CN112034683A - Fluoropolymer for photoresist, top anti-reflection film composition comprising same and application of fluoropolymer to photoresist - Google Patents
Fluoropolymer for photoresist, top anti-reflection film composition comprising same and application of fluoropolymer to photoresist Download PDFInfo
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- CN112034683A CN112034683A CN202010773715.6A CN202010773715A CN112034683A CN 112034683 A CN112034683 A CN 112034683A CN 202010773715 A CN202010773715 A CN 202010773715A CN 112034683 A CN112034683 A CN 112034683A
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- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/305—Saturated compounds containing more than one carboxyl group containing ether groups, groups, groups, or groups
- C07C59/315—Saturated compounds containing more than one carboxyl group containing ether groups, groups, groups, or groups containing halogen
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- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
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Abstract
The present invention relates to a fluoropolymer for photoresist, a top antireflective film composition comprising the same, and its use in photoresist. The structural formula of the fluorine-containing polymer for the photoresist is as follows: CF2(CF3) CF2- [ O-CF (CF3) CF2] n-O-CF (CF3) COO-R, wherein n is in the range of 1-8, and R is H, NH4 or one or more of other similar structures; based on the weight of the whole polymer, the content a of the polymer component with n ≦ 1 is 0-12%, the content b of the polymer component with n being 2 is 55-80%, the content c of the polymer component with n being 3 is 15-30%, the content d of the polymer component with n being 4 is 0-15%, the content e of the polymer component with n being more than or equal to 5 is 0-8%, b + c is more than or equal to 80%, and a, d and e are simultaneously 0 or any one of 0 or simultaneously not 0. The fluorine-containing polymer meeting the specific composition requirements of the invention is obtained by controlling the content distribution of polymer components with different molecular weights in the fluorine-containing polymer, and the fluorine-containing polymer is easy to degrade, low in toxicity, environment-friendly and capable of being used for preparing top anti-reflection with lower refractive index.
Description
Technical Field
The invention relates to the technical field of top anti-reflection films for photoresists, in particular to a fluorine-containing polymer for preparing a top anti-reflection film, a composition for preparing the top anti-reflection film containing the fluorine-containing polymer, and a top anti-reflection film for photoresists prepared from the fluorine-containing polymer or the composition.
Background
The photolithography technique is a method for transferring a semiconductor circuit pattern on a photomask to a silicon wafer, and the photomask is irradiated by laser or an electron beam to change the material properties of photosensitive substances on the wafer due to light sensitivity, so that the pattern transfer process is completed. However, the existing photolithography process has the technical problem of light scattering, which can cause low dimensional accuracy of photoresist imaging and can not process patterns correctly. The current mainstream solution is to add a bottom anti-reflective film or a top anti-reflective film before and after photoresist coating. Among them, the top anti-reflection film mainly aims to reduce interference of light in a photoresist, prevent a change in a width of a photoresist line due to a change in a thickness of the photoresist, and is required to have a low refractive index and a high transmittance.
Known top antireflective films can be formed by applying a composition containing a fluorine-containing compound on the top surface of a photoresist. The fluorine-containing compound has the characteristics of large molecular volume and small atomic refractive index, has low refractive index, has the advantages of positive correlation between the refractive index of the fluorine-containing compound and the fluorine content of the fluorine-containing compound, has easy coating property, easy film forming property, capability of developing in an aqueous solution system and the like, can be removed together with the photoresist through a developing solution, and is very suitable for preparing and forming the top reflection
Chinese patent application CN1666154A discloses an anti-reflective coating composition consisting essentially of an alkali-soluble fluoropolymer- [ CF2CF(ORfCOOH)]- (Rf represents a linear or branched perfluoroalkyl group, which may contain ether oxygen atoms), an acid, an amine and a solvent. Chinese patent application CN101568991A discloses an anti-reflective coating forming composition comprising a specific naphthalene compound, a polymer (- [ CF)2CF(ORfCOOH)]-) and a solvent. Japanese patent application JP09006008A discloses a water-soluble pattern forming material using a fluorine-containing polymer (F- [ CF (CF))3)CF2-O]p- CF(CF3) COOH as a surfactant, wherein p is an integer of 1 to 10, but the surfactant cannot satisfy the condition as an antireflection film. Japanese patent application JP10069091A discloses a composition for a top anti-reflection film comprising a perfluoroalkylether carboxylic acid (F- [ CF (CF) ]3)CF2-O]m-CF(CF3) COOH, wherein m is an integer from 1 to 10, preferably an integer from 2 to 4), homopolymers or copolymers of N-vinylpyrrolidone and an aqueous solution of at least one amino acid derivative. Taiwan patent application TW200928594A discloses a composition for a top anti-reflection film comprising the general formula Rf-O- [ CF (CF)3)CF2-O]m-CF(CF3) A fluorine-containing compound of COOH (wherein Rf is a partially or perfluoro substituted alkyl group, and m is an integer of 0 to 10), an amine compound, and a water-soluble polymer.
The fluoropolymer for the top anti-reflection film in the above prior art is useful for forming a top anti-reflection film for lithography, but has some disadvantages in terms of processability, film formability, refractive index, or raw material cost.
Disclosure of Invention
In view of the technical problems in the prior art described above, it is an object of the present invention to provide a fluoropolymer useful for preparing a top anti-reflective film for photoresist, a composition for preparing a top anti-reflective film for photoresist comprising the same, and a top anti-reflective film for photoresist prepared therefrom. The fluorine-containing polymer is easy to produce, low in raw material cost, low in toxicity, easy to degrade and environment-friendly, and the composition containing the fluorine-containing polymer and used for preparing the top anti-reflection film has good solution stability and film forming property, the pH value of the composition can be matched with that of photoresist, the top anti-reflection film with a low refractive index can be prepared, atomization cannot occur, light scattering and standing wave effects can be avoided, pattern defects possibly generated in the photoetching process can be reduced, and the quality of photoetching patterns is improved.
The purpose of the invention is realized by the following technical scheme:
a fluoropolymer for use in preparing a top antireflective film for a photoresist, characterized by the structural formula:
CF2(CF3)CF2-[O-CF(CF3)CF2]n-O-CF(CF3)COO-R
wherein n is in the range of 1-8, R is H, NH4Or one or more of other similar structures;
based on the weight of the whole polymer, the content a of the polymer component with n ≦ 1 is 0-12%, the content b of the polymer component with n being 2 is 55-80%, the content c of the polymer component with n being 3 is 15-30%, the content d of the polymer component with n being 4 is 0-15%, the content e of the polymer component with n being more than or equal to 5 is 0-8%, b + c is more than or equal to 80%, and a, d and e are simultaneously 0 or any one of 0 or simultaneously different from 0.
The present inventors have intensively studied and found that when the composition of the above-mentioned fluoropolymer according to the present application satisfies the above-mentioned conditions, the composition solution for forming a top anti-reflective film prepared therefrom has good solution stability and good moldability, and at the same time, the anti-reflective film prepared therefrom has a refractive index of 1.41 to 1.44 at 248nm, can effectively reduce the refractive index under laser irradiation at a wavelength of 248nm, and can be used as a top anti-reflective film for a photoresist.
The present inventors have intensively studied and found that when the content a is more than 12%, the moldability of the composition prepared from the fluoropolymer is poor and pores are liable to occur on the film surface; when the content e is more than 8%, the composition prepared by the fluorine-containing polymer has poor solution stability, is easy to generate gel and agglomerate, has poor film forming property, is uneven in formed film distribution, is easy to generate holes on the film surface and is easy to atomize; when the content d is more than 15%, the composition prepared from the fluoropolymer has poor solution stability, is liable to gel and agglomerate, and the composition has generally poor moldability, and the formed film tends to be unevenly distributed and to have pores on the film surface; when the content c is more than 30 percent, the viscosity of the composition is increased, the dispersion is uneven, the solution stability is poor, gel and floccule appear, and holes appear on the surface of a film during film forming; when the content c is less than 15%, the surface of the formed film has more radioactive shapes, surface atomization occurs within 1 to 3 days, and a light scattering phenomenon occurs when the film is used as an antireflection film, resulting in a standing wave effect; when the content b is less than 55%, the solution stability is poor, gel and flocculent precipitates appear, and oily substances appear on the surface of the formed film, so that the dispersion is not uniform.
Further, the number average molecular weight of the fluoropolymer is 600 to 1300, more preferably 650 to 1100.
Further, the content a is 0 to 10%, preferably 0 to 8%, more preferably 2 to 8%. The content b is 60 to 80%, preferably 60 to 75%. The content c is 18 to 30%, preferably 18 to 28%. The content d is 3-15%, preferably 5-15%. The content e is 0 to 6%, more preferably 0 to 4%.
The fluorine-containing polymer can polymerize hexafluoropropylene oxide by photo-oxidation, catalytic oligomerization, plasma or anionic polymerization, and then react with water, amine and ester compounds respectively to form the corresponding fluorine-containing polymer containing carboxylic acid groups, amine groups and ester groups.
The present invention also provides a composition for preparing a top antireflective film for a photoresist comprising any one of the fluoropolymers described previously herein.
Further, the composition for preparing a top anti-reflection film contains 1 to 15%, preferably 2 to 12%, more preferably 2 to 8% by weight of the fluoropolymer.
Further, the composition for producing a top anti-reflection film further comprises a water-soluble resin, and the molar ratio of the fluorine-containing polymer to the water-soluble resin is 1:2 to 1:30, preferably 1:3 to 1: 25.
The water-soluble resin may be one or more selected from the group consisting of polyvinylpyrrolidones, polyacrylics, and polyurethanes, and may be a water-soluble resin obtained by substituting all or part of hydrogen atoms of alkyl groups of the water-soluble resin with fluorine atoms. The number average molecular weight of the water-soluble resin is 3000-30000, preferably 4000-26000 and more preferably 6000-22000.
The polyvinylpyrrolidone can be polyvinylpyrrolidone, or the polyvinylpyrrolidone and other monomer polymers, and the polyvinylpyrrolidone can be used alone or in combination.
The polyacrylic acid can be polyacrylic acid, or polyacrylic acid and other monomer polymers, and the polyacrylic acid can be used alone or in a mixture.
The polyurethanes refer to polyurethane, and can also be polymers of polyurethane and other monomers, and the polyurethanes can be used alone or in a mixture.
Further, the composition for preparing the top anti-reflective film further includes amine, and the content of the amine may be 0.2 wt% to 2 wt%, preferably 0.3 to 1 wt%. The amine can be one or more of structures such as ammonia water, tetramethylammonium hydroxide, alkanolamine, arylamine, alkylamine and the like, and the tetramethylammonium hydroxide is preferred.
The composition for preparing the top anti-reflective film further comprises water and/or a water-soluble organic solvent, which may be an alcohol, a ketone, or an ester; preferably, the water-soluble organic solvent is methanol, ethanol, isopropanol, acetone, methyl acetate, ethyl lactate, dimethylformamide or dimethyl sulfoxide.
The present invention also provides the use of any one of the fluoropolymers of the present invention described above for the preparation of a top antireflective film for a photoresist.
The present invention also provides a top antireflective film for a photoresist made from a feedstock comprising any of the fluoropolymers or any of the compositions of the present invention described above.
The invention has the following beneficial effects:
the fluorine-containing polymer meeting the specific composition requirements of the invention is obtained by controlling the content distribution of polymer components with different polymerization degrees in the fluorine-containing polymer, the fluorine-containing polymer is easy to produce, low in raw material cost, easy to degrade, low in toxicity and environment-friendly, the prepared composition solution for preparing the top anti-reflection film has good solution stability and film forming property, meanwhile, the refractive index of the prepared anti-reflection film under a light source of 248nm is 1.41-1.44, atomization cannot occur, light scattering and standing wave effects can be avoided, meanwhile, the pH of the composition is well matched with the pH of a photoresist, and the composition can be used as the top anti-reflection film for the photoresist, so that the standing wave effect in the photoresist process is reduced, and the yield of the photoresist process is improved.
Drawings
FIGS. 1a to 1g are photographs showing the condition of solutions of compositions prepared from perfluoropolyether carboxylic acids of examples 1 to 7 of the present application after they have been left for 14 days, FIGS. 1a, 1b, 1c, 1d, 1e, 1f and 1g corresponding to examples 1 to 7, respectively;
FIGS. 2a-2c are photographs of the solution condition of the composition prepared from the perfluoropolyether carboxylic acid of comparative example 2, and FIGS. 2a, 2b, and 2c are photographs of the day 3, day 7, and day 14, respectively, on standing;
FIGS. 3a-3c are photographs of the solution condition of the composition prepared from the perfluoropolyether carboxylic acid of comparative example 3, and FIGS. 3a, 3b, and 3c are photographs of the day 3, day 7, and day 14, respectively, on standing;
FIGS. 4a-4c are photographs of the solution condition of the composition prepared from the perfluoropolyether carboxylic acid of comparative example 4, and FIGS. 4a, 4b, and 4c are photographs of day 2, day 7, and day 14, respectively, on standing;
FIGS. 5a-5c are photographs of the solution condition of the composition prepared from the perfluoropolyether carboxylic acid of comparative example 6, and FIGS. 5a, 5b, and 5c are photographs of the day 3, day 7, and day 14, respectively, on standing;
FIGS. 6a-6g and FIGS. 6a ' -6g ' are photographs of films formed from compositions made from perfluoropolyether carboxylic acids of examples 1-7 of the present application, FIGS. 6a, 6b, 6c, 6d, 6e, 6f, and 6g correspond to macro-photographs of examples 1-7, respectively, and FIGS. 6a ', 6b ', 6c ', 6d ', 6e ', 6f ', and 6g ' correspond to micro-photographs of examples 1-7, respectively;
FIGS. 7a-7g are photomicrographs taken with a microscope of films formed from compositions made from perfluoropolyether carboxylic acids of examples 1-7 of the present application after 3 days of standing, FIGS. 7a, 7b, 7c, 7d, 7e, 7f, and 7g corresponding to examples 1-7, respectively;
FIGS. 8a-8f and FIGS. 8a '-8 f' are photographs of films formed from compositions made from the perfluoropolyether carboxylic acids of comparative examples 1-6 of the present application, FIGS. 8a, 8b, 8c, 8d, 8e, and 8f correspond to macro-photographs of comparative examples 1-6, respectively, and FIGS. 8a ', 8 b', 8c ', 8 d', 8e ', and 8 f' are micro-photographs of comparative examples 1-6;
FIGS. 9a and 9b are photomicrographs taken with a microscope after 3 days of standing for films formed from the compositions prepared from the perfluoropolyether carboxylic acids of comparative examples 2 and 5, respectively, of this application.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
Preparation of perfluoropolyether carboxylic acid:
firstly, adding a solvent of 50ml of acetonitrile and 50ml of tetraethylene glycol dimethyl ether into a 1L polymerization kettle, then adding 5g of catalyst KF into the polymerization kettle, stirring and mixing uniformly, replacing three times with high-purity nitrogen, pumping negative pressure to-0.1 MPa, cooling to a set temperature of 0 ℃, and introducing 50g of hexafluoropropylene oxide. The reaction process is controlled by feeding at regular time (50g/h), and the temperature is controlled between 0 and 10 ℃. After hexafluoropropylene oxide was added to 1000g, the pressure was returned to normal pressure, and after the reaction was completed, the stirring was continued for two hours, and the stirring was stopped and returned to room temperature to obtain a mixture.
And (3) layering the mixture, centrifuging and filtering the reaction product at the lower layer to separate the reaction product, and adding the reaction product into a distillation device. The perfluoropolyether acyl fluoride with the purity of more than 99 percent (purity tested by a gas chromatograph) is obtained by rectification and purification.
Adding perfluoropolyether acyl fluoride into a 1L acid conversion kettle, and mixing according to the volume ratio of the perfluoropolyether acyl fluoride to water of 1:3 adding water, heating to reflux for four hours, continuously heating to 90 ℃, demulsifying, standing, separating liquid to remove water on the upper part, repeating the step for 2 times, heating to 110 ℃, and removing residual water and hydrogen fluoride to obtain the perfluoropolyether carboxylic acid.
By controlling the polymerization degree of the perfluoropolyether acyl chloride, the following perfluoropolyether carboxylic acid with the following general structure is respectively obtained:
CF2(CF3)CF2-[O-CF(CF3)CF2]n-O-CF(CF3)COOH
perfluoropolyether carboxylic acid A, n with n being 1 is perfluoropolyether carboxylic acid B, n with 2 is perfluoropolyether carboxylic acid C, n with 4 is perfluoropolyether carboxylic acid D, n with 5 is perfluoropolyether carboxylic acid E, n with 8 is perfluoropolyether carboxylic acid F.
Example 1
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 10% of perfluoropolyether carboxylic acid a, 66% of perfluoropolyether carboxylic acid B, 19% of perfluoropolyether carboxylic acid C, 1% of perfluoropolyether carboxylic acid D, 4% of perfluoropolyether carboxylic acid E. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Example 2:
mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 4% of perfluoropolyether carboxylic acid a, 58% of perfluoropolyether carboxylic acid B, 28% of perfluoropolyether carboxylic acid C, 8% of perfluoropolyether carboxylic acid D, 2% of perfluoropolyether carboxylic acid F. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Example 3:
mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 78% of perfluoropolyether carboxylic acid B, 18% of perfluoropolyether carboxylic acid C, 4% of perfluoropolyether carboxylic acid D. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Example 4:
mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 56% of perfluoropolyether carboxylic acid B, 26% of perfluoropolyether carboxylic acid C, 13% of perfluoropolyether carboxylic acid D, 5% of perfluoropolyether carboxylic acid E. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Example 5:
mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: 3% by weight of perfluoropolyether carboxylic acid a, 73% by weight of perfluoropolyether carboxylic acid B, 16% by weight of perfluoropolyether carboxylic acid C, 7% by weight of perfluoropolyether carboxylic acid D, 1% by weight of perfluoropolyether carboxylic acid F. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Example 6
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 6% of perfluoropolyether carboxylic acid a, 61% of perfluoropolyether carboxylic acid B, 23% of perfluoropolyether carboxylic acid C, 10% of perfluoropolyether carboxylic acid D. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Example 7
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 1% of perfluoropolyether carboxylic acid a, 69% of perfluoropolyether carboxylic acid B, 21% of perfluoropolyether carboxylic acid C, 3% of perfluoropolyether carboxylic acid D, 6% of perfluoropolyether carboxylic acid E. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Comparative example 1
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 13% of perfluoropolyether carboxylic acid a, 63% of perfluoropolyether carboxylic acid B, 19% of perfluoropolyether carboxylic acid C, 1% of perfluoropolyether carboxylic acid D, 4% of perfluoropolyether carboxylic acid E. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Comparative example 2
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 1% of perfluoropolyether carboxylic acid a, 70% of perfluoropolyether carboxylic acid B, 17% of perfluoropolyether carboxylic acid C, 3% of perfluoropolyether carboxylic acid D, 9% of perfluoropolyether carboxylic acid E. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Comparative example 3
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 56% of perfluoropolyether carboxylic acid B, 26% of perfluoropolyether carboxylic acid C, 17% of perfluoropolyether carboxylic acid D, 1% of perfluoropolyether carboxylic acid E. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Comparative example 4
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 4% of perfluoropolyether carboxylic acid a, 58% of perfluoropolyether carboxylic acid B, 32% of perfluoropolyether carboxylic acid C, 4% of perfluoropolyether carboxylic acid D, 2% of perfluoropolyether carboxylic acid F. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Comparative example 5
Mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: 3% by weight of perfluoropolyether carboxylic acid a, 73% by weight of perfluoropolyether carboxylic acid B, 14% by weight of perfluoropolyether carboxylic acid C, 9% by weight of perfluoropolyether carboxylic acid D, 1% by weight of perfluoropolyether carboxylic acid F. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
Comparative example 6:
mixing the perfluoropolyether carboxylic acids with different polymerization degrees according to the following mixing ratio: by weight, 53% of perfluoropolyether carboxylic acid B, 29% of perfluoropolyether carboxylic acid C, 13% of perfluoropolyether carboxylic acid D, 5% of perfluoropolyether carboxylic acid E. Perfluoropolyether carboxylic acids were thus prepared, the specific compositions of which are shown in table 1.
< method for measuring number average molecular weight >
The number average molecular weight of the perfluoropolyether carboxylic acid is measured by an acid value method, which specifically comprises the following steps:
1ml of the recording data m (g) for the weight of the perfluoropolyether carboxylic acid to be tested is removed, 35ml of water and 15ml of absolute ethanol are added, titration is carried out with a sodium hydroxide solution of the nominal concentration c (mol/ml) and the volume v (ml) of sodium hydroxide consumed is recorded when the titration is carried out to a pH of 7. The number average molecular weight of the perfluoropolyether carboxylic acid is calculated according to the following formula:
number average molecular weight of perfluoropolyether carboxylic acid (M/cv)
Formulation of composition for preparing top anti-reflective film
Using the perfluoropolyether carboxylic acids of examples 1-7 and comparative examples 1-6, compositions for top antireflective films were formulated by the following steps:
preparing 0.016 mol of perfluoropolyether carboxylic acid into 5 mass percent aqueous solution, mixing with 5 mass percent polyvinylpyrrolidone aqueous solution according to the molar ratio of the perfluoropolyether carboxylic acid to the polyvinylpyrrolidone of 1:10, stirring to obtain transparent solution, wherein the polyvinylpyrrolidone used is from the alatin
Polyvinylpyrrolidone K16-18; adding 5 mass% of tetramethylammonium hydroxide solution to the solution under stirring, wherein the molar ratio of tetramethylammonium hydroxide to perfluoropolyether carboxylic acid is 0.9: 1; then, adding oxalic acid to adjust the pH value to 2.0-2.5; filtering to obtain a composition solution.
The solution stability, film forming property and refractive index of each of the prepared compositions were evaluated by the following methods, and the results thereof are shown in table 1.
< method for evaluating solution stability >
250ml of the prepared composition solution for antireflection film production was placed in a 500ml beaker, left to stand, the condition of the solution was visually observed, and the time at which it appeared to precipitate flocs was recorded as a stabilization time h (in days) to evaluate the stability, 14 days being an observation cut-off time. The larger the h value, the better the solution stability.
< method for evaluating film Forming Property >
Each of the composition solutions for preparing an antireflection film was coated on a silicon wafer (4 inches, supplier TOPVENTOR, type P, boron-doped, thickness of about 525 μm, diameter of about 100mm) by using a spin coater (U.S. Laurell, type: WS-650MZ-23NPPB), baked at 100 ℃ for 90 seconds, and cooled to form a corresponding film. The film formation was visually observed and microscopically observed with the aid of a metallographic microscope (MIT 500, aust optical instruments ltd, Chongqing), the film formation of the composition was evaluated, and macroscopic and microscopic photographs were taken with a digital camera and a metallographic microscope, respectively.
< method for evaluating fogging >
The film formed in the film formation evaluation was stored at a temperature of 23 ± 2 ℃ and a humidity of 50 ± 5% RH for 3 days, and then the film was microscopically observed with the aid of a metallographic microscope (MIT 500, aust optical instruments ltd, Chongqing) and a photomicrograph was taken to evaluate whether or not the film was atomized. Observing the surface of the film under a microscope, and if a large number of liquid drops do not appear on the surface of the film, determining that the film is not atomized; if a large number of droplets appear on the surface of the film, it is considered that fogging has occurred.
< method of measuring refractive index >
Each of the composition solutions for antireflection film preparation was coated on a silicon wafer (4 inches, supplier TOPVENTOR, type P, boron-doped, thickness about 525 μm, diameter about 100mm) using a spin coater (Laurell, USA, type: WS-650MZ-23NPPB), baked at 100 ℃ for 90 seconds, and cooled to form a coating film. The refractive index at 248nm was determined using an ellipsometer model Wallon RC2, USA.
TABLE 1
| Numbering | Content a | Content b | Content c | Content d | Content e | Number average moleculeMeasurement of | Stabilization time/day | Film forming property | Situation of atomization | Refractive index |
| Example 1 | 10％ | 66％ | 19％ | 1％ | 4％ | 702.2 | 14 | Uniform and non-porous | Is free of | 1.42 |
| Example 2 | 4％ | 58％ | 28％ | 8％ | 2％ | 746.4 | 14 | Uniform and non-porous | Is free of | 1.43 |
| Example 3 | 0％ | 78％ | 18％ | 4％ | 0％ | 693.9 | 14 | Uniform and non-porous | Is free of | 1.44 |
| Example 4 | 0％ | 56％ | 26％ | 13％ | 5％ | 775.2 | 14 | Uniform and non-porous | Is free of | 1.41 |
| Example 5 | 3％ | 73％ | 16％ | 7％ | 1％ | 713.8 | 14 | Uniform and non-porous | Is free of | 1.42 |
| Example 6 | 6％ | 61％ | 23％ | 10％ | 0％ | 725.4 | 14 | Uniform and non-porous | Is free of | 1.42 |
| Example 7 | 1％ | 69％ | 21％ | 3％ | 6％ | 737.0 | 14 | Uniform and non-porous | Is free of | 1.43 |
| Comparative example 1 | 13％ | 63％ | 19％ | 1％ | 4％ | 697.2 | 14 | Uneven, multiple holes | Is free of | 1.41 |
| Comparative example 2 | 1％ | 70％ | 17％ | 3％ | 9％ | 745.3 | 3 | Uneven, multiple holes | Is provided with | 1.44 |
| Comparative example 3 | 0％ | 56％ | 26％ | 17％ | 1％ | 768.6 | 3 | Non-uniform, perforated holes | Is free of | 1.41 |
| Comparative example 4 | 4％ | 58％ | 32％ | 4％ | 2％ | 733.7 | 2 | Uneven, multiple holes | Is free of | 1.43 |
| Comparative example 5 | 3％ | 73％ | 14％ | 9％ | 1％ | 717.2 | 14 | Unevenness of | Is provided with | 1.42 |
| Comparative example 6 | 0％ | 53％ | 29％ | 13％ | 5％ | 780.2 | 3 | Unevenness of | Is free of | 1.41 |
Note: 1) the percentages in the table are by weight, the number average molecular weight referring to the number average molecular weight of the perfluoropolyether carboxylic acid;
2) the amounts a, b, c, d, e are each as defined herein, e.g., the amount of perfluoropolyether carboxylic acid component in which a is n.ltoreq.1.
As can be seen from Table 1 and FIGS. 1a-1g, the solutions of the compositions prepared from the perfluoropolyether carboxylic acids of examples 1-7 that meet the requirements for the content of the components of the present application remain clear, do not precipitate flocs, and have good solution stability after being left to stand for 14 days. Further, as can be seen from table 1 and fig. 6a to 6g, fig. 6a '-6 g', fig. 7a to 7g, the perfluoropolyether carboxylic acids of examples 1 to 7 of the present application produced compositions capable of obtaining a film having a uniform surface, having good moldability, and the film did not show fogging, and at the same time, produced antireflection films having a refractive index of 1.41 to 1.44 at 248nm, which were effective in reducing the refractive index under laser irradiation at a wavelength of 248nm, without light scattering and standing wave effect, and which were useful as top antireflection films for photoresists.
As can be seen from Table 1 and FIGS. 8a and 8 a', the perfluoropolyether carboxylic acid of comparative example 1 contains 13% of perfluoropolyether carboxylic acid component having n ≦ 1, i.e., the content of component a is greater than 12%, which results in poor moldability of the composition prepared therefrom, and the formed film has many distinct holes.
As can be seen from Table 1, FIGS. 2a-2c and FIGS. 8b, 8 b', 9a, the stability of the solution of the composition prepared from the perfluoropolyether carboxylic acid of comparative example 2 is poor because the perfluoropolyether carboxylic acid contains 9% of the perfluoropolyether carboxylic acid component having n.gtoreq.5, i.e., the component e is greater than 8%, and gels and agglomerates appear on day 3 of standing, and until day 14 of standing, gels and agglomerates still appear in the solution; the composition prepared therefrom had poor moldability, the formed film was unevenly distributed and had many distinct holes, and the film was fogged after standing for 3 days.
As can be seen from Table 1, FIGS. 3a to 3c and FIGS. 8c and 8 c', since the perfluoropolyether carboxylic acid of comparative example 3 contains 17% of the perfluoropolyether carboxylic acid component having n of 4, i.e., the content of component d is more than 15%, the solution stability of the composition prepared therefrom is poor, gels and agglomerates appear on day 3 of standing, and until day 14 of standing, gels and agglomerates still appear in the solution; the compositions prepared therefrom had very poor moldability, and the films formed were markedly unevenly distributed and had pores.
As can be seen from Table 1, FIGS. 4a to 4c and FIGS. 8d and 8 d', since the perfluoropolyether carboxylic acid of comparative example 4 contains 32% of the perfluoropolyether carboxylic acid component having n of 3, i.e., the content of component c is more than 30%, the solution stability of the composition prepared therefrom is poor, gels and agglomerates appear on day 2 of standing, and gels and agglomerates still exist in the solution until day 14 of standing; the composition thus prepared had poor moldability, and the resulting film had many holes.
As can be seen from Table 1 and FIGS. 8e, 8 e', 9b, since the perfluoropolyether carboxylic acid of comparative example 5 contains 14% of the perfluoropolyether carboxylic acid component having n of 3, i.e., the content of component c is less than 15%, the moldability of the composition prepared therefrom is poor, the distribution of the formed film is not uniform, the film surface appears more radioactive in shape, and the film is fogged after standing for day 3.
As can be seen from Table 1, FIGS. 5a to 5c and FIGS. 8f and 8 f', since the perfluoropolyether carboxylic acid of comparative example 6 contains 53% of the perfluoropolyether carboxylic acid component having n of 2, i.e., the component b content is less than 55%, the solution stability of the composition prepared therefrom is poor, gels and agglomerates appear on day 3 of standing, and until day 14 of standing, gels and agglomerates still appear in the solution; the composition prepared therefrom had poor moldability, and oily substances appeared on the surface of the formed film, and the dispersion was not uniform.
Therefore, the composition solution prepared from the perfluoropolyether carboxylic acid meeting the component content requirements of the application has good solution stability and good molding property, and meanwhile, the prepared antireflection film has the refractive index of 1.41-1.44 under 248nm, does not generate atomization, can effectively reduce the refractive index under the irradiation of laser with the wavelength of 248nm, can avoid light scattering and standing wave effect, and can be used as a top antireflection film for photoresist. Compositions prepared from perfluoropolyether carboxylic acids that do not meet the requirements for the content of components herein have problems of poor solution stability and/or poor moldability and/or fogging of the formed film, which in turn leads to difficulty in use as top antireflective films for photoresists.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the foregoing preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. A fluoropolymer for use in preparing a top antireflective film for a photoresist, characterized by the structural formula:
CF2(CF3)CF2-[O-CF(CF3)CF2]n-O-CF(CF3)COO-R
wherein n is in the range of 1-8, R is H, NH4Or one or more of other similar structures;
based on the weight of the whole polymer, the content a of the polymer component with n ≦ 1 is 0-12%, the content b of the polymer component with n being 2 is 55-80%, the content c of the polymer component with n being 3 is 15-30%, the content d of the polymer component with n being 4 is 0-15%, the content e of the polymer component with n being more than or equal to 5 is 0-8%, b + c is more than or equal to 80%, and a, d and e are simultaneously 0 or any one of 0 or simultaneously not 0.
2. The fluoropolymer for manufacturing a top antireflective film for photoresist according to claim 1, wherein the average molecular weight of the fluoropolymer is between 600 and 1300, more preferably between 650 and 1100.
3. The fluoropolymer for manufacturing a top antireflective film for photoresist according to claim 1 or 2, wherein the content b is 60 to 80%, preferably 60 to 75%.
4. The fluoropolymer for manufacturing a top antireflective film for photoresist according to any one of the preceding claims, characterized in that content a is 0-10%, preferably 0-8%, more preferably 2-8%.
5. The fluoropolymer for manufacturing a top antireflective film for photoresist according to any one of the preceding claims, wherein content c is 18-30%, preferably 18-28%.
6. The fluoropolymer for manufacturing a top antireflective film for photoresist according to any one of the preceding claims, characterized in that the content d is 3-15%, preferably 5-15%.
7. A composition for producing a top antireflective film for a photoresist, characterized in that it comprises the fluoropolymer according to any one of claims 1 to 6.
8. The composition for preparing a top anti-reflective film for a photoresist according to claim 7, characterized in that it contains 1 to 15%, preferably 2 to 12% by weight of the fluoropolymer.
9. The composition for preparing a top antireflective film for a photoresist according to claim 7 or 8, further comprising a water-soluble resin, wherein the molar ratio of the fluorine-containing polymer to the water-soluble resin is 1:2 to 1:30, preferably 1:3 to 1: 25.
10. A top antireflective film for a photoresist prepared from a starting material comprising the fluoropolymer of any one of claims 1-6 or the composition of any one of claims 7-9.
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| WO2022027945A1 (en) * | 2020-08-04 | 2022-02-10 | 甘肃华隆芯材料科技有限公司 | Fluorine-containing polymer for photoresist, top anti-reflection film composition comprising fluorine-containing polymer, and application of fluorine-containing polymer in photoresist |
| CN114035405A (en) * | 2022-01-07 | 2022-02-11 | 甘肃华隆芯材料科技有限公司 | Composition for preparing top anti-reflection film for photoresist, top anti-reflection film for photoresist and fluorine-containing composition |
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| WO2022027945A1 (en) * | 2020-08-04 | 2022-02-10 | 甘肃华隆芯材料科技有限公司 | Fluorine-containing polymer for photoresist, top anti-reflection film composition comprising fluorine-containing polymer, and application of fluorine-containing polymer in photoresist |
| CN114035405A (en) * | 2022-01-07 | 2022-02-11 | 甘肃华隆芯材料科技有限公司 | Composition for preparing top anti-reflection film for photoresist, top anti-reflection film for photoresist and fluorine-containing composition |
| WO2023131085A1 (en) * | 2022-01-07 | 2023-07-13 | 甘肃华隆芯材料科技有限公司 | Composition for preparing top anti-reflective film, top anti-reflective film, and fluorine-containing composition |
| TWI815441B (en) * | 2022-01-07 | 2023-09-11 | 大陸商甘肅華隆芯材料科技有限公司 | Composition for preparing top antireflective coating for photoresist, top antireflective coating for photoreist and fluorine-containing composition |
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