to 25 mol%.^a
R^b= CR^cR^dAre almost random (ran) in the homopolymer or copolymer.
dom) mode and optionally one or more monomeric CRs^aR^b= CR ^c R^dMay be contained in an amount of 40 to 60 mol%.^aR^b= CR ^c R^dEnter the copolymer in an approximately alternating fashion.

[0014]   The present invention also provides the absorbance / micron (A) at wavelengths of 140-186 nm.
We also provide vacuum ultraviolet (VUV) transmissive materials with a / micrometer of ≤ 1 and this material
Is CH₂= CHCF₃And CF₂= CF₂; CH₂= CFH and CF₂= CFCl; CH ₂ = CHF and CClH = CF₂[The ratio of the monomers in this case is about 1: 2 to about 2: 1.
In the range]; perfluoro (2-methylene-4-methyl-1,3-dioxo
Orchid) and perfluoro (2,2-dimethyl-1,3-dioxole); amorphous group
Perfluoro (2-methylene-4-methyl-1,3-di
Oxolane) and vinylidene fluoride; and an amorphous vinyl copolymer;
Homopolymerization of perfluoro (2-methylene-4-methyl-1,3-dioxolane)
Comprising the body.

The present invention further comprises a thin skin comprising the ultraviolet (UV) transparent material shown above,
Anti-reflective coatings, light transmissive glues, light guides and resists are also provided.

The present invention further provides a copolymer composition comprising 40-60 mol% hexafluoroisobutylene and 60-40 mol% trifluoroethylene poly (hexafluoroisobutylene: trifluoroethylene) and a hexamer. Also provided is a copolymer composition comprising 40-60 mol% fluoroisobutylene and 60-40 mol% vinyl fluoride poly (hexafluoroisobutylene: vinyl fluoride).

DETAILED DESCRIPTION OF THE INVENTION The present invention provides fluoropolymer compositions and their use in particular electronic applications.

Specific abbreviations used throughout this specification are: TFE tetrafluoroethylene HFP hexafluoropropylene VF vinyl fluoride CTFE chlorotrifluoroethylene VF vinylidene fluoride HFIB hexafluoroisobutylene TrFE trifluoroethylene. PDD 4,5-difluoro-2,2-bis (trifluoromethyl) -1,
3-Dioxole PMD Perfluoro (2-methylene-4-methyl-1,3-dioxolane) Teflon (TM) AF 2400 PDD: TFE 89:11 Teflon (TM) AF 1601 PDD: TFE 68:32 Teflon (TM). ) AF 1200 PDD: TFE 48:52 ClDFE 1-chloro-2,2-difluoroethylene PPVE perfluoro (propyl vinyl ether) PMVE perfluoro (methyl vinyl ether) VOAc vinyl acetate VOH vinyl alcohol TrP 3,3,3-trifluoro Propen Fluorinert ™ FC-75 3M is manufactured by Fluorinert ™ FC-40 3M, an electronics fluid believed to be nearly perfluoro (butyltetrahydrofuran) manufactured by 3M. 2,2'-bis (2-amidino-propane) dihydrochloride, an initiator manufactured by Vazo ™ 56 WSP DuPont, which is believed to be nearly perfluoro (tributylamine) DSC Differential Scanning Calorimeter The use of 157 nm light in the next generation of lithographic printing creates new photochemical problems that lithographic printing did not encounter at longer wavelengths. The energy of a 157 nm photon (a light amount of 182 kcal / mol or 7.9 eV) is
Ordinary chemical bonds such as C-F (108-116 kcal / mol), C-H (9
8-105 kcal / mol), C-C (88-97 kcal / mol) and C-
It is large enough to break Cl (82-86 kcal / mol) bonds and the like. The maximum absorbance values of selected hydrocarbons and fluorocarbon compounds are shown in Table 1.

[0019]

[Table 1]

¹ B. A. Lombos, P .; Sauvageau and C.I. Sandorfy
Chem. Phys. Lett. , 1967, 42. ² K. Seki, H .; Tanaka, T .; Ohta, Y. Aoki, A.A. Ima
mura, H .; Fujimoto, H.M. Yamamoto, H.M. Inokuch
i, Phys. Scripta, 41, 167 (1990).

As can be seen from the above table, the maximum UV absorbance shifts to the longer wavelength side as the chain length increases for both hydrocarbons and fluorocarbons. The fluorocarbon chain (CF ₂ ) _n absorbs near 157 nm in the range of n = 6 (142 nm) to n = 172 (161 nm), but the hydrocarbon chain (CH ₂ ) _n has n = 2 as early as possible.
Shows absorption at 157 nm. In addition, the resistance of fluorocarbon chains to UV absorption is clearly higher than that of hydrocarbon chains, so when the industry seeks high UV transparency, the degree to which it shifts towards complete fluorine substitution is high. It is not surprising that the is getting bigger. However, unless the chain length exceeds the length of (CH ₂ ) ₁ or (CF ₂ ) ₆ to obtain satisfactory transmission, a polymer that is completely transparent at 157 nm. It seems impossible to get. Consistent with this, for example, V. N. Vasilets et al., J. Pol
y. Sci, Part A, Poly. Chem. , 36, 2215 (1998), poly (tetrafluoroethylene / hexafluoropropylene), ie [poly (TFE / HFP)] [Teflon ™ AF FEP], showed a strong absorption at 147 nm and was photochemical. It has been reported to deteriorate. Similarly, we have found that poly (hexafluoropropylene: tetrafluoroethylene (1: 1)) is 1
It was confirmed that it showed a high absorption at 57 nm (Table 2, A / micron = 3.6 @
157 nm).

In lithographic printing, the polymer plays an important role in several areas: one role is to play with any granularity in the photomask object plane to ensure that the lithographic image is defect-free. The polymer thin film is masked with a mask pattern (mask pattern) for the purpose of preventing contamination.
It is the role said to put it on rn). The skin is a free standing polymer membrane, typically 0.8 microns thick, which is typically mounted in a 5 inch square frame. Such thin coatings provide a lithographic wavelength for efficient imaging.
) Is highly transmissive to light (transparency or transmi
ssion) and should not darken or burst even after prolonged exposure in the optical stepper. In the current lithographic printing wavelength skins, the use of skins having a transmittance of> 99% by developing a polymer exhibiting a very low absorptivity and a thin film interference effect. 157 nm photolithographic printing (photo
The SEMATECH target for thin skin used in Lithography is 0.1
75 million laser pulses of mJ / cm ² , i.e. a radiation dose of 157 nm light of 7.
The transmittance is 9 over the exposure life of 5 kJ.
More than 8%.

The thin skin having a transmittance of 98% corresponds to an absorbance A of about 0.01 per 1 μm of film thickness. This absorbance is defined by Equation 1, and in this Equation 1,
Base 10 logarithm of the absorbance A per micron of film thickness divided by the transmittance of the substrate divided by the transmittance of the polymer membrane sample placed on this substrate. Is defined as the amount divided by the polymer film thickness. Formula 1

[0024]

[Equation 1]

In this manner, the absorbance A is expressed in units of reciprocal microns (ie 1 / micron),
Here, 1 micron of the polymer film thickness is 1 micrometer or 1 um. For the determination of the absorbance / micron of polymer membranes discussed here, the CaF ₂
The measurements were performed on a polymer film that was spin coated on the substrate. The VUV transmittance of each CaF ₂ substrate was measured before spin coating of the polymer film. Next, the VUV transmission exhibited by the polymer film as placed on its individual CaF ₂ substrate was measured and, using the measured film thickness (reported in Table 2) and Equation 1, Absorbance /
The micron value was determined as a function of wavelength, and the absorbance / micron value at the wavelength of 157 nm is shown in Table 2. For some materials, two types of films with different thicknesses are shown in Table 2 and also the absorbance / micron values given by each film.

Laser plasma light source, sample chamber with the ability to perform both transmission and reflectance measurements, 1 meter monochromator and 1024 element photodiode covered with sodium salicylate phosphor A VUV spectrophotometer using an (element photodiode) detector was used to measure the VUV transmittance of the CaF ₂ substrate and the polymer film on the CaF ₂ substrate. This is R. H. Fre
nch, “Laser-Plasma Sourced, Temperatur
e Dependent VUV Spectrophotometer Us
ing Dispersive Analysis ", Physica Scr
ipta, 41, 4, 404-8, (1990), which is incorporated herein by reference, and is discussed in more detail.

The absorbance per micron of polymer is used to measure the average transmission exhibited by unsupported thin films made from the polymer. In FIG. 1, the transmittance T (expressed in%) of the polymer skin at 157 nm as a function of the absorbance at 157 nm (expressed in reciprocal microns) is calculated from 0.4 to 0.0. Shown over the absorbance range. In this calculation, the effect of thin film interference exhibited by the thin film is ignored. Shows the results for thin coatings with thicknesses in the range 0.2 microns to 1 micron,
This result shows that the transmittance of the thin skin can be increased by reducing the thickness of the thin film regardless of the specific polymer used. In this way, the approach of increasing the transmittance of the thin skin is limited in its application range because the thin film is a non-supporting polymer film and it is necessary to have sufficient mechanical strength and integrity. Was done. Such mechanical requirements suggest that polymers with relatively high glass transition temperatures T _g should be used to achieve polymer film thicknesses of 0.6 microns and above. The target absorbance / micron is 157n when a polymer is used for thin skin applications.
It can be seen from Figure 1 that the absorbance at m / micron is <0.02.

FIG. 2 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 1601 and Cytop ™ compared to the wavelength lambda (λ) (expressed in nanometers). . The absorbance / micron shown at Cytop at 157 nanometers is a value of 1.9 / micron, while Teflon ™
The absorbance exhibited by AF 1601 is 0.42 / micron, which is Cy.
About 5 times lower than that of top. We have found that even though Teflon ™ AF 1601 has an absorbance of 0.42 / micron at 157 nm, this degree of absorbance is too high to use it as a skin used at 157 nm. This is shown in Example 1.

Variable angle spectroscopic ellipsometry (VASE) 1
Used at three angles of incidence covering the 86-800 nm wavelength range (which corresponds to a range of energies of 1.5-6.65 eV), this was used for a single angle of incidence of 143-275 nm (which is 4. VU carried out in the energy range of 5-8.67 eV)
Optical characteristics (refractive index “n” and extinction coefficient “k”) were measured in combination with V ellipsometry (VUV-VASE) measurement. The polymer film was spin coated on a silicon substrate. VASE Ellipsometer
rs) is from J. A. Woollam Company (645 M Street
, Suite 102, Lincoln, NE 68508 USA). Optical model in which the film is located on the substrate
At the same time using the optical constants (optical constants)
Adapted. Generally, O. S. Heavens, Optical Pro
parts of Thin Solid Films, pp. 55-62, D
over, NY, 1991 (incorporated herein by reference).
checking ...

Since it is known that the optical characteristics depend on the spectrum, it is necessary to calculate the transmittance of a thin film having an arbitrary thickness by using an unsupported thin film optical model in which the thickness of the polymer film is specified. And then the transmittance and reflectance of the thin film can be calculated. In this way, the thickness of the thin coating can be optimized so that the thin skin maximizes thin film interference in the transmission spectrum exhibited at the desired lithographic printing wavelength. Such transmission maximums exist for various film thicknesses, which are determined by the index of refraction of the polymer, the lithographic wavelength of interest, and the film thickness. When the reflectance of a properly adjusted etalon thin film shows a minimum value with respect to the reflectance, the transmittance of the thin film becomes maximum, which is the reflectance that the thin film shows at the lithographic printing wavelength. Corresponds to the minimum and the maximum transmittance. Extinction coefficient k in equation 2
And the extinction coefficient α and the absorbance A per micron, where lambda is the wavelength of light. This relationship is useful when comparing the results of absorbance measurements and ellipsometry measurements. The above relationship for A is accurate if the light scattering that occurs within the polymer film (as may occur due to the crystallinity of the polymer), thin film interference effects and surface scattering effects is minimal. Formula 2

[0031]

[Equation 2]

Polymeric materials with very low absorbance / micron or extinction coefficient and low refractive index values also provide anti-reflective coatings and optical adhesives.
It also has a very important application as s). Materials with low absorbance can be used for the purpose of reducing the amount of light reflected from the surface of the transparent substrate, which has a relatively high refractive index, as taught herein. This reduction in the amount of light reflected is accompanied by an increase in the amount of light transmitted through the transparent substrate material. VF ₂ : PDD, VF ₂ : H shows that such a material with low absorbance / micron exhibits an antireflection coating effect.
The results can be seen in the case of FP, HFIB: TrFE and HFIB: VF, where the absorbance of the polymer on the CaF ₂ substrate shows a negative absorbance / micron when the film is very thin. . This corresponds to a higher light transmittance at 157 nm through the polymer film on the CaF ₂ substrate than at a bare CaF ₂ substrate. The thickness of the polymer film as measured by us for VF ₂ : HFP, HFIB: TrFE and HFIB: VF was much thicker (also listed in Table 2) and in this case no anti-reflective coating effect was observed. It can be seen that the absorbance / micron exhibited by such polymers is positive and very small.

Such polymers can also be used in optical elements.
They can also be used as adhesives when bonding together and because of their low absorbance / micron and low index of refraction values, they are the light that occurs at the air / substrate interface present in the optical element. , And also directs more light as the transmitted light travels from one optical element to the next optical element included in the system.

The materials of the present invention are useful in the manufacture of transmissive optical elements used in the vacuum ultraviolet region, such as lenses and beam splitters.

The material can also be used as an element in a compound lens designed to reduce chromatic aberration. Currently, the transparent focus element (transm)
CaF ₂ and possibly silica without hydroxyl are the only ones that appear to show sufficient transmission at 157 nm to be used in issisting elements. It is also generally known that an achromatic lens can be created using a second material having a different refractive index and dispersion (eg R. Kingslake, Academic Press, Inc., 1978).
, Lens Design Fundamentals, p. 77). For the HFIB: VF as described in Example 4, the data shown in FIG.
By ier fitting, it can be seen that it exhibits a refractive index of 1.4942 at 157 nm and a dispersion of 0.00220 nm ⁻¹ . Edward D.D. Pal
ik, “Hnadbook of Optical Constants of
Solids II ", p. 831, Academic Press, Inc.
By similarly fitting the refractive index data for CaF ₂ by A., Boston, MA (1991) and French, it was 1.55 at 157 nm.
It can be seen that it has a refractive index of 84 and a dispersion rate of 0.00234 nm ⁻¹ . Thus, it is expected that the use of one of such materials in cooperation with CaF ₂ will allow the construction of an achromatic lens from said material and other similar materials described in this application.

An additional area in which the polymer plays an important role is in the optical latent image (optical la).
As a photosensitive photoresist that captures a tent image). In the case of photoresists, light must pass through the entire thickness of the optical latent image resist layer, producing well defined vertical sidewalls during photoimaging and then into the developed polymer. A desired resist image should be produced. When a polymer is used as a resist at 157 nm, the thickness of this resist is about 200
If it is limited to 0Å, it may have a very high extinction coefficient A per micrometer of film thickness such as <~ 2-3.

WO 9836324 describes carbon / fluorine polymers, such as poly (tetrafluoroethylene / hexafluoropropylene), as a thin film that exhibits an absorbance A / μ of 0.1 to 1 when used at 140 to 200 nm. Is disclosed. The data shown in Table 1 above, which is derived from a literature source, is a report by Vasilets [V. N. Vasilets et al., J. Poly.
Sci. , Part A, Poly. Chem. , 36, 2215 (1998)], and the data shown in Table 2, which combines Applicant's data with additional literature data, casts doubt on the above disclosure. For example, poly (tetrafluoroethylene: hexafluoropropylene), that is, polymer # 14 in Table 2 has an A / μ value shown at 157 nm.
Is relatively strong at 3.9, which is the industrial target for thin skin (A / μ <0.01)
In addition to satisfying the above condition, the target of looseness of resist (A / μ <2-3) is not satisfied. Japanese patent 072952076 includes Cytop ™ and Teflo.
The bilayer film of n (TM) AF 1600 is claimed as a thin film. Cytop
(Trademark) has an A / μ of 1.9 at 157 nm (polymer # 13, Table 2).
And the A / μ of Teflon ™ AF 1600 is 0.4 (polymer # 7, Table 2). This is surprising in view of the data in Table 1, which shows that there is a significantly higher UV absorption at 160 nm whenever the number of CF ₂ groups linked in a chain exceeds about 6 Not that. In fact, W. H. Buck
And P.C. R. Resnick reported that more than 30% of the CF ₂ units of Teflon ™ AF 1600 were present as (CF ₂ ) _n continuations with n> 6, which indicated that A / u 0.4 [J. Scher
irs, Modern Fluoropolymers, John Wiley
, New York, 1997, Chapter 22, p. 401]. Unless it is possible to break the interactions that contribute to such absorption, it is impossible to find polymers based on carbon that exhibit complete transmission at wavelengths shorter than about 160 nm. Seem.

In Table 2 below, the absorbance / micrometer (A / μm) of the partially fluorine-substituted and completely fluorine-substituted polymer film spin-coated on the CaF ₂ crystal is shown at 157 nm.
). The polymers are listed in descending order of absorbance. In some cases, more than one sample of various polymers was prepared in one example. Therefore, the items described in the table are identified by both the example number (first column) and the sample number. In addition, the figure numbers showing the spectra exhibited by the various polymers are cross-referenced to the table.

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

[Table 9]

[0047]

[Table 10]

[0048]

[Table 11]

[0049]

[Table 12]

[0050]

[Table 13]

[0051]

[Table 14]

[0052]

[Table 15]

[0053]

[Table 16]

[0054]

[Table 17]

[0055]

[Table 18]

[0056]

[Table 19]

[0057]

[Table 20]

[0058]

[Table 21]

[0059]

[Table 22]

[0060]   Three types among the acyclic polymer structures listed in Table 2 (polymer VF₂: HFP, HFI
B: TrFE and HFIB: VF) have a detectable UV absorption at 157 nm.
Not shown. They are vinylidene fluoride (VF)₂) Or hexafluoroisobu
It is a copolymer containing any of the ethylene (HFIB). VF₂And HFI
B has common special structural features. For example, hexafluoroisobutylene
When the monomer itself is used, CH₂Continuation is -C (CF₃)₂− In segment
Therefore, the length before breaking is CH₂CH₂Can be: For vinylidene fluoride
Similarly, CH₂CF is continuous₂The length before being destroyed by CH₂CH₂Is less than or
CF₂CH is continuous₂CF before being destroyed by₂CF₂Can be: That is, CX ₂ = CY₂Monomer, eg VF₂And HFIB, etc., show a wide range of phases between C-F bonds.
Judging from the possible existence of extensive interactions or interactions between C—H bonds.
When cut off, it has a "self-interrupting" characteristic
To do. The rigid five-membered ring of PDD also has an unfavorable morphology for interactions.
Has the associated implications of forcing. PDD / TFE copolymer # 5
, # 7 and # 8, the absorbance is between 52 and 32 TFE content and 1
It drops from 0.6 to 0.4 and 0.0 as it goes down to 1 mol%. Immediately
If the PDD content is increased (CF₂)_nTransparent due to interruption of continuation
The property is improved. Other complete fluorine substitutions that will perform the same interrupt function as PDDs
It is predicted that it will be possible to find ring structures or partially fluorine-substituted ring structures
.

A solution of TFE: HFP and a solution of TrFE: HFP were placed on a CaF ₂ substrate 6
Spin coatings at spin speeds of 000 rpm produced polymer films with thicknesses of 1850 angstroms and 1389 angstroms, respectively. The VUV absorbance measurement was then used to determine the absorbance per micron.

Another example is shown in which the absorbance / micron at 157 nm was lowered by introducing TrFE instead of TFE. FIG. 8 shows TFE: HFP and TrFE: HF.
The absorbance exhibited by P (expressed in units of reciprocal microns) is shown versus wavelength lambda (λ) (expressed in units of nanometers). The presence of CHF carbons in the CF ₂ = CFH monomer causes an interruption to the long CF ₂ run.

This reduces the absorbance of TFE: HFP at 157 nm at 3.9 / micron to that of TrFE / HFP at 1.37 / micron. This effect is also exhibited by the maximum absorbance of TFE: HFP polymer being Tr.
It can also be understood as a transition to the shorter wavelength of the FE: HFP polymer.

Thus, we have found that PDD and CX ₂ = CY ₂ monomers [where X = -F or -CF ₃ and Y = -H] and optionally other monomers CR ^a R ^b. = CR ^c R ^d
{Wherein R ^a , R ^b or R ^c can be any one or all of these can be H or F, and R ^d can introduce solubility or crystallinity. if necessary to _{destroy, F, -CF 3, -OR f} [ where -R _f is C _n F _{2n + 1} (wherein,
n = 1 to 3)] and may be OH (when R ^c = H)} and is highly transparent to light at <186 nm (A / μ
<1 and more preferably A / u <0.1) types of polymers are specified. When the CR ^a R ^b = CR ^c R ^d monomer is randomly polymerized together with the PDD or CX ₂ = CY ₂ monomer, increasing the concentration statistically results in CR ^a R ^b = CR ^c R ^It is not possible to make it greater than ~ 25 mole percent because the length of the ^d- series will be so long that absorption will take place considerably. This means that the A / μ drops from 0.6 to 0.4 and 0.0 as the TFE content is reduced from ~ 52 to 32 and 11 mole percent, as mentioned above. : TFE copolymer (Teflon ™ AF 1200 in Table 2 respectively, Tefl
on ™ AF 1601, Teflon ™ AF 2400 polymer).
When the CR ^a R ^b = CR ^c R ^d monomer is polymerized in an alternating manner with PDD or CX ₂ = CY ₂ monomer, the concentration of CR ^a R ^b = CR ^c R ^d monomer may be increased. It can be forgiven at a higher price. This example is a 1: 1 HFIB: TrFE copolymer, which has an A / μ of -0.05 (Table 2, polymer number 3). Of course, random and alternating structures are by no means 100% ideal, and some monomers naturally tend to undergo block polymerization themselves or not themselves, thus random The CR ^a R ^b = CR ^c R ^d limit for the structure is approximately 25% and the CR ^a R ^b = CR ^c R ^d limit for the alternating structure is approximately 50%. Other combinations showing very high permeability include CH ₂ ═CHCF ₃ : CF ₂ ═CF ₂ , C
H ₂ ═CHF: CF ₂ ═CFCl, CH ₂ ═CHF: CClH═CF ₂ ˜2: 1 to 1: 2 copolymers are included. Suitable monomers for CX ₂ = CY ₂ include vinylidene fluoride and hexafluoroisobutylene. Suitable CR ^a R ^b = CR ^c R ^d monomers are those that introduce asymmetric centers into the polymer chain to increase solubility and destroy crystallinity, such as vinyl fluoride, Examples include trifluoroethylene, hexafluoropropylene and chlorotrifluoroethylene. Finally, it should be pointed out that creating a highly permeable structure as defined above does not automatically create a polymer useful for all of the claimed applications.
For example, it has already been pointed out that the use of poly (vinylidene fluoride) as a completely transparent and transparent optical material is excluded because it exhibits crystallinity [ie, poly (vinylidene fluoride) is a thin film. The reason why it cannot be used as is not the absorbance but the physical reason (light scattering). As another example, poly (perfluorodimethyldioxole) is too insoluble to spin coat it as a thick film. In the case of poly (perfluorodimethyldioxole), by coating a liquid monomer and causing the polymerization to occur at an appropriate place,
You can avoid it. The monomer can be diluted, optionally with a solvent and / or an initiator, and placed where the membrane is desired to produce a membrane with a thickness greater than about 250 nm. The polymer can be deposited at the desired location by initiating the polymerization by suitable physical and / or chemical means. As a result of subsequent removal of the solvent, the resulting polymer film can be made thicker than that which can be produced using conventional solvent coating techniques. As a final example, poly [vinylidene fluoride / perfluoro (methyl vinyl ether)] is a viscous rubbery material that is not useful as a self-supporting thin film, but is useful as a glue. As used herein the term "amorphous fluoropolymer",
This means a fluoropolymer that shows no melting point when analyzed by a differential scanning calorimeter. The absence of a melting point means that no more than 1 Joule / gram of thermal event associated with melting occurs.

Reference to a monomer as a precursor to a permeable polymer is meant to imply that it will homopolymerize or form a copolymer with any of the other monomers listed. Not something to do. For example, hexafluoroisobutylene does not form an effective amount of a homopolymer of standard molecular weight under normal conditions or copolymerize with tetrafluoroethylene. Claiming the use of such materials at 140 to 186 nm, they also form polymers that show excellent transmission at long wavelengths up to 800 nm, and they also at shorter wavelengths. It may also be suitable for use in certain applications. Particularly preferred wavelength is 140-160 nm, 1
50-160 nm is more preferred and 155-159 nm is most preferred.

Examples Many of the polymers tested were obtained as commercial samples. Teflon ™ AF 1200: DuPont (Wilmington, DE)
) Teflon (TM) AF 1600: DuPont Teflon (TM) AF 2400: DuPont Cytop (TM): Asahi Glass, poly [perfluoro (butenyl vinyl ether)] U.S. Patent No. 5,478,905 (December 26, 1995). Sun, using the procedure described in Poly (hexafluoropropylene: tetrafluoroethylene, ~ 1
1) was produced.

Many of the remaining polymer compositions are known in the art and were prepared by standard methods. Typically, the autoclave was charged with the monomer, solvent and initiator and heated to initiate the polymerization. Hexafluoropropylene oxide dimer Peroxide 1 (DP) for most polymerizations

[0068]

[Chemical 1]

Was used to initiate the polymerization at ambient temperature. DP with a solvent such as Vertrel ™ XF (CF ₃ CFHCFHCF ₂ CF ₃ ) or 3M Performance.
e Fluid PF-5080 (mostly perfluorooctane) was prepared and used as a 0.05 to 0.2 molar solution. The production of DP is a standard laboratory procedure [Chengue et al., J. Am. Org. Chem. , 47, 2009 (1
982)] or, if necessary, the jet mixer method (1999 10
It can be conveniently carried out using U.S. Pat. No. 5,962,746, dated May 5. The polymer was then isolated by evaporation or filtration after collecting the reaction mixture. The composition of the polymer was measured by elemental analysis or NMR. Procedures are given for the preparation of new compositions and representative procedures for already known compositions.

A polymer film was formed by spin-coating a solution of the polymer on a CaF ₂ substrate, and then applied to a sample of the polymer film while being positioned on this substrate, followed by baking. Apply bake) so that no residual solvent remains in the polymer film. After baking, baking is performed at a temperature of 120 ° C. to 250 ° C. using a hot plate.
C. range for 2 to 5 minutes or overnight in a vacuum oven. The spin rates of these samples are listed in Table 2.

Polymer film thickness measurements were made using single or multiple wavelength ellipsometry as discussed below, or by a Filmmetrics Model F20 thin film measuring device (Filmmetrics, Inc., 7675 Daggest St.,
Suite 140, San Diego, CA 92111-2255). The film thickness is reported in Table 2. Some materials have different thicknesses 2
The types of membranes are shown in the table and the absorbance / micron value for each membrane is shown.

Comparative Example A Teflon ™ AF 1601 A solution of Teflon ™ AF 1601 was placed on a CaF ₂ substrate at 6000r.
A polymer film having a thickness of 3323 angstrom was formed by spin coating at a spin speed of pm. The VUV absorbance measurement was then used to determine the absorbance per micron.

Teflon ™ AF 1601 is a PDD: TFE 68:32 polymer, which is currently used as a skin polymer designed for use at lithographic printing wavelengths of 248 nm and 193 nm. The absorbance / micron for light at 157 nm is 0.42 / micron as determined by VUV absorbance measurement. This corresponds from FIG. 1 that even if the thickness of the thin film is only 0.2 μm, the transmittance of the thin film is less than 70%, and, of course, the thin film is properly designed. It is unlikely that the results are additionally influenced by the thin film interference effect.

For the purpose of measuring the VUV optical properties of Teflon ™ AF 1601, Teflon ™ AF 160 placed on a silicon wafer.
VUV ellipsometry was performed on one polymer sample to measure the refractive index and the extinction coefficient, which are shown in FIG. Teflon ™ AF 1601 has a refractive index of 1.4251 at 157 nm. The measured extinction coefficient at 157 nm corresponds to an absorbance / micron of 0.35 / micron, which is also shown in Table 2.

The optical properties of such Teflon ™ AF 1601 and the O.S. S. The Heavens method can be used to design thin etalon coatings that are tailored to minimize the reflection of the unsupported thin coating and maximize the skin transmittance. Is a thin film that causes optical fringes depending on the wavelength dependence of reflection or transmittance of the thin film due to constructive and destructive interference of light from the front surface and the back surface of the film (Max Born and Emil. A book by Wolf, "Principl"
es of Optics ", Pergamon Press, New Yor
k, 6th edition, copyright 1980, pages 329-333)]. In the case of a thin film having a thickness of 6059 angstroms, the transmittance at 157 nm in the thin skin is 65.7%, while the reflectance at 157 nm in the thin skin is 0.4%. Figure 4 shows Tefl designed as a tuned unsupported etalon with a thickness of 6059 Angstroms.
on (TM) AF 1601 Thin Skin Spectral Transmission (expressed in absolute units)
Is compared to the wavelength lambda (expressed in units of nanometers). The interference fringes exhibited by the tuned etalon can be clearly seen as a function of wavelength. FIG. 5 shows Teflon ™ AF 160 designed as a tuned unsupported etalon with a film thickness of 6059 Å.
1 shows the spectral reflectance (expressed in absolute units) of the thin skin of No. 1 against wavelength lambda (expressed in units of nanometers). The interference edge exhibited by the tuned etalon can be clearly seen as a function of wavelength, and the minimum reflectance of this thin skin is 157 nm.
, Which contributes to the maximum skin transmission at such lithographic wavelengths. Teflon ™ AF 160 with a thickness of 6335 Angstroms
In the thin film of No. 1, the adjusted etalon was not optimized so as to show the maximum thin skin transmittance at 157 nm, and the transmittance at the thin skin of 157 nm was 59.4%, while The reflectance shown at 157 nm is as high as 8.1%.

FIG. 6 shows a Teflon ™ AF 1601 thin film prepared with etalon 1
The transmission shown at a lithographic wavelength of 57 nm is shown as a function of thin film thickness. Due to the fact that this film has a thin film interference edge, the skin transmittance varies with the thickness,
This results in maximum and minimum values for thin skin transmission. An optimally tailored etalon skin design would correspond to a membrane with sufficient thickness and mechanical integrity to maximize transmission. As will be further seen, skins designed from such materials will exhibit substantially lower transmission than the 98% transmission target for skins for 157 nm.

Thin skin designed from Teflon ™ AF 1601 cannot achieve a thin skin transmission of greater than 98%. Much higher absorbance at 157 nm / micron C
Even thin skins designed from ytop (TM) will have low thin skin transmission at 157nm. This means that there is a need for a method for producing a polymer having a dramatically low absorbance / micron at 157 nm so as to satisfy the desired transmittance of 98% at 157 nm in a thin film. Is shown. Therefore, we need polymers that exhibit substantially lower absorbance / micron.

Example 1- A solution of PDD / TFE Teflon ™ AF 1200, 1601 and 2400 was Ca.
Polymer films having thicknesses of 4066 angstroms, 3323 angstroms and 2133 angstroms were prepared by spin coating on an F ₂ substrate at a spin speed of 6000 rpm. The VUV absorbance measurement was then used to determine the absorbance per micron.

FIG. 7 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 1200 versus wavelength lambda (λ) (expressed in units of nanometers) for Sample 8. The measured absorbance at 157 nm / micron is 0.6
4 / micron. The measured absorbance / micron at 193 nm is 0.004 / micron. The measured absorbance / micron at 248 nm is -0.001 / micron.

FIG. 7 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 1601 versus wavelength lambda (λ) (expressed in units of nanometers) for sample 7a. The measured absorbance / micron at 157 nm is 0.
42 / micron. The measured absorbance at 193 nm / micron is 0.02 / micron. The measured absorbance at 248 nm / micron is 0.01 / micron.

FIG. 7 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 2400 versus wavelength lambda (λ) (expressed in units of nanometers) for Sample 5. Absorbance measured at 157 nm / micron is 0.0
It is 07 / micron. The measured absorbance at 193 nm / micron is -0.06 /
It is micron. The measured absorbance / micron at 248 nm is -0.06 / micron.

One way to dramatically reduce the absorbance of PDD: TFE polymer at 157 nm is to increase the percentage of PDD included in the polymer. VF ₂
And, like HFIB, the rigid five-membered ring of PDD has a similar effect, namely, by pushing in the unfavorable morphology when judging the possibility that C—F bonds and C—F bonds may cause a wide range of interactions. Shows a "self-interrupting" effect. This is Te
The absorbances (expressed in units of reciprocal microns) of flon ™ AF 1200, Teflon ™ AF 1601 and Teflon ™ AF 2400 were compared to the wavelength lambda (λ) (expressed in nanometers). Figure 7
This figure shows the absorbance of such a polymer at 157 nm /
It proves that micron is low. Teflo, a PDD / TFE copolymer
157 nm when comparing n (TM) AF 1200, 1601 and 2400
The absorbance / micron drops to 0.6 to 0.4 / micron and 0.01 / micron as the TFE content drops from 52 to 32 and 11 mol%. That is, when the content of PDD is increased, interruption to (CF ₂ ) _n continuation occurs, so that the transmittance is improved. It is anticipated that it would be possible to find other fully or partially fluorinated ring structures that would perform the same function as the PDD does.

Example 2-Preparation of HFIB / TrFE poly (hexafluoroisobutylene: trifluoroethylene (1: 1)) 75 ml of stainless steel autoclave was cooled to <-20 ° C and C
25 ml Cl ₂ FCF ₂ Cl and ˜0.17 M in Vertrel ™ XF
5 DP of DP was charged. The autoclave was cooled and evacuated, and then 10 g of trifluoroethylene and 20 g of hexafluoroisobutylene were further charged. The reaction mixture was shaken overnight at ambient temperature (28 to 33 ° C.), removed from the autoclave and then evaporated to form a glassy film which was heated to 75 ° C.
In a vacuum oven for 72 hours for further drying. 3.33 g of white solid
Obtained. A solution was produced by shaking this polymer (3.24 g) with an acetic ester of 1-methoxy-2-propanol (PGMEA) (6.99 g).
After mixing this solution with 0.2 g of chromatographic silica gel and 0.2 g of decolorizing carbon, it is first passed through a 0.45μ glass microfiber syringe filter [Whatman, Autovial ™] and then at 0. 45μ PTFE Membrane Syringe Filter [Whatman, Autovial ™]
Passed through. CHF fluorine of trifluoroethylene located at -180 to -220 ppm shown by fluorine NMR of this solution was -58 to -65 ppm.
By contrasted to CF ₃ fluorine hexafluoroisobutylene located at the integrating it, hexafluoroisobutylene: trifluoroacetic ethylene to 1: was confirmed to be 1. An optical substrate (optical substr
ATE) was spin-coated with a thick film and the absorbance was measured. Sample Preparation and Results: A solution of HFIB: TrFE at 3000 rpm and 600 on a CaF ₂ substrate.
By spin coating at a spin speed of 0 rpm, the thickness is 12,146, respectively.
Polymer films of angstrom and 1500 angstrom were produced. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 9, the absorbance (expressed in units of reciprocal microns) of HFIB: TrFE (3: 2) for sample 3a is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The absorbance / micron at 157 nm measured with the thicker polymer film is 0.012 / micron. The measured absorbance / micron at 193 nm is 0.005 / micron. The measured absorbance / micron at 248 nm is -0.001 / micron.

Example 3-Preparation of HFIB / VF poly (hexafluoroisobutylene: vinyl fluoride (3: 2)) A 75 ml stainless steel autoclave was cooled to <-20 ° C and C
25 ml Cl ₂ FCF ₂ Cl and ~ 0.07M in Vertrel ™ XF.
10 ml of DP was charged. After cooling this autoclave and exhausting it, 16 g of hexafluoroisobutylene and 5 g of vinyl fluoride were further charged. The reaction mixture was shaken overnight at ambient temperature (18 to 26 ° C.), removed from the autoclave as a dense gel, then evaporated and further pumped down using a vacuum pump for 96 hours. It was put in a vacuum oven at 75 ° C. and dried for 22 hours. 19 g of a brittle white solid was obtained, which had a T _g of 58 ° C. (nitrogen, 10 ° C./min, second heating) and no detectable T _m . Calculated value for (HFIB) ₃ (VF) ₂ : C 32.89% H 2.07% Measured value: C 32.83% H 2.08% Preparation of solution and results: 2- Shake with heptanone (12 g)
g) to produce a solution. The solution was passed through a 0.45μ glass fine fiber syringe filter [Whatman, Autovial ™], and then the filtrate was used to spin-coat a thick film on an optical substrate for absorbance measurement. Sample preparation and results: HFIB: VF solution on CaF ₂ substrate at 3000 rpm and 6000 r.
Spin coating at a spin speed of pm (revolutions per minute) produced polymer films with thicknesses of 14,386 angstroms and 2870 angstroms, respectively. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 9 shows the absorbance of HFIB: VF (1: 1) for sample 4a (
(Reciprocal units of microns) are shown versus wavelength lambda (λ) (expressed in units of nanometers). The absorbance / micron at 157 nm measured with the thicker polymer film is 0.027 / micron. The measured absorbance at 193 nm / micron is 0.020 / micron. The measured absorbance / micron at 248 nm is 0.008 / micron.

For the purpose of measuring the VUV optical properties of HFIB: VF, VUV ellipsometry was performed on the HFIB: VF polymer sample placed on a silicon wafer to measure the refractive index and the extinction coefficient. Then, they are shown in FIG. Tefl
The refractive index shown by on (trademark) AF 1601 at 157 nm is 1.50. The measured extinction coefficient at 157 nm corresponds to an absorbance / micron of 0.022 / micron, which is also shown in Table 2.

The optical properties of such HFIB: VF and the O.S. S. Hea
The Vens method can be used to design an etalon thin film tailored to minimize reflection and maximize skin transmittance of the unsupported thin film. 366 thickness
In the case of a thin film of 0 angstrom, the transmittance shown at the thin skin at 157 nm is 98.
%, On the other hand, the reflectance of the thin skin at 157 nm is 0.08%. Figure 11
Figure 3 shows the spectral transmission (expressed in absolute units) of a HFIB: VF skin designed as a controlled unsupported etalon with a film thickness of 3660 Angstroms versus wavelength lambda (expressed in nanometers). The interference edge exhibited by the tuned etalon is clearly visible as a function of wavelength. In FIG. 12, the film thickness is 36
HFIB: V designed as a 60 Angstrom tuned unsupported etalon
The spectral reflectance (expressed in absolute units) of the F skin is shown versus wavelength lambda (expressed in nanometers). The interference edge exhibited by the tuned etalon can be clearly seen as a function of wavelength, and the minimum reflectance of this thin skin is 157 nm.
, Which contributes to the maximum skin transmission at such lithographic wavelengths. The etalon prepared as a thin film for 157 nm of HFIB: VF with a film thickness of 3660 angstroms is 157n with a thin skin transmittance of 98% at 157 nm.
It is a thin skin for m.

FIG. 13 shows the transmission as a function of thin film thickness for a HFIB: VF tuned etalon thin film at a lithographic printing wavelength of 157 nm. Due to the fact that the membrane has thin film interference edges, there is an oscillation in the skin permeability with thickness, which leads to maximum and minimum skin permeability.

Example 4- Preparation of VF ₂ / PDD sample and results: A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F beforehand.
Cool to −20 ° C., to which is further added Perkadox ™ 16N [bis (4-t
-Butylcyclohexyl) peroxydicarbonate] and 20 g of perfluorodimethyldioxole (PDD) were evacuated, and after evacuation, 10.4 g of vinylidene fluoride (VF ₂ ) was charged. A thick oil formed upon heating to 70 ° C. for 18 hours. 17 g of white hard foam are obtained by evaporating in air, drying under pump vacuum for 22 hours and drying in an oven at 75 ° C. for 24 hours.
Obtained. Elemental analysis (C ₅ F ₈ O ₂ ) 1 (C ₂ H ₂ F ₂ ) 1 measured value: C 28.99% H 1.11% Calculated value: C 29.05% H 1.08% DSC, 10 ° C / min, nitrogen: T _g = 56 ° C (first heating) By shaking 4 g of poly (PDD / VF ₂ ) with T _g not detected in the second heating together with 16 g of hexafluorobenzene. After forming a viscous solution, it was filtered through a 0.45 micron glass fiber syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PDD was spin-coated on a CaF ₂ substrate at a spin speed of 6000 rpm to produce a polymer film with a thickness of 2097 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 9 shows the absorbance (expressed in units of reciprocal microns) of VF ₂ : PDD versus wavelength lambda (λ) (expressed in units of nanometers) for Sample 2. The absorbance / micron at 157 nm measured with the thicker polymer film is -0.04 / micron. In this way, 15 materials with extremely high transmittance are
The negative value of the absorbance / micron at 7 nm indicates that there is an antireflective coating effect. The measured absorbance at 193 nm / micron is 0.02 / micron. The measured absorbance / micron at 248 nm is 0.08 / micron.

Example 5- Preparation of VF ₂ / HFP Samples and Results: Poly (vinylidene fluoride / hexafluoropropylene) produced using the method of US Pat. No. 4,985,520 (1/15/91). ) The sample was characterized.

Composition by fluorine NMR in deuteroacetone: HFP with 21 mol% VF _2.
Is 79 mol% DSC, 10 ° C./min, nitrogen: T _g = -22.5 ° C. (second heating) Inherent viscosity (acetone, 25 ° C.) = 0.753 dL / g VF ₂ : HFP solution CaF ₂ 3000 and 6000 rpm (1
By spin coating at a spin speed of (revolutions per minute), a thickness of 69,80 can be obtained.
Polymer films of 0 Å and 1641 Å were produced.
The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 9, the absorbance (expressed in units of reciprocal microns) of VF ₂ : HFP (79:21) is compared to the wavelength lambda (λ) (expressed in units of nanometers) for sample 1a. Indicate. The absorbance / micron at 157 nm measured with the thicker polymer film is 0.015 / micron. The measured absorbance / micron at 193 nm is 0.005 / micron. The measured absorbance at 248 nm / micron is 0.003 / micron.

Example 6-VF ₂ / HFP, VF ₂ / PDD, HFIB / TrFE Thin Skin We have a polymer at 157 nm which exhibits an absorbance / micron on the order of 0.01 / micron, eg VF ₂ : HFP, VF ₂ : PDD and HFIB: TrFE etc. can be used to design tailored etalon skins with high transmission and substantial film thickness. FIG. 14 shows the transmittance as a function of thin film thickness for a prepared etalon thin film of a polymer having an absorbance per micron of 0.01 and a refractive index of 1.50 at the lithographic printing wavelength of 157 nm. Show. It should be noted that the maximum thin skin transmittance exceeds the target specification of 98% when the thickness of the thin film is 8371 angstroms or less.

Example 7-TFE / TrP A. Polymerization of tetrafluoroethylene (TFE) and 3,3,3-trifluoropropene (TrP) A 240 ml autoclave was charged with 20 ml of CF ₂ ClCCl ₂ F and <-2.
After cooling to 0 ° C., 10% DP of 0.17 M in CF ₃ CFHCFHCF ₂ CF ₃ is used.
ml was added. After further cooling this autoclave and exhausting it, TrP was reduced to 10
g and 40 g of TFE were added. After shaking overnight at room temperature, the autoclave was evacuated to evaporate the flowing reaction mixture and pump at room temperature under pump vacuum at room temperature.
It took time to finish. This gave 9.96 g of a sticky colorless gum. Elemental analysis (C ₃ H ₃ F ₃ ) ₅ (C ₂ H ₄ ) ₆ measured value: C 29.86 H 1.74 calculated value: C 30.02 H 1.40 DSC, 10 ° C./min, nitrogen: T _g = 8.8 ° C. (2nd heating) Solution Preparation and Results: 4 g of poly (TFE / TrP) was shaken with 12 g of hexafluorobenzene to form a solution, then 0.45 μ Filtered through a glass fine fiber syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of TFP: TFE (5: 6) was spin-coated on a CaF ₂ substrate to form a polymer film having a thickness of 41413 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 15, the absorbance (expressed in units of reciprocal microns) of TFP: TFE (5: 6) for sample 17 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance at 157 nm / micron is 0.149 /
It is micron. The measured absorbance / micron at 193 nm is 0.008 / micron. The measured absorbance / micron at 248 nm is -0.00085 / micron. B. Used as a glue for quartz and aluminum Aluminum coupons with dimensions 1 "wide, 3" long and 122 mils thick, and 1 "wide, 3" long and 65 mils thick Both of the quartz slides with C were rinsed with CF ₂ ClCCl ₂ F and then air dried.

4 g of poly (TFE / TrP) prepared above was shaken with 12 g of hexafluorobenzene at room temperature to form a clear colorless solution, then 0.45
It was passed through a μ glass fiber filter. Add 3 drops of the solution to one end of the aluminum coupon and place a quartz slide on top of the last one of the quartz slides.
Pressed down so that the inch overlaps the last inch of the aluminum coupon. This caused some excess fluid to be extruded and the remaining polymer solution to wet the overlapping areas and spread evenly throughout. Two C-Clamps (Stock # 72020, ACCO USA Inc., 770-S ACC
O Plaza, Wheeling, IL 60090) was used to evaporate the hexafluorobenzene solvent at room temperature for 3 days while holding the aluminum coupon and quartz slide in place. One such assembly was placed in a 50 ° C. vacuum oven with the C clamp still attached to it and heated for 16 hours. The assembly was removed from the oven, allowed to cool, the C-clamp was removed, and an Instron was used to remove the 3 ″ jaw separ.
ation) and crosshead speed of 1 "/ min.
) Was used to measure the force required to pull the quartz slide away from the aluminum coupon. It took 12 pounds. The second assembly was heated with the C-clamp still attached to it in a vacuum oven at 50 ° C for 20 hours and in a vacuum oven at 75 ° C for 24 hours. At this point In
The force required to pull the aluminum coupon away from the quartz slide using a stron was 127 pounds. C. Use as a glue for thin-skinned polymer 10 g of poly (HFIB / VF) (Example 2A below) is dissolved in 40 g of 2-heptanone, 1 g of decolorizing carbon + 1 g of chromatography alumina + 1 g of chromatography Add silica gel, filter through a 0.45μ PTFE syringe filter, and use a 5 mil casting knife to Tefl.
It was cast on an on (TM) FEP sheet and dried in air to yield a thin skin polymer, poly (HFIB / VF), as a film. The poly (HFIB / VF) film produced in this manner was treated with the above-mentioned Teflon ™.
It could be lifted and peeled from the FEP sheet as a colorless transparent film having a thickness of about 0.5 to 1 mil.

Next, a paste solution was prepared. 0.1 g of poly (TFE / Tr
P) was dissolved in 1 g of hexafluorobenzene to form a solution.

This sizing solution was used to produce several spots of ~ 1/2 "on an aluminum coupon measuring 1" wide, 3 "long and 122 mil thick. After drying the glue spots in air for 39 minutes in air, the coupons were placed in an air oven for 8 minutes at 60 ° C. The aluminum coupons were removed hot from the oven immediately upon top of the poly (TFE / TrP) deposit. A sample of poly (HFIB / VF) film was lightly pressed with a finger to the eye, and visually the poly (HFIB / VF) film moistened and adhered to the poly (TFE / TrP) spots. The poly (HFIB / VF) film could be peeled off and stretched without difficulty when the aluminum coupon was still hot. After returning to room temperature, the poly (HFIB / VF) film was not peeled off from the aluminum but was torn.
The adhesion between the skin polymer [poly (HFIB / VF)] was very strong, exceeding the strength of the skin polymer.

Example 8-HFIB / VF A. Polymerization of Hexafluoroisobutylene (HFIB) and Vinyl Fluoride (VF) 200 ml of water and Vazo ™ 56 in a 400 ml autoclave.
0.05 g of WSP initiator was charged. After cooling this autoclave and exhausting it, 80 g of hexafluoroisobutylene and 25 g of vinyl fluoride were added. After shaking at 50 ° C for ~ 48 hours, the autoclave was evacuated,
An opalescent blue emulsion was collected. This emulsion was placed in a Waring blender to disintegrate by vigorous stirring, filtered, and then washed 4 times with 100 ml of methyl alcohol in the Waring blender. Drying was performed under a pump vacuum for 6 days to obtain 30 g of a white powder and a solid. Elemental analysis (C ₄ F ₆ H ₂ ) ₄₇ (C ₂ H ₃ F) ₅₃ measured value: C 34.80% H 2.57% Calculated value: C 34.79% H 2.51% DSC, 10 ° C. / Min, nitrogen: T _g = 70 ° C. (second heating) T _m was not detected Inherent viscosity (THF, 25 ° C.): 0.379 dL / g GPC (in THF) Mw = 192,000 Mn = 92 A second sample of poly (HFIB / VF) was prepared using the same emulsion polymerization method and the thermal transitions it exhibits were examined in detail in a modulated DSC. A glass transition was detected at both 69.5 ° C and 195 ° C during the second heating. No melt transition was observed during the first and second heating. Solution Preparation and Results: A solution was prepared by shaking 10 g of the polymer with 40 g of 2-heptanone, followed by a 0.45μ glass microfiber syringe filter [Whatma.
n, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of HFIB: VF was spin-coated on a CaF ₂ substrate to produce a polymer film with a thickness of 9239 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 15 shows the absorbance (expressed in reciprocal units of microns) of HFIB: VF for sample 18 versus wavelength lambda (λ) (expressed in nanometers). The measured absorbance / micron at 157 nm is 0.005 / micron. The measured absorbance at 193 nm / micron is -0.00082 / micron. The measured absorbance at 248 nm / micron is -0.002 / micron. B. Used as a glue for quartz and aluminum Aluminum coupons having a width of 1 ", a length of 3" and a thickness of 122 mils, and quartz having a width of 1 "and a length of 3" and a thickness of 65 mils. Both slides were rinsed with CF ₂ ClCCl ₂ F and then air dried.

2 g of poly (HFIB / VF) prepared above was shaken with 18 g of acetone at room temperature to form a colorless transparent solution, which was then passed through a 0.45 μ glass fiber filter. Add the solution to one end of the aluminum coupon.
A drop was made and a quartz slide was pressed down onto it so that the last inch of the quartz slide overlapped the last inch of the aluminum coupon. This caused some excess fluid to be extruded and the remaining polymer solution to wet the overlapping areas and spread evenly throughout. Two C-clamps (stock number 72020, ACCO USA Inc., 770-S ACCO Pla
za, Wheeling, IL 60090) was used to evaporate the acetone solvent at room temperature for 3 days while holding the aluminum coupon and quartz slide in place. One such assembly was placed in a 50 ° C. vacuum oven with the C clamp still attached to it and heated for 16 hours. The assembly was removed from the oven, cooled, the C-clamp removed, and the In
using a 3 "jaw separation and a 1" / min crosshead speed,
The force required to pull the quartz slide away from the aluminum coupon was measured. It cost one pound. The second assembly was heated with the C clamp still attached to it in a vacuum oven at 50 ° C. for 16 hours and then in a vacuum oven at 75 ° C. for 24 hours. At this point Instron
The force required to pull the aluminum coupon away from the quartz slide with a.

[0107] Example 9-VF ₂ / PMVE A. Vinylidene fluoride (VF ₂ ) and perfluoromethyl vinyl ether (PM
Polymerization of VE) ~ 210 ml autoclave with 50 ml CF ₂ ClCCl ₂ F and CF ₃
The CFHCFHCF ₂ CF ₃ DP solvent ~0.2M was 10ml packed. After cooling this autoclave and exhausting it, 26 g of VF ₂ and 33 g of PMVE
added. After shaking at ambient temperature (18-26 ° C.) overnight, the autoclave was evacuated to recover a viscous solution. The excess solvent was evaporated under nitrogen and the polymer was dried under vacuum at room temperature for 72 hours and then in a vacuum oven at 75 ° C. for 28 hours (33 g). Elemental analysis (C ₂ F ₂ H ₂ ) ₅ (C ₃ F ₆ O) ₂ measured value: C 29.64% H 1.73% Calculated value: C 29.47% H 1.55% DSC, 10 ° C. / min, nitrogen: T _g = -32 ℃ (2-th heating) inherent _{viscosity, CF 3 CFHCFHCF 2 CF 3,} 25 ℃: 0.722dL
/ G Solution preparation and results: A solution was produced by shaking 4 g of the polymer with 16 g of hexafluorobenzene. This solution was passed through a 0.45 µ glass fine fiber syringe filter [Whatman, Autovial (trademark)], and then a thick film was spin-coated on an optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PMVE (5: 2) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 72,750 Å. Next, VU
Absorbance per micron was determined using V absorbance measurements.

FIG. 15 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : PMVE (5: 2) versus wavelength lambda (λ) (expressed in units of nanometers) for sample 19. Indicate. Absorbance measured at 157 nm / micron is 0.016
/ Micron. The measured absorbance / micron at 193 nm is 0.006 / micron. The measured absorbance at 248 nm / micron is 0.004 / micron. B. Used as a glue for quartz and aluminum Aluminum coupons having a width of 1 ", a length of 3" and a thickness of 122 mils, and quartz having a width of 1 "and a length of 3" and a thickness of 65 mils. Both slides were rinsed with CF ₂ ClCCl ₂ F and then air dried.

About 0.2 g of poly (VF ₂ : PMVE) was chopped into 3 to 4 pieces and then placed on one end of the aluminum coupon. A quartz slide was pressed down on top of it so that the last inch of the quartz slide overlaps the last inch of the aluminum coupon. 2 C-clamps (stock number 720
20, ACCO USA Inc. , 770-S ACCO Plaza, Wh
eeling, IL 60090) while holding the aluminum coupon and quartz slide in place while this assembly was placed in a vacuum oven at 76-80 ° C for 22 hours with the C-clamp still attached to it. Upon inclusion, this spread the polymer as a colorless transparent layer, pushing excess polymer from the edges. The assembly is removed from the oven, allowed to cool, the C-clamp is removed, and then the quartz slide is pulled away from the aluminum coupon using an Instron with 3 "jaw separation and 1" / min crosshead speed. The force required for was measured. It took 105.3 pounds. Separation occurred in the polymer layer and both the aluminum and quartz retained the remaining polymer. The force required to pull apart a second sample prepared in the same manner was 101.0 pounds with an average force of 103 pounds.

[0111] The autoclave CF ₂ ClCCl ₂ F of Example 10-VF ₂ / PMVE 210ml were charged 50 ml <-2
After cooling to 0 ° C., 10 μm of DP of 0.2 M in CF ₃ CFHCFHCF ₂ CF ₃ is used.
1 was added. After exhausting the autoclave, 33 g of perfluoro (methyl vinyl ether) (PMVE) and 13 g of vinylidene fluoride (VF ₂ ) were used.
Filled. Shaking the autoclave at room temperature overnight produces a solution which is evaporated to a soft polymer which is then further dried under pump vacuum for 29 hours and in a vacuum oven at 75 ° C. I went for 20 hours. This gave 31 g of a soft polymer suitable for use as glue. Calculated value for (C ₂ H ₂ F ₂ ) ₁₃ (C ₃ F ₆ O) ₁₀ : C 26.98% H 1.05% Measured value: C 27.21% H 0.88% DSC, 10 ° C / min , Nitrogen: T _g = -29 ° C (second heating) Inherent viscosity, 2-heptanone: 0.166 dL / g Solution preparation and results: 4 g of the polymer was shaken with 16 g of hexafluorobenzene. A solution was formed. This solution was passed through a 0.45 µ glass fine fiber syringe filter [Whatman, Autovial (trademark)], and then a thick film was spin-coated on an optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PMVE (13:10) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 25,970 Å. next,
Absorbance per micron was determined using VUV absorbance measurements.

FIG. 16 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : PMVE (13:10) versus wavelength lambda (λ) (expressed in units of nanometers) for sample 20. Indicate. Absorbance measured at 157 nm / micron is 0.0
34 / micron. Absorbance measured at 193 nm / micron is 0.015 /
It is micron. The measured absorbance at 248 nm / micron is 0.018 / micron.

[0114] Example 11-VF ₂ / PPVE A. Vinylidene fluoride (VF ₂ ) and perfluoro (propyl vinyl ether)
Polymerization of (PPVE) 50 ml of CF ₂ ClCCl ₂ F was charged into a 210 ml autoclave and <-2
After cooling to 0 ° C., 10 μm of DP of 0.2 M in CF ₃ CFHCFHCF ₂ CF ₃ is used.
1 was added. After cooling this autoclave and exhausting it, 13 g of VF ₂ and 53 g of PPVE were added. After shaking overnight at ambient temperature (22-26 ° C), the autoclave was evacuated and the solution was collected. After evaporation of excess solvent under nitrogen, the polymer was dried under vacuum at room temperature for 72 hours and at 75 ° C. for 28 hours (
45 g). Elemental analysis (C ₂ F ₂ H ₂ ) ₇ (C ₅ F ₁₀ O) ₅ measured value: C 26.17% H 0.88% Calculated value: C 26.34% H 0.79% DSC, 10 ° C. / min, nitrogen: T _g = -32 ℃ (2-th heating) inherent viscosity, hexafluorobenzene, 25 ℃: 0.169dL / g solution of preparation and results: the polymer of 4g with hexafluorobenzene of 16g The solution was formed by shaking. This solution was passed through a 0.45 µ glass fine fiber syringe filter [Whatman, Autovial (trademark)], and then a thick film was spin-coated on an optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PPVE (7: 5) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 29,874 Å. Next, VU
Absorbance per micron was determined using V absorbance measurements.

FIG. 15 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : PPVE (7: 5) versus wavelength lambda (λ) (expressed in nanometers) for sample 21. Indicate. The measured absorbance at 157 nm / micron is 0.028
/ Micron. The measured absorbance / micron at 193 nm is -0.003 / micron. The measured absorbance / micron at 248 nm is -0.00074 / micron. B. Use as a glue for thin skin polymers 10 g of poly (HFIB / VF) (Example 8A shown above) was added to 40 g of 2
-Dissolve in heptanone, add 1 g decolorizing carbon + 1 g chromatographic alumina + 1 g silica gel, filter through a 0.45μ PTFE syringe filter and use a 5 mil casting knife to Teflon ™ FE.
After pouring it on the P sheet, it is dried with air to give poly (HFIB /
VF) was produced as a polymer film. Poly (HFI) produced in this manner
The B / VF) film could be lifted and peeled from the Teflon ™ FEP sheet as a colorless transparent film about 0.5 to 1 mil thick.

Next, a paste solution was prepared. 0.1 g of poly (VF ₂ / PP) prepared above
A solution was produced by dissolving VE) in 1 g of hexafluorobenzene.
This sizing solution was used to generate ~ 1/2 "spots on an aluminum coupon having dimensions of 1" wide, 3 "long and 122 mils thick. After drying for 39 minutes, the coupon was placed in an oven under nitrogen at 62 ° C. for 13 minutes, the aluminum coupon was removed hot from the oven and immediately placed on top of the poly (VF ₂ / PPVE) deposit with a poly (VF ₂ / PPVE) deposit. The HFIB / VF) membrane sample was lightly pressed with a finger, and after the aluminum coupon returned to room temperature, the poly (HFIB / VF) membrane was either lap shear or peeled back mode. A tear occurred when it was pulled with a polymer for glue [poly (VF ₂ / PPVE)] and a polymer for thin skin [poly (H
FIB / VF)] was very strong, exceeding the strength of this skin polymer.

Example 12-VF ₂ / HFP A. Poly (vinylidene fluoride / hexafluoropropylene) (VF ₂ / HFP
) Samples Characterization was performed on vinylidene fluoride / hexafluoropropylene samples produced using the method of US Pat. No. 4,985,520 (1/15/91).

Composition by fluorine NMR in deuteroacetone: HFP at 21 mol% VF _2.
79 mol% DSC, 10 ° C./min, nitrogen: T _g = -22.5 ° C. (second heating) Inherent viscosity (acetone, 25 ° C.): 0.753 dL / g Solution preparation and result: 3 g of poly (VF ₂ / HFP) was shaken with 17 g of 2-heptanone to form a solution, and then a 0.45 µ glass fine fiber syringe filter [W
hatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : HFP (79:21) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 13,000 Å. Next, V
UV absorbance measurements were used to determine the absorbance per micron.

FIG. 15 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : HFP (79:21) versus wavelength lambda (λ) (expressed in nanometers) for sample 22. Indicate. Absorbance measured at 157 nm / micron is 0.01
4 / micron. Absorbance measured at 193 nm / micron is -0.002 /
It is micron. Absorbance measured at 248 nm / micron is -0.00056 /
It is micron. B. Used as a glue for quartz and aluminum Aluminum coupons having a width of 1 ", a length of 3" and a thickness of 122 mils, and quartz having a width of 1 "and a length of 3" and a thickness of 65 mils. Both slides were rinsed with CF ₂ ClCCl ₂ F and then air dried.

About 0.2 g of the poly (VF ₂ : PMVE) was chopped into 3 to 4 pieces and then placed on one end of the aluminum coupon. A quartz slide was pressed down on top of it so that the last inch of the quartz slide overlaps the last inch of the aluminum coupon. 2 C-clamps (stock number 7)
2020, ACCO USA Inc. , 770-S ACCO Plaza,
Using Wheeling, IL 60090), hold the aluminum coupon and quartz slide in place while placing this assembly in a vacuum oven at 76-80 ° C for 22 hours with the C-clamp still attached to it. Upon entry, the polymer spread as a clear colorless layer. Remove the assembly from the oven, allow it to cool, remove the C-clamp, and then
A ron was used to measure the force required to pull the quartz slide away from the aluminum coupon using a 3 ″ jaw separation and a 1 ″ / min crosshead speed.
It took 133.3 pounds. The force required to pull apart a second sample prepared in the same manner was 121.6 lbs, resulting in an average force of 127
It was pound. In the second of these two experiments, separation occurred in the polymer layer and both the aluminum and quartz retained the remaining polymer. In the first of the above two experiments, separation occurred between the polymer and the glass. In each case, the remaining polymer could be neatly separated from the glass and aluminum as a single piece. C. Use as a glue for thin-skinned polymer 40 g of 10 g of poly (HFIB / VF) (Example 2A shown above)
-Dissolve in heptanone, add 1 g decolorizing carbon + 1 g chromatographic alumina + 1 g silica gel, filter through a 0.45μ PTFE syringe filter and use a 5 mil casting knife to Teflon ™ FE.
After pouring it on the P sheet, it is dried with air to give poly (HFIB /
VF) was produced as a polymer film. Poly (HFI) produced in this manner
The B / VF) film could be lifted and peeled from the Teflon ™ FEP sheet as a colorless transparent film about 0.5 to 1 mil thick.

Next, a paste solution was prepared. 0.1 g of poly (VF ₂ / PP) prepared above
A solution was produced by dissolving VE) in 1 g of hexafluorobenzene.

This sizing solution was used to generate ~ 1/2 "spots on an aluminum coupon having dimensions of 1" wide, 3 "long and 122 mil thick. After air drying for 39 minutes, the coupon was placed in a nitrogen blanket oven for 13 minutes at 62 ° C. The aluminum coupon was removed hot from the oven immediately upon top of the poly (VF ₂ / HFP) deposit. Poly (HFIB /
The (VF) membrane sample was lightly pressed with a finger. After the aluminum coupon returned to room temperature, tearing occurred when the poly (HFIB / VF) film was pulled in the lap shear mode. When the poly (HFIB / VF) itself is later peeled off, the poly (V
F ₂ / HFP) Adhesive failure between glue and aluminum
ure) and the poly (VF ₂ / HFP) adhesive layer cleanly separated from the aluminum and showed no debonding from the poly (HFIB / VF). This means that the polymer for thin skin [Poly (HFIB / VF)] and the polymer for glue [
It indicates that the adhesion between the poly (VF ₂ / HFP)] is excellent.

Example 13-HFP / PMVE / VF ₂ 210 ml of a Hastelloy C autoclave was cooled to <-20 ° C and then charged with 20 ml of ~ 0.17M DP in CF ₃ CFHCFHCF ₂ CF ₃ . After exhausting the autoclave, 33 g of perfluoro (methyl vinyl ether) (PMVE), 26 g of vinylidene fluoride (VF ₂ ), 26 g of hexafluoropropylene (HFP) and 1 g of anhydrous hydrogen chloride (chain transfer agent).
g filled. Shaking of the autoclave at room temperature overnight yielded a colorless oil which was devolatized for 24 hours in air, 19 hours under pump vacuum and then 5 days in a vacuum oven at 75 ° C. When done, 47 g of a transparent resin with a tackiness suitable for use as glue were produced. Composition by Fluorine NMR: VF ₂ 63.1 mol% PMVE 27 mol% HFP 10 mol% Inherent viscosity, acetone, 25 ° C .: 0.120 dL / g Solution preparation and results: 4 g of the polymer 12 g of 2-heptanone. A cloudy solution was obtained by shaking with to form a solution. This solution was added to 0.45μ glass microfiber and Teflon ™ syringe filter [Whatman, Autovi.
al (trademark)], and then the filtrate was used to spin-coat a thick film on an optical substrate to measure the absorbance.

A solution of HFP: PMVE: VF ₂ (10:27:63) was spin coated onto the CaF ₂ substrate to produce a polymer film with a thickness of 316,500 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 16, for sample 23, HFP: PMVE: VF ₂ (10:27:
63) shows the absorbance (expressed in units of reciprocal microns) versus the wavelength lambda (λ) (expressed in units of nanometers). The measured absorbance / micron at 157 nm is 0.008 / micron. The measured absorbance / micron at 193 nm is -0.00048 / micron. The measured absorbance / micron at 248 nm is -0.00045 / micron.

Example 14-HFIB / VF An 85 ml autoclave was filled with two stainless steel balls having a diameter of 3/8 ",
This was sealed, evacuated, cooled to <-20 ° C, and then CF ₃ CFHCF
The DP of the HCF in ₂ CF _{3 ~0.17M} was sucked into a 10ml. The autoclave is further cooled and hexafluoroisobutylene (HFIB) is added to 70 ° C at -50 ° C.
After addition of g, 10 psig of liquid vinyl fluoride (VF) was added at ~ -35 ° C.
At this point the liquid-filled autoclave was warmed to room temperature with shaking. The pressure inside this autoclave reaches a maximum of 7780 psi at 25 ° C,
Finishing was performed at 29 ° C. under 103 psig for about 10 hours, and the following operation was performed (in
to the run). The solid polymer product was dried under a pump vacuum for 72 hours to obtain 57 g of a white solid having a glass transition temperature of 115 ° C. (HFIB) ₅₉ (VF) ₄₁ Calculated: C 33.04% H 2.11% measured: C 33.02% H 2.31% DSC , 10 ℃ / min, nitrogen: T _g = 115 ℃ ( Second heating) No Tm detected (both first heating and second heating) Inherent viscosity (THF, 25 ° C): 0.183 dL / g Solution preparation and results: 48 g of 12 g of the polymer A solution was produced by shaking with 2-heptanone. This solution was passed through a 0.45μ glass microfiber and a Teflon ™ syringe filter [Whatman, Autovial ™], and then the filtrate was used to spin coat a thick film onto an optical substrate to measure the absorbance. I went.

A solution of HFIB: VF (10: 7) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 7500 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 16, the absorbance (expressed in units of reciprocal microns) of HFIB: VF (10: 7) is plotted against the wavelength lambda (λ) (expressed in units of nanometers) for sample 24. Show. Absorbance measured at 157 nm / micron is -0.01
3 / micron. The measured absorbance at 193 nm / micron is -0.016 /
It is micron. The measured absorbance / micron at 248 nm is -0.011 / micron.

Example 15-PDD / PMVE A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to 0 ° C., add 1 to 0.2M DP in CF ₃ CFHCFHCF ₂ CF _3.
0 ml and 11.6 ml of perfluorodimethyldioxole (PDD) were added. After exhausting the autoclave, 4.5 g of perfluoro (methyl vinyl ether) (PMVE) was charged. Shaking of the autoclave at room temperature overnight produced a gelatinous product that was evaporated and further dried for 29 hours under pump vacuum and 20 hours in a vacuum oven at 75 ° C. This gave 18 g of product. Calculated value for (PDD) ₆ (PMVE) ₅ : C 23.56% Measured value: C 23.87% DSC, 10 ° C./min, nitrogen: T _g = 133 ° C. Inherent viscosity [Fluorinert ™ FC-40]. : 0.161d
L / g Solution Preparation and Results: 4 g of the polymer was shaken with 16 g of Fluorinert ™ FC-40 to produce a cloudy solution. This solution was passed through a 0.45μ glass fine fiber syringe filter [Whatman, Autovial ™] and after adding 0.6 g of chromatographic alumina and 0.6 g of chromatographic silica gel, 0.45μ of Teflon ( ™) syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of PDD: PFMVE (6: 5) was spin-coated on a CaF ₂ substrate to form a polymer film having a thickness of 12,450 angstroms. next,
Absorbance per micron was determined using VUV absorbance measurements.

In FIG. 16, the absorbance (expressed in units of reciprocal microns) of PDD: PFMVE (6: 5) for sample 25 is plotted against wavelength lambda (λ) (expressed in units of nanometers). Show. Absorbance measured at 157 nm / micron is 0.20
9 / micron. The measured absorbance / micron at 193 nm is 0.006 / micron. The measured absorbance / micron at 248 nm is 0.013 / micron.

Example 16-VF / ClDFE A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to ° C., the DP of CF ₃ CFHCFHCF in ₂ CF _{3 ~0.17M} it was added 10ml thereto. After exhausting the autoclave, vinyl fluoride (VF)
6.4 g and 1-chloro-2,2-difluoroethylene (ClDFE) 9
． 8g was filled. Shaking of the autoclave at room temperature overnight produced a damp paste which was dried for 4 days under pump vacuum and 28 hours in a vacuum oven at 75 ° C. This gave 8 g of product. Calculated value for (C ₂ H ₃ F) ₂₀ (C ₂ HF ₂ Cl) ₁₁ : C 37.16% H 3.57% Measured value: C 37.39% H 3.30% DSC, 10 ° C./min. Nitrogen: T _g = 97 ° C. (first heating) T _g was not detected on the second heating Inherent viscosity [acetone]: 0.220 dL / g Solution preparation and results: 4 g of the polymer 16 g A solution was formed by shaking with heptanone. Add this solution to a 0.45μ glass microfiber syringe filter [Whatm
an, Autovial (trademark)], the filtrate was used to spin-coat a thick film on an optical substrate, and the absorbance was measured.

A solution of VF: ClDFE (20:11) was spin-coated on a CaF ₂ substrate to produce a polymer film with a thickness of 9461 angstroms. Next, V
UV absorbance measurements were used to determine the absorbance per micron.

FIG. 17 shows the absorbance (expressed in units of reciprocal microns) of VF: ClDFE (20:11) versus wavelength lambda (expressed in units of nanometers) for sample 26. Show. The measured absorbance at 157 nm / micron is 0.2
26 / micron. Absorbance measured at 193 nm / micron is 0.036 /
It is micron. The measured absorbance at 248 nm / micron is 0.003 / micron.

Example 17-PDD / VF ₂ After cooling an autoclave of 75 ml to <-20 ° C, it was added with CF ₃ CFHC.
10 ml of FHCF ₂ CF ₃ , CF ₃ CFHCFHCF ₂ CF ₃ ~ 0.17M D
5 ml of P and 20 g of perfluorodimethyldioxole (PDD) were charged. After exhausting the autoclave, vinylidene fluoride (VF ₂ ) was added to 13
g filled. When the autoclave was shaken at room temperature overnight, a viscous oil was formed, which was subjected to volatile removal in air and under pump vacuum for 32 hours.
By performing this in a vacuum oven at 5 ° C. for 23 hours, 16 g of a white resin was obtained. Calculated value for (PDD) ₁ (VF ₂ ) ₂ : C 29.05% H 1.08% Measured value: C 29.35% H 1.08% DSC, 10 ° C / min, nitrogen: 52 ° C? (Weak) Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.278 Solution preparation and results: 2 g of poly (PDD / VF ₂ ) was shaken with 8 g of 2-hexafluorobenzene to form a solution. It was The solution was passed through a 0.45μ glass fine fiber syringe filter [Whatman, Autovial ™], and then the filtrate was used to spin-coat a thick film on an optical substrate for absorbance measurement.

A solution of PDD / VF ₂ (1: 2) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 82,000 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 17, the absorbance (expressed in units of reciprocal microns) of PDD / VF ₂ (1: 2) for sample 27 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Indicate. Absorbance measured at 157 nm / micron is 0.009 /
It is micron. The measured absorbance / micron at 193 nm is 0.003 / micron. The measured absorbance / micron at 248 nm is -0.00030 / micron.

Example 18A-PDD / VF ₂ After cooling 75 ml of an autoclave to <-20 ° C, CF ₃ CFHC was added to it.
20 ml of FHCF ₂ CF ₃ , CF ₃ CFHCFHCF ₂ CF ₃ ~ 0.17M D
5 ml of P and 20 g of perfluorodimethyldioxole (PDD) were charged. After exhausting the autoclave, 6 g of vinylidene fluoride (VF ₂ )
Filled. Shaking of the autoclave at room temperature overnight produces a viscous oil that is devolatized in air and pumped under vacuum for 32 hours, then 75
By performing this in a vacuum oven at 0 ° C. for 23 hours, 16 g of a white resin was obtained. Calculated value for (C ₅ F ₈ O ₂ ) ₅ (C ₂ H ₂ F ₂ ) ₁ : C 26.11% H 0.37% Measured value: C 26.03% H 0.53% DSC, 10 ° C / Min, nitrogen: 96 ℃? (Weak) Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.671 Solution preparation and results: 2 g of poly (PDD / VF ₂ ) were shaken with 18 g of 1H-perfluorohexane to give a cloudy solution. Was generated. The solution was passed through a 0.45μ glass microfiber syringe filter [Whatman, Autovial ™] using a packing of chromatographic silica gel with the aid of filtration to replace the 1H-perfluorohexane lost by evaporation. After adding an additional approximately 1H-perfluorohexane in approximately equal amounts, the filtrate was filtered again through a 0.45μ Teflon ™ syringe filter [Whatman, Autovial ™]. At this point, a thick film was spin-coated on the optical substrate using the transparent filtrate, and the absorbance was measured.

Example 18B- A 400 ml stainless steel autoclave coated with PDD / VF ₂ Teflon ™ was cooled to <-20 ° C and then it was charged with 90% CF ₃ CFHCFHCF ₂ CF ₃ .
ml, a CF ₃ CFHCFHCF ₂ CF ₃ in 30ml and perfluoro dimethyl dioxole a DP ~0.1M was 120g filled. The autoclave was pressurized to 100 psi with nitrogen and evacuated 10 times. Finally, after adding 58 g of vinylidene fluoride (VF ₂ ), the autoclave was shaken at room temperature overnight. The resulting dense gel was dried under nitrogen, then under pump vacuum and finally in a vacuum oven at 75 ° C. for 4 days to give a white resin
22 g was obtained. Calculated value for (C ₅ F ₈ O ₂ ) ₅ (C ₂ H ₂ F ₂ ) ₈ : C 28.42% H 0.93% Measured value: C 28.22% H 1.16% DSC, 10 ° C / Min, nitrogen: 59 ° C. Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.576 Solution preparation: 1.70 g of poly (PDD / VF ₂ ) was shaken with 15.3 g of hexafluorobenzene to form a solution. Was generated. It was filtered through a 0.45μ glass fiber fine fiber syringe filter [Whatman, Autovial ™] to produce a clear colorless solution. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of PDD / VF ₂ (5: 8) was spin-coated on the CaF ₂ substrate to form a polymer film with a thickness of 38,298 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 19, the absorbance (expressed in units of reciprocal microns) of PDD / VF ₂ (5: 8) is compared to the wavelength lambda (λ) (expressed in units of nanometers) for sample 29. Indicate. The measured absorbance at 157 nm / micron is 0.018 /
It is micron. The measured absorbance / micron at 193 nm is 0.010 / micron. The measured absorbance at 248 nm / micron is 0.000057 / micron.

[0144] in Hastelloy C autoclave of Example _{19A-HFIB / VF 2 / VF} 210ml CF 2 ClCCl 2 F
50 ml, and cooled to <−20 ° C., and then CF ₃ CFHCFHCF ₂ C
The DP in F ₃ ~0.2M was added 15ml. After exhausting the autoclave, 32 g of hexafluoroisobutylene (HFIB) and vinylidene fluoride (V
3 g of F ₂ ) and 7 g of vinyl fluoride (VF). Shaking of the autoclave at room temperature overnight produced a thick paste of a white solid which was dried under nitrogen under pump vacuum for 70 hours and in a vacuum oven at 75 ° C. for 23 hours. Thereby, 33 g of product showing an analytical value in conformity with the range of possible stoichiometry
Obtained. Calculated value of (C ₄ H ₂ F ₆ ) ₃ (C ₂ H ₃ F) ₁ (C ₂ H ₂ F ₂ ) ₁ : C 31.91% H 1.84% (C ₄ H ₂ F ₆ ) ₅ ( Calculated value for C ₂ H ₃ F) ₁ (C ₂ H ₂ F ₂ ) ₃ : C 31.78% H 1.81% Measured value: C 31.78% H 1.88% DSC, 10 ° C./min. Nitrogen: T _g = 48 ° C. Inherent viscosity [acetone, 25 ° C.]: 0.030 dL / g Solution preparation and results: 8 g of the polymer was shaken with 20 g of heptanone to form a cloudy solution. Using 1 g of a packing of chromatographic alumina with the aid of filtration, the solution was made into a 0.45μ glass fiber syringe filter [Whatman, A
utovial (TM)], 0.45 [mu] Teflon (TM) syringe filter [Whatman, Autovial (TM)] and 0.45 [mu] Tef.
It was passed through a lon ™ syringe filter [Whatman, Autovial ™]. At this point, a thick film was spin-coated on the optical substrate using the transparent filtrate, and the absorbance was measured.

Example 19B-HFIB / VF / VF ₂ 200 ml of deionized water in a 400 ml autoclave, Vazo ™ 5
6 After loading 0.05 g of WSP initiator, pressurizing to 100 psi with nitrogen and venting 10 times. This autoclave was cooled to <-20 ° C. and exhausted, and then 82 g of hexafluoroisobutylene (HFIB), 13 g of vinylidene fluoride (VF ₂ ) and 14 g of vinyl fluoride (VF) were further charged. The contents of this autoclave were shaken at 50 ° C. for ˜64 hours. The resulting solid and emulsion mixture was frozen and thawed. Vacuum filtration and 200ml
The fluffy white solid was obtained by washing the inside of the filter twice with
There were some dark yellow lumps present which were removed. The remaining white fluff was washed two more times with 150 ml of methyl alcohol while it was in the filter. After suction-drying the white fluff on the filter, further drying was performed for 5 days under a pump vacuum to obtain 16 g of a polymer. Composition by Fluorine NMR: 41 mol% HFIB, 37 mol% VF, 22 mol% VF ₂ DSC, 10 ° C./min, nitrogen: 71 ° C. Inherent viscosity [tetrahydrofuran, 25 ° C.]: 0.523 Preparation of solution: 3g of poly (HFIB / VF / VF ₂₎ solution to produce a by shaking with 17g of 2-heptanone. Add it to a 0.45μ glass fiber fine fiber syringe filter and then a 0.45μ PTFE syringe filter [Whatm
, Autovial ™] to give a clear but slightly yellow solution. A film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of HFIB / VF / VF ₂ (41:37:22) was spin coated on the CaF ₂ substrate to form a polymer film with a thickness of 5289 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 19 shows that HFIB / VF / VF ₂ (41: 37: 2) for sample 31.
The absorbance (expressed in the unit of reciprocal micron) indicated by 2) is shown in comparison with the wavelength lambda (λ) (expressed in the unit of nanometer). The measured absorbance / micron at 157 nm is 0.016 / micron. The measured absorbance at 193 nm / micron is -0.010 / micron. Absorbance measured at 248 nm / micron is -0
． 002 / micron.

Example 20-PDD / TrFE In an autoclave of 75 ml, 40 ml water and Vazo ™ 56 WS.
0.1 g of P initiator was charged. After cooling the autoclave to <-20 ° C,
10 g of perfluorodimethyldioxole (PDD) was added. After exhausting the autoclave, 5 g of trifluoroethylene (TrFE) was added. When shaking was performed at 70 ° C. for 10 hours, a polymer mass was formed, and after separation of the mass, 75
It was placed in a vacuum oven at 0 ° C. and dried for 72 hours (9.9 g). Elemental analysis (C ₅ F ₈ O ₂ ) ₁ (C ₂ F ₃ H) ₁ measured value: C 25.51% H 0.55% Calculated value: C 25.79% H 0.31% DSC, 10 ° C. / Min, nitrogen: T _g = 150 ° C.? (Weak, second heat) Inherent viscosity [hexafluorobenzene, 25 ° C.]: 1.3 dL / g Solution preparation and results: Shaking 1 g of the polymer with 33 g of Fluorinert ™ Fc-75. After forming the solution in, was filtered through a 0.45μ glass microfiber syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of PDD: TrFE (1: 1) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 7688 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 16, the absorbance (expressed in units of reciprocal microns) of PDD: TrFE (1: 1) for sample 9 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance / micron at 157 nm is 0.03 / micron. The measured absorbance / micron at 193 nm is -0.004 / micron. The measured absorbance / micron at 248 nm is -0.001 / micron.

Example 21-CTFE / VF A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to 0 ° C., 5 to 0.1M DP in CF ₃ CFHCFHCF ₂ CF _{3 is} added to this.
ml was added. After exhausting the autoclave, 17 g of chlorotrifluoroethylene (CTFE) and 7 g of vinyl fluoride (VF) were charged. Shaking of the autoclave at room temperature overnight resulted in a swollen gel, which was dried under air, under pump vacuum for 96 hours and in a vacuum oven at 75 ° C. for 25 hours.
This gave 18 g of product. Calculated value for (C ₂ F ₃ Cl) ₁ (C ₂ H ₃ F) ₁ : C 29.56% H 1.86% Cl 21.82% Measured value: C 29.74% H 1.83% Cl 21 80% DSC, 10 ° C./min, nitrogen: T _g = 86 ° C. (first heating) Inherent viscosity [acetone, 25 ° C.]: 1.08 dL / g Solution preparation and results: 15 g of 2 g of the polymer A solution was formed by shaking with heptanone. Add this solution to a 0.45μ glass fiber syringe filter [Whatman
, Autovial (TM)], and the filtrate was used to spin coat a thick film onto an optical substrate for absorbance measurement.

A solution of CTFE: VF (1: 1) was spin-coated on a CaF ₂ substrate to yield polymer films 1850 Å and 17,644 Å thick. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 18, the absorbance (expressed in units of reciprocal microns) of CTFE: VF (1: 1) for sample 6b is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. Absorbance at 157 nm / measured with thicker membrane /
The micron is 0.388 / micron. 193n measured using thicker film
The absorbance at m / micron is 0.016 / micron. The absorbance / micron at 248 nm measured with the thicker film is 0.006 / micron.

Sample 10-VF ₂ / TrFE A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F, and <-20
After cooling to 0 ° C., 5 to 0.1M DP in CF ₃ CFHCFHCF ₂ CF _{3 is} added to this.
ml was added. After exhausting the autoclave, vinylidene fluoride (VF ₂
) And 12 g of trifluoroethylene (TrFE). Shaking of the autoclave at room temperature overnight produced a damp white solid which was dried under pump vacuum and in a vacuum oven at 75 ° C. for 24 hours. This gave 14 g of product. Calculated value for (C ₂ H ₃ F ₂ ) ₅ (C ₂ F ₃ H) ₂ : C 34.73% H 2.50% Measured value: C 34.78% H 2.48% DSC, 10 ° C / min nitrogen: first T _g = 55 ℃ 2 th T _g = 98 and 147 ° C. the inherent viscosity [acetone, 25 ° C.] of the heating of the heating: 1.087dL / g solution of preparation and results: 3.11 g above A solution was formed by shaking the polymer with 34.32 g of 1-methoxy-2-propanol acetate. The resulting cloudy solution (with particulates) was filtered through a 0.45μ glass fiber syringe filter [Whatm
an, Autovial (TM)] was difficult. This solution (2.8
Evaporation of 2 g) gave 0.220 g of residue (solids amount was 7.8% by weight, compared to 8.3% expected assuming no solids were removed by filtration). ). A thick film was spin-coated on an optical substrate and the absorbance was measured.

A solution of VF ₂ : TrFE (5: 2) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 4500 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 18 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : TrFE (5: 2) versus wavelength lambda (λ) (expressed in nanometers) for Sample 10. Indicate. Absorbance at 157 nm / micron is 0.924
/ Micron. The measured absorbance / micron at 193 nm is 0.188 / micron. The measured absorbance / micron at 248 nm is 0.083 / micron.

Example 23-HFIB / VOH A. Hexafluoroisobutylene (HFIB) / vinyl acetate (VOAc) copolymer 400 ml autoclave was filled with 50 ml of CF ₂ ClCCl ₂ F, 27 ml of vinyl acetate and 50 ml of DP of 0.1M in CF ₃ CFHCFHCF ₂ CF ₃ . . After cooling this autoclave and exhausting it, 49 g of HFIB was further added.
Filled. A viscous pale yellow solution formed after shaking overnight at room temperature. The polymer was precipitated by adding 400 ml of methyl alcohol. Filtration, drying under a pump vacuum and drying in a vacuum oven at 75 ° C. were performed for 19 hours to obtain 52 g of poly (HFIB / VOAc) having an inherent viscosity of 0.13 in acetone at 25 ° C. B. Hexafluoroisobutylene (HFIB) / vinyl alcohol (VOH) copolymer Poly (HFIB / VOAc) (50 grams) produced above, methyl alcohol (500 ml) and 25% by weight sodium methoxide in methyl alcohol ( 25 ml) was refluxed for 6 hours. Methyl alcohol is ~ 86 during this time
Methyl alcohol was additionally added since 0 ml was distilled. A rubbery precipitate formed upon addition of the resulting polymer solution to water. After decanting the water, the precipitate was taken up with 200 ml of methyl alcohol and W
Reprecipitation was carried out with 500 ml of water in an aring blender. Vacuum filtration, drying under a pump vacuum and subsequent drying in a vacuum oven at 75 ° C. for 24 hours gave 37 g of poly (HFIB / VOH) as off-white particles. Calculated value for (C ₄ H ₂ F ₆ ) ₁ (C ₂ H ₄ O) ₁ : C 34.63% H 2.91% Measured value: C 34.34% H 2.73% DSC, 10 ° C / min , Nitrogen: T _g = 90 ° C. (second heating) Solution preparation and results: A solution was formed by shaking 3.28 g of the polymer with 34.91 g of 1-methoxy-2-propanol acetate. It was The solution was passed through a 0.45μ glass fiber syringe filter [Whatman, Autovial ™] to give a slightly cloudy pale yellow solution. The solution was treated with 0.4 g of decolorizing carbon, filtered again, then treated with 0.58 g of silica gel and filtered a third time. The solution was still pale yellow but not cloudy. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of HFIB: VA (1: 1) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 1350 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 17, the absorbance (expressed in units of reciprocal microns) of HFIB: VA (1: 1) for sample 32 is plotted against wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance at 157 nm / micron is 0.350 /
It is micron. The measured absorbance at 193 nm / micron is -0.047 / micron. The measured absorbance / micron at 248 nm is -0.107 / micron.

Sample 12-HFP / TrFE A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to ° C., the DP of CF ₃ CFHCFHCF in ₂ CF _{3 ~0.17M} it was added 5ml thereto. After exhausting the autoclave, 12 g of hexafluoropropylene (HFP) and 12 g of trifluoroethylene (TrFE) were filled. Shaking of the autoclave at room temperature overnight yielded a damp white solid which was dried under pump vacuum for 22 hours and in a vacuum oven at 75 ° C for 2 hours.
I went for 4 hours. This gave 12 g of product. Composition by fluorine NMR: HFP 2 mol% and TrFE 98 mol% DSC, 10 ° C./min, nitrogen: T _m = 179 ° C., T _g was not detected inherent viscosity [acetone, 25 ° C.]: 0.912 dL Preparation of a solution: 2.5 g of poly (HFP / TrFE) was shaken with acetic ester of methyl ether of propylene glycol (50 ml) to form a cloudy solution. 0.45μ PTFE syringe filter [Whatman, Autovia
l (TM)] to give a clear filtrate. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of HFP: TrFE (2:98) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 1389 Å. Next, VU
Absorbance per micron was determined using V absorbance measurements.

FIG. 8 shows the absorbance (expressed in units of reciprocal microns) of HFP: TrFE versus wavelength lambda (λ) (expressed in units of nanometers) for Sample 12. The measured absorbance / micron at 157 nm is 1.37 / micron. The measured absorbance / micron at 193 nm is 0.143 / micron. Two
The measured absorbance / micron at 48 nm is -0.02 / micron.

Sample 14-HFP / TFE A hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) copolymer was prepared using the method of US Pat. No. 5,478,905 (December 26, 1995). . This polymer had 60 wt% HFP and 40 wt% TFE and had an inherent viscosity of 0.407 dL / g [Fluorinert
(Trademark) FC-75 in a solvent at 25 ° C.]. Solution Preparation: Shaking 31.6 g of HFP / TFE copolymer with 986 g of PF-5080 (Performance Fluid manufactured by 3M, which is believed to be mostly perfluorooctane). To form a solution. 0.
Vacuum filtration through a 45μ filter gave a clear filtrate. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of HFP: TFE (1: 1) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 1850 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 8 shows the absorbance (HFP: TFE (1: 1)) of sample 14 (
(Reciprocal units of microns) are shown versus wavelength lambda (λ) (expressed in units of nanometers). The measured absorbance / micron at 157 nm is 3.9 / micron. The measured absorbance / micron at 193 nm is 0.086 / micron. The measured absorbance / micron at 248 nm is 0.073 / micron.

Sample 15-VF ₂ / CTFE 75 ml autoclave was cooled to <-20 ° C to which 25 ml CF ₂ ClCCl ₂ F and 5 ml ~ 0.1M DP in CF ₃ CFHCFHCF ₂ CF ₃ were added.
Filled. After exhausting the autoclave, vinylidene fluoride (VF ₂ )
9.6 g and 17 g of chlorotrifluoroethylene (CTFE).
Shaking the autoclave at room temperature overnight produces a viscous white fluid which evaporates to a resilient solid which is then dried under pump vacuum for 1 hour. And it performed in the vacuum oven of 75 degreeC for 30 hours. This gave 19 g of product. _{(C 2 F 2 H 2)} 5 (C 2 F 3 Cl) 4 Calculated: C 27.50% H 1.28% Cl 18.04% measured: C 27.26% H 1.41% Cl 17.91% DSC, 10 ° C./min, nitrogen: T _g = 99 ° C. Inherent viscosity [acetone, 25 ° C.]: 0.546 dL / g Solution preparation: 3 g poly (VF ₂ / CTFE) 20 g 2- After shaking with heptanone to form a solution, 0.45μ glass fiber syringe filter [Wh
atman, Autovial ™]. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A polymer film was formed by spin coating a solution of VF ₂ : CTFE (5: 4) onto a CaF ₂ substrate. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 18 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : CTFE (5: 4) versus wavelength lambda (λ) (expressed in nanometers) for sample 15. Indicate. The measured absorbance / micron at 157 nm is 5.6 / micron. The measured absorbance / micron at 193 nm is 0.27 / micron. The measured absorbance / micron at 248 nm is 0.12 / micron.

Sample 16-PMD / TFE A 75 ml autoclave was cooled to <-20 ° C. and CF ₃ CFHCF was added to it.
The DP of HCF in ₂ CF _{3 ~0.14M} 5ml, the CF ₃ CFHCFHCF ₂ CF ₃ and 11.6ml filled with 25ml and perfluoro (2-methylene-4-methyl-1,3-dioxolane) (PMD). After evacuation of this tube, 5 g of tetrafluoroethylene (TFE) was further charged. Shaking at room temperature overnight produced a viscous milk-colored oil. Evaporation under nitrogen under pump vacuum for 76 hours and 7
The resin was aged in a vacuum oven at 5 ° C. for 24 hours to obtain 20 g of resin, which was assumed to be a copolymer having PMD: TFE of ˜2: 1 (PMD and TFE were ˜2.
1: 1 monomer ratio). DSC, 10 ° C./min, nitrogen: no T _g detected Inherent viscosity [Fluorinert ™ FC-75, 25 ° C.]: 0.
Preparation of 142 dL / g solution: 2.14 g poly (PMD / TFE) to 26.2 g Fluorinert (
0.45 after forming a cloudy solution by shaking with Trademark) FC-40.
0.45μ glass fiber syringe filter [Whatman, Autov after mixing with 0.2 g of chromatographic silica + 0.2 g of decolorizing carbon through a μ glass fiber filter [Whatman, Autovial ™].
ial ™] and finally 0.45μ PTFE difilter [Wh
Atman, Autovial ™]. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of PMD: TFE (1: 1) was spin-coated on a CaF ₂ substrate to form a 2207 Å thick polymer film. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 18, the absorbance (expressed in units of reciprocal microns) of PMD: TFE (1: 1) for sample 16 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance / micron at 157 nm is 1.17 / micron. The measured absorbance / micron at 193 nm is -0.015 / micron. The measured absorbance at 248 nm / micron is 0.07 / micron.

Example 28-PMD / TFE A glass jar for 1 ounce samples was fitted with a rubber septum, flushed with nitrogen, flushed with nitrogen, cooled with dry ice, and then perfluoro (2-methylene-4-methyl-1). , 3-dioxolane) the DP of 3ml and CF ₃ CFHCFHCF in ₂ CF _{3 ~0.17M} was 0.5ml injected. The bottle was placed in ice water and allowed to warm slowly to room temperature over the next few hours with magnetic stirring. After ~ 62 hours at room temperature, the contents of the bottle, the rigid foam, is dried under pump vacuum and then 1
Drying in a vacuum oven at 50 ° C. for 17 hours and trituration with a spatula gave 4.1 g of white fines. DSC, 10 ° C./min, nitrogen: T _g = 135 ° C. Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.155 dL / g Solution preparation: 2 g of poly (PMD) is shaken with 18 g of hexafluorobenzene. After producing the solution, 0.45μ glass fiber syringe filter [Wha
tman, Autovial ™]. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

By spin-coating a solution of PMD on a CaF ₂ substrate, a thickness of 14.8% was obtained.
An 18 angstrom polymer film was produced. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 17 shows the absorbance (expressed in units of reciprocal microns) of PMD versus wavelength lambda (λ) (expressed in units of nanometers) for sample 33. The measured absorbance / micron at 157 nm is 0.603 / micron. 1
The measured absorbance / micron at 93 nm is -0.0007 / micron. 24
The measured absorbance / micron at 8 nm is -0.0001 / micron.

Example 29-PMD / PDD A glass jar for 1 ounce sample was fitted with a rubber septum, flushed with nitrogen and flushed with nitrogen, cooled with dry ice, and then perfluoro (2-methylene-4-methyl-1). , 3-dioxolane) (PMD) in 3 ml, perfluorodimethyldioxole (PDD) in 3 ml and CF ₃ CFHCFHCF ₂ CF ₃ in ˜0.17.
0.5 ml of DP of M was injected. The bottle was placed in ice water and allowed to warm slowly to room temperature over the next few hours with magnetic stirring. After ˜62 hours at room temperature, the contents of the bottle, a rigid foam, were dried under pump vacuum and then in a vacuum oven at 150 ° C. for 17 hours and milled with a spatula to give a white fines. 8.6 g was obtained. DSC, 10 ° C./min, Nitrogen: T _g = 147 ° C. Solution Preparation: After shaking 2 g of poly (PMD / PDD) with 18 g of hexafluorobenzene to form a partially gelatinous partial solution. , 0.45 [mu] glass fiber syringe filter [Whatman, Autovial (TM)] through a ~ 1/8 inch deep chromatographic silica gel padding. By sending a part of this solution to ¹⁹ F NMR, it was confirmed that the composition of the dissolved polymer was 50 mol% PMD and 50 mol% PDD. A thick film was spin-coated on the optical substrate using the remaining filtrate, and the absorbance was measured.

A PMD: PDD solution was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 12,762 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 17 shows the absorbance (expressed in units of reciprocal microns) of PMD: PDD versus wavelength lambda (λ) (expressed in units of nanometers) for sample 34. The measured absorbance / micron at 157 nm is 0.404 / micron. The measured absorbance / micron at 193 nm is 0.006 / micron.
The measured absorbance at 248 nm / micron is -0.002 / micron.

Example 30-PMD / VF ₂ An autoclave of 75 ml was cooled to <-20 ° C and CF ₃ CFHCF was added to it.
The DP of HCF in ₂ CF _{3 ~0.17M} 5ml, the CF ₃ CFHCFHCF ₂ CF ₃ and 11.6ml filled with 15ml and perfluoro (2-methylene-4-methyl-1,3-dioxolane) (PMD). This autoclave was purged with nitrogen to 100p
After pressurizing and evacuating si 10 times, vinylidene fluoride (
9.6 g of VF ₂ ) was charged. Shaking at room temperature overnight produced a white solid. Evaporate under nitrogen for 16 hours under pump vacuum and 32 in a 77 ° C. vacuum oven.
By agitating for a period of time, 23 g of a resin was obtained. Calculated value for (C ₅ F ₈ O ₂ ) ₁ (C ₂ H ₂ F ₂ ) ₂ : C 29.05% H 1.08% Measured value: C 28.71% H 1.38% Preparation of solution: 1 g Of poly (PMD / TFE) was shaken with 19 g of hexafluorobenzene to form a partial solution, followed by a 0.45μ glass fiber filter [
Whatman, Autovial ™] was passed through a chromatographic silica padding of ~ 1/4 "in depth. A portion of this solution was sent to ¹⁹ F NMR for composition of the dissolved polymer. Confirmed that the PMD was 54 mol% and the vinylidene fluoride was 46 mol% .The remaining filtrate was used to spin-coat a thick film on the optical substrate, and the absorbance was measured.

Sample 11-PDD: CTFE poly (perfluorodimethyldioxole / chlorotrifluoroethylene),
That is, poly (PDD / CTFE) has been reported many times in the literature, for example, in US Pat. No. 4,754,009. Poly (PDD / C used here
TFE) was poly (PDD / CTFE) produced by aqueous emulsion polymerization. Calculated value for (C ₅ F ₈ O ₂ ) ₁₀ (C ₂ F ₃ Cl) ₂₃ : C 22.52% Cl 15.93% Measured value: C 22.41% Cl 15.94% Preparation of solution: 1. A pale yellow solution was produced by shaking 5 g of poly (PDD / CTFE) with 30 ml of hexafluorobenzene and then passed through a 0.45μ glass fiber filter [Whatman, Autovial ™]. Since this solution was too viscous to spin coat easily, 11.2 g of this solution was further diluted with 10.1 g of hexafluorobenzene. A thick film was spin-coated on an optical substrate using this diluted solution, and the absorbance was measured.

A solution of PDD: CTFE (10:23) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 1903 Å. Next, V
UV absorbance measurements were used to determine the absorbance per micron.

In FIG. 18, the absorbance (expressed in units of reciprocal microns) of PDD: CTFE (10:23) for sample 11 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance at 157 nm / micron is 1.4
4 / micron. The measured absorbance / micron at 193 nm is 0.018 / micron. The measured absorbance / micron at 248 nm is 0.046 / micron.

[Brief description of drawings]

FIG. 1 shows the transmittance T (expressed in%) of the polymer skin at 157 nm as a function of the absorbance at 157 nm (expressed in units of reciprocal microns) from 0.4. Described over an absorbance range of 0.0. In this calculation, the thin film interference effect exhibited by the thin film was ignored.

FIG. 2 shows Teflon ™ AF 1601 (Sample 7a) and Cyt.
The absorbance (expressed in units of reciprocal microns) exhibited by op (TM) 9 (Sample 13) is described versus wavelength lambda ([lambda]) (expressed in units of nanometers).

FIG. 3 shows Te with a thickness of 2146 angstroms located on a silicon substrate.
The flon ™ AF 1601 film (Sample 7b) is described in terms of measured refractive index n and extinction coefficient k measured by VUV spectroscopic ellipsometry versus wavelength lambda (expressed in nanometers).

FIG. 4 shows the spectral transmission (in absolute units) of the Teflon ™ AF 1601 skins designed as an unsupported tuned etalon with a film thickness of 6059 Å in wavelength lambda (in nanometers). Represent) to describe. The interference edge exhibited by this tuning etalon can be clearly seen as a function of wavelength.

FIG. 5 shows the spectral reflectance (expressed in absolute units) of a Teflon ™ AF 1601 skin designed as an unsupported tuned etalon with a film thickness of 6059 Å in wavelength lambda (in nanometers). Represent) to describe. The interference edge exhibited by this tuned etalon can be clearly seen as a function of wavelength and the minimum of the reflection exhibited by the skin is found at 157 nm, which is the skin transmission at such lithographic wavelengths. Contribute to maximizing.

FIG. 6 describes the transmittance of the prepared Teflon ™ AF 1601 thin etalon coating at 157 nm, the lithographic printing wavelength, as a function of thin coating thickness. Since there is a thin film interference edge in this film, the skin transmittance oscillates with the thickness, so that the skin transmittance has a maximum value and a minimum value. An optimally tailored etalon skin design would correspond to a membrane with sufficient mechanical integrity and thickness to maximize transmission. As will be further seen, skins designed from such materials exhibit a transmission substantially lower than the target transmission of the 157 nm skin.

FIG. 7 shows Teflon ™ AF 1200 (Sample 8), Teflon.
™ AF 1601 (Sample 7a) and Teflon ™ AF 2
The absorbance (expressed in units of reciprocal microns) exhibited by 400 (Sample 5) is described versus wavelength lambda (λ) (expressed in units of nanometers). By increasing the PDD content of such a polymer to reduce the TFE content of the polymer from 52% to 32% and 11%, the length of any (CF ₂ ) _n continuous present in this polymer is increased. Note that the absorbance / micron decreases dramatically with decreasing length.

FIG. 8 shows the absorbance (in reciprocal units of microns) of TFE: HFP (Sample 14) and TrFE: HFP (Sample 12) in wavelength lambda (λ) (in nanometers). Described in contrast to. CF ₂ = CFH Monomer to HF
The presence of carbon causes an interruption so that the CF ₂ run is not lengthened. This effect is also exhibited by the TFE: HFP polymer having an absorption maximum value of TrFE: HFP.
It is also possible to understand that the polymer shifts to the short wavelength side.

FIG. 9 shows VF ₂ : PDD (Sample 2), VF ₂ : HFP (Sample 1), HF.
The absorbance (expressed in units of reciprocal microns) of IB: TrFE (Sample 3) and HFIB: VF (Sample 4) is described versus wavelength lambda (λ) (expressed in nanometers).

FIG. 10 shows the measured refractive index n and extinction coefficient k of a HFIB: VF film (Sample 4a) having a thickness of 14,386 angstroms, which is placed on a silicon substrate, measured by VUV spectroscopic ellipsometry. Lambda (expressed in nanometers)
Described in contrast to.

FIG. 11 shows the spectral transmission (expressed in absolute units) of the HFIB: VF skin designed as an unsupported tuned etalon with a film thickness of 3660 Å in wavelength lambda (expressed in nanometers). Describe them in contrast. The interference edge exhibited by this tuning etalon can be clearly seen as a function of wavelength.

FIG. 12 shows the spectral reflectance (expressed in absolute units) of the HFIB: VF skin designed as an unsupported tuned etalon with a film thickness of 3660 Å in wavelength lambda (expressed in nanometers). Describe them in contrast. The interference edge exhibited by this tuned etalon can be clearly seen as a function of wavelength and the minimum of the reflection exhibited by the skin is found at 157 nm, which is the skin transmission at such lithographic wavelengths. Contribute to maximizing.

FIG. 13 shows HFI having a transmittance of 0.022 and a refractive index of 1.5 per micron.
B: The TF adjusted etalon thin film shows the transmittance at the lithographic printing wavelength of 157 nm as a function of the thin film thickness. Note that the maximum transmission exhibited by this skin at thin film thicknesses up to 3660 Angstroms exceeds the target specification of 98%.

FIG. 14 shows that the transmittance of a thin etalon thin film prepared from a polymer having a transmittance of 0.01 per micron and a refractive index of 1.5 is thin at a planographic printing wavelength of 157 nm. Described as a function of film thickness. It should be noted that the maximum transmittance shown when the skin has a thin film thickness of 8371 angstroms exceeds the target specification of 98%.

FIG. 15 shows TFP: TFE (5: 6) (sample 17), HFIB: VF (sample 18), VF ₂ : PFMVE (5: 2) (sample 19), VF ₂ : PFP.
VE (7: 5) (Sample 21) and VF ₂ : HFP (79:21) (Sample 22) showed the absorbance (expressed in units of reciprocal microns) of wavelength lambda (λ) (
(Expressed in units of nanometers).

FIG. 16 shows PDD: TrFE (1: 1) (Sample 9), VF ₂ : PFMVE.
(13:10) (Sample 20), HFP: PFMVE: VF ₂ (2: 5: 2)
(Sample 23), HFIB: VF (10: 7) (Sample 24) and PDD
: PFMVE (6: 5) (Sample 25) shows the absorbance (expressed in units of reciprocal microns) versus the wavelength lambda (λ) (expressed in units of nanometers).

FIG. 17   In FIG. 17, VF: ClDFE (20:11) (Sample 26), PDD: VF ₂ (1: 2) (Sample 27), HFIB: VA (1: 1) (Sample 32),
Absorbance of PMD (Sample 33) and PMD: PDD (Sample 34)
Wavelength lambda (λ) (expressed in units of reciprocal microns) (expressed in units of nanometers)
It is described in contrast to

FIG. 18 shows CTFE: VF (1: 1) (sample 6b), VF ₂ : TrFE (
5: 2) (Sample 10), PDD: CTFE (10:23) (Sample 11)
, VF ₂ : CTFE (5: 4) (Sample 15) and PMD: TFE (1: 1).
) (Sample 18) shows the absorbance (expressed in units of reciprocal microns) versus the wavelength lambda (λ) (expressed in units of nanometers).

FIG. 19 shows PDD: VF ₂ (5: 8) (Sample 29) and HFIB: VF.
: VF ₂ (41:37:22) (Sample 19) shows the absorbance (expressed in units of reciprocal microns) versus the wavelength lambda (λ) (expressed in units of nanometers).

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission Date] December 7, 2001 (2001.12.7)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Contents of correction]

Title: Ultraviolet and vacuum ultraviolet transparent polymer compositions and their use

[Claims]

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to partially fluorinated and fully fluorinated polymers that are substantially transparent to ultraviolet radiation at wavelengths of about 140 nanometers to 186 nanometers.

BACKGROUND OF THE INVENTION The semiconductor industry is the foundation of the $ 1 trillion electronics industry. In the semiconductor industry, Mo is constantly
The density of integrated circuits is doubling every 18 months in an attempt to satisfy the requirements of ore's law, most of which is due to optical lithographic printing.
There is a constant need for improvements in the ability to reduce the features when printing features on silicon in a graph. The circuit pattern is included in the photomask and the optical stepper (s)
The pattern of the mask is projected onto the photoresist layer on the silicon wafer using a stepper). Present lithographic printing is done using 248 nm light,
Lithographic printing using 3 nm light is just in the early stages of production. Alternatives to lithographic printing using neither visible light nor UV light, i.e. the next generation of lithographic printing using X-rays, e-beams or EUV radiation, are not ripe enough for production. The industry has concluded through the International Association of SEMATECH that lithographic printing based on 157 nm light will be the next technological step. 157 nm is located in the spectral region called vacuum ultraviolet (VUV) and this range extends from 186 nm to less than 50 nm. When using such VUV lithographic printing, it is necessary to use a material that is transparent in such a range. Specifically, the standardization of new lithographic printing using light at 157 nm results in the need for new polymeric materials based on the transmission requirements at 157 nm. With the ongoing use of new technologies, there is a continuing need for improved materials useful at shorter wavelengths.

Certain fluoropolymers have already been identified as useful in optical applications such as light guides, antireflective coatings and layers, skins and glues, and the like. Most of this work has been done at wavelengths above 200 nm, and there is little interest in the absorbance of perfluoropolymers at such wavelengths.

WO 9836324 (August 20, 1998, Mitsui Chemical)
al Inc. ), A resin consisting of only C and F, optionally in combination with a silicon polymer having a siloxane backbone, from 140 to 200 nm.
It is disclosed to be used as a thin film having an absorbance / micrometer of 0.1 to 1.0 at the ultraviolet wavelength of. In addition to the data presented in this document, measurements made by the applicant on fluoropolymers (see Table I below) show that the absorbances of the C and F fluoropolymers at least at 157 nm are WO 98363
It is shown to be much larger than A / μ = 0.1-1 as claimed in 24.

WO 9822851 (May 28, 1998, Mitsui Chemical)
al Inc. ) Claims the use of a tacky photo-degradable polymer which, when coated on the inside of a pellicle frame, fixes the particles of dust. The composition of such a pressure-sensitive adhesive material predominantly low molecular weight - (CF ₂ -CXR
) It consists of a copolymer, wherein, X is halogen and R is -Cl or -CF _3. For the purpose of improving creep resistance, a polymer having a higher molecular weight such as poly (perfluorobutenyl vinyl ether), poly [(tetrafluoroethylene / perfluoro- (
2,2-Dimethyl-1,3-dioxole)], poly (tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride), poly (hexafluoropropylene / vinylidene fluoride) or poly (chlorotolylfluoroethylene / vinylidene fluoride) ) Is added as a small component. Examples of such techniques have all been made using poly (chlorotrifluoroethylene) as a low molecular weight adhesive, poly (chlorotrifluoroethylene) strongly absorbing and claiming light at 157 nm. The advantage shown as a benefit of the formulation is the tackiness after long-term exposure to UV degradation (UV degradation shown is only at 248 nm).
It should be noted that it is only a retention (not permeable).

Japanese Patent 07295207 (November 10, 1995, Shinetsu C
hem. Ind Co. ) For the purpose of increasing the strength of Cytop (trademark) CT
XS (poly (CF ₂ ═CFOCF ₂ CF ₂ CF═CF ₂ )) was added to Teflon ™.
A bilayer skin in combination with AF 1600 is claimed. Both Teflon ™ AF 1600 and Cytop ™ exhibit strong absorption at 157 nm (see Table 2).

US Pat. No. 5,286,567 (February 15, 1994, Shin-Etsu)
Chemical Co. , Ltd. ), A copolymer made of tetrafluoroethylene and a 5-membered cyclic perfluoroether monomer, which is made hydrophilic by plasma treatment and thus has antistatic properties, is used as a thin skin. Is being billed. The presence of 5-membered ring monomer and tetrafluoroethylene is not always A / μ.
It is shown in Table 2 that the criteria are not sufficient to yield <0.1, and of the five such polymers shown in Table 2, only one polymer satisfies the above goal. Only.

European Patent No. 416528 [March 13, 1991, DuPont (DuP
ont)] has a refractive index of 1.24-1.41 at a wavelength of 190-820 nm.
It is claimed to use the amorphous fluoropolymers of the above as a skin.

Japanese Patent 01241557 (Bando Chemical Industr
ies, Ltd. , September 26, 1989), vinylidene fluoride (VF ₂ )
, Tetrafluoroethylene / hexafluoropropylene (TFE / HFP), ethylene / tetrafluoroethylene (E / TFE), TFE / CF ₂ = CFORf
, TFE / HFP / CF ₂ = CFORf, chlorotrifluoroethylene (CTF
E), E / CTFE, CTFE / VF 2 and made from vinyl fluoride (VF) (co) polymers have been used can be used at the 280-360nm thin skin is claimed.

Japanese Patent 59048766 (March 21, 1984, Mitsui Toat
su Chemicals, Inc. ), It is claimed that a stretched film of poly (vinylidene fluoride) is used as a film having a good transmittance at 200 to 400 nm.

Many of the fluoropolymers cited in the references cited above are fairly cloudy to the eye, because they are crystalline and therefore have high light transmission and circuit patterning. This is because it seems to scatter light to a degree that is not desirable for accurate reproduction. Poly (vinylidene fluoride), Poly (chlorotrifluoroethylene)
, Poly (tetrafluoroethylene / ethylene), commercial poly (tetrafluoroethylene / hexafluoropropylene) compositions and poly (ethylene / chlorotrifluoroethylene) all exhibit such crystallinity and are optically hazy materials. Is. Therefore, more recent references include Cytop (TM) and Teflon (TM) A.
In the direction of F, it is because they are completely fluorine-substituted, combined with excellent optical clarity, solubility and no crystallinity. Because it is. However, as shown in the discussion below, Cytop ™ and Teflon ™
Most grades of AF do not show the required transmission at 157 nm.

It is an object of the present invention by providing partially fluorinated and fully fluorinated polymers which are substantially transparent to UV radiation in the wavelength range from 140 to 186 nanometers, especially 157 nanometers. Overcoming the challenges associated with technology.

SUMMARY OF THE INVENTION The present invention provides for electromagnetic radiation in the wavelength range of 140 to 186 nanometers to be emitted from an electromagnetic radiation source and from 140 to at least some of the passages of the radiation so emitted. A receptor that responds to electromagnetic radiation in the 186 nanometer wavelength range.
or) is positioned so that it has a pattern in space or time (a pattern).
ern in space or time is thereupon im
at least one optical element (opti) exhibiting an absorbance of <1 / micrometer.
cal element) between the radiation source and the receptor and deriving information from the pattern so provided, wherein the optical element comprises: Copolymer of CH ₂ ═CHCF ₃ and CF ₂ ═CF ₂ , CH ₂ ═CFH and CF ₂ ═CFCl
Copolymer of CH ₂ ═CHF and CClH═CF ₂ [the ratio of the monomers of said copolymer is in the range of about 1: 2 to about 2: 1], and the formula CX ₂ ═CH _{2 A} copolymer comprising units of two or more different monomers represented by the formula: wherein X is F or CF ₃ , and ≦ 60 mol% of perfluoro-2,2-dimethyl- Perfluoro (2-methylene), a copolymer made from 1,3-dioxole and one or more monomers of the formula CX ₂ ═CH _{2 where} X is F or CF _3. -4-methyl-1
, 3-Dioxolane) and perfluoro (2,2-dimethyl-1,3-dioxole) copolymer, and perfluoro (2-methylene-4-methyl-1,3-dioxolane) and vinylidene fluoride Combined, poly (perfluoro (2-methylene-4
-Methyl-1,3-dioxolane)).

The invention also relates to a source of electromagnetic radiation in the wavelength range from 140 to 186 nanometers, which is located in the optical path of at least part of the radiation which can be emitted from said source.
A receptor sensitive to radiation in the wavelength range of 40-186 nanometers, located between the source and the receptor and having an absorbance of <1.0 per micrometer in the wavelength range of 140-186 nanometers. An optical system comprising: at least one optical element shown; and means for producing a pattern of said radiation when electromagnetic radiation emitted from said source is projected onto said receptor, here, the optical element is a copolymer of CH ₂ = CHCF ₃ and _{CF 2 = CF 2, CH 2} = CFH and CF ₂ = CFCl
Copolymer of CH ₂ ═CHF and CClH═CF ₂ [the ratio of the monomers of said copolymer is in the range of about 1: 2 to about 2: 1], and the formula CX ₂ ═CH _{2 A} copolymer comprising units of two or more different monomers represented by the formula: wherein X is F or CF ₃ , and ≦ 60 mol% of perfluoro-2,2-dimethyl- Perfluoro (2-methylene), a copolymer made from 1,3-dioxole and one or more monomers of the formula CX ₂ ═CH _{2 where} X is F or CF _3. -4-methyl-1
, 3-Dioxolane) and perfluoro (2,2-dimethyl-1,3-dioxole) copolymer, and perfluoro (2-methylene-4-methyl-1,3-dioxolane) and vinylidene fluoride Combined, poly (perfluoro (2-methylene-4
-Methyl-1,3-dioxolane)).

The present invention also provides a skin, an anti-reflective coating, optionally optically clear glues, a light guide and a resist comprising the above-mentioned UV transparent material.

The present invention further provides a copolymer composition comprising 40-60 mol% hexafluoroisobutylene and 60-40 mol% trifluoroethylene poly (hexafluoroisobutylene: trifluoroethylene). To do.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides fluoropolymer compositions and their use in particular electronic applications.

Specific abbreviations used throughout this specification are: TFE tetrafluoroethylene HFP hexafluoropropylene VF vinyl fluoride CTFE chlorotrifluoroethylene VF vinylidene fluoride HFIB hexafluoroisobutylene TrFE trifluoroethylene. PDD 4,5-difluoro-2,2-bis (trifluoromethyl) -1,
3-Dioxole PMD Perfluoro (2-methylene-4-methyl-1,3-dioxolane) Teflon (TM) AF 2400 PDD: TFE 89:11 Teflon (TM) AF 1601 PDD: TFE 68:32 Teflon (TM). ) AF 1200 PDD: TFE 48:52 ClDFE 1-chloro-2,2-difluoroethylene PPVE perfluoro (propyl vinyl ether) PMVE perfluoro (methyl vinyl ether) VOAc vinyl acetate VOH vinyl alcohol TrP 3,3,3-trifluoro Propen Fluorinert ™ FC-75 3M is manufactured by Fluorinert ™ FC-40 3M, an electronics fluid believed to be nearly perfluoro (butyltetrahydrofuran) manufactured by 3M. 2,2'-bis (2-amidino-propane) dihydrochloride, an initiator manufactured by Vazo ™ 56 WSP DuPont, which is believed to be nearly perfluoro (tributylamine) DSC Differential Scanning Calorimeter The use of 157 nm light in the next generation of lithographic printing creates new photochemical problems that lithographic printing did not encounter at longer wavelengths. The energy of a 157 nm photon (a light amount of 182 kcal / mol or 7.9 eV) is
Ordinary chemical bonds such as C-F (108-116 kcal / mol), C-H (9
8-105 kcal / mol), C-C (88-97 kcal / mol) and C-
It is large enough to break Cl (82-86 kcal / mol) bonds and the like. The maximum absorbance values of selected hydrocarbons and fluorocarbon compounds are shown in Table 1.

[0019]

[Table 1]

¹ B. A. Lombos, P .; Sauvageau and C.I. Sandorfy
Chem. Phys. Lett. , 1967, 42. ² K. Seki, H .; Tanaka, T .; Ohta, Y. Aoki, A.A. Ima
mura, H .; Fujimoto, H.M. Yamamoto, H.M. Inokuch
i, Phys. Scripta, 41, 167 (1990).

As can be seen from the above table, the maximum UV absorbance shifts to the longer wavelength side as the chain length increases for both hydrocarbons and fluorocarbons. The fluorocarbon chain (CF ₂ ) _n absorbs near 157 nm in the range of n = 6 (142 nm) to n = 172 (161 nm), but the hydrocarbon chain (CH ₂ ) _n has n = 2 as early as possible.
Shows absorption at 157 nm. In addition, the resistance of fluorocarbon chains to UV absorption is clearly higher than that of hydrocarbon chains, so when the industry seeks high UV transparency, the degree to which it shifts towards complete fluorine substitution is high. It is not surprising that the is getting bigger. However, unless the chain length exceeds the length of (CH ₂ ) ₁ or (CF ₂ ) ₆ to obtain satisfactory transmission, a polymer that is completely transparent at 157 nm. It seems impossible to get. Consistent with this, for example, V. N. Vasilets et al., J. Pol
y. Sci, Part A, Poly. Chem. , 36, 2215 (1998), poly (tetrafluoroethylene / hexafluoropropylene), ie [poly (TFE / HFP)] [Teflon ™ AF FEP], showed a strong absorption at 147 nm and was photochemical. It has been reported to deteriorate. Similarly, we have found that poly (hexafluoropropylene: tetrafluoroethylene (1: 1)) is 1
It was confirmed that it showed a high absorption at 57 nm (Table 2, A / micron = 3.6 @
157 nm).

In lithographic printing, the polymer plays an important role in several areas: one role is to play with any granularity in the photomask object plane to ensure that the lithographic image is defect-free. The polymer thin film is masked with a mask pattern (mask pattern) for the purpose of preventing contamination.
It is the role said to put it on rn). The skin is a free standing polymer membrane, typically 0.8 microns thick, which is typically mounted in a 5 inch square frame. Such thin coatings provide lithographic wave lengths for efficient imaging.
) Is highly transmissive to light (transparency or transmi
ssion) and should not darken or burst even after prolonged exposure in the optical stepper. In the current lithographic printing wavelength skins, the use of skins having a transmittance of> 99% by developing a polymer exhibiting a very low absorptivity and a thin film interference effect. 157 nm photolithographic printing (photo
The SEMATECH target for thin skin used in Lithography is 0.1
75 million laser pulses of mJ / cm ² , i.e. a radiation dose of 157 nm light of 7.
The transmittance is 9 over the exposure life of 5 kJ.
More than 8%.

The thin skin having a transmittance of 98% corresponds to an absorbance A of about 0.01 per 1 μm of film thickness. This absorbance is defined by Equation 1, and in this Equation 1,
Base 10 logarithm of the absorbance A per micron of film thickness divided by the transmittance of the substrate divided by the transmittance of the polymer membrane sample placed on this substrate. Is defined as the amount divided by the polymer film thickness. Formula 1

[0024]

[Equation 1]

In this manner, the absorbance A is expressed in units of reciprocal microns (ie 1 / micron),
Here, 1 micron of the polymer film thickness is 1 micrometer or 1 um. For the determination of the absorbance / micron of polymer membranes discussed here, the CaF ₂
The measurements were performed on a polymer film that was spin coated on the substrate. The VUV transmittance of each CaF ₂ substrate was measured before spin coating of the polymer film. Next, the VUV transmission exhibited by the polymer film as placed on its individual CaF ₂ substrate was measured and, using the measured film thickness (reported in Table 2) and Equation 1, Absorbance /
The micron value was determined as a function of wavelength, and the absorbance / micron value at the wavelength of 157 nm is shown in Table 2. For some materials, two types of films with different thicknesses are shown in Table 2 and also the absorbance / micron values given by each film.

Laser plasma light source, sample chamber with the ability to perform both transmission and reflectance measurements, 1 meter monochromator and 1024 element photodiode covered with sodium salicylate phosphor A VUV spectrophotometer using an (element photodiode) detector was used to measure the VUV transmittance of the CaF ₂ substrate and the polymer film on the CaF ₂ substrate. This is R. H. Fre
nch, “Laser-Plasma Sourced, Temperatur
e Dependent VUV Spectrophotometer Us
ing Dispersive Analysis ", Physica Scr
ipta, 41, 4, 404-8, (1990), which is incorporated herein by reference, and is discussed in more detail.

The absorbance per micron of polymer is used to measure the average transmission exhibited by unsupported thin films made from the polymer. In FIG. 1, the transmittance T (expressed in%) of the polymer skin at 157 nm as a function of the absorbance at 157 nm (expressed in reciprocal microns) is calculated from 0.4 to 0.0. Shown over the absorbance range. In this calculation, the effect of thin film interference exhibited by the thin film is ignored. Shows the results for thin coatings with thicknesses in the range 0.2 microns to 1 micron,
This result shows that the transmittance of the thin skin can be increased by reducing the thickness of the thin film regardless of the specific polymer used. In this way, the approach of increasing the transmittance of the thin skin is limited in its application range because the thin film is a non-supporting polymer film and it is necessary to have sufficient mechanical strength and integrity. Was done. Such mechanical requirements suggest that polymers with relatively high glass transition temperatures T _g should be used to achieve polymer film thicknesses of 0.6 microns and above. The target absorbance / micron is 157n when a polymer is used for thin skin applications.
It can be seen from Figure 1 that the absorbance at m / micron is <0.02.

FIG. 2 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 1601 and Cytop ™ compared to the wavelength lambda (λ) (expressed in nanometers). . The absorbance / micron shown at Cytop at 157 nanometers is a value of 1.9 / micron, while Teflon ™
The absorbance exhibited by AF 1601 is 0.42 / micron, which is Cy.
About 5 times lower than that of top. We have found that even though Teflon ™ AF 1601 has an absorbance of 0.42 / micron at 157 nm, this degree of absorbance is too high to use it as a skin used at 157 nm. This is shown in Example 1.

Variable angle spectroscopic ellipsometry (VASE) 1
Used at three angles of incidence covering the 86-800 nm wavelength range (which corresponds to a range of energies of 1.5-6.65 eV), this was used for a single angle of incidence of 143-275 nm (which is 4. VU carried out in the energy range of 5-8.67 eV)
Optical characteristics (refractive index “n” and extinction coefficient “k”) were measured in combination with V ellipsometry (VUV-VASE) measurement. The polymer film was spin coated on a silicon substrate. VASE Ellipsometer
rs) is from J. A. Woollam Company (645 M Street
, Suite 102, Lincoln, NE 68508 USA). Optical model in which the film is located on the substrate
At the same time using the optical constants (optical constants)
Adapted. Generally, O. S. Heavens, Optical Pro
parts of Thin Solid Films, pp. 55-62, D
over, NY, 1991 (incorporated herein by reference).
checking ...

Since it is known that the optical characteristics depend on the spectrum, it is necessary to calculate the transmittance of a thin film having an arbitrary thickness by using an unsupported thin film optical model in which the thickness of the polymer film is specified. And then the transmittance and reflectance of the thin film can be calculated. In this way, the thickness of the thin coating can be optimized so that the thin skin maximizes thin film interference in the transmission spectrum exhibited at the desired lithographic printing wavelength. Such transmission maximums exist for various film thicknesses, which are determined by the index of refraction of the polymer, the lithographic wavelength of interest, and the film thickness. When the reflectance of a properly adjusted etalon thin film shows a minimum value with respect to the reflectance, the transmittance of the thin film becomes maximum, which is the reflectance that the thin film shows at the lithographic printing wavelength. Corresponds to the minimum and the maximum transmittance. Extinction coefficient k in equation 2
And the extinction coefficient α and the absorbance A per micron, where lambda is the wavelength of light. This relationship is useful when comparing the results of absorbance measurements and ellipsometry measurements. The above relationship for A is accurate if the light scattering that occurs within the polymer film (as may occur due to the crystallinity of the polymer), thin film interference effects and surface scattering effects is minimal. Formula 2

[0031]

[Equation 2]

Polymeric materials with very low absorbance / micron or extinction coefficient and low refractive index values also provide anti-reflective coatings and optical adhesives.
It also has a very important application as s). Materials with low absorbance can be used for the purpose of reducing the amount of light reflected from the surface of the transparent substrate, which has a relatively high refractive index, as taught herein. This reduction in the amount of light reflected is accompanied by an increase in the amount of light transmitted through the transparent substrate material. VF ₂ : PDD, VF ₂ : H shows that such a material with low absorbance / micron exhibits an antireflection coating effect.
The results can be seen in the case of FP, HFIB: TrFE and HFIB: VF, where the absorbance of the polymer on the CaF ₂ substrate shows a negative absorbance / micron when the film is very thin. . This corresponds to a higher light transmittance at 157 nm through the polymer film on the CaF ₂ substrate than at a bare CaF ₂ substrate. The thickness of the polymer film as measured by us for VF ₂ : HFP, HFIB: TrFE and HFIB: VF was much thicker (also listed in Table 2) and in this case no anti-reflective coating effect was observed. It can be seen that the absorbance / micron exhibited by such polymers is positive and very small.

Such polymers can also be used in optical elements.
They can also be used as adhesives when bonding together and because of their low absorbance / micron and low index of refraction values, they are the light that occurs at the air / substrate interface present in the optical element. , And also directs more light as the transmitted light travels from one optical element to the next optical element included in the system.

The materials of the present invention are useful in the manufacture of transmissive optical elements used in the vacuum ultraviolet region, such as lenses and beam splitters.

The material can also be used as an element in a compound lens designed to reduce chromatic aberration. Currently, the transparent focus element (transm)
CaF ₂ and possibly silica without hydroxyl are the only ones that appear to show sufficient transmission at 157 nm to be used in issisting elements. It is also generally known that an achromatic lens can be created using a second material having a different refractive index and dispersion (eg R. Kingslake, Academic Press, Inc., 1978).
, Lens Design Fundamentals, p. 77). For the HFIB: VF as described in Example 4, the data shown in FIG.
By ier fitting, it can be seen that it exhibits a refractive index of 1.4942 at 157 nm and a dispersion of 0.00220 nm ⁻¹ . Edward D.D. Pal
ik, “Hnadbook of Optical Constants of
Solids II ", p. 831, Academic Press, Inc.
By similarly fitting the refractive index data for CaF ₂ by A., Boston, MA (1991) and French, it was 1.55 at 157 nm.
It can be seen that it has a refractive index of 84 and a dispersion rate of 0.00234 nm ⁻¹ . Thus, it is expected that the use of one of such materials in cooperation with CaF ₂ will allow the construction of an achromatic lens from said material and other similar materials described in this application.

An additional area in which the polymer plays an important role is in the optical latent image (optical la).
As a photosensitive photoresist that captures a tent image). In the case of photoresists, light must pass through the entire thickness of the optical latent image resist layer, producing well defined vertical sidewalls during photoimaging and then into the developed polymer. A desired resist image should be produced. When a polymer is used as a resist at 157 nm, the thickness of this resist is about 200
If it is limited to 0Å, it may have a very high extinction coefficient A per micrometer of film thickness such as <~ 2-3.

WO 9836324 describes carbon / fluorine polymers, such as poly (tetrafluoroethylene / hexafluoropropylene), as a thin film that exhibits an absorbance A / μ of 0.1 to 1 when used at 140 to 200 nm. Is disclosed. The data shown in Table 1 above, which is derived from a literature source, is a report by Vasilets [V. N. Vasilets et al., J. Poly.
Sci. , Part A, Poly. Chem. , 36, 2215 (1998)], and the data shown in Table 2, which combines Applicant's data with additional literature data, casts doubt on the above disclosure. For example, poly (tetrafluoroethylene: hexafluoropropylene), that is, polymer # 14 in Table 2 has an A / μ value shown at 157 nm.
Is relatively strong at 3.9, which is the industrial target for thin skin (A / μ <0.01)
In addition to satisfying the above condition, the target of looseness of resist (A / μ <2-3) is not satisfied. Japanese patent 072952076 includes Cytop ™ and Teflo.
The bilayer film of n (TM) AF 1600 is claimed as a thin film. Cytop
(Trademark) has an A / μ of 1.9 at 157 nm (polymer # 13, Table 2).
And the A / μ of Teflon ™ AF 1600 is 0.4 (polymer # 7, Table 2). This is surprising in view of the data in Table 1, which shows that there is a significantly higher UV absorption at 160 nm whenever the number of CF ₂ groups linked in a chain exceeds about 6 Not that. In fact, W. H. Buck
And P.C. R. Resnick reported that more than 30% of the CF ₂ units of Teflon ™ AF 1600 were present as (CF ₂ ) _n continuations with n> 6, which indicated that A / u 0.4 [J. Scher
irs, Modern Fluoropolymers, John Wiley
, New York, 1997, Chapter 22, p. 401]. Unless it is possible to break the interactions that contribute to such absorption, it is impossible to find polymers based on carbon that exhibit complete transmission at wavelengths shorter than about 160 nm. Seem.

In Table 2 below, the absorbance / micrometer (A / μm) of the partially fluorine-substituted and completely fluorine-substituted polymer film spin-coated on the CaF ₂ crystal is shown at 157 nm.
). The polymers are listed in descending order of absorbance. In some cases, more than one sample of various polymers was prepared in one example. Therefore, the items described in the table are identified by both the example number (first column) and the sample number. In addition, the figure numbers showing the spectra exhibited by the various polymers are cross-referenced to the table.

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

[Table 9]

[0047]   Three types among the acyclic polymer structures listed in Table 2 (polymer VF₂: HFP, HFI
B: TrFE and HFIB: VF) have a detectable UV absorption at 157 nm.
Not shown. They are vinylidene fluoride (VF)₂) Or hexafluoroisobu
It is a copolymer containing any of the ethylene (HFIB). VF₂And HFI
B has common special structural features. For example, hexafluoroisobutylene
When the monomer itself is used, CH₂Continuation is -C (CF₃)₂− In segment
Therefore, the length before breaking is CH₂CH₂Can be: For vinylidene fluoride
Similarly, CH₂CF is continuous₂The length before being destroyed by CH₂CH₂Is less than or
CF₂CH is continuous₂CF before being destroyed by₂CF₂Can be: That is, CX ₂ = CY₂Monomer, eg VF₂And HFIB, etc., show a wide range of phases between C-F bonds.
Judging from the possible existence of extensive interactions or interactions between C—H bonds.
When cut off, it has a "self-interrupting" characteristic
To do. The rigid five-membered ring of PDD also has an unfavorable morphology for interactions.
Has the associated implications of forcing. PDD / TFE copolymer # 5
, # 7 and # 8, the absorbance is between 52 and 32 TFE content and 1
It drops from 0.6 to 0.4 and 0.0 as it goes down to 1 mol%. Immediately
If the PDD content is increased (CF₂)_nTransparent due to interruption of continuation
The property is improved. Other complete fluorine substitutions that will perform the same interrupt function as PDDs
It is predicted that it will be possible to find ring structures or partially fluorine-substituted ring structures
.

A solution of TFE: HFP and a solution of TrFE: HFP were placed on a CaF ₂ substrate 6
Spin coatings at spin speeds of 000 rpm produced polymer films with thicknesses of 1850 angstroms and 1389 angstroms, respectively. The VUV absorbance measurement was then used to determine the absorbance per micron.

Another example is shown in which the absorbance / micron at 157 nm is lowered by introducing TrFE instead of TFE. FIG. 8 shows TFE: HFP and TrFE: HF.
The absorbance exhibited by P (expressed in units of reciprocal microns) is shown versus wavelength lambda (λ) (expressed in units of nanometers). The presence of CHF carbons in the CF ₂ = CFH monomer causes an interruption to the long CF ₂ run.

This reduces the absorbance of TFE: HFP at 157 nm of 3.9 / micron to that of TrFE / HFP at 1.37 / micron. This effect is also exhibited by the maximum absorbance of TFE: HFP polymer being Tr.
It can also be understood as a transition to the shorter wavelength of the FE: HFP polymer.

Thus, we have found that PDD and CX ₂ = CY ₂ monomers [where X = -F or -CF ₃ and Y = -H] and optionally other monomers CR ^a R ^b. = CR ^c R ^d
{Wherein R ^a , R ^b or R ^c can be any one or all of these can be H or F, and R ^d can introduce solubility or crystallinity. if necessary to _{destroy, F, -CF 3, -OR f} [ where -R _f is C _n F _{2n + 1} (wherein,
n = 1 to 3)] and may be OH (when R ^c = H)} and is highly transparent to light at <186 nm (A / μ
<1 and more preferably A / u <0.1) types of polymers are specified. When the CR ^a R ^b = CR ^c R ^d monomer is randomly polymerized together with the PDD or CX ₂ = CY ₂ monomer, increasing the concentration statistically results in CR ^a R ^b = CR ^c R ^It is not possible to make it greater than ~ 25 mole percent because the length of the ^d- series will be so long that absorption will take place considerably. This means that the A / μ drops from 0.6 to 0.4 and 0.0 as the TFE content is reduced from ~ 52 to 32 and 11 mole percent, as mentioned above. : TFE copolymer (Teflon ™ AF 1200 in Table 2 respectively, Tefl
on ™ AF 1601, Teflon ™ AF 2400 polymer).
When the CR ^a R ^b = CR ^c R ^d monomer is polymerized in an alternating manner with PDD or CX ₂ = CY ₂ monomer, the concentration of CR ^a R ^b = CR ^c R ^d monomer may be increased. It can be forgiven at a higher price. This example is a 1: 1 HFIB: TrFE copolymer, which has an A / μ of -0.05 (Table 2, polymer number 3). Of course, random and alternating structures are by no means 100% ideal, and some monomers naturally tend to undergo block polymerization themselves or not themselves, thus random The CR ^a R ^b = CR ^c R ^d limit for the structure is approximately 25% and the CR ^a R ^b = CR ^c R ^d limit for the alternating structure is approximately 50%. Other combinations showing very high permeability include CH ₂ ═CHCF ₃ : CF ₂ ═CF ₂ , C
H ₂ ═CHF: CF ₂ ═CFCl, CH ₂ ═CHF: CClH═CF ₂ ˜2: 1 to 1: 2 copolymers are included. Suitable monomers for CX ₂ = CY ₂ include vinylidene fluoride and hexafluoroisobutylene. Suitable CR ^a R ^b = CR ^c R ^d monomers are those that introduce asymmetric centers into the polymer chain to increase solubility and destroy crystallinity, such as vinyl fluoride, Examples include trifluoroethylene, hexafluoropropylene and chlorotrifluoroethylene. Finally, it should be pointed out that creating a highly permeable structure as defined above does not automatically create a polymer useful for all of the claimed applications.
For example, it has already been pointed out that the use of poly (vinylidene fluoride) as a completely transparent and transparent optical material is excluded because it exhibits crystallinity [ie, poly (vinylidene fluoride) is a thin film. The reason why it cannot be used as is not the absorbance but the physical reason (light scattering). As another example, poly (perfluorodimethyldioxole) is too insoluble to spin coat it as a thick film. In the case of poly (perfluorodimethyldioxole), this can be avoided by coating the liquid monomer and allowing the polymerization to take place in the proper place. The monomer can be diluted, optionally with a solvent and / or an initiator, and placed where the membrane is desired to produce a membrane with a thickness greater than about 250 nm. The polymer can be deposited at the desired location by initiating the polymerization by suitable physical and / or chemical means. As a result of subsequent removal of the solvent, the resulting polymer film can be made thicker than that which can be produced using conventional solvent coating techniques. As a final example,
Poly [vinylidene fluoride / perfluoro (methyl vinyl ether)] is a rubbery substance which is not useful as a self-supporting thin film but has a viscosity useful as a paste. As used herein, the term "amorphous fluoropolymer" means a fluoropolymer that does not exhibit a melting point when analyzed by a differential scanning calorimeter. The absence of a melting point means that no more than 1 Joule / gram of thermal event associated with melting occurs.

Reference to a monomer as a precursor to a permeable polymer is meant to imply that it will homopolymerize or form a copolymer with any of the other monomers mentioned. Not a thing. For example, hexafluoroisobutylene does not form an effective amount of a homopolymer of standard molecular weight under normal conditions or copolymerize with tetrafluoroethylene. Claiming the use of such materials at 140 to 186 nm, they also form polymers that show excellent transmission at long wavelengths up to 800 nm, and they also at shorter wavelengths. It may also be suitable for use in certain applications. Particularly preferred wavelength is 140-160 nm,
150-160 nm is more preferred and 155-159 nm is most preferred.

Examples Many of the polymers tested were obtained as commercial samples. Teflon ™ AF 1200: DuPont (Wilmington, DE)
) Teflon (TM) AF 1600: DuPont Teflon (TM) AF 2400: DuPont Cytop (TM): Asahi Glass, poly [perfluoro (butenyl vinyl ether)] U.S. Patent No. 5,478,905 (December 26, 1995). Sun, using the procedure described in Poly (hexafluoropropylene: tetrafluoroethylene, ~ 1
1) was produced.

Many of the remaining polymer compositions are known in the art and were prepared by standard methods. Typically, the autoclave was charged with monomer, solvent and initiator and heated to initiate polymerization. Hexafluoropropylene oxide dimer Peroxide 1 (DP) for most polymerizations

[0055]

[Chemical 1]

The polymerization was initiated at ambient temperature with. DP with a solvent such as Vertrel ™ XF (CF ₃ CFHCFHCF ₂ CF ₃ ) or 3M Performance.
e Fluid PF-5080 (mostly perfluorooctane) was prepared and used as a 0.05 to 0.2 mol solution. The production of DP is a standard laboratory procedure [Chengue et al., J. Am. Org. Chem. , 47, 2009 (
1982)] or as required by the jet mixer method (1999 1
It can be conveniently carried out using U.S. Pat. No. 5,962,746, issued Oct. 5.
The polymer was then isolated by evaporation or filtration after collecting the reaction mixture. The composition of the polymer was measured by elemental analysis or NMR. Procedures are given for the preparation of new compositions and representative procedures for already known compositions.

A polymer film was formed by spin-coating a solution of the polymer on a CaF ₂ substrate, which was then applied and baked on a sample of the polymer film in a state of being positioned on this substrate material ( Post apply bake) so that no residual solvent remains in the polymer membrane. After baking, the temperature is changed from 120 ° C to 25 ° C using a hot plate.
It was performed in the range of 0 ° C. for 2 to 5 minutes or in a vacuum oven overnight. The spin rates of these samples are listed in Table 2.

Polymer film thickness measurements were made using single or multiple wavelength ellipsometry as discussed below, or by a Filmmetrics Model F20 thin film measurement device (Filmmetrics, Inc., 7675 Daggest St.,
Suite 140, San Diego, CA 92111-2255). The film thickness is reported in Table 2. Some materials have different thicknesses 2
The types of membranes are shown in the table and the absorbance / micron value for each membrane is shown.

Comparative Example A Teflon ™ AF 1601 A solution of Teflon ™ AF 1601 was placed on a CaF ₂ substrate at 6000r.
A polymer film having a thickness of 3323 angstrom was formed by spin coating at a spin speed of pm. The VUV absorbance measurement was then used to determine the absorbance per micron.

Teflon ™ AF 1601 is a PDD: TFE 68:32 polymer that is currently used as a skin polymer designed for use at lithographic printing wavelengths of 248 nm and 193 nm. The absorbance / micron for light at 157 nm is 0.42 / micron as determined by VUV absorbance measurement. This corresponds from FIG. 1 that even if the thickness of the thin film is only 0.2 μm, the transmittance of the thin film is less than 70%, and, of course, the thin film is properly designed. It is unlikely that the results are additionally influenced by the thin film interference effect.

For the purpose of measuring the VUV optical properties of Teflon ™ AF 1601, Teflon ™ AF 160 placed on a silicon wafer.
VUV ellipsometry was performed on one polymer sample to measure the refractive index and the extinction coefficient, which are shown in FIG. Teflon ™ AF 1601 has a refractive index of 1.4251 at 157 nm. The measured extinction coefficient at 157 nm corresponds to an absorbance / micron of 0.35 / micron, which is also shown in Table 2.

The optical properties of such Teflon ™ AF 1601 and the O.S. S. The Heavens method can be used to design thin etalon coatings that are tailored to minimize the reflection of the unsupported thin coating and maximize the skin transmittance. Is a thin film that causes optical fringes depending on the wavelength dependence of reflection or transmittance of the thin film due to constructive and destructive interference of light from the front surface and the back surface of the film (Max Born and Emil. A book by Wolf, "Principl"
es of Optics ", Pergamon Press, New Yor
k, 6th edition, copyright 1980, pages 329-333)]. In the case of a thin film having a thickness of 6059 angstroms, the transmittance at 157 nm in the thin skin is 65.7%, while the reflectance at 157 nm in the thin skin is 0.4%. Figure 4 shows Tefl designed as a tuned unsupported etalon with a thickness of 6059 Angstroms.
on (TM) AF 1601 Thin Skin Spectral Transmission (expressed in absolute units)
Is compared to the wavelength lambda (expressed in units of nanometers). The interference fringes exhibited by the tuned etalon can be clearly seen as a function of wavelength. FIG. 5 shows Teflon ™ AF 160 designed as a tuned unsupported etalon with a film thickness of 6059 Å.
1 shows the spectral reflectance (expressed in absolute units) of the thin skin of No. 1 against wavelength lambda (expressed in units of nanometers). The interference edge exhibited by the tuned etalon can be clearly seen as a function of wavelength, and the minimum reflectance of this thin skin is 157 nm.
, Which contributes to the maximum skin transmission at such lithographic wavelengths. Teflon ™ AF 160 with a thickness of 6335 Angstroms
In the thin film of No. 1, the adjusted etalon was not optimized so as to show the maximum thin skin transmittance at 157 nm, and the transmittance at the thin skin of 157 nm was 59.4%, while The reflectance shown at 157 nm is as high as 8.1%.

FIG. 6 shows a tuned thin etalon coating of Teflon ™ AF 1601.
The transmission shown at a lithographic wavelength of 57 nm is shown as a function of thin film thickness. Due to the fact that this film has a thin film interference edge, the skin transmittance varies with the thickness,
This results in maximum and minimum values for thin skin transmission. An optimally tailored etalon skin design would correspond to a membrane with sufficient thickness and mechanical integrity to maximize transmission. As will be further seen, skins designed from such materials will exhibit substantially lower transmission than the 98% transmission target for skins for 157 nm.

Thin skin designed from Teflon ™ AF 1601 cannot achieve a thin skin permeability of greater than 98%. Much higher absorbance at 157 nm / micron C
Even thin skins designed from ytop (TM) will have low thin skin transmission at 157nm. This means that there is a need for a method for producing a polymer having a dramatically low absorbance / micron at 157 nm so as to satisfy the desired transmittance of 98% at 157 nm in a thin film. Is shown. Therefore, we need polymers that exhibit substantially lower absorbance / micron.

Example 1- A solution of PDD / TFE Teflon ™ AF 1200, 1601 and 2400 was Ca.
Polymer films having thicknesses of 4066 angstroms, 3323 angstroms and 2133 angstroms were prepared by spin coating on an F ₂ substrate at a spin speed of 6000 rpm. The VUV absorbance measurement was then used to determine the absorbance per micron.

FIG. 7 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 1200 versus wavelength lambda (λ) (expressed in units of nanometers) for Sample 8. The measured absorbance at 157 nm / micron is 0.6
4 / micron. The measured absorbance / micron at 193 nm is 0.004 / micron. The measured absorbance / micron at 248 nm is -0.001 / micron.

FIG. 7 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 1601 versus wavelength lambda (λ) (expressed in units of nanometers) for sample 7a. The measured absorbance / micron at 157 nm is 0.
42 / micron. The measured absorbance at 193 nm / micron is 0.02 / micron. The measured absorbance at 248 nm / micron is 0.01 / micron.

FIG. 7 shows the absorbance (expressed in units of reciprocal microns) of Teflon ™ AF 2400 versus wavelength lambda (λ) (expressed in units of nanometers) for Sample 5. Absorbance measured at 157 nm / micron is 0.0
It is 07 / micron. The measured absorbance at 193 nm / micron is -0.06 /
It is micron. The measured absorbance / micron at 248 nm is -0.06 / micron.

One way to dramatically reduce the absorbance of PDD: TFE polymer at 157 nm is to increase the percentage of PDD included in the polymer. VF ₂
And, like HFIB, the rigid five-membered ring of PDD has a similar effect, namely, by pushing in the unfavorable morphology when judging the possibility that C—F bonds and C—F bonds may cause a wide range of interactions. Shows a "self-interrupting" effect. This is Te
The absorbances (expressed in units of reciprocal microns) of flon ™ AF 1200, Teflon ™ AF 1601 and Teflon ™ AF 2400 were compared to the wavelength lambda (λ) (expressed in nanometers). Figure 7
This figure shows the absorbance of such a polymer at 157 nm /
It proves that micron is low. Teflo, a PDD / TFE copolymer
157 nm when comparing n (TM) AF 1200, 1601 and 2400
The absorbance / micron drops to 0.6 to 0.4 / micron and 0.01 / micron as the TFE content drops from 52 to 32 and 11 mol%. That is, when the content of PDD is increased, interruption to (CF ₂ ) _n continuation occurs, so that the transmittance is improved. It is anticipated that it would be possible to find other fully or partially fluorinated ring structures that would perform the same function as the PDD does.

Example 2-Preparation of HFIB / TrFE poly (hexafluoroisobutylene: trifluoroethylene (1: 1)) A 75 ml stainless steel autoclave was cooled to <-20 ° C and C
25 ml Cl ₂ FCF ₂ Cl and ˜0.17 M in Vertrel ™ XF
5 DP of DP was charged. The autoclave was cooled and evacuated, and then 10 g of trifluoroethylene and 20 g of hexafluoroisobutylene were further charged. The reaction mixture was shaken overnight at ambient temperature (28 to 33 ° C.), removed from the autoclave and then evaporated to form a glassy film which was heated to 75 ° C.
In a vacuum oven for 72 hours for further drying. 3.33 g of white solid
Obtained. A solution was produced by shaking this polymer (3.24 g) with an acetic ester of 1-methoxy-2-propanol (PGMEA) (6.99 g).
After mixing this solution with 0.2 g of chromatographic silica gel and 0.2 g of decolorizing carbon, it is first passed through a 0.45μ glass microfiber syringe filter [Whatman, Autovial ™] and then at 0. 45μ PTFE Membrane Syringe Filter [Whatman, Autovial ™]
Passed through. CHF fluorine of trifluoroethylene located at -180 to -220 ppm shown by fluorine NMR of this solution was -58 to -65 ppm.
By contrasted to CF ₃ fluorine hexafluoroisobutylene located at the integrating it, hexafluoroisobutylene: trifluoroacetic ethylene to 1: was confirmed to be 1. An optical substrate (optical substr
ATE) was spin-coated with a thick film and the absorbance was measured. Sample Preparation and Results: A solution of HFIB: TrFE at 3000 rpm and 600 on a CaF ₂ substrate.
By spin coating at a spin speed of 0 rpm, the thickness is 12,146, respectively.
Polymer films of angstrom and 1500 angstrom were produced. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 9 shows the absorbance (expressed in units of reciprocal microns) of HFIB: TrFE (3: 2) versus wavelength lambda (λ) (expressed in nanometers) for sample 3a. Show. The absorbance / micron at 157 nm measured with the thicker polymer film is 0.012 / micron. The measured absorbance / micron at 193 nm is 0.005 / micron. The measured absorbance / micron at 248 nm is -0.001 / micron.

Example 3-Preparation of HFIB / VF poly (hexafluoroisobutylene: vinyl fluoride (3: 2)) A 75 ml stainless steel autoclave was cooled to <-20 ° C and C
25 ml Cl ₂ FCF ₂ Cl and ~ 0.07M in Vertrel ™ XF.
10 ml of DP was charged. After cooling this autoclave and exhausting it, 16 g of hexafluoroisobutylene and 5 g of vinyl fluoride were further charged. The reaction mixture was shaken overnight at ambient temperature (18 to 26 ° C.), removed from the autoclave as a dense gel, then evaporated and further pumped down using a vacuum pump for 96 hours. It was put in a vacuum oven at 75 ° C. and dried for 22 hours. 19 g of a brittle white solid was obtained, which had a T _g of 58 ° C. (nitrogen, 10 ° C./min, second heating) and no detectable T _m . Calculated value for (HFIB) ₃ (VF) ₂ : C 32.89% H 2.07% Measured value: C 32.83% H 2.08% Preparation of solution and results: 2- Shake with heptanone (12 g)
g) to produce a solution. The solution was passed through a 0.45μ glass fine fiber syringe filter [Whatman, Autovial ™], and then the filtrate was used to spin-coat a thick film on an optical substrate for absorbance measurement. Sample preparation and results: HFIB: VF solution on CaF ₂ substrate at 3000 rpm and 6000 r.
Spin coating at a spin speed of pm (revolutions per minute) produced polymer films with thicknesses of 14,386 angstroms and 2870 angstroms, respectively. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 9 shows the absorbance (HFB: VF (1: 1)) of sample 4a (
(Reciprocal units of microns) are shown versus wavelength lambda (λ) (expressed in units of nanometers). The absorbance / micron at 157 nm measured with the thicker polymer film is 0.027 / micron. The measured absorbance at 193 nm / micron is 0.020 / micron. The measured absorbance / micron at 248 nm is 0.008 / micron.

For the purpose of measuring the VUV optical properties of HFIB: VF, VUV ellipsometry was performed on the HFIB: VF polymer sample placed on a silicon wafer to measure the refractive index and the extinction coefficient. Then, they are shown in FIG. Tefl
The refractive index shown by on (trademark) AF 1601 at 157 nm is 1.50. The measured extinction coefficient at 157 nm corresponds to an absorbance / micron of 0.022 / micron, which is also shown in Table 2.

The optical properties of such HFIB: VF and the O.S. S. Hea
The Vens method can be used to design an etalon thin film tailored to minimize reflection and maximize skin transmittance of the unsupported thin film. 366 thickness
In the case of a thin film of 0 angstrom, the transmittance shown at the thin skin at 157 nm is 98.
%, On the other hand, the reflectance of the thin skin at 157 nm is 0.08%. Figure 11
Figure 3 shows the spectral transmission (expressed in absolute units) of a HFIB: VF skin designed as a controlled unsupported etalon with a film thickness of 3660 Angstroms versus wavelength lambda (expressed in nanometers). The interference edge exhibited by the tuned etalon is clearly visible as a function of wavelength. In FIG. 12, the film thickness is 36
HFIB: V designed as a 60 Angstrom tuned unsupported etalon
The spectral reflectance (expressed in absolute units) of the F skin is shown versus wavelength lambda (expressed in nanometers). The interference edge exhibited by the tuned etalon can be clearly seen as a function of wavelength, and the minimum reflectance of this thin skin is 157 nm.
, Which contributes to the maximum skin transmission at such lithographic wavelengths. The etalon prepared as a thin film for 157 nm of HFIB: VF with a film thickness of 3660 angstroms is 157n with a thin skin transmittance of 98% at 157 nm.
It is a thin skin for m.

FIG. 13 shows the transmission as a function of thin film thickness for a HFIB: VF tuned etalon thin film at a lithographic printing wavelength of 157 nm. Due to the fact that the membrane has thin film interference edges, there is an oscillation in the skin permeability with thickness, which leads to maximum and minimum skin permeability.

Example 4- Preparation of VF ₂ / PDD sample and results: A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F beforehand.
Cool to −20 ° C., to which is further added Perkadox ™ 16N [bis (4-t
-Butylcyclohexyl) peroxydicarbonate] and 20 g of perfluorodimethyldioxole (PDD) were evacuated, and after evacuation, 10.4 g of vinylidene fluoride (VF ₂ ) was charged. A thick oil formed upon heating to 70 ° C. for 18 hours. 17 g of white hard foam are obtained by evaporating in air, drying under pump vacuum for 22 hours and drying in an oven at 75 ° C. for 24 hours.
Obtained. Elemental analysis (C ₅ F ₈ O ₂ ) 1 (C ₂ H ₂ F ₂ ) 1 measured value: C 28.99% H 1.11% Calculated value: C 29.05% H 1.08% DSC, 10 ° C / min, nitrogen: T _g = 56 ° C (first heating) By shaking 4 g of poly (PDD / VF ₂ ) with T _g not detected in the second heating together with 16 g of hexafluorobenzene. After forming a viscous solution, it was filtered through a 0.45 micron glass fiber syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PDD was spin coated on a CaF ₂ substrate at a spin speed of 6000 rpm to produce a polymer film with a thickness of 2097 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 9 shows the absorbance (expressed in units of reciprocal microns) of VF ₂ : PDD for Sample 2 versus wavelength lambda (λ) (expressed in units of nanometers). The absorbance / micron at 157 nm measured with the thicker polymer film is -0.04 / micron. In this way, 15 materials with extremely high transmittance are
The negative value of the absorbance / micron at 7 nm indicates that there is an antireflective coating effect. The measured absorbance at 193 nm / micron is 0.02 / micron. The measured absorbance / micron at 248 nm is 0.08 / micron.

Example 5- Preparation and Results of VF ₂ / HFP Samples: Poly (vinylidene fluoride / hexafluoropropylene) produced using the method of US Pat. No. 4,985,520 (1/15/91). ) The sample was characterized.

Composition by fluorine NMR in deuteroacetone: HFP at 21 mol% VF _2.
Is 79 mol% DSC, 10 ° C./min, nitrogen: T _g = -22.5 ° C. (second heating) Inherent viscosity (acetone, 25 ° C.) = 0.753 dL / g VF ₂ : HFP solution CaF ₂ 3000 and 6000 rpm (1
By spin coating at a spin speed of (revolutions per minute), a thickness of 69,80 can be obtained.
Polymer films of 0 Å and 1641 Å were produced.
The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 9 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : HFP (79:21) with respect to Sample 1a versus wavelength lambda (λ) (expressed in units of nanometers). Indicate. The absorbance / micron at 157 nm measured with the thicker polymer film is 0.015 / micron. The measured absorbance / micron at 193 nm is 0.005 / micron. The measured absorbance at 248 nm / micron is 0.003 / micron.

Example 6-VF ₂ / HFP, VF ₂ / PDD, HFIB / TrFE Thin Skin We have shown that at 157 nm a polymer showing an absorbance / micron on the order of 0.01 / micron, eg VF ₂ : HFP, VF ₂ : PDD and HFIB: TrFE etc. can be used to design tailored etalon skins with high transmission and substantial film thickness. FIG. 14 shows the transmittance as a function of thin film thickness for a prepared etalon thin film of a polymer having an absorbance per micron of 0.01 and a refractive index of 1.50 at the lithographic printing wavelength of 157 nm. Show. It should be noted that the maximum thin skin transmittance exceeds the target specification of 98% when the thickness of the thin film is 8371 angstroms or less.

Example 7-TFE / TrP A. Polymerization of tetrafluoroethylene (TFE) and 3,3,3-trifluoropropene (TrP) A 240 ml autoclave was charged with 20 ml of CF ₂ ClCCl ₂ F and <-2.
After cooling to 0 ° C., 10% DP of 0.17 M in CF ₃ CFHCFHCF ₂ CF ₃ is used.
ml was added. After further cooling this autoclave and exhausting it, TrP was reduced to 10
g and 40 g of TFE were added. After shaking overnight at room temperature, the autoclave was evacuated to evaporate the flowing reaction mixture and pump at room temperature under pump vacuum at room temperature.
It took time to finish. This gave 9.96 g of a sticky colorless gum. Elemental analysis _{(C 3 H 3 F 3)} 5 (C 2 H 4) 6 measurements: C 29.86 H 1.74 Calculated: C 30.02 H 1.40 DSC, 10 ℃ / min, nitrogen: T _g = 8.8 ° C. (2nd heating) Solution Preparation and Results: 4 g of poly (TFE / TrP) was shaken with 12 g of hexafluorobenzene to form a solution, then 0.45 μ Filtered through a glass fine fiber syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of TFP: TFE (5: 6) was spin-coated on a CaF ₂ substrate to form a polymer film having a thickness of 41413 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 15, the absorbance (expressed in units of reciprocal microns) of TFP: TFE (5: 6) for sample 17 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance at 157 nm / micron is 0.149 /
It is micron. The measured absorbance / micron at 193 nm is 0.008 / micron. The measured absorbance / micron at 248 nm is -0.00085 / micron. B. Used as a glue for quartz and aluminum Aluminum coupons with dimensions 1 "wide, 3" long and 122 mils thick, and 1 "wide, 3" long and 65 mils thick Both of the quartz slides with C were rinsed with CF ₂ ClCCl ₂ F and then air dried.

4 g of poly (TFE / TrP) prepared above was shaken at room temperature with 12 g of hexafluorobenzene to form a clear colorless solution, then 0.4
Pass through a 5μ glass fiber filter. Three drops of the solution were applied to one end of the aluminum coupon and a quartz slide was pressed down on it so that the last 1 inch of the quartz slide overlaps the last 1 inch of the aluminum coupon. This caused some excess fluid to be extruded and the remaining polymer solution to wet the overlapping areas and spread evenly throughout. Two C-Clamps (Stock # 72020, ACCO USA Inc., 770-S AC
The hexafluorobenzene solvent was allowed to evaporate at room temperature for 3 days using a CO Plaza, Wheeling, IL 60090) while holding the aluminum coupon and quartz slide in place. One such assembly was placed in a 50 ° C. vacuum oven with the C clamp still attached to it and heated for 16 hours. The assembly was removed from the oven, allowed to cool, the C-clamp was removed, and an Instron was used to remove the 3 ″ jaw sepa.
and crosshead speed of 1 "/ min.
d) was used to measure the force required to pull the quartz slide away from the aluminum coupon. It took 12 pounds. The second assembly was heated with the C-clamp still attached to it in a vacuum oven at 50 ° C for 20 hours and in a vacuum oven at 75 ° C for 24 hours. I at this point
The force required to pull the aluminum coupon away from the quartz slide using an nstron was 127 pounds. C. Use as a glue for thin-skinned polymer 10 g of poly (HFIB / VF) (Example 2A below) is dissolved in 40 g of 2-heptanone, 1 g of decolorizing carbon + 1 g of chromatography alumina + 1 g of chromatography Add silica gel, filter through a 0.45μ PTFE syringe filter, and use a 5 mil casting knife to Tefl.
After being cast on an on (trademark) FEP sheet and dried by air, poly (HFIB / VF), which is a polymer for thin skin, was produced as a film. The poly (HFIB / VF) film produced in this manner was treated with the above-mentioned Teflon ™.
It could be lifted and peeled from the FEP sheet as a colorless transparent film having a thickness of about 0.5 to 1 mil.

Next, a paste solution was prepared. 0.1 g of poly (TFE / Tr
P) was dissolved in 1 g of hexafluorobenzene to form a solution.

This sizing solution was used to produce several spots of ½ ″ on an aluminum coupon measuring 1 ″ wide, 3 ″ long and 122 mil thick. After drying the glue spots in air for 39 minutes, the coupons were placed in an air oven for 8 minutes at 60 ° C. The aluminum coupon was removed hot from the oven immediately upon top of the poly (TFE / TrP) deposit. A sample of poly (HFIB / VF) film was lightly pressed with a finger to the eye, and visually the poly (HFIB / VF) film moistened and adhered to the poly (TFE / TrP) spots. The poly (HFIB / VF) film could be easily peeled off and stretched when the aluminum coupon was still hot. After returning to room temperature, the poly (HFIB / VF) film was not peeled off from the aluminum but was torn.
The adhesion between the skin polymer [poly (HFIB / VF)] was very strong, exceeding the strength of the skin polymer.

Example 8-HFIB / VF A. Polymerization of Hexafluoroisobutylene (HFIB) and Vinyl Fluoride (VF) 200 ml of water and Vazo ™ 56 in a 400 ml autoclave.
0.05 g of WSP initiator was charged. After cooling this autoclave and exhausting it, 80 g of hexafluoroisobutylene and 25 g of vinyl fluoride were added. After shaking at 50 ° C for ~ 48 hours, the autoclave was evacuated,
An opalescent blue emulsion was collected. This emulsion was placed in a Waring blender to disintegrate by vigorous stirring, filtered, and then washed 4 times with 100 ml of methyl alcohol in the Waring blender. Drying was performed under a pump vacuum for 6 days to obtain 30 g of a white powder and a solid. Elemental analysis (C ₄ F ₆ H ₂ ) ₄₇ (C ₂ H ₃ F) ₅₃ measured value: C 34.80% H 2.57% Calculated value: C 34.79% H 2.51% DSC, 10 ° C. / Min, nitrogen: T _g = 70 ° C. (second heating) T _m was not detected Inherent viscosity (THF, 25 ° C.): 0.379 dL / g GPC (in THF) Mw = 192,000 Mn = 92 A second sample of poly (HFIB / VF) was prepared using the same emulsion polymerization method, and the thermal transitions it exhibited were examined in detail in a modulated DSC. A glass transition was detected at both 69.5 ° C and 195 ° C during the second heating. No melt transition was observed during the first and second heating. Solution Preparation and Results: A solution was prepared by shaking 10 g of the polymer with 40 g of 2-heptanone, followed by a 0.45μ glass microfiber syringe filter [Whatma.
n, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of HFIB: VF was spin coated onto a CaF ₂ substrate to produce a polymer film with a thickness of 9239 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 15 shows the absorbance (expressed in reciprocal units of microns) of HFIB: VF for sample 18 versus wavelength lambda (λ) (expressed in nanometers). The measured absorbance / micron at 157 nm is 0.005 / micron. The measured absorbance at 193 nm / micron is -0.00082 / micron. The measured absorbance at 248 nm / micron is -0.002 / micron. B. Used as a glue for quartz and aluminum Aluminum coupons having a width of 1 ", a length of 3" and a thickness of 122 mils, and quartz having a width of 1 "and a length of 3" and a thickness of 65 mils. Both slides were rinsed with CF ₂ ClCCl ₂ F and then air dried.

2 g of poly (HFIB / VF) prepared above was shaken at room temperature with 18 g of acetone to form a colorless transparent solution, which was then passed through a 0.45 μ glass fiber filter. Add the solution to one end of the aluminum coupon.
A drop was made and a quartz slide was pressed down onto it so that the last inch of the quartz slide overlapped the last inch of the aluminum coupon. This caused some excess fluid to be extruded and the remaining polymer solution to wet the overlapping areas and spread evenly throughout. Two C-clamps (stock number 72020, ACCO USA Inc., 770-S ACCO Pla
za, Wheeling, IL 60090) was used to evaporate the acetone solvent at room temperature for 3 days while holding the aluminum coupon and quartz slide in place. One such assembly was placed in a 50 ° C. vacuum oven with the C clamp still attached to it and heated for 16 hours. The assembly was removed from the oven, cooled, the C-clamp removed, and the In
using a 3 "jaw separation and a 1" / min crosshead speed,
The force required to pull the quartz slide away from the aluminum coupon was measured. It cost one pound. The second assembly was heated with the C clamp still attached to it in a vacuum oven at 50 ° C. for 16 hours and then in a vacuum oven at 75 ° C. for 24 hours. At this point Instron
The force required to pull the aluminum coupon away from the quartz slide with a.

[0094] Example 9-VF ₂ / PMVE A. Vinylidene fluoride (VF ₂ ) and perfluoromethyl vinyl ether (PM
Polymerization of VE) ~ 210 ml autoclave with 50 ml CF ₂ ClCCl ₂ F and CF ₃
The CFHCFHCF ₂ CF ₃ DP solvent ~0.2M was 10ml packed. After cooling this autoclave and exhausting it, 26 g of VF ₂ and 33 g of PMVE
added. After shaking at ambient temperature (18-26 ° C.) overnight, the autoclave was evacuated to recover a viscous solution. The excess solvent was evaporated under nitrogen and the polymer was dried under vacuum at room temperature for 72 hours and then in a vacuum oven at 75 ° C. for 28 hours (33 g). Elemental analysis (C ₂ F ₂ H ₂ ) ₅ (C ₃ F ₆ O) ₂ measured value: C 29.64% H 1.73% Calculated value: C 29.47% H 1.55% DSC, 10 ° C. / min, nitrogen: T _g = -32 ℃ (2-th heating) inherent _{viscosity, CF 3 CFHCFHCF 2 CF 3,} 25 ℃: 0.722dL
/ G Solution preparation and results: A solution was produced by shaking 4 g of the polymer with 16 g of hexafluorobenzene. This solution was passed through a 0.45 µ glass fine fiber syringe filter [Whatman, Autovial (trademark)], and then a thick film was spin-coated on an optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PMVE (5: 2) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 72,750 Å. Next, VU
Absorbance per micron was determined using V absorbance measurements.

FIG. 15 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : PMVE (5: 2) with respect to the wavelength lambda (λ) (expressed in units of nanometers) for sample 19. Indicate. Absorbance measured at 157 nm / micron is 0.016
/ Micron. The measured absorbance / micron at 193 nm is 0.006 / micron. The measured absorbance at 248 nm / micron is 0.004 / micron. B. Used as a glue for quartz and aluminum Aluminum coupons having a width of 1 ", a length of 3" and a thickness of 122 mils, and quartz having a width of 1 "and a length of 3" and a thickness of 65 mils. Both slides were rinsed with CF ₂ ClCCl ₂ F and then air dried.

About 0.2 g of poly (VF ₂ : PMVE) was chopped into 3 to 4 pieces and then placed on one end of the aluminum coupon. A quartz slide was pressed down on top of it so that the last inch of the quartz slide overlaps the last inch of the aluminum coupon. 2 C-clamps (stock number 720
20, ACCO USA Inc. , 770-S ACCO Plaza, Wh
eeling, IL 60090) while holding the aluminum coupon and quartz slide in place while this assembly was placed in a vacuum oven at 76-80 ° C for 22 hours with the C-clamp still attached to it. Upon inclusion, this spread the polymer as a colorless transparent layer, pushing excess polymer from the edges. The assembly is removed from the oven, allowed to cool, the C-clamp is removed, and then the quartz slide is pulled away from the aluminum coupon using an Instron with 3 "jaw separation and 1" / min crosshead speed. The force required for was measured. It took 105.3 pounds. Separation occurred in the polymer layer and both the aluminum and quartz retained the remaining polymer. The force required to pull apart a second sample prepared in the same manner was 101.0 pounds with an average force of 103 pounds.

[0098] The autoclave CF ₂ ClCCl ₂ F of Example 10-VF ₂ / PMVE 210ml were charged 50 ml <-2
After cooling to 0 ° C., 10 μm of DP of 0.2 M in CF ₃ CFHCFHCF ₂ CF ₃ is used.
1 was added. After exhausting the autoclave, 33 g of perfluoro (methyl vinyl ether) (PMVE) and 13 g of vinylidene fluoride (VF ₂ ) were used.
Filled. Shaking the autoclave at room temperature overnight produces a solution which is evaporated to a soft polymer which is then further dried under pump vacuum for 29 hours and in a vacuum oven at 75 ° C. I went for 20 hours. This gave 31 g of a soft polymer suitable for use as glue. Calculated value for (C ₂ H ₂ F ₂ ) ₁₃ (C ₃ F ₆ O) ₁₀ : C 26.98% H 1.05% Measured value: C 27.21% H 0.88% DSC, 10 ° C / min , Nitrogen: T _g = -29 ° C (second heating) Inherent viscosity, 2-heptanone: 0.166 dL / g Solution preparation and results: 4 g of the polymer was shaken with 16 g of hexafluorobenzene. A solution was formed. This solution was passed through a 0.45 µ glass fine fiber syringe filter [Whatman, Autovial (trademark)], and then a thick film was spin-coated on an optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PMVE (13:10) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 25,970 Å. next,
Absorbance per micron was determined using VUV absorbance measurements.

FIG. 16 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : PMVE (13:10) with respect to wavelength lambda (λ) (expressed in units of nanometers) for sample 20. Indicate. Absorbance measured at 157 nm / micron is 0.0
34 / micron. Absorbance measured at 193 nm / micron is 0.015 /
It is micron. The measured absorbance at 248 nm / micron is 0.018 / micron.

Example 11-VF ₂ / PPVE A. Vinylidene fluoride (VF ₂ ) and perfluoro (propyl vinyl ether)
Polymerization of (PPVE) 50 ml of CF ₂ ClCCl ₂ F was charged into a 210 ml autoclave and <-2
After cooling to 0 ° C., 10 μm of DP of 0.2 M in CF ₃ CFHCFHCF ₂ CF ₃ is used.
1 was added. After cooling this autoclave and exhausting it, 13 g of VF ₂ and 53 g of PPVE were added. After shaking overnight at ambient temperature (22-26 ° C), the autoclave was evacuated and the solution was collected. After evaporation of excess solvent under nitrogen, the polymer was dried under vacuum at room temperature for 72 hours and at 75 ° C. for 28 hours (
45 g). Elemental analysis (C ₂ F ₂ H ₂ ) ₇ (C ₅ F ₁₀ O) ₅ measured value: C 26.17% H 0.88% Calculated value: C 26.34% H 0.79% DSC, 10 ° C. / min, nitrogen: T _g = -32 ℃ (2-th heating) inherent viscosity, hexafluorobenzene, 25 ℃: 0.169dL / g solution of preparation and results: the polymer of 4g with hexafluorobenzene of 16g The solution was formed by shaking. This solution was passed through a 0.45 µ glass fine fiber syringe filter [Whatman, Autovial (trademark)], and then a thick film was spin-coated on an optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : PPVE (7: 5) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 29,874 Å. Next, VU
Absorbance per micron was determined using V absorbance measurements.

FIG. 15 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : PPVE (7: 5) with respect to wavelength lambda (λ) (expressed in units of nanometers) for sample 21. Indicate. The measured absorbance at 157 nm / micron is 0.028
/ Micron. The measured absorbance / micron at 193 nm is -0.003 / micron. The measured absorbance / micron at 248 nm is -0.00074 / micron. B. Use as a glue for thin skin polymers 10 g of poly (HFIB / VF) (Example 8A shown above) was added to 40 g of 2
-Dissolve in heptanone, add 1 g decolorizing carbon + 1 g chromatographic alumina + 1 g silica gel, filter through a 0.45μ PTFE syringe filter and use a 5 mil casting knife to Teflon ™ FE.
After pouring it on the P sheet, it is dried with air to give poly (HFIB /
VF) was produced as a polymer film. Poly (HFI) produced in this manner
The B / VF) film could be lifted and peeled from the Teflon ™ FEP sheet as a colorless transparent film about 0.5 to 1 mil thick.

Next, a paste solution was prepared. 0.1 g of poly (VF ₂ / PP) prepared above
A solution was produced by dissolving VE) in 1 g of hexafluorobenzene.
This sizing solution was used to generate ~ 1/2 "spots on an aluminum coupon having dimensions of 1" wide, 3 "long and 122 mils thick. After drying for 39 minutes, the coupon was placed in an oven under nitrogen at 62 ° C. for 13 minutes, the aluminum coupon was removed hot from the oven and immediately placed on top of the poly (VF ₂ / PPVE) deposit with a poly (VF ₂ / PPVE) deposit. The HFIB / VF) membrane sample was lightly pressed with a finger, and after the aluminum coupon returned to room temperature, the poly (HFIB / VF) membrane was either lap shear or peeled back mode. A tear occurred when it was pulled with a polymer for glue [poly (VF ₂ / PPVE)] and a polymer for thin skin [poly (H
FIB / VF)] was very strong, exceeding the strength of this skin polymer.

Example 12-VF ₂ / HFP A. Poly (vinylidene fluoride / hexafluoropropylene) (VF ₂ / HFP
) Samples Characterization was performed on vinylidene fluoride / hexafluoropropylene samples produced using the method of US Pat. No. 4,985,520 (1/15/91).

Composition by fluorine NMR in deuteroacetone: HFP at 21 mol% VF _2.
79 mol% DSC, 10 ° C./min, nitrogen: T _g = -22.5 ° C. (second heating) Inherent viscosity (acetone, 25 ° C.): 0.753 dL / g Solution preparation and result: 3 g of poly (VF ₂ / HFP) was shaken with 17 g of 2-heptanone to form a solution, and then a 0.45 µ glass fine fiber syringe filter [W
hatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of VF ₂ : HFP (79:21) was spin coated on the CaF ₂ substrate to form a polymer film with a thickness of 13,000 Å. Next, V
UV absorbance measurements were used to determine the absorbance per micron.

FIG. 15 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : HFP (79:21) versus wavelength lambda (expressed in units of nanometers) for sample 22. Indicate. Absorbance measured at 157 nm / micron is 0.01
4 / micron. Absorbance measured at 193 nm / micron is -0.002 /
It is micron. Absorbance measured at 248 nm / micron is -0.00056 /
It is micron. B. Used as a glue for quartz and aluminum Aluminum coupons having a width of 1 ", a length of 3" and a thickness of 122 mils, and quartz having a width of 1 "and a length of 3" and a thickness of 65 mils. Both slides were rinsed with CF ₂ ClCCl ₂ F and then air dried.

About 0.2 g of the poly (VF ₂ : PMVE) was chopped into 3 to 4 pieces and then placed on one end of the aluminum coupon. A quartz slide was pressed down on top of it so that the last inch of the quartz slide overlaps the last inch of the aluminum coupon. 2 C-clamps (stock number 7)
2020, ACCO USA Inc. , 770-S ACCO Plaza,
Using Wheeling, IL 60090), hold the aluminum coupon and quartz slide in place while placing this assembly in a vacuum oven at 76-80 ° C for 22 hours with the C-clamp still attached to it. Upon entry, the polymer spread as a clear colorless layer. Remove the assembly from the oven, allow it to cool, remove the C-clamp, and then
A ron was used to measure the force required to pull the quartz slide away from the aluminum coupon using a 3 ″ jaw separation and a 1 ″ / min crosshead speed.
It took 133.3 pounds. The force required to pull apart a second sample prepared in the same manner was 121.6 lbs, resulting in an average force of 127
It was pound. In the second of these two experiments, separation occurred in the polymer layer and both the aluminum and quartz retained the remaining polymer. In the first of the above two experiments, separation occurred between the polymer and the glass. In each case, the remaining polymer could be neatly separated from the glass and aluminum as a single piece. C. Use as a glue for thin-skinned polymer 40 g of 10 g of poly (HFIB / VF) (Example 2A shown above)
-Dissolve in heptanone, add 1 g decolorizing carbon + 1 g chromatographic alumina + 1 g silica gel, filter through a 0.45μ PTFE syringe filter and use a 5 mil casting knife to Teflon ™ FE.
After pouring it on the P sheet, it is dried with air to give poly (HFIB /
VF) was produced as a polymer film. Poly (HFI) produced in this manner
The B / VF) film could be lifted and peeled from the Teflon ™ FEP sheet as a colorless transparent film about 0.5 to 1 mil thick.

Next, a paste solution was prepared. 0.1 g of poly (VF ₂ / PP) prepared above
A solution was produced by dissolving VE) in 1 g of hexafluorobenzene.

This sizing solution was used to generate ~ 1/2 "spots on an aluminum coupon having dimensions of 1" wide, 3 "long and 122 mils thick. After air drying for 39 minutes, the coupon was placed in a nitrogen blanket oven for 13 minutes at 62 ° C. The aluminum coupon was removed hot from the oven immediately upon top of the poly (VF ₂ / HFP) deposit. Poly (HFIB /
The (VF) membrane sample was lightly pressed with a finger. After the aluminum coupon returned to room temperature, tearing occurred when the poly (HFIB / VF) film was pulled in the lap shear mode. When the poly (HFIB / VF) itself is later peeled off, the poly (V
F ₂ / HFP) Adhesive failure between glue and aluminum
ure) and the poly (VF ₂ / HFP) adhesive layer cleanly separated from the aluminum and showed no debonding from the poly (HFIB / VF). This means that the polymer for thin skin [Poly (HFIB / VF)] and the polymer for glue [
It indicates that the adhesion between the poly (VF ₂ / HFP)] is excellent.

Example 13-HFP / PMVE / VF ₂ 210 ml of a Hastelloy C autoclave was cooled to <-20 ° C and then charged with 20 ml of 0.17M DP in CF ₃ CFHCFHCF ₂ CF ₃ . After exhausting the autoclave, 33 g of perfluoro (methyl vinyl ether) (PMVE), 26 g of vinylidene fluoride (VF ₂ ), 26 g of hexafluoropropylene (HFP) and 1 g of anhydrous hydrogen chloride (chain transfer agent).
g filled. Shaking of the autoclave at room temperature overnight yielded a colorless oil which was devolatized for 24 hours in air, 19 hours under pump vacuum and then 5 days in a vacuum oven at 75 ° C. When done, 47 g of a transparent resin with a tackiness suitable for use as glue were produced. Composition by Fluorine NMR: VF ₂ 63.1 mol% PMVE 27 mol% HFP 10 mol% Inherent viscosity, acetone, 25 ° C .: 0.120 dL / g Solution preparation and results: 4 g of the polymer 12 g of 2-heptanone. A cloudy solution was obtained by shaking with to form a solution. This solution was added to 0.45μ glass microfiber and Teflon ™ syringe filter [Whatman, Autovi.
al (trademark)], and then the filtrate was used to spin-coat a thick film on an optical substrate to measure the absorbance.

A solution of HFP: PMVE: VF ₂ (10:27:63) was spin coated onto the CaF ₂ substrate to produce a polymer film with a thickness of 316,500 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 16, for sample 23, HFP: PMVE: VF ₂ (10:27:
63) shows the absorbance (expressed in units of reciprocal microns) versus the wavelength lambda (λ) (expressed in units of nanometers). The measured absorbance / micron at 157 nm is 0.008 / micron. The measured absorbance / micron at 193 nm is -0.00048 / micron. The measured absorbance / micron at 248 nm is -0.00045 / micron.

Example 14-HFIB / VF An 85 ml autoclave was filled with two 3/8 "diameter stainless steel balls,
This was sealed, evacuated, cooled to <-20 ° C, and then CF ₃ CFHCF
The DP of the HCF in ₂ CF _{3 ~0.17M} was sucked into a 10ml. The autoclave is further cooled and hexafluoroisobutylene (HFIB) is added to 70 ° C at -50 ° C.
After addition of g, 10 psig of liquid vinyl fluoride (VF) was added at ~ -35 ° C.
At this point the liquid-filled autoclave was warmed to room temperature with shaking. The pressure inside this autoclave reaches a maximum of 7780 psi at 25 ° C,
Finishing was performed at 29 ° C. under 103 psig for about 10 hours, and the following operation was performed (in
to the run). The solid polymer product was dried under a pump vacuum for 72 hours to obtain 57 g of a white solid having a glass transition temperature of 115 ° C. Calculated value for (HFIB) ₅₉ (VF) ₄₁ : C 33.04% H 2.11% Measured value: C 33.02% H 2.31% DSC, 10 ° C./min, nitrogen: T _g = 115 ° C. ( Second heating) No Tm detected (both first and second heating) Inherent viscosity (THF, 25 ° C): 0.183 dL / g Solution preparation and results: 48 g of 12 g of the polymer A solution was produced by shaking with 2-heptanone. This solution was passed through a 0.45μ glass microfiber and a Teflon ™ syringe filter [Whatman, Autovial ™], and then the filtrate was used to spin coat a thick film onto an optical substrate to measure the absorbance. I went.

A solution of HFIB: VF (10: 7) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 7500 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 16, the absorbance (expressed in units of reciprocal microns) of HFIB: VF (10: 7) is plotted against the wavelength lambda (λ) (expressed in nanometers) for sample 24. Show. Absorbance measured at 157 nm / micron is -0.01
3 / micron. The measured absorbance at 193 nm / micron is -0.016 /
It is micron. The measured absorbance / micron at 248 nm is -0.011 / micron.

Example 15-PDD / PMVE A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to 0 ° C., add 1 to 0.2M DP in CF ₃ CFHCFHCF ₂ CF _3.
0 ml and 11.6 ml of perfluorodimethyldioxole (PDD) were added. After exhausting the autoclave, 4.5 g of perfluoro (methyl vinyl ether) (PMVE) was charged. Shaking of the autoclave at room temperature overnight produced a gelatinous product that was evaporated and further dried for 29 hours under pump vacuum and 20 hours in a vacuum oven at 75 ° C. This gave 18 g of product. Calculated value for (PDD) ₆ (PMVE) ₅ : C 23.56% Measured value: C 23.87% DSC, 10 ° C./min, nitrogen: T _g = 133 ° C. Inherent viscosity [Fluorinert ™ FC-40]. : 0.161d
L / g Solution Preparation and Results: 4 g of the polymer was shaken with 16 g of Fluorinert ™ FC-40 to produce a cloudy solution. This solution was passed through a 0.45μ glass fine fiber syringe filter [Whatman, Autovial ™] and after adding 0.6 g of chromatographic alumina and 0.6 g of chromatographic silica gel, 0.45μ of Teflon ( ™) syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of PDD: PFMVE (6: 5) was spin-coated on a CaF ₂ substrate to form a polymer film having a thickness of 12,450 angstroms. next,
Absorbance per micron was determined using VUV absorbance measurements.

In FIG. 16, the absorbance (expressed in units of reciprocal microns) of PDD: PFMVE (6: 5) for sample 25 is plotted against wavelength lambda (λ) (expressed in units of nanometers). Show. Absorbance measured at 157 nm / micron is 0.20
9 / micron. The measured absorbance / micron at 193 nm is 0.006 / micron. The measured absorbance / micron at 248 nm is 0.013 / micron.

Example 16-VF / ClDFE A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to ° C., the DP of CF ₃ CFHCFHCF in ₂ CF _{3 ~0.17M} it was added 10ml thereto. After exhausting the autoclave, vinyl fluoride (VF)
6.4 g and 1-chloro-2,2-difluoroethylene (ClDFE) 9
． 8g was filled. Shaking of the autoclave at room temperature overnight produced a moist paste which was dried under pump vacuum for 4 days and in a vacuum oven at 75 ° C. for 28 hours. This gave 8 g of product. Calculated value for (C ₂ H ₃ F) ₂₀ (C ₂ HF ₂ Cl) ₁₁ : C 37.16% H 3.57% Measured value: C 37.39% H 3.30% DSC, 10 ° C./min. Nitrogen: T _g = 97 ° C. (first heating) T _g was not detected on the second heating Inherent viscosity [acetone]: 0.220 dL / g Solution preparation and results: 4 g of the polymer 16 g A solution was formed by shaking with heptanone. Add this solution to a 0.45μ glass microfiber syringe filter [Whatm
an, Autovial (trademark)], the filtrate was used to spin-coat a thick film on an optical substrate, and the absorbance was measured.

A solution of VF: ClDFE (20:11) was spin-coated on a CaF ₂ substrate to produce a polymer film with a thickness of 9461 Å. Next, V
UV absorbance measurements were used to determine the absorbance per micron.

In FIG. 17, the absorbance (expressed in units of reciprocal microns) of VF: ClDFE (20:11) for sample 26 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance at 157 nm / micron is 0.2
26 / micron. Absorbance measured at 193 nm / micron is 0.036 /
It is micron. The measured absorbance at 248 nm / micron is 0.003 / micron.

Example 17-PDD / VF ₂ 75 ml of an autoclave was cooled to <-20 ° C and then CF ₃ CFHC.
10 ml of FHCF ₂ CF ₃ , CF ₃ CFHCFHCF ₂ CF ₃ ~ 0.17M D
5 ml of P and 20 g of perfluorodimethyldioxole (PDD) were charged. After exhausting the autoclave, vinylidene fluoride (VF ₂ ) was added to 13
g filled. When the autoclave was shaken at room temperature overnight, a viscous oil was formed, which was subjected to volatile removal in air and under pump vacuum for 32 hours.
By performing this in a vacuum oven at 5 ° C. for 23 hours, 16 g of a white resin was obtained. Calculated value for (PDD) ₁ (VF ₂ ) ₂ : C 29.05% H 1.08% Measured value: C 29.35% H 1.08% DSC, 10 ° C / min, nitrogen: 52 ° C? (Weak) Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.278 Solution preparation and results: 2 g of poly (PDD / VF ₂ ) was shaken with 8 g of 2-hexafluorobenzene to give a solution. Was generated. After passing the solution through a 0.45μ glass microfiber syringe filter [Whatman, Autovial ™],
A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of PDD / VF ₂ (1: 2) was spin-coated on the CaF ₂ substrate to form a polymer film with a thickness of 82,000 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

FIG. 17 compares the absorbance (expressed in units of reciprocal microns) of PDD / VF ₂ (1: 2) with respect to wavelength lambda (λ) (expressed in units of nanometers) for sample 27. Indicate. Absorbance measured at 157 nm / micron is 0.009 /
It is micron. The measured absorbance / micron at 193 nm is 0.003 / micron. The measured absorbance / micron at 248 nm is -0.00030 / micron.

Example 18A-PDD / VF ₂ After cooling 75 ml of an autoclave to <-20 ° C, CF ₃ CFHC was added to it.
20 ml of FHCF ₂ CF ₃ , CF ₃ CFHCFHCF ₂ CF ₃ ~ 0.17M D
5 ml of P and 20 g of perfluorodimethyldioxole (PDD) were charged. After exhausting the autoclave, 6 g of vinylidene fluoride (VF ₂ )
Filled. Shaking of the autoclave at room temperature overnight produces a viscous oil that is devolatized in air and pumped under vacuum for 32 hours, then 75
By performing this in a vacuum oven at 0 ° C. for 23 hours, 16 g of a white resin was obtained. Calculated value for (C ₅ F ₈ O ₂ ) ₅ (C ₂ H ₂ F ₂ ) ₁ : C 26.11% H 0.37% Measured value: C 26.03% H 0.53% DSC, 10 ° C / Min, nitrogen: 96 ℃? (Weak) Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.671 Solution preparation and results: 2 g of poly (PDD / VF ₂ ) were shaken with 18 g of 1H-perfluorohexane to give a cloudy solution. Was generated. The solution was passed through a 0.45μ glass microfiber syringe filter [Whatman, Autovial ™] using a packing of chromatographic silica gel with the aid of filtration to replace the 1H-perfluorohexane lost by evaporation. After adding an additional approximately 1H-perfluorohexane in approximately equal amounts, the filtrate was filtered again through a 0.45μ Teflon ™ syringe filter [Whatman, Autovial ™]. At this point, a thick film was spin-coated on the optical substrate using the transparent filtrate, and the absorbance was measured.

Example 18B- A 400 ml stainless steel autoclave coated with PDD / VF ₂ Teflon ™ was cooled to <-20 ° C and then 90% CF ₃ CFHCFHCF ₂ CF ₃ was added thereto.
ml, a CF ₃ CFHCFHCF ₂ CF ₃ in 30ml and perfluoro dimethyl dioxole a DP ~0.1M was 120g filled. The autoclave was pressurized to 100 psi with nitrogen and evacuated 10 times. Finally, after adding 58 g of vinylidene fluoride (VF ₂ ), the autoclave was shaken at room temperature overnight. The resulting dense gel was dried under nitrogen, then under pump vacuum and finally in a vacuum oven at 75 ° C. for 4 days to give a white resin
22 g was obtained. Calculated value for (C ₅ F ₈ O ₂ ) ₅ (C ₂ H ₂ F ₂ ) ₈ : C 28.42% H 0.93% Measured value: C 28.22% H 1.16% DSC, 10 ° C / Min, nitrogen: 59 ° C. Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.576 Solution preparation: 1.70 g of poly (PDD / VF ₂ ) was shaken with 15.3 g of hexafluorobenzene to form a solution. Was generated. It was filtered through a 0.45μ glass fiber fine fiber syringe filter [Whatman, Autovial ™] to produce a clear colorless solution. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of PDD / VF ₂ (5: 8) was spin coated on the CaF ₂ substrate to form a polymer film with a thickness of 38,298 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

FIG. 19 compares the absorbance (expressed in units of reciprocal microns) of PDD / VF ₂ (5: 8) with respect to the wavelength lambda (λ) (expressed in units of nanometers) for sample 29. Indicate. The measured absorbance at 157 nm / micron is 0.018 /
It is micron. The measured absorbance / micron at 193 nm is 0.010 / micron. The measured absorbance at 248 nm / micron is 0.000057 / micron.

[0131] in Hastelloy C autoclave of Example _{19A-HFIB / VF 2 / VF} 210ml CF 2 ClCCl 2 F
50 ml, and cooled to <−20 ° C., and then CF ₃ CFHCFHCF ₂ C
The DP in F ₃ ~0.2M was added 15ml. After exhausting the autoclave, 32 g of hexafluoroisobutylene (HFIB) and vinylidene fluoride (V
3 g of F ₂ ) and 7 g of vinyl fluoride (VF). Shaking of the autoclave at room temperature overnight produced a thick paste of a white solid which was dried under nitrogen for 70 hours under pump vacuum and 23 hours in a vacuum oven at 75 ° C. This gives 33 products with analytical values that are in the range of possible stoichiometry.
g was obtained. Calculated value of (C ₄ H ₂ F ₆ ) ₃ (C ₂ H ₃ F) ₁ (C ₂ H ₂ F ₂ ) ₁ : C 31.91% H 1.84% (C ₄ H ₂ F ₆ ) ₅ ( Calculated value for C ₂ H ₃ F) ₁ (C ₂ H ₂ F ₂ ) ₃ : C 31.78% H 1.81% Measured value: C 31.78% H 1.88% DSC, 10 ° C./min. Nitrogen: T _g = 48 ° C. Inherent viscosity [acetone, 25 ° C.]: 0.030 dL / g Solution preparation and results: 8 g of the polymer was shaken with 20 g of heptanone to form a cloudy solution. Using 1 g of a packing of chromatographic alumina with the aid of filtration, the solution was made into a 0.45μ glass fiber syringe filter [Whatman, A
utovial (TM)], 0.45 [mu] Teflon (TM) syringe filter [Whatman, Autovial (TM)] and 0.45 [mu] Tef.
It was passed through a lon ™ syringe filter [Whatman, Autovial ™]. At this point, a thick film was spin-coated on the optical substrate using the transparent filtrate, and the absorbance was measured.

Example 19B-HFIB / VF / VF ₂ 200 ml of deionized water in a 400 ml autoclave, Vazo ™ 5
6 After loading 0.05 g of WSP initiator, pressurizing to 100 psi with nitrogen and venting 10 times. This autoclave was cooled to <-20 ° C. and exhausted, and then 82 g of hexafluoroisobutylene (HFIB), 13 g of vinylidene fluoride (VF ₂ ) and 14 g of vinyl fluoride (VF) were further charged. The contents of this autoclave were shaken at 50 ° C. for ˜64 hours. The resulting solid and emulsion mixture was frozen and thawed. Vacuum filtration and 200ml
The fluffy white solid was obtained by washing the inside of the filter twice with
There were some dark yellow lumps present which were removed. The remaining white fluff was washed two more times with 150 ml of methyl alcohol while it was in the filter. After suction-drying the white fluff on the filter, further drying was performed under pump vacuum for 5 days to obtain 16 g of a polymer. Composition by Fluorine NMR: 41 mol% HFIB, 37 mol% VF, 22 mol% VF ₂ DSC, 10 ° C./min, nitrogen: 71 ° C. Inherent viscosity [tetrahydrofuran, 25 ° C.]: 0.523 Preparation of solution: 3g of poly (HFIB / VF / VF ₂₎ solution to produce a by shaking with 17g of 2-heptanone. Add it to a 0.45μ glass fiber fine fiber syringe filter and then a 0.45μ PTFE syringe filter [Whatm
, Autovial ™] to give a clear but slightly yellow solution. A film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of HFIB / VF / VF ₂ (41:37:22) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 5289 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 19 shows that for sample 31, HFIB / VF / VF ₂ (41: 37: 2
The absorbance (expressed in the unit of reciprocal micron) indicated by 2) is shown in comparison with the wavelength lambda (λ) (expressed in the unit of nanometer). The measured absorbance / micron at 157 nm is 0.016 / micron. The measured absorbance at 193 nm / micron is -0.010 / micron. Absorbance measured at 248 nm / micron is -0
． 002 / micron.

Example 20-PDD / TrFE In an autoclave of 75 ml, 40 ml of water and Vazo ™ 56 WS.
0.1 g of P initiator was charged. After cooling the autoclave to <-20 ° C,
10 g of perfluorodimethyldioxole (PDD) was added. After exhausting the autoclave, 5 g of trifluoroethylene (TrFE) was added. When shaking was performed at 70 ° C. for 10 hours, a polymer mass was formed, and after separation of the mass, 75
It was placed in a vacuum oven at 0 ° C. and dried for 72 hours (9.9 g). Elemental analysis (C ₅ F ₈ O ₂ ) ₁ (C ₂ F ₃ H) ₁ measured value: C 25.51% H 0.55% Calculated value: C 25.79% H 0.31% DSC, 10 ° C. / Min, nitrogen: T _g = 150 ° C.? (Weak, second heat) Inherent viscosity [hexafluorobenzene, 25 ° C.]: 1.3 dL / g Solution preparation and results: Shaking 1 g of the polymer with 33 g of Fluorinert ™ Fc-75. After forming the solution in, was filtered through a 0.45μ glass microfiber syringe filter [Whatman, Autovial ™]. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of PDD: TrFE (1: 1) was spin-coated on a CaF ₂ substrate to produce a polymer film with a thickness of 7688 Å. Next, VUV
Absorbance measurements were used to determine the absorbance per micron.

In FIG. 16, the absorbance (expressed in units of reciprocal microns) of PDD: TrFE (1: 1) for sample 9 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance / micron at 157 nm is 0.03 / micron. The measured absorbance / micron at 193 nm is -0.004 / micron. The measured absorbance / micron at 248 nm is -0.001 / micron.

Example 21-CTFE / VF A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to 0 ° C., 5 to 0.1M DP in CF ₃ CFHCFHCF ₂ CF _{3 is} added to this.
ml was added. After exhausting the autoclave, 17 g of chlorotrifluoroethylene (CTFE) and 7 g of vinyl fluoride (VF) were charged. Shaking of the autoclave at room temperature overnight resulted in a swollen gel, which was dried under air, under pump vacuum for 96 hours and in a vacuum oven at 75 ° C. for 25 hours.
This gave 18 g of product. Calculated value for (C ₂ F ₃ Cl) ₁ (C ₂ H ₃ F) ₁ : C 29.56% H 1.86% Cl 21.82% Measured value: C 29.74% H 1.83% Cl 21 80% DSC, 10 ° C./min, nitrogen: T _g = 86 ° C. (first heating) Inherent viscosity [acetone, 25 ° C.]: 1.08 dL / g Solution preparation and results: 15 g of 2 g of the polymer A solution was formed by shaking with heptanone. Add this solution to a 0.45μ glass fiber syringe filter [Whatman
, Autovial (TM)], and the filtrate was used to spin coat a thick film onto an optical substrate for absorbance measurement.

A solution of CTFE: VF (1: 1) was spin-coated on a CaF ₂ substrate to yield polymer films 1850 Å and 17,644 Å thick. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 18, the absorbance (expressed in units of reciprocal microns) of CTFE: VF (1: 1) for sample 6b is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. Absorbance at 157 nm / measured with thicker membrane /
The micron is 0.388 / micron. 193n measured using thicker film
The absorbance at m / micron is 0.016 / micron. The absorbance / micron at 248 nm measured with the thicker film is 0.006 / micron.

Sample 10-VF ₂ / TrFE In an autoclave of 75 ml, 25 ml of CF ₂ ClCCl ₂ F was charged, and <-20
After cooling to 0 ° C., 5 to 0.1M DP in CF ₃ CFHCFHCF ₂ CF _{3 is} added to this.
ml was added. After exhausting the autoclave, vinylidene fluoride (VF ₂
) And 12 g of trifluoroethylene (TrFE). Shaking of the autoclave at room temperature overnight produced a damp white solid which was dried under pump vacuum and in a vacuum oven at 75 ° C. for 24 hours. This gave 14 g of product. Calculated value for (C ₂ H ₃ F ₂ ) ₅ (C ₂ F ₃ H) ₂ : C 34.73% H 2.50% Measured value: C 34.78% H 2.48% DSC, 10 ° C / min nitrogen: first T _g = 55 ℃ 2 th T _g = 98 and 147 ° C. the inherent viscosity [acetone, 25 ° C.] of the heating of the heating: 1.087dL / g solution of preparation and results: 3.11 g above A solution was formed by shaking the polymer with 34.32 g of 1-methoxy-2-propanol acetate. The resulting cloudy solution (with particulates) was filtered through a 0.45μ glass fiber syringe filter [Whatm
an, Autovial (TM)] was difficult. This solution (2.8
Evaporation of 2 g) gave 0.220 g of residue (solids amount was 7.8% by weight, compared to 8.3% expected assuming no solids were removed by filtration). ). A thick film was spin-coated on an optical substrate and the absorbance was measured.

A solution of VF ₂ : TrFE (5: 2) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 4500 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 18 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : TrFE (5: 2) versus wavelength lambda (λ) (expressed in units of nanometers) for sample 10. Indicate. Absorbance at 157 nm / micron is 0.924
/ Micron. The measured absorbance / micron at 193 nm is 0.188 / micron. The measured absorbance / micron at 248 nm is 0.083 / micron.

Example 23-HFIB / VOH A. Hexafluoroisobutylene (HFIB) / vinyl acetate (VOAc) copolymer 400 ml autoclave was filled with 50 ml of CF ₂ ClCCl ₂ F, 27 ml of vinyl acetate and 50 ml of DP of 0.1M in CF ₃ CFHCFHCF ₂ CF ₃ . . After cooling this autoclave and exhausting it, 49 g of HFIB was further added.
Filled. A viscous pale yellow solution formed after shaking overnight at room temperature. The polymer was precipitated by adding 400 ml of methyl alcohol. Filtration, drying under a pump vacuum and drying in a vacuum oven at 75 ° C. were performed for 19 hours to obtain 52 g of poly (HFIB / VOAc) having an inherent viscosity of 0.13 in acetone at 25 ° C. B. Hexafluoroisobutylene (HFIB) / vinyl alcohol (VOH) copolymer Poly (HFIB / VOAc) (50 grams) produced above, methyl alcohol (500 ml) and 25% by weight sodium methoxide in methyl alcohol ( 25 ml) was refluxed for 6 hours. Methyl alcohol is ~ 86 during this time
Methyl alcohol was additionally added since 0 ml was distilled. A rubbery precipitate formed upon addition of the resulting polymer solution to water. After decanting the water, the precipitate was taken up with 200 ml of methyl alcohol and W
Reprecipitation was carried out with 500 ml of water in an aring blender. Vacuum filtration, drying under a pump vacuum and subsequent drying in a vacuum oven at 75 ° C. for 24 hours gave 37 g of poly (HFIB / VOH) as off-white particles. Calculated value for (C ₄ H ₂ F ₆ ) ₁ (C ₂ H ₄ O) ₁ : C 34.63% H 2.91% Measured value: C 34.34% H 2.73% DSC, 10 ° C / min , Nitrogen: T _g = 90 ° C. (second heating) Solution preparation and results: A solution was formed by shaking 3.28 g of the polymer with 34.91 g of 1-methoxy-2-propanol acetate. It was The solution was passed through a 0.45μ glass fiber syringe filter [Whatman, Autovial ™] to give a slightly cloudy pale yellow solution. The solution was treated with 0.4 g of decolorizing carbon, filtered again, then treated with 0.58 g of silica gel and filtered a third time. The solution was still pale yellow but not cloudy. A thick film was spin-coated on the optical substrate using the filtrate, and the absorbance was measured.

A solution of HFIB: VA (1: 1) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 1350 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 17, the absorbance (expressed in units of reciprocal microns) of HFIB: VA (1: 1) for sample 32 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance at 157 nm / micron is 0.350 /
It is micron. The measured absorbance at 193 nm / micron is -0.047 / micron. The measured absorbance / micron at 248 nm is -0.107 / micron.

Sample 12-HFP / TrFE A 75 ml autoclave was charged with 25 ml of CF ₂ ClCCl ₂ F and <-20
After cooling to ° C., the DP of CF ₃ CFHCFHCF in ₂ CF _{3 ~0.17M} it was added 5ml thereto. After exhausting the autoclave, 12 g of hexafluoropropylene (HFP) and 12 g of trifluoroethylene (TrFE) were filled. Shaking of the autoclave at room temperature overnight yielded a damp white solid which was dried under pump vacuum for 22 hours and in a vacuum oven at 75 ° C for 2 hours.
I went for 4 hours. This gave 12 g of product. Composition by fluorine NMR: HFP 2 mol% and TrFE 98 mol% DSC, 10 ° C./min, nitrogen: T _m = 179 ° C., T _g was not detected inherent viscosity [acetone, 25 ° C.]: 0.912 dL Preparation of a solution: 2.5 g of poly (HFP / TrFE) was shaken with acetic ester of methyl ether of propylene glycol (50 ml) to form a cloudy solution. 0.45μ PTFE syringe filter [Whatman, Autovia
l (TM)] to give a clear filtrate. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of HFP: TrFE (2:98) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 1389 Å. Next, VU
Absorbance per micron was determined using V absorbance measurements.

FIG. 8 shows the absorbance (expressed in units of reciprocal microns) of HFP: TrFE versus wavelength lambda (λ) (expressed in units of nanometers) for sample 12. The measured absorbance / micron at 157 nm is 1.37 / micron. The measured absorbance / micron at 193 nm is 0.143 / micron. Two
The measured absorbance / micron at 48 nm is -0.02 / micron.

Sample 14-HFP / TFE A hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) copolymer was prepared using the method of US Pat. No. 5,478,905 (December 26, 1995). . This polymer had 60 wt% HFP and 40 wt% TFE and had an inherent viscosity of 0.407 dL / g [Fluorinert
(Trademark) FC-75 in a solvent at 25 ° C.]. Solution Preparation: Shaking 31.6 g of HFP / TFE copolymer with 986 g of PF-5080 (Performance Fluid manufactured by 3M, which is believed to be mostly perfluorooctane). To form a solution. 0.
Vacuum filtration through a 45μ filter gave a clear filtrate. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of HFP: TFE (1: 1) was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 1850 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 8 shows the absorbance (HFP: TFE (1: 1)) of sample 14 (
(Reciprocal units of microns) are shown versus wavelength lambda (λ) (expressed in units of nanometers). The measured absorbance / micron at 157 nm is 3.9 / micron. The measured absorbance / micron at 193 nm is 0.086 / micron. The measured absorbance / micron at 248 nm is 0.073 / micron.

Sample 15-VF ₂ / CTFE 75 ml autoclave was cooled to <-20 ° C. to which 25 ml CF ₂ ClCCl ₂ F and 5 ml ~ 0.1M DP in CF ₃ CFHCFHCF ₂ CF ₃ were added.
Filled. After exhausting the autoclave, vinylidene fluoride (VF ₂ )
9.6 g and 17 g of chlorotrifluoroethylene (CTFE).
Shaking the autoclave at room temperature overnight produces a viscous white fluid which evaporates to a resilient solid which is then dried under pump vacuum for 1 hour. And it performed in the vacuum oven of 75 degreeC for 30 hours. This gave 19 g of product. _{(C 2 F 2 H 2)} 5 (C 2 F 3 Cl) 4 Calculated: C 27.50% H 1.28% Cl 18.04% measured: C 27.26% H 1.41% Cl 17.91% DSC, 10 ° C./min, nitrogen: T _g = 99 ° C. Inherent viscosity [acetone, 25 ° C.]: 0.546 dL / g Solution preparation: 3 g poly (VF ₂ / CTFE) 20 g 2- After shaking with heptanone to form a solution, 0.45μ glass fiber syringe filter [Wh
atman, Autovial ™]. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A polymer film was formed by spin coating a solution of VF ₂ : CTFE (5: 4) onto a CaF ₂ substrate. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 18 compares the absorbance (expressed in units of reciprocal microns) of VF ₂ : CTFE (5: 4) with respect to wavelength lambda (λ) (expressed in units of nanometers) for sample 15. Indicate. The measured absorbance / micron at 157 nm is 5.6 / micron. The measured absorbance / micron at 193 nm is 0.27 / micron. The measured absorbance / micron at 248 nm is 0.12 / micron.

Sample 16-PMD / TFE 75 ml of autoclave was cooled to <-20 ° C and CF ₃ CFHCF was added to it.
The DP of HCF in ₂ CF _{3 ~0.14M} 5ml, the CF ₃ CFHCFHCF ₂ CF ₃ and 11.6ml filled with 25ml and perfluoro (2-methylene-4-methyl-1,3-dioxolane) (PMD). After evacuation of this tube, 5 g of tetrafluoroethylene (TFE) was further charged. Shaking at room temperature overnight produced a viscous milk-colored oil. Evaporation under nitrogen under pump vacuum for 76 hours and 7
The resin was aged in a vacuum oven at 5 ° C. for 24 hours to obtain 20 g of resin, which was assumed to be a copolymer having PMD: TFE of ˜2: 1 (PMD and TFE were ˜2.
1: 1 monomer ratio). DSC, 10 ° C./min, nitrogen: no T _g detected Inherent viscosity [Fluorinert ™ FC-75, 25 ° C.]: 0.
Preparation of 142 dL / g solution: 2.14 g poly (PMD / TFE) to 26.2 g Fluorinert (
0.45 after forming a cloudy solution by shaking with Trademark) FC-40.
0.45μ glass fiber syringe filter [Whatman, Autov after mixing with 0.2 g of chromatographic silica + 0.2 g of decolorizing carbon through a μ glass fiber filter [Whatman, Autovial ™].
ial ™] and finally 0.45μ PTFE difilter [Wh
Atman, Autovial ™]. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

A solution of PMD: TFE (1: 1) was spin coated on a CaF ₂ substrate to form a 2207 Å thick polymer film. The VUV absorbance measurements were then used to determine the absorbance per micron.

In FIG. 18, the absorbance (expressed in units of reciprocal microns) of PMD: TFE (1: 1) for sample 16 is plotted against wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance / micron at 157 nm is 1.17 / micron. The measured absorbance / micron at 193 nm is -0.015 / micron. The measured absorbance at 248 nm / micron is 0.07 / micron.

Example 28-PMD / TFE A glass jar for 1 ounce sample was fitted with a rubber septum, flushed with nitrogen and flushed with dry ice, then cooled with dry ice and then perfluoro (2-methylene-4-methyl-1). , 3-dioxolane) the DP of 3ml and CF ₃ CFHCFHCF in ₂ CF _{3 ~0.17M} was 0.5ml injected. The bottle was placed in ice water and allowed to warm slowly to room temperature over the next few hours with magnetic stirring. After ~ 62 hours at room temperature, the contents of the bottle, the rigid foam, is dried under pump vacuum and then 1
Drying in a vacuum oven at 50 ° C. for 17 hours and trituration with a spatula gave 4.1 g of white fines. DSC, 10 ° C./min, nitrogen: T _g = 135 ° C. Inherent viscosity [hexafluorobenzene, 25 ° C.]: 0.155 dL / g Solution preparation: 2 g of poly (PMD) is shaken with 18 g of hexafluorobenzene. After producing the solution, 0.45μ glass fiber syringe filter [Wha
tman, Autovial ™]. A thick film was spin-coated on the optical substrate using this filtrate, and the absorbance was measured.

By spin-coating a solution of PMD on a CaF ₂ substrate, the thickness was increased to 14.8%.
An 18 angstrom polymer film was produced. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 17 shows the absorbance (expressed in units of reciprocal microns) of PMD versus wavelength lambda (λ) (expressed in units of nanometers) for sample 33. The measured absorbance / micron at 157 nm is 0.603 / micron. 1
The measured absorbance / micron at 93 nm is -0.0007 / micron. 24
The measured absorbance / micron at 8 nm is -0.0001 / micron.

Example 29-PMD / PDD A glass jar for 1 ounce sample was fitted with a rubber septum, flushed with nitrogen and cooled with dry ice, then perfluoro (2-methylene-4-methyl-1). , 3-dioxolane) (PMD) in 3 ml, perfluorodimethyldioxole (PDD) in 3 ml and CF ₃ CFHCFHCF ₂ CF ₃ in ˜0.17.
0.5 ml of DP of M was injected. The bottle was placed in ice water and allowed to warm slowly to room temperature over the next few hours with magnetic stirring. After ˜62 hours at room temperature, the contents of the bottle, a rigid foam, were dried under pump vacuum and then in a vacuum oven at 150 ° C. for 17 hours and milled with a spatula to give a white fines. 8.6 g was obtained. DSC, 10 ° C./min, Nitrogen: T _g = 147 ° C. Solution Preparation: After shaking 2 g of poly (PMD / PDD) with 18 g of hexafluorobenzene to form a partially gelatinous partial solution. , 0.45 [mu] glass fiber syringe filter [Whatman, Autovial (TM)] through a ~ 1/8 inch deep chromatographic silica gel padding. By sending a part of this solution to ¹⁹ F NMR, it was confirmed that the composition of the dissolved polymer was 50 mol% PMD and 50 mol% PDD. A thick film was spin-coated on the optical substrate using the remaining filtrate, and the absorbance was measured.

A solution of PMD: PDD was spin-coated on a CaF ₂ substrate to form a polymer film with a thickness of 12,762 Å. The VUV absorbance measurements were then used to determine the absorbance per micron.

FIG. 17 shows the absorbance (expressed in units of reciprocal microns) of PMD: PDD versus wavelength lambda (λ) (expressed in units of nanometers) for sample 34. The measured absorbance / micron at 157 nm is 0.404 / micron. The measured absorbance / micron at 193 nm is 0.006 / micron.
The measured absorbance at 248 nm / micron is -0.002 / micron.

Example 30-PMD / VF ₂ An autoclave of 75 ml was cooled to <-20 ° C and CF ₃ CFHCF was added thereto.
The DP of HCF in ₂ CF _{3 ~0.17M} 5ml, the CF ₃ CFHCFHCF ₂ CF ₃ and 11.6ml filled with 15ml and perfluoro (2-methylene-4-methyl-1,3-dioxolane) (PMD). This autoclave was purged with nitrogen to 100p
After pressurizing and evacuating si 10 times, vinylidene fluoride (
9.6 g of VF ₂ ) was charged. Shaking at room temperature overnight produced a white solid. Evaporate under nitrogen for 16 hours under pump vacuum and 32 in a 77 ° C. vacuum oven.
By agitating for a period of time, 23 g of a resin was obtained. Calculated value for (C ₅ F ₈ O ₂ ) ₁ (C ₂ H ₂ F ₂ ) ₂ : C 29.05% H 1.08% Measured value: C 28.71% H 1.38% Preparation of solution: 1 g Of poly (PMD / TFE) was shaken with 19 g of hexafluorobenzene to form a partial solution, followed by a 0.45μ glass fiber filter [
Whatman, Autovial ™] was passed through a chromatographic silica padding of ~ 1/4 "in depth. A portion of this solution was sent to ¹⁹ F NMR for composition of the dissolved polymer. Confirmed that the PMD was 54 mol% and the vinylidene fluoride was 46 mol% .The remaining filtrate was used to spin-coat a thick film on the optical substrate, and the absorbance was measured.

Sample 11-PDD: CTFE poly (perfluorodimethyldioxole / chlorotrifluoroethylene),
That is, poly (PDD / CTFE) has been reported many times in the literature, for example, in US Pat. No. 4,754,009. Poly (PDD / C used here
TFE) was poly (PDD / CTFE) produced by aqueous emulsion polymerization. Calculated value for (C ₅ F ₈ O ₂ ) ₁₀ (C ₂ F ₃ Cl) ₂₃ : C 22.52% Cl 15.9 3% Measured value: C 22.41% Cl 15.9 4% Solution preparation: A pale yellow solution was produced by shaking 2.5 g of poly (PDD / CTFE) with 30 ml of hexafluorobenzene and then passed through a 0.45μ glass fiber filter [Whatman, Autovial ™]. . Since this solution was too viscous to spin coat easily, 11.2 g of this solution was further diluted with 10.1 g of hexafluorobenzene. A thick film was spin-coated on an optical substrate using this diluted solution, and the absorbance was measured.

A solution of PDD: CTFE (10:23) was spin-coated on a CaF ₂ substrate to form a polymer film having a thickness of 1903 Å. Next, V
UV absorbance measurements were used to determine the absorbance per micron.

In FIG. 18, the absorbance (expressed in units of reciprocal microns) of PDD: CTFE (10:23) for sample 11 is compared to the wavelength lambda (λ) (expressed in units of nanometers). Show. The measured absorbance at 157 nm / micron is 1.4
4 / micron. The measured absorbance / micron at 193 nm is 0.018 / micron. The measured absorbance / micron at 248 nm is 0.046 / micron.

[Brief description of drawings]

FIG. 1 shows the transmittance T (expressed in%) of the polymer skin at 157 nm as a function of the absorbance at 157 nm (expressed in units of reciprocal microns) from 0.4. Described over an absorbance range of 0.0. In this calculation, the thin film interference effect exhibited by the thin film was ignored.

FIG. 2 shows Teflon ™ AF 1601 (Sample 7a) and Cyt.
The absorbance (expressed in units of reciprocal microns) exhibited by op (TM) 9 (Sample 13) is described versus wavelength lambda ([lambda]) (expressed in units of nanometers).

FIG. 3 shows Te with a thickness of 2146 angstroms located on a silicon substrate.
The flon ™ AF 1601 film (Sample 7b) is described in terms of measured refractive index n and extinction coefficient k measured by VUV spectroscopic ellipsometry versus wavelength lambda (expressed in nanometers).

FIG. 4 shows the spectral transmission (in absolute units) of the Teflon ™ AF 1601 skins designed as an unsupported tuned etalon with a film thickness of 6059 Å in wavelength lambda (in nanometers). Represent) to describe. The interference edge exhibited by this tuning etalon can be clearly seen as a function of wavelength.

FIG. 5 shows the spectral reflectance (expressed in absolute units) of a Teflon ™ AF 1601 skin designed as an unsupported tuned etalon with a film thickness of 6059 Å in wavelength lambda (in nanometers). Represent) to describe. The interference edge exhibited by this tuned etalon can be clearly seen as a function of wavelength and the minimum of the reflection exhibited by the skin is found at 157 nm, which is the skin transmission at such lithographic wavelengths. Contribute to maximizing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme Coat (reference) H01L 21/027 H01L 21/30 502R 515D (72) Inventor Zumsteg, Fredrik Klaus, Delaware, United States 19810 Wilmington Silver Side Road 2715 F Term (Reference) 4J040 DC091 GA03 LA10 MB03 NA20 4J100 AC22P AC23Q AC24P AC25Q AC26Q AC27Q AC31Q AE39Q AR32P BB07P CA01 CA04 CA05 JA03 5F046 CB10 CB12 CB25

Claims (36)

[Claims] 1. An absorbance of ≦ 1 / micron (at a wavelength of 140-186 nm).
Vacuum ultraviolet (VUV) transparent material exhibiting A / micrometer, which is perfluoro-2,2-dimethyl-1,3-dioxole or CX ₂ = CY ₂ [wherein
X is -F or -CF ₃ and Y is amorphous Biniruhomo polymer or amorphous vinyl perfluoro-2,2-dimethyl-1,3-dioxole and CX ₂ = CY ₂ of a H] A vacuum ultraviolet (VUV) transparent material comprising a copolymer. 2. Further, 0 to 25 mol% of one or more monomers CR ^a R ^b = CR ^c.
R ^d {wherein each R ^a , R ^b and R ^c are each independently selected from H or F, and R ^d is -F, -CF ₃ , -OR _f [where R _f. Is C _n F _{2n + 1} (where
n = 1 to 3)] and -OH (when R ^c = H) are selected from the group consisting of the above-mentioned CR ^a R ^b = CR ^c R ^d The vacuum ultraviolet (VUV) transparent material of claim 1, wherein the homopolymer or copolymer is incorporated in a substantially random fashion. 3. Further 40 to 60 mol% of one or more monomers CR^aR^b= CR ^c R^d{Where R^a, R^bAnd R^cAre each independently selected from H or F
, And R^dIs -F, -CF₃, -OR_f[Where R_fIs C_nF_{2n + 1}(here,
n = 1 to 3)] and -OH (R^c= H)
Are also included, and in this case the CR^aR^b= CR^cR^dIs the homopolymer
Alternatively, the vacuum ultraviolet rays according to claim 1, wherein the ultraviolet rays enter the copolymer in an almost alternating manner.
VUV) transparent material. 4. Absorbance ≦ 1 / micron (at wavelengths 140-186 nm).
Vacuum ultraviolet (VUV) transparent material exhibiting A / micrometer, CH ₂ =
CHCF ₃ and _{CF 2 = CF 2; CH 2} = CFH and CF ₂ = CFCl; is CH ₂ = CHF and CClH = CF ₂ [ratio of monomers in this case about 1: 2 to about 2: 1 range Yes]; perfluoro (2-methylene-4-methyl-1,3-dioxolane) and perfluoro (2,2-dimethyl-1,3-dioxole); any proportion of perfluoro (that gives an amorphous composition. 2-methylene-4-methyl-1,3-dioxolane) and vinylidene fluoride; an amorphous vinyl copolymer; and perfluoro (2-methylene-4-methyl-1,3-dioxolane) A vacuum ultraviolet (VUV) transparent material comprising a homopolymer. 5. The UV transparent material is ≤0 at a wavelength of 140 to 186 nm.
． An ultraviolet (UV) transparent material according to claims 1 to 4 having an A / micrometer of 8. 6. The UV-transparent material has ≦ 0 at a wavelength of 150 to 160 nm.
． An ultraviolet (UV) transparent material according to claim 5 exhibiting A / micrometer of 2. 7. The UV transmissive material has ≦ 0 at wavelengths of 155 to 159 nm.
． 7. An ultraviolet (UV) transparent material according to claim 6 having an A / micrometer of 1. 8. The ultraviolet (UV) transparent material according to claim 1, which comprises a homopolymer of perfluoro-2,2-dimethyl-1,3-dioxole. 9. The ultraviolet (UV) transparent material according to claim 8, wherein the homopolymer of perfluoro-2,2-dimethyl-1,3-dioxole is present as a layer or film having a thickness of more than 250 nm. 10. Perfluoro-2,2-dimethyl-1,3-dioxole and one or more monomers CX ₂ ═CY ₂ [wherein X is —F or —CF ₃ and Y is H. The ultraviolet (UV) transmissive material of claim 1, comprising a copolymer of 11. The copolymer is perfluoro-2,2-dimethyl-1,3.
The ultraviolet (U) according to claim 10, which is a copolymer of -dioxole and vinylidene fluoride.
V) Transparent material. 12. The polymer comprises> 75 mol% perfluoro-2,2-dimethyl-1,3-dioxole and the structure CR ^a R ^b = CR ^c R ^d {wherein each R ^a , R ^b and R ^c is each independently selected from H or F, and R ^d is —F, —C
F _3, -OR _f [wherein the _{R f C n F 2n + 1} ( where the n = 1 3) a] is selected from the group consisting of and -OH (when R ^c = H) } The ultraviolet (UV) transparent material according to claim 2, which is a substantially random copolymer made of one or more monomers represented by 13. A copolymer made from> 75 mol% perfluoro-2,2-dimethyl-1,3-dioxole and <25 mol% tetrafluoroethylene. The ultraviolet (UV) transparent material described. 14. The polymer comprises 40-60 mol% CX.₂= CY₂[here,
X is -F or -CF₃And Y is H] and 60 to 40 mol%
Build CR^aR^b= CR^cR^d{Where each R^a, R^bAnd R^cAre independently H or
Or F, and R^dIs -F, -CF₃, -OR_f[Where R_fIs C _n F_{2n + 1}(Where n = 1 to 3)] and -OH (R^c= When H)
Are almost alternating copolymers made from monomers represented by
An ultraviolet (UV) transparent material according to claim 3. 15. The copolymer has a monomer ratio of about 60:40 to about 40 :.
15. The ultraviolet (UV) transparent material according to claim 14, which is a hexafluoroisobutylene / trifluoroethylene copolymer of 60. 16. The copolymer has a monomer ratio of about 60:40 to about 40:40.
The ultraviolet (UV) transparent material according to claim 14, which is a hexafluoroisobutylene / vinyl fluoride copolymer of 60. 17. The copolymer comprises> 75 mol% CX.₂= CY₂[Where X
Is -F or -CF₃And Y is H] and <25 mol% of the structure CR^aR ^b = CR^cR^d{Where each R^a, R^bAnd R^cAre each independently from H or F
Selected and R^dIs -F, -CF₃, -OR_f[Where R_fIs C_nF_{2n + 1}(
Where n = 1 to 3)] and -OH (R^c= H))
A substantially random copolymer made from monomers represented by
2. An ultraviolet (UV) transparent material according to 2. 18. The copolymer is> 75 mol% vinylidene fluoride and <25.
18. The ultraviolet (UV) transparent material according to claim 17, which is a copolymer made from mol% hexafluoropropylene. 19. The copolymer comprises 60-40 mol% vinyl fluoride and 40-
A copolymer made from 60 mol% chlorotrifluoroethylene.
4. An ultraviolet (UV) transparent material according to 4. 20. A thin film comprising the ultraviolet (UV) transparent material according to claim 1. 21. An anti-reflective coating comprising the ultraviolet (UV) transmissive material of claims 1-4. 22. A light transmissive glue comprising the ultraviolet (UV) transmissive material of claims 1-4. 23. A light guide comprising an ultraviolet (UV) transparent material according to claim 1. 24. A resist comprising the ultraviolet (UV) transparent material according to claim 1. 25. The resist according to claim 24, further comprising a dissolution responsive monomer. 26. A transmissive optical element comprising the ultraviolet (UV) transmissive material of claim 1. 27. A copolymer composition comprising 40-60 mol% hexafluoroisobutylene and 60-40 mol% trifluoroethylene poly (hexafluoroisobutylene: trifluoroethylene). 28. An amorphous copolymer composition comprising 40-60 mol% hexafluoroisobutylene and 60-40 mol% vinyl fluoride poly (hexafluoroisobutylene: vinyl fluoride). 29. The copolymer composition of claim 27 or 28 which exhibits an A / micron of <1 at 140-186 nm. 30. The copolymer composition of claim 29 which exhibits an A / micron of <0.8 at 140-186 nm. 31. The copolymer composition of claim 30 which exhibits an A / micron of <0.2 at 150-186 nm. 32. The copolymer composition of claim 31, which exhibits an A / micron of <0.1 at 155-186 nm. 33. A method of producing a PDD film having a thickness of greater than 250 nm, comprising: a) optionally diluting the monomer with a solvent and / or an initiator and placing the film where desired and b). A method comprising the steps of initiating polymerization by physical and / or chemical means. 34. Use of the polymer according to claim 18, as an adhesive. 35. Use of the polymer according to claim 18, as an adhesive when attaching a thin skin to a photomask. 36. Use of the polymer according to claim 18, as an adhesive when attaching a thin skin to a frame.