Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/093—Halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/095—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/10—Homopolymers or copolymers of unsaturated ethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
  • C09J129/10—Homopolymers or copolymers of unsaturated ethers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
  • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/02—Halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/28—Non-macromolecular organic substances
  • C08L2666/32—Halogen-containing compounds

Definitions

• compositions comprising fluorinated polymers and fluorinated liquids, said compositions useful in the manufacture of articles substantially transparent to ultraviolet radiation at wavelengths from approximately 150 nanometer to 200 nanometers.
• TECHNICAL BACKGROUND OF THE INVENTION The semiconductor industry is the foundation of the trillion dollar electronics industry. The semiconductor industry continues to meet the demands of Moore's law, whereby integrated circuit density doubles every 18 months, in large part because of continuous improvement of optical lithography's ability to print smaller features on silicon.
• the circuit pattern is contained in the photomask, and an optical stepper is used to project this mask pattern into the photoresist layer on the silicon wafer.
• 157 nm lies in the region of the spectrum referred to as the vacuum uv (VUV), which range extends from 186 nm down to below 50 nm.
• VUV vacuum uv
• WO 9836324 discloses the use of resins consisting solely of C and
• pellicle membranes having an absorbance/micrometer of 0.1 to 1.0 at UV wavelengths from 140 to 200 nm.
• VUV vacuum ultraviolet
• This invention provides a fluoropolymer composition
• a fluoropolymer composition comprising vinyl fluoropolymers and a liquid selected from the group consisting of i) cyclic, linear, or branched hydrofluorocarbons having 2 to
• a method comprising causing a source to emit electromagnetic radiation in the wavelength range from 150 nanometers to 260 nanometers; disposing a target surface in the path of at least a portion of said electromagnetic radiation in such a manner that at least a portion of said target surface will be thereby illuminated; and interposing in the path of at least a portion of said electromagnetic radiation between said target surface and said source a shaped article comprising a vinyl fluoropolymer and a liquid said liquid being selected from the group consisting of i) cyclic, linear, or branched hydrofluorocarbons having 2 to
• an apparatus comprising an activateable source of electromagnetic radiation in the wavelength range of 150-260 nanometers; and a shaped article comprising a vinyl fluoropolymer and a liquid said liquid being selected from the group consisting of i) cyclic, linear, or branched hydrofluorocarbons having 2 to
• Figure 1 describes the absorbance in units of inverse micrometers for CF 3 CFHCFHCF 2 CF 3 , VertrelTM XF versus wavelength lambda ( ⁇ ) in units of nanometers.
• Figure 2 describes the absorbance in units of inverse micrometers for CF3CH2CF2CH3, SolkaneTM 365 mfc versus wavelength lambda ( ⁇ ) in units of nanometers.
• Figure 3 describes the absorbance in units of inverse micrometers for HCF 2 O(CF 2 O) n (CF2CF2O) m CF 2 H H-GaldenTM ZT 85 versus wavelength lambda ( ⁇ ) in units of nanometers.
• Figure 4 describes the absorbance in units of inverse micrometers for CF 3 CF 2 CF 2 OCFHCF 3 FreonTM E1 versus wavelength lambda ( ⁇ ) in units of nanometers.
• Figure 5 describes the absorbance in units of inverse micrometers for HCF 2 O(CF2 ⁇ ) n (CF2CF2 ⁇ ) m CF 2 H H-GaldenTM ZT 130 versus wavelength lambda ( ⁇ ) in units of nanometers.
• Figure 6 describes the absorbance in units of inverse micrometers for ⁇ -C 8 F 1 8 Performance FluidTM 5080 versus wavelength lambda ( ⁇ ) in units of nanometers. Measurement saturated below 154 nm.
• Figure 7 describes the absorbance in units of inverse micrometers for ⁇ Perfluoro(butyltetrahydrofuran) FluorinertTM FC-75 versus wavelength lambda ( ⁇ ) in units of nanometers. Measurement saturated below 154 nm.
• Figure 8 describes the absorbance in units of inverse micrometers for ⁇ N(CF2CF 2 CF 2 CF 3 ) 3 FluorinertTM FC-40 versus wavelength lambda ( ⁇ ) in units of nanometers. Measurement saturated below 155 nm.
• Figure 9 describes the absorbance in units of inverse micrometers for CF 3 CF(CF 3 )CF(OC 2 H 5 )CF2CF 2 CF 3 NOVECTM HFE-7500 versus wavelength lambda ( ⁇ ) in units of nanometers. Measurement saturated below 167 nm.
• Figure 10 describes the absorbance in units of inverse micrometers for Hexafluoropropylene/Propylene Cyclic Dimer versus wavelength lambda ( ⁇ ) in units of nanometers. . Measurement saturated below 180 nm.
• Figure 11 describes the absorbance in units of inverse micrometers for hexafluorobenzene versus wavelength lambda ( ⁇ ) in units of nanometers. . Measurement saturated below 266 nm.
• Figure 12 describes the absorbance in units of inverse micrometers for Vertrel 245 versus wavelength lambda ( ⁇ ) in units of nanometers. Measurement saturated below 152 nm.
• Figure 13 describes the absorbance in units of inverse micrometers for 1 ,1,2,2-Tetrafluorocyclobutane versus wavelength lambda ( ⁇ ) in units of nanometers. Measurement saturated below 175 nm.
• Figure 14 describes the absorbance in units of inverse micrometers for 1-ethoxy-1,1,2,2-tetrafluoroethane versus wavelength lambda ( ⁇ ) in units of nanometers. Measurement saturated below 148 nm.
• solvent is employed to mean a liquid medium in which a fluorinated polymer is dissolved or dispersed.
• solvent is also taken to mean a liquid which may be incorporated into a polymer and which has the effect of plasticizing the polymer.
• fluorinated is employed to mean both partially or fully fluorinated; that is to say, the term “fluorinated” encompasses both hydrofluorocarbons and perfluorocarbons.
• amorphous is employed to mean exhibiting no endotherm of greater magnitude than 1 joule/gram, in differential scanning calorimetry (DSC) according to ASTM D-4591-01.
• DSC differential scanning calorimetry
• a "crystalline” polymer by contrast, exhibits a melting endotherm of greater than 5 joules/gram in the same test.
• a fluorinated polymer may be in the form of a film or coating which has been deposited from a solution or dispersion of the polymer.
• it can be very difficult to remove all traces of the solvent from the resultant polymer film or coating. There can be as much as 10% by weight of solvent remaining in the polymeric film or coating during use.
• VUV vacuum ultraviolete
• this invention provides a composition
• a composition comprising a vinyl fluoropolymer and a liquid selected from the group consisting of i) cyclic, linear, or branched hydrofluorocarbons having 2 to
• vinyl fluoropolymer suitable for use in the practice of the invention.
• One of skill in the art will be aware of a large number of such polymers employed in UV applications, most particularly photolithography.
• the spectroscopic transmittance at the wavelength of interest will vary considerably from one polymer to another, and that a polymer which may be preferred at one wavelength may be less preferred at another while both said wavelengths fall within the range of 140-286 nm.
• the thermomechanical properties of a polymer are also important, and that the choice of any particular polymer and polymer/solvent combination will likely represent a tradeoff involving the many properties of the suitable polymer compositions.
• crystalline and amorphous polymers are suitable for the practice of the present invention.
• amorphous polymers are preferred because of reduced light scattering.
• crystalline polymers which in general exhibit superior thermomechanical properties, are preferred. While the principal focus in the present invention is photolithography at 157 nm, the inventors hereof contemplate quite wide applicability of the compositions, methods, and apparati encompassed by the instant invention.
• ether oxygen can replace one or more of the carbons providing that at least one of the carbons adjacent to any ether oxygen is perfluorinated. More preferred are amorphous fluoropolymers which exhibit A ( ⁇ nrr
• composition of the invention is useful for forming pellicles, lenses, light guides, anti-reflective coatings and layers, windows, protective coatings, and adhesives.
• This invention provides polymer- liquid compositions useful for the spin-coating, precipitation, and handling of polymers such that even were up to 10 % of the processing liquids left as a residue in the polymer, after bulk liquid removal, the residual liquid would contribute minimally to absorption in the vacuum ultraviolet at wavelengths from 150 to 286 nm.
• the composition herein is employed in a pellicle film useful in 157 nm photolithography for the purpose of preparing electronic circuits.
• a preferred polymer for the practice of the present invention is spin coated onto a glass or silica substrate.
• the pellicle film can contain up to 10 wt % residual solvent.
• excess solvent is removed by baking. However this is not effective in removing all solvent, and can damage the thin pellicle film-typically 0.8 micrometers in thickness.
• solvents which can be present at a concentration of 10 % by weight in a polymer film of a thickness of 1 micrometer said solvent causing a decrease in optical transmission of said film by no more than 1 percentage point vs. 100% transmission.
• This criterion translates into a requirement that a solvent suitable for the practice of the present invention must exhibit an absorbance in units of inverse micrometers ( ⁇ r ⁇ r 1 ) of A/ ⁇ ⁇ ⁇ 0.044 in the wavelength range of 150 to 200 nm.
• preferred liquids exhibit a boiling point in the range of -40 to 200°C, preferably from 50 to 180°C, most preferably from 100 to 150°C.
• liquids should have a boiling point from -40 to 200°C, preferably from 50 to 180°C, most preferably from 100 to 150°C.
• Solvents preferred for the practice of the present invention include
• CF 3 CFHCFHCF 2 CF 3 CF 3 CH 2 CF 2 CH 3 , HCF 2 O(CF2 ⁇ ) n (CF2CF2 ⁇ ) m CF 2 H (with a boiling point falling in the range of 80 to 140°C), CF 3 CF 2 CF 2 OCFHCF 3 , CF 3 CF 2 CF 2 OCF(CF 3 )CF 2 OCFHCF 3 , F(CF 2 ) 6 F, and F(CF 2 ) 8 F.
• compositions of the present invention are useful, depending on concentration and properties of the polymer in the solution or dispersion hereof, in the fabrication of sheets, layers, coatings, films of UV transparent material which are in turn used in optical applications in pellicles, lenses, light guides, anti-reflective coatings and layers, windows, protective coatings, and glues where light absorption is required to be low.
• compositions of the present invention may conveniently be prepared by cryogenically grinding the polymer to a powder and then add ing the thus ground polymer to the solvent while stirring to form a solution of about 30% solids for the purpose of forming a shaped article or coating. After the formation thereof, the thus formed article may be subject to heating and/or vacuum to remove residual solvent. According to the present invention, it may be found convenient to allow as much as 10 % by weight of solvent to remain in the shaped article because it will have negligible effect on the transmission of the thus formed shaped article.
• the present invention provides a method comprising causing a source to emit electromagnetic radiation in the wavelength range from 150 nanometers to 260 nanometers; disposing a target surface in the path of at least a portion of said electromagnetic radiation in such a manner that at least a portion of said , target surface will be thereby illuminated; and interposing in the path of at least a portion of said electromagnetic radiation between said target surface and said source a shaped article comprising a fluoropolymer composition exhibiting an absorbance/micrometer ⁇ 1 at wavelengths in the range of 150 to 260 nm and a heat of fusion of ⁇ 1 J/g a source of electromagnetic radiation such as a lamp (such as a mercury or mercury- xenon lamp, a deuterium lamp or other gas discharge lamp of either the sealed or flowing gas type), an excimer lamp such as produces 172 nm radiation or other lamps), a laser (such as the excimer gas discharge lasers which produce 248 nm electromagnetic radiation from KrF gas,
• a lamp
• the source is an excimer gas discharge laser emitting at 157 nm, 193 nm, or 248 nm, most preferably, 157 nm.
• At least a portion of the light emitted from the source is directed to a target surface at least a portion of which will be illuminated by the incident light.
• the target surface is to be a photopolymer surface which undergoes light-induced chemical reaction in response the incidence of the radiation.
• Clariant has just introduced a 157 nm fluoropolymer resist under the name AZ EXP FX 1000P which is likely a hydrofluorocarbon polymer incorporating ring structures for etch stability and protected fluoroalcohol groups for aqueous base solubility.
• a substrate typically a silicon wafer.
• the features are formed on the substrate by electromagnetic radiation which is impinged, imagewise, on a photoresist composition applied to the silicon wafer. Areas of the photoresist composition which are exposed to the electromagnetic radiation change chemically and/or physically to form a latent image which can be processed into an image for semiconductor device fabrication. Positive working photoresist compositions generally are utilized for semiconductor device manufacture.
• the photoresist composition typically is applied to the silicon wafer by spin coating.
• the silicon wafer may have various other layers applied to it in additional processing steps. Examples of such additional layers such as are known in the art include but are not limited to a hard mask layer, typically of silicon dioxide or silicon nitride, and an antireflective layer. Typically the thickness of the resist layer is sufficient to resist the dry chemical etch processes used in transferring a pattern to the silicon wafer.
• a photoresist is typically comprised of a polymer, a spin coating solvent and at least one photoactive component. The photoresists can either be positive-working or negative-working. Positive-working photoresists are preferred.
• photoresists can optionally comprise dissolution inhibitors and/or other additional components such as are commonly employed in the art.
• additional components include but are not limited to, resolution enhancers, adhesion promoters, residue reducers, coating aids, plasticizers, and T g (glass transition temperature) modifiers
• the photoresist composition generally comprises a film forming polymer which may be photoactive and a photosensitive composition that contains one or more photoactive components.
• the photoactive component Upon exposure to electromagnetic radiation (e.g., UV light), the photoactive component acts to change the rheological state, solubility, surface characteristics, refractive index, color, optical characteristics or other such physical or chemical characteristics of the photoresist composition.
• the photoresist compositions suitable for use in the process of the instant invention are sensitive in the ultraviolet region of the electromagnetic spectrum and especially to those wavelengths ⁇ 365 nm.
• Imagewise exposure of the resist compositions of this invention can be done at many different UV wavelengths including, but not limited to, 365 nm, 248 nm, 193 nm, 157 nm, and lower wavelengths.
• Imagewise exposure is preferably done with ultraviolet light of 248 nm, 193 nm, 157 nm, or lower wavelengths, more preferably it is done with ultraviolet light of 193 nm, 157 nm, or lower wavelengths, and most preferably, it is done with ultraviolet light of 157 nm or lower wavelengths.
• Imagewise exposure can either be done digitally with a laser or equivalent device or non-digitally with use of a photomask.
• Suitable laser devices for imaging of the compositions of this invention include, but are not limited to, an argon-fluorine excimer laser with UV output at 193 nm, a krypton-fluorine excimer laser with UV output at 248 nm, and a fluorine (F2) laser with output at 157 nm.
• F2 laser fluorine
• the polymers suitable for use in the present invention can be formulated as a positive resist wherein the areas exposed to UV light become sufficiently acidic to be selectively washed out with aqueous base.
• a given copolymer for aqueous processability (aqueous development) in use is typically a carboxylic acid-containing and/or fluoroalcohol-containing copolymer (after exposure) containing at least one free carboxylic acid group and/or fluoroalcohol group.
• the level of acid groups e.g., free carboxylic acid or fluoroalcohol groups is determined for a given composition by optimizing the amount needed for good development in aqueous alkaline developer.
• the copolymer of the photoresist When an aqueous processible photoresist is coated or otherwise applied to a substrate and imagewise exposed to UV light, the copolymer of the photoresist must have sufficient protected acid groups and/or unprotected acid groups so that when exposed to UV the exposed photoresist will become developable in basic solution.
• the photoresist layer will be removed during development in portions which are exposed to UV radiation but will be substantially unaffected in unexposed portions during development by aqueous alkaline liquids such as wholly aqueous solutions containing 0.262 N tetramethylammonium hydroxide (with development at 25°C usually for less than or equal to 120 seconds) or 1% sodium carbonate by weight (with development at a temperature of 30°C usually for less than 2 or equal to 2 minutes).
• aqueous alkaline liquids such as wholly aqueous solutions containing 0.262 N tetramethylammonium hydroxide (with development at 25°C usually for less than or equal to 120 seconds) or 1% sodium carbonate by weight (with development at a temperature of 30°C usually for less than 2 or equal to 2 minutes).
• aqueous alkaline liquids such as wholly aqueous solutions containing 0.262 N tetramethylammonium hydroxide (with development at 25°C usually for less than or equal to 120 seconds)
• Halogenated solvents are preferred and fluorinated solvents are more preferred.
• the target surface may be an optical sensor which produces an electronic, optical, or chemical signal in response to the incidentradiation such as in the signal or image wise receiver in an optical, electo-optical or electronic detector used in time based, wavelength based or spatially resolved optical communications systems.
• the electromagnetic radiation incident on the target surface, and its time variation, spatial variation and/or its wavelength (spectral) variations can be used to encode information which can then be decoded at the detector.
• the target surface may be a electro-optical receptor of the type used for light to energy conversion.
• the target surface may be a specimen undergoing microscopic examination in the wavelength range of 150-260 nm.
• the target surface may be a luminescent surface caused to luminesce upon incidence of the 150-260 nm radiation employed in the method of the invention such as in a imaging system used as an optical imaging display.
• the target surface may be a specimen undergoing materials processing, such as laser ablation, laser trimming laser melting, laser marking in the wavelength range from 150 nm to 260 nm,
• a shaped article comprising a transparent fluoropolymer composition as hereinbelow described, is interposed between the light source and the target.
• the fluoropolymer composition of the invention is employed in an adhesive.
• the fluoropolymer composition is employed as a coating or an element to provent the outgassing under irradiation of dissimilar materials in the system so as to reduce optical contamination by more optically absorbing materials.
• the adhesive-like material is used as a coating or element or so as to capture and immobilize particulate contaminants, to avoid their further migration and deposition in the system.
• the fluoropolymer composition of the invention is employed as a coating on a non optical element (such as a support structure in an optical instrument), an optical element (such as a mirror, a lens, a beam splitter, a tuned etalon, a detetecor, a pellicle).
• the fluoropolymer composition is itself a shaped article such as a lens or other optical element (such as a mirror, a lens, a beam splitter, a tuned etalon, a detetecor, a pellicle,) or non optical component (such as a support structure in an optical instrument).
• the fluoropolymer composition is in the form of a pellicle, a free standing membrane mounted on a frame (which can be metallic, glass, polymer or other material) which is attached (adhesively or using other methods such as magnetism) to onto the surface of a photomask employed in a photolithographic process conducted in the wavelength region from 150 nm to 260 nm.
• the photolithographic process employs a laser emitting radiation at 157 nm, 193 nm, or 248 nm. Most preferably, the photolithographic process employs a laser emitting 157 nm radiation.
• an apparatus comprising an activateable source of electromagnetic radiation in the wavelength range of 150-260 nanometers; and a shaped article comprising the fluoropolymer composition of the invention exhibiting an absorbance ( ⁇ m- 1 ) ⁇ 1 at wavelengths from 150 to 260 nm and a heat of fusion of ⁇ 1 J/g
• an activateable light source of the type described hereinabove as suitable for use in the method of the invention.
• activateable is meant that the light source may be, in conventional terms, “on” or “off but if in the "off” state may be turned on by conventional means.
• This light source may also have multiple wavelengths (as is used in wavelength division multiplexing in optical communications) through the use of lamps or multiple lasers of different wavelengths.
• a light source which may be "off when so desired, as when the apparatus is not being used, or is being shipped.
• the light source of the invention can be activated - that is, turned “on” - when it is desired to use it as, for example, in the method of the present invention.
• the light source emits electromagnetic radiation in the wavelength range from 150 nm-260 nm.
• Light sources suitable for use in the apparatus of the invention include a lamp (such as a mercury or mercury-xenon lamp, a deuterium lamp or other gas discharge lamp of either the sealed or flowing gas type), an excimer lamp such as produces 172 nm radiation or other lamps), a laser (such as the excimer gas discharge lasers which produce 248 nm electromagnetic radiation from KrF gas, 193 nm radiation from ArF gas or 157 nm from F2 gas, or frequency up converterd as by non linear optical processes of laser whose emission in the ultraviolet, visible or infrared), a black body light source at a temperature of at least 2000 degrees kelvin , an example of such a black body light source being a laser plasma light source where by a high powered laser is focused to a small size onto a metal, ceramic or gas target, and a plasma is formed as for example in the samarium laser plasma light source whereby a black body temperature on the order of 250,000 degrees Kelvin is achieved, and black body radiation from the infrared
• a shaped article comprising the fluoropolymer of the invention.
• the shaped article is disposed to lie within the path of electromagnetic radiation emitted from the souce when the source is activated or "turned on.”
• the shaped article employs the fluoropolymer compositionof the invention in an adhesive .
• the fluoropolymer composition is employed as a coating on an optical or non-optical element.
• the fluoropolymer composition is itself formed into a shaped article such as a lens or other optical component.
• the fluoropolymer composition is in the form of a pellicle, a protective film typically 0.6 to 1 micron thick that is mounted on a frame that is attached in turn to the surface of a photomask employed in a photolithographic process conducted in the wavelength region from 150 nm to 260 nm.
• the apparatus of the invention need not encompass a target surface.
• the apparatus of the invention could be employed as a portable or transportable optical irradiation system with a light source and a set of optical components which could be used on a variety of target surfaces in several locations.
• Pellicle film thickness can be optimized such that the pellicle will exhibit a thin film interference with a maximum in the transmission spectrum at the desired lithographic wavelength. The spectral transmission maximum of a properly tuned etalon pellicle film occurs where the spectral reflectance of the pellicle film exhibits a minimum.
• Polymers suitable for the practice of the invention exhibit very low absorbance/micron, at least ⁇ 1, preferably ⁇ 0.5, more preferably ⁇ 0.1 , and most preferably ⁇ 0.01. Those which further exhibit values of the index of refraction which match the index of adjacent optical elements have important uses antireflective index matching materials and optically clear index matching adhesives, those which exhibit intermediate values of the index of refraction between those of an optical element and either the ambient (with an index of 1 for example) or a second djacent element of a different index of refraction have important applications as anti-reflection coatings and those have a low value of the index of refractions below 1.8, or preferably below 1.6 or more preferably below 1.45 have very important applications as multiplayer anti-reflection coatings. Such polymers can be used to reduce the light reflected from the surface of a transparent substrate of a relatively higher index of refraction. This decrease in the reflected light, leads to a concomitant increase in the light transmitted through the transparent substrate material.
• the transmission measurements of the fluid samples listed in Table 1 were made using a Harrick Scientific Corp. (Harrick Scientific Corporation Ossining, NY) Demountable Liquid Cell model DLC-M13 as shown in Figure 3.
• the DLC-M13 was mounted in a VUV- Vase model VU- 302 spectroscopic ellipsometer (J.A. Woolman Co., Inc. Lincoln, NE).
• the liquid specimen to be tested was held in a cell formed between parallel CaF2 windows by insertion of a Teflon® ring between the windows.
• Teflon® rings of 6 and 25 micrometer thickness were used, providing two optical path lengths through two aliquots of the same sample. While charging the cell, care was taken to avoid bubbles in the 8 mm diameter window aperture.
• the optical absorbance, A ( ⁇ r 1 ) as defined in Equation 1, is the base 10 logarithm of the ratio of the transmission of the CaF 2 windows at the test wavelength divided by the transmission at that wavelength of the test sample (windows plus experimental specimen) divided by the thickness (t) of or optical path length through the test specimen Equation 1.
• Equation 2 The spectral transmission was measured at both cell thicknesses (t 1 and t 2 ) and the incremental decrease in transmission (T- j and T ) with the increase in the sample's optical path length provided the optical absorbance / micrometer using Equation 2. Equation 2.
• Al ⁇ m log 1 o(r ⁇ )-log 10 (7 2 ) t 2 — t,
• a transmission difference of ⁇ 0.1 % is near the limit of the measurement method. In such a case, a thicker sample, with a longer path length, is required to keep the measured transmission drop larger than the instrument's sensitivity.
• Example 9 A 400 ml stainless steel autoclave was loaded with 0.2 g Vazo® 56 WSP [2,2'-azobis(2-amidinopropane)dihydrochloride] and 200 ml of deionized water containing 0.1 g of F(CF 2 ) ⁇ 6 . 8 (CH 2 ) 3 NH 3 CI. The autoclave was chilled, evacuated, and further loaded with 80 g of
• a solution was made by agitating 2 g of the poly(HFIB/VF) so prepared with 18 g of Solkane® 365 mfc (CF3CH2CF2CH3). Adding 0.5 g of chromatographic alumina and 0.5 g of chromatographic silica gel and filtering through a 0.45 micron PTFE syringe filter (Whatman®
• VUV transmission of the CaF2 substrates and the polymer films on the CaF2 substrates were measured using a VUV spectrophotometer using a laser plasma light source, a sample chamber capable of both transmission and reflectance measurements, a 1 meter monochromator and a sodium salicylate phosphor coated 1024 element photodiode detector. This is discussed in greater detail in R. H. French, "Laser-Plasma Sourced, Temperature Dependent VUV Spectrophotometer Using Dispersive Analysis", Physica Scripta, 41 , 4, 404 8, (1990).
• the film thickness was determined using a Filmetrics (Filmetrics Inc., San Diego, CA model F20 thin film measurement system.
• the values of the absorbance/micron for the polymers were calculated from 145 nm to longer wavelengths, including at 157, 193, and 248 nm.
• the prepared solution was spin coated onto a CaF2 substrate at a spin speed of 1500 rpm for a period of 60 seconds using a Brewer CEE 100b model Spin Coater (Brewer Science, 2401 Brewer Drive, Rolla, MO 65401 USA). The sample was then removed from the spinner and put on the hot plate of the spin coater at 60 degrees centrigrade for a post apply bake. This produced a film of 1986 nm thickness.
• Comparative Example 7 A solution was made by agitating 2 g of the poly(HFIB ⁇ /F) prepared in Example 9 with 18 g of hexafluorobenzene. Adding 0.5 g of chromatographic alumina and 0.5 g of chromatographic silica gel and filtering through an 0.45 micron PTFE syringe filter (Whatman® Autovial® 0.45 micron PTFE membrane) gave a clear colorless filtrate. Following the procedures of Example 9: The solution so prepared was spin coated on to a CaF 2 substrate at a spin speed of 6000 rpm for a period of 60 seconds. The sample was then removed from the spin coater and put the spin coater's hot plate at 60 degrees centrigrade for a post apply bake. This produced and produced a film of 2090 nm thickness. After spinning from hexafluorobenzene, a solvent with an A ⁇ »

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