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WO2024041660A1 - 磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用 - Google Patents

磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用 Download PDF

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Publication number
WO2024041660A1
WO2024041660A1 PCT/CN2023/115303 CN2023115303W WO2024041660A1 WO 2024041660 A1 WO2024041660 A1 WO 2024041660A1 CN 2023115303 W CN2023115303 W CN 2023115303W WO 2024041660 A1 WO2024041660 A1 WO 2024041660A1
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Prior art keywords
substituted
unsubstituted
group
photoacid generator
sulfonate
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PCT/CN2023/115303
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English (en)
French (fr)
Inventor
钱彬
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
常州强力光电材料有限公司
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Publication of WO2024041660A1 publication Critical patent/WO2024041660A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • 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
    • G03F7/025—Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to the technical field of photosensitive materials. Specifically, it relates to a sulfonate photoacid generator and its preparation method, patterning method, resist composition and application thereof.
  • Photoacid generator is one of the key components of chemically amplified photoresist, and its structure and performance have a great impact on lithography images.
  • photoacid generators With the development of the semiconductor industry, people's demand for high-definition patterns continues to grow. At the same time, there is also an expansion of the applicable types of photoacid generators, and the performance of photoacid generators, especially low diffusivity, high solubility, and high acid production. Characteristics such as efficiency put forward higher requirements.
  • sulfonate compounds of naphthalene anhydride are widely known as photoinitiators in the semiconductor field, most current resist formulations require the addition of additives to inhibit acid migration or enhance pattern fastness.
  • the main purpose of the present invention is to provide a sulfonate photoacid generator and its preparation method, patterning method, resist composition and application thereof, so as to solve the problem of acid migration and photolithographic pattern fastness in the prior art. Bad question.
  • a sulfonate ester photoacid generator has the following general formula (I):
  • R 1 is selected from a substituted or unsubstituted C 2 to C 25 hydrocarbon group, a substituted or unsubstituted C 2 to C 25 alkoxy group, a substituted or unsubstituted C 2 to C 25 alkylthio group.
  • R 2 is selected from a C 1 to C 20 alkyl group, a C 6 to C 18 substituted or unsubstituted aryl group, camphor group, camphorquinone group, Any one of the naphthyl azide groups.
  • a method for preparing the aforementioned sulfonate photoacid generator includes: step S1, reacting compound 1 with R 1 ′Y to generate compound 2; step S1 S2, perform a hydroxylamination reaction on compound 2 with hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound; step S3, perform an esterification reaction on the hydroxylamine compound with R 2 SO 2 X 2 or (R 2 SO 2 ) 2 O to obtain sulfonic acid Ester photoacid generator; the structural formulas of Compound 1 and Compound 2 are as follows:
  • X 1 is selected from any one of -H, -OH, -SH and halogen atoms
  • R 1 ′Y reacts with the X 1 substituent in compound 1 to generate the R 1 substituent.
  • R 1 R 1 ′
  • a resist composition including a resin component and an acid generator, and the acid generator is the above-mentioned sulfonate photoacid generator.
  • a patterning method which includes mixing, film forming and patterning processing of a resist composition, which is the aforementioned resist composition.
  • an application of the aforementioned resist composition includes applying the resist composition to the preparation of protective films, interlayer insulating materials, and pattern transfer materials for electronic components. middle.
  • the molecule of the sulfonate photoacid generator with general formula I in this application contains a sulfonate group, and the sulfonate group is directly connected to the imide structure, and the structure has photosensitive cleavage Characteristics: N-O bonds can be broken under active energy ray irradiation to produce different types of sulfonic acids.
  • the above-mentioned active energy rays are active energy rays with wavelengths between 300 and 450nm in the near-ultraviolet and visible light regions. In particular, they have high sensitivity and strong absorption for active energy rays with a wavelength of 365nm (i-line), which will include the sulfonate.
  • the resist composition of the acid ester photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkali developer, due to the improvement in sensitivity of the sulfonate photoacid generator, it can form a film with excellent Sensitivity and good contrast patterns, even when forming fine patterns, can have sufficiently high resolution and sensitivity.
  • the substituent of the sulfonate photoacid generator of the present invention contains an epoxy group structure, which can open the ring under acidic and high-temperature conditions, but does not open the ring under neutral and high-temperature conditions, thereby helping to reduce The dosage of additives in the resist reduces the diffusion of photoacid molecules and improves the firmness of the photolithography pattern.
  • the present invention provides a sulfonate photoacid generator and its preparation method and pattern. Chemical methods, resist compositions and their applications.
  • a sulfonate ester photoacid generator is provided.
  • the sulfonate ester photoacid generator has the following general formula (I):
  • R 1 is selected from a substituted or unsubstituted C 2 to C 25 hydrocarbon group, a substituted or unsubstituted C 2 to C 25 alkoxy group, a substituted or unsubstituted C 2 to C 25 alkylthio group.
  • R 2 is selected from a C 1 to C 20 alkyl group, a C 6 to C 18 substituted or unsubstituted aryl group, camphor group, camphorquinone group, Any one of the naphthyl azide groups.
  • the sulfonate photoacid generator with the general formula I in this application contains a sulfonate group in its molecule.
  • the sulfonate group is directly connected to the imide structure.
  • This structure has photosensitive cleavage characteristics and can be activated when irradiated with active energy rays. N-O bond cleavage can occur under the conditions to produce different types of sulfonic acids.
  • the above-mentioned active energy rays are active energy rays with wavelengths between 300 and 450nm in the near-ultraviolet and visible light regions. In particular, they have high sensitivity and strong absorption for active energy rays with a wavelength of 365nm (i-line), which will include the sulfonate.
  • the resist composition of the acid ester photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkali developer, due to the improvement in sensitivity of the sulfonate photoacid generator, it can form a film with excellent Sensitivity and good contrast patterns, even when forming fine patterns, can have sufficiently high resolution and sensitivity.
  • the substituent of the sulfonate photoacid generator of the present invention contains an epoxy group structure, which can open the ring under acidic and high-temperature conditions, but does not open the ring under neutral and high-temperature conditions, thereby helping to reduce The dosage of additives in the resist reduces the diffusion of photoacid molecules and improves the firmness of the photolithography pattern.
  • the substituted or unsubstituted C 2 to C 25 hydrocarbon group is selected from the group consisting of substituted or unsubstituted C 2 to C 25 linear alkyl group, substituted or unsubstituted C 3 to C 25 Any one of branched alkyl groups, substituted or unsubstituted C 4 to C 25 alkenyl groups, substituted or unsubstituted C 4 to C 25 alkynyl groups; preferably R 1 is selected from substituted or unsubstituted C 6 to C 17 branched alkyl group, substituted or unsubstituted C 9 to C 16 alkenyl group, substituted or unsubstituted C 9 to C 18 alkynyl group, substituted or unsubstituted C 6 to C 17 alkyl group Any one of an oxygen group and a substituted or unsubstituted C 6 to C 15 alkylthio group;
  • the substituted or unsubstituted C 6 to C 17 branched alkyl group is selected from Any one of them; preferably the substituted or unsubstituted C 9 to C 16 alkenyl group is selected from Any one of them; preferably the substituted or unsubstituted C 9 to C 18 alkynyl group is selected from Any one of them; preferably the substituted or unsubstituted C 6 to C 17 alkoxy group is selected from Any one of them; preferably the substituted or unsubstituted C 6 to C 15 alkylthio group is selected from Among them, "*" is the position where R 1 is connected to the naphthalene ring of the sulfonate photoacid generator.
  • R 1 is selected from a substituted or unsubstituted C 9 to C 16 alkenyl group, a substituted or unsubstituted C 9 to C 18 alkynyl group, Any one of substituted or unsubstituted C 6 to C 17 alkoxy groups; considering that the alkenyl group is prone to yellowing, for a transparent system, it is more preferred that R 1 is selected from substituted or unsubstituted C 9 to C 18 alkyne group, any one of substituted or unsubstituted C 6 to C 17 alkoxy groups.
  • the above-mentioned epoxy group is a C 2 to C 5 epoxy group, and preferably the epoxy group is selected from Any one of them, further preferably
  • the number of ring carbon atoms of the epoxy group will affect the difficulty of ring opening.
  • the preferred epoxy group is more conducive to improving the ring opening of the sulfonate photoacid generator under acidic and high temperature conditions.
  • the C 1 to C 20 alkyl group is selected from substituted or unsubstituted C 1 to C 20 linear alkyl groups.
  • R 2 is selected from C 1 to C 10 alkyl groups , any one of a C 6 to C 10 substituted or unsubstituted aryl group, a substituted or unsubstituted C 3 to C 10 cycloalkyl group, a camphor group, a camphorquinone group, or a naphthyl azide group; further , preferably R 2 is selected from a substituted or unsubstituted C 1 to C 8 linear alkyl group, a substituted or unsubstituted C 3 to C 8 branched alkyl group, a substituted or unsubstituted C 3 to C 5 ring Any one of an alkyl group, a substituted or unsubstituted phenyl group, a camphor group, a camphorquinone
  • the structural formula of the above-mentioned sulfonate photoacid generator is selected from the group consisting of: any one or more of them, thereby further improving the photoinduced
  • a method for preparing the aforementioned sulfonate ester photoacid generator includes: step S1, reacting compound 1 with R 1 ′Y, Generate compound 2; step S2, perform a hydroxylamination reaction on compound 2 with hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound; step S3, esterify the hydroxylamine compound with R 2 SO 2 X 2 or (R 2 SO 2 ) 2 O Reaction to obtain a sulfonate photoacid generator; the structural formulas of Compound 1 and Compound 2 are as follows:
  • X 1 is selected from any one of -H, -OH, -SH and halogen atoms
  • R 1 ′Y reacts with the X 1 substituent in compound 1 to generate the R 1 substituent.
  • R 1 R 1 ′
  • the 4-substituted naphthalene anhydride (compound 1) can be reacted with terminally substituted R 1 'Y (halogenated hydrocarbons, alkenes, alkynes, alcohols and other substances) through Friedel-Crafts reaction, Heck coupling reaction, addition Different types of reactions such as formation reaction or Click reaction are used to obtain the naphthalene anhydride (compound 2) substituted by R 1 at the 4-position, in which R 1 ′Y can be purchased, or can be obtained through primary alcohol, carboxylic acid, terminal alkene, terminal olefin, etc. It is prepared by esterification, etherification and addition reactions between alkynes and halogenated hydrocarbons.
  • step S2 the naphthalene anhydride substituted with R1 at the 4-position undergoes a hydroxylamination reaction with a hydroxylaminating reagent under alkaline or acidic conditions to generate a hydroxylamine compound, wherein the hydroxylaminating reagent can be hydroxylamine sulfate or hydroxylamine hydrochloride, preferably hydroxylamine.
  • the reaction temperature is controlled between 25 and 100°C, and more preferably between 75 and 100°C, which is more conducive to improving the efficiency of the hydroxylamination reaction.
  • an esterification reaction occurs between the hydroxylamine compound and the acylating reagent in an inert solvent under alkaline conditions to generate a sulfonate ester compound.
  • the temperature of the esterification reaction is preferably controlled between -10°C and 60°C, and more preferably between 0°C and 25°C, which is more conducive to improving the efficiency of the esterification reaction.
  • raw materials and reagents used in the above preparation method are all known compounds in the prior art, and can be obtained commercially or conveniently prepared through known processes, and will not be described again here.
  • the sulfonate ester photoacid generator of the present invention can be used for any known uses of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, and resists for MEMS. , materials for stereolithography and micro-stereolithography, etc.
  • the photoacid generator in the resist composition the resist can be prepared together with the resin having an acid-dissociating group and used in semiconductor photolithography.
  • a resist composition including a resin component and an acid generator, and the acid generator is the aforementioned sulfonate photoacid generator.
  • the resist composition of the present invention can be divided into positive-type compositions and negative-type compositions according to applications.
  • the positive composition generally contains a resin component (B1) that increases the solubility in an alkali developer through the action of an acid.
  • B1 a resin component that increases the solubility in an alkali developer through the action of an acid.
  • the negative composition uses a resin-crosslinking agent component (B2) that is cross-linked by the action of an acid and is insoluble in an organic developer.
  • the exposed area is catalyzed by the acid generated by the photoacid generator, and the resin reacts with the cross-linking agent to form a polymer that is insoluble in the organic developer and remains, while the unexposed area is dissolved and removed by the organic developer, and finally forms a negative type Figure, among which, for the specific resin component (B1) and resin-crosslinking agent component (B2), please refer to the specific content disclosed in paragraphs [0046] to [0076] of the Chinese patent application with application number 202011299973.1, here No longer.
  • the sulfonate photoacid generator can break the N-O bond to generate sulfonic acid under the irradiation of active energy rays. Through the PEB process, the exposed area and the unexposed area can be aligned. Differences in developer solubility.
  • the sulfonate photoacid generator product can be used alone or in a mixture of two or more.
  • the resist composition including the sulfonate ester photoacid generator and the resin component is used for dissolution exposure with an alkali developer.
  • a photosensitive composition even fine patterns can be formed with sufficiently high resolution and sensitivity.
  • the amount of additives in the resist can be reduced, the diffusion of photoacid molecules can be reduced, and the firmness of the photolithographic pattern can be improved.
  • the above-mentioned resin component has an acid-labile group protected by a protecting group, and the acid-labile group is selected from at least one of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group; preferably The content of the acid-labile group accounts for 1 to 80% of the resin component content, preferably 3 to 70%; the preferred protecting group includes at least one of the groups represented by formula (a) and formula (b):
  • R 3 is selected from a substituted or unsubstituted C 1 to C 20 linear alkyl group, a substituted or unsubstituted C 3 to C 20 branched alkyl group, a substituted or unsubstituted C Any one or more of 3 to C 20 cycloalkyl groups, preferably R 3 is selected from substituted or unsubstituted C 1 to C 10 straight chain alkyl groups, substituted or unsubstituted C 3 to C 10 branched alkyl groups. Any one or more of an alkyl group and a substituted or unsubstituted C 3 to C 10 cycloalkyl group.
  • R 3 is selected from a substituted or unsubstituted C 1 to C 6 linear alkyl group. , any one or more of substituted or unsubstituted C 3 to C 6 branched alkyl groups, substituted or unsubstituted C 3 to C 6 cycloalkyl groups, preferably the substitution described when R 3 has a substituent
  • the group is selected from any one or more of halogen, hydroxyl, cyano, C 1 to C 4 linear alkyl, C 3 to C 5 branched alkyl, and the preferred substituent is selected from fluorine atom, methyl , any one or more of ethyl groups, preferably one or more C atoms in R 3 can be substituted by any heteroatom in O, S, N or Si; further, preferably R 3 is selected from methoxy group , ethoxy, n-propoxy, n-butoxy, tert-butoxy, benzyloxy, 1-methoxyethoxy, 1-ethoxy
  • the resin component of the above type is beneficial to its synergistic effect with the sulfonate photoacid generator to obtain a strong photolithography pattern.
  • the dosage of the above-mentioned acid generator can refer to the dosage of conventional acid generators in the prior art.
  • the weight content of the acid generator is 0.5 to 5% relative to the mass of the solid content of the resist composition. , preferably 1 to 3%, so that good sensitivity can be exerted and the development effect can be improved.
  • the solvent is used to dissolve various components in the resist composition to form a uniform solution, and is used to adjust its viscosity and coating properties to facilitate film formation.
  • the resist composition may also contain conventional additives in this field, which will not be described again here.
  • a patterning method including mixing, film forming and patterning processing of a resist composition, which is the above-mentioned resist combination. things.
  • a resin solution dissolved or dispersed in an organic solvent can be applied on a substrate using, for example, spin coating, and then heated to volatilize the solvent, thereby forming a resist composition on the substrate.
  • the film is etched, and then light irradiation (that is, exposure) in the shape of a wiring pattern is performed, and then a post-exposure heat treatment (PEB) is performed, followed by alkaline development to form a wiring pattern.
  • PEB post-exposure heat treatment
  • the drying conditions of the coated resin solution vary depending on the solvent used, but it is preferably carried out at 50 to 150°C and within the range of 1 to 30 minutes, that is, it is appropriately determined based on the amount of residual solvent (mass percentage) after drying, etc. .
  • the wiring pattern shape is irradiated with light.
  • Light irradiation can use low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (such as argon lasers, dye lasers, Nitrogen laser, LED, helium cadmium laser), etc., preferably high-pressure mercury lamp and LED lamp.
  • the temperature of the post-exposure heat treatment is usually 40 to 200°C, preferably 60 to 150°C. If it is less than 40°C, the deprotection reaction or the cross-linking reaction cannot fully proceed, so the difference in solubility between the exposed part and the unexposed part is insufficient to form a pattern. If it is higher than 200°C, there is a problem of reduced productivity.
  • the above heating time is usually 0.5 to 30 minutes.
  • the alkali development method includes the use of an alkali developer.
  • the alkaline developer can be selected from aqueous solutions of 0.1 to 10% (mass percentage) tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate.
  • the alkaline developer can also include water-soluble organic solvents, such as Methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N-methylpyrrolidone, etc.
  • the development method can be selected from dipping method, spray method and spray method, with spray method being preferred.
  • the temperature of the developer is preferably used at 25 to 40° C., the development time is appropriately determined according to the thickness of the resist film, and finally a pattern corresponding to the mask is obtained.
  • an application of the above-mentioned resist composition includes applying the resist composition to protective films, interlayer insulating materials, and patterns of electronic components. Preparing transfer materials.
  • the above-mentioned applications can specifically include forming an interlayer insulating film from the resist composition for use in TFTs and panels of liquid crystal display devices; it can also be used as a protective film for color filters and spacers, and as PS photoresist and BCS photoresist. Resistor is used for pattern transfer.
  • the above-mentioned electronic components include, but are not limited to, liquid crystal display devices, organic EL display devices, Micro-LED, Mini-LED and quantum dot LED display devices and other electronic components.
  • the preparation method of the sulfonate photoacid generator 28 can be referred to Example 1.
  • T6-1 and T6-2 please refer to Example 6.
  • sulfonate photoacid generator 52 For the preparation of the sulfonate photoacid generator 52, refer to Example 7, and replace the p-toluenesulfonyl chloride raw material with butanesulfonyl chloride.
  • Examples 9 to 21 respectively replaced the substrates and adjusted the reaction conditions accordingly to obtain other corresponding sulfonate ester photoacid generators 2, 11, 13, 14, 18, and 21. ,24,25,27,29,32,36,39.
  • Example 7 For the preparation of the sulfonate photoacid generator 49, refer to Example 7, and replace the raw material of p-toluenesulfonyl chloride with suspended camphorsulfonyl chloride.
  • Example 7 For the preparation of the sulfonate photoacid generator 51, refer to Example 7, and replace the raw material of p-toluenesulfonyl chloride with propanesulfonyl chloride.
  • Example 7 For the preparation of the sulfonate photoacid generator 53, refer to Example 7, and replace the p-toluenesulfonyl chloride raw material with 2-trifluoromethylbenzenesulfonyl chloride.
  • the performance of the sulfonate ester photoacid generator synthesized in Examples 1 to 24 and the sulfonate ester photoacid generator synthesized in Comparative Example 1 was evaluated respectively.
  • the evaluation indicators include molar absorption coefficient, solubility and chemical stability.
  • the compound was diluted to 0.25 mmol/L with acetonitrile, and the absorbance of a cuvette length of 1 cm was measured in the range of 200 to 600 nm using a UV-visible spectrophotometer (UPG-752).
  • the nonionic photoacid generator of Comparative Example 1 is Record it as A*1.
  • the photoacid generator of the present invention has a high molar absorption coefficient at 365nm, has strong light absorption ability, can fully utilize light energy, and can ensure a high utilization rate in resist applications. , and showed good solubility.
  • Resist Composition Examples 1 to 31 and Resist Composition Comparative Examples 1 to 6 in Table 3 uniformly dissolve each raw material in PGMEA (propylene glycol methyl ether acetate) to obtain the solid content concentration. Approximately 20% (mass percent) of the resist composition.
  • PGMEA propylene glycol methyl ether acetate
  • the component types and contents of the sulfonate photoacid generator (A), resin component (B), and acid binding agent triethylamine (C) are as shown in Table 3.
  • the resin component (B) adopts type B 1 resin and is composed of repeating units represented by formula B 11 , formula B 12 and formula B 13 .
  • the numerical value at the lower right of each repeating unit represents the content (mass) of the repeating unit in the resin. percentage).
  • the weight average molecular weight of B 1 resin is approximately 10,000.
  • the sulfonate ester photoacid generator (A) is the sulfonate ester photoacid generator of Example 1.
  • composition Example 1 The difference from Composition Example 1 is that: the sulfonate ester photoacid generator (A) adopts the sulfonate ester photoacid generators of Examples 2 to 24 in sequence.
  • the difference from Composition Example 5 is that the resin component (B) adopts B2 type resin, which is composed of repeating units represented by formula B21 , formula B22 and formula B23 .
  • the numerical value on the lower right of each repeating unit indicates The content (mass %) of this repeating unit in the resin.
  • the weight average molecular weight of B2 resin is approximately 10,000.
  • the difference from Composition Example 5 is that the resin component (B) adopts B3 type resin and is composed of repeating units represented by formula B31 and formula B32 .
  • the numerical value on the lower right of each repeating unit indicates that the repeating unit is in Content in resin (mass %).
  • the weight average molecular weight of B3 resin is approximately 10,000.
  • composition Example 5 The difference from Composition Example 5 is that the content of the sulfonate photoacid generator is different.
  • composition Example 5 The difference from Composition Example 5 is that no acid binding agent is added.
  • composition Example 6 The difference from Composition Example 6 is that no acid binding agent is added.
  • composition Example 7 The difference from Composition Example 7 is that no acid binding agent is added.
  • Composition Example 5 The difference from Composition Example 5 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used.
  • Composition Example 6 The difference from Composition Example 6 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used.
  • Composition Example 7 The difference from Composition Example 7 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used.
  • composition Comparative Example 1 The difference from Composition Comparative Example 1 is that no acid binding agent is added.
  • composition Comparative Example 2 The difference from Composition Comparative Example 2 is that no acid binding agent is added.
  • composition comparative example 3 The difference from composition comparative example 3 is that no acid binding agent is added.
  • the resist composition of each Example and Comparative Example was coated with a film thickness of 1 ⁇ m capable of forming a pattern to form a coating film.
  • the formed coating film was pre-baked at 90°C for 100 seconds.
  • the coating film was exposed through a hole pattern forming mask with a diameter of 10 ⁇ m while gradually changing the exposure amount (exposure wavelength: 365 nm), and then developed with a 2.0% tetramethylammonium hydroxide aqueous solution at 25°C for 30 seconds. .
  • the minimum exposure required to form a 10 ⁇ m diameter hole pattern was determined by the above method. From the minimum exposure value obtained, the sensitivity was evaluated according to the following criteria: " ⁇ " indicates a sensitivity of -50mJ/ cm2 or less, and " ⁇ " indicates a sensitivity of -300mJ/cm2 or more.
  • the sulfonate photoacid generator with the general formula I in this application contains a sulfonate group in its molecule.
  • the sulfonate group is directly connected to the imide structure.
  • This structure has photosensitive cleavage characteristics and can be activated when irradiated with active energy rays. N-O bond cleavage can occur under the conditions to produce different types of sulfonic acids.
  • the above-mentioned active energy rays are active energy rays with wavelengths between 300 and 450nm in the near-ultraviolet and visible light regions. In particular, they have high sensitivity and strong absorption for active energy rays with a wavelength of 365nm (i-line), which will include the sulfonate.
  • the resist composition of the acid ester photoacid generator and the resin component is used to dissolve the exposed photosensitive composition in an alkali developer, due to the improvement in sensitivity of the sulfonate photoacid generator, it can form a film with excellent Sensitivity and good contrast patterns, even when forming fine patterns, can have sufficiently high resolution and sensitivity.
  • the substituent of the sulfonate photoacid generator of the present invention contains an epoxy group structure, which can open the ring under acidic and high-temperature conditions, but does not open the ring under neutral and high-temperature conditions, thereby helping to reduce The dosage of additives in the resist reduces the diffusion of photoacid molecules and improves the firmness of the photolithography pattern.

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Abstract

本发明提供了一种磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用。磺酸酯类光产酸剂具有通式(I)，其中R1选自取代或未取代的C2～C25的烃基、取代或未取代的C2～C25的烷氧基、取代或未取代的C2～C25的烷硫基中的任意一种，其中的-CH2-可任选地被-O-、-S-、-CO-、-O-CO-或-COO-取代，其中的C原子也可任选地被N原子取代，且R1的末端至少含有一个取代或未取代的C2～C10的环氧基；R2选自C1～C20的烷基、C6～C18的取代或未取代的芳基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种。以上磺酸酯类光产酸剂可减少光酸分子扩散，提高光刻图案的牢固性。

Description

磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用
本申请是以CN申请号为202211038021.3，申请日为2022年8月26日的中国申请为基础，并主张其优先权，该CN申请的公开内容再次作为整体引入本申请中。
技术领域
本发明涉及感光材料技术领域，具体而言，涉及一种磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用。
背景技术
光产酸剂是化学增幅型光致抗蚀剂的关键组成之一，其结构和性能对光刻图像有较大影响。随着半导体行业的发展，人们对高精细化图案的需求不断增长，同时也对光产酸剂适用种类的扩展、以及对光产酸剂的性能特别是低扩散性、高溶解性、高产酸率等特性提出了更高的要求。虽然萘酐的磺酸酯类化合物在半导体领域中用作光引发剂已被广泛知悉，但是目前的抗蚀剂配方大都需要添加助剂来抑制酸迁移或增强图案牢固性。
发明内容
本发明的主要目的在于提供一种磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用，以解决现有技术中酸迁移、光刻图案牢固性较差的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种磺酸酯类光产酸剂，该磺酸酯类光产酸剂具有如下通式(I)：
其中，R1选自取代或未取代的C2～C25的烃基、取代或未取代的C2～C25的烷氧基、取代或未取代的C2～C25的烷硫基中的任意一种，其中的-CH2-可任选地被-O-、-S-、-CO-、-O-CO-或-COO-取代，其中的C原子也可任选地被N原子取代，且取代或未取代的C2～C25的烃基、取代或未取代的C2～C25的烷氧基、取代或未取代的C2～C25的烷硫基中的末端至少含有一个取代或未取代的C2～C10的环氧基；R2选自C1～C20的烷基、C6～C18的取代或未取代的芳基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种。
根据本发明的另一个方面，提供了一种前述的磺酸酯类光产酸剂的制备方法，该制备方法包括：步骤S1，将化合物1与R1′Y进行反应，生成化合物2；步骤S2，将化合物2与盐酸羟胺或硫酸羟胺进行羟胺化反应，生成羟胺化合物；步骤S3，将羟胺化合物与R2SO2X2或(R2SO2)2O进行酯化反应，得到磺酸酯类光产酸剂；化合物1与化合物2的结构式如下：
其中，X1选自-H、-OH、-SH、卤素原子中的任意一种，Y选自-OH、-CH＝CH2、-C≡CH、卤素原子中的任意一种，X2为卤素原子，R1′Y与化合物1中的X1取代基反应生成R1取代基，当Y为卤素原子时，R1＝R1′，当Y为OH时，R1＝R1′-O-，当Y为-CH＝CH2时，R1＝R1’-CH＝CH-，当Y为-C≡CH时，R1＝R1’-C≡C-，R1、R2同上述的R1、R2。
根据本发明的又一个方面，提供了一种抗蚀剂组合物，包括树脂组分和产酸剂，该产酸剂为上述的磺酸酯类光产酸剂。
根据本发明的又一个方面，提供了一种图形化方法，包括对抗蚀剂组合物进行混合、成膜和图形化处理，该抗蚀剂组合物为前述的抗蚀剂组合物。
根据本发明的又一个方面，提供了一种前述的抗蚀剂组合物的应用，该应用包括将抗蚀剂组合物应用于电子组件的保护膜、层间绝缘材料、图型转移材料的制备中。
应用本发明的技术方案，本申请中具有通式I的磺酸酯类光产酸剂的分子中含有磺酸酯基，该磺酸酯基与酰亚胺结构直接相连，该结构具有感光裂解特性，在活性能量射线照射下能够发生N-O键断裂而产生不同类型的磺酸。上述活性能量射线是近紫外光区域、可见光区域的波长在300～450nm之间的活性能量射线，特别是对波长365nm(i线)的活性能量射线具有高灵敏度和较强吸收，将包括该磺酸酯类光产酸剂和树脂组分的抗蚀剂组合物用于碱显影液溶解曝光的感光性组合物时，由于磺酸酯类光产酸剂感光度的提升，从而可以形成具有优异的灵敏度和良好对比度的图案，即使是形成精细图案，也可以具有足够高的分辨率和灵敏度。与此同时，本发明的磺酸酯类光产酸剂的取代基中含有环氧基结构，在酸性、高温条件下可开环，中性、高温条件下不开环，从而有助于减少抗蚀剂中助剂的用量，减少光酸分子扩散，提高光刻图案的牢固性。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
如背景技术所分析的，现有技术中存在酸迁移、光刻图案牢固性较差的问题，为解决该问题，本发明提供了一种磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用。
在本申请的一种典型的实施方式中，提供了一种磺酸酯类光产酸剂，该磺酸酯类光产酸剂具有如下通式(I)：
其中，R1选自取代或未取代的C2～C25的烃基、取代或未取代的C2～C25的烷氧基、取代或未取代的C2～C25的烷硫基中的任意一种，其中的-CH2-可任选地被-O-、-S-、-CO-、-O-CO-或-COO-取代，其中的C原子也可任选地被N原子取代，且取代或未取代的C2～C25的烃基、取代或未取代的C2～C25的烷氧基、取代或未取代的C2～C25的烷硫基中的末端至少含有一个取代或未取代的C2～C10的环氧基；R2选自C1～C20的烷基、C6～C18的取代或未取代的芳基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种。
本申请中具有通式I的磺酸酯类光产酸剂的分子中含有磺酸酯基，该磺酸酯基与酰亚胺结构直接相连，该结构具有感光裂解特性，在活性能量射线照射下能够发生N-O键断裂而产生不同类型的磺酸。上述活性能量射线是近紫外光区域、可见光区域的波长在300～450nm之间的活性能量射线，特别是对波长365nm(i线)的活性能量射线具有高灵敏度和较强吸收，将包括该磺酸酯类光产酸剂和树脂组分的抗蚀剂组合物用于碱显影液溶解曝光的感光性组合物时，由于磺酸酯类光产酸剂感光度的提升，从而可以形成具有优异的灵敏度和良好对比度的图案，即使是形成精细图案，也可以具有足够高的分辨率和灵敏度。与此同时，本发明的磺酸酯类光产酸剂的取代基中含有环氧基结构，在酸性、高温条件下可开环，中性、高温条件下不开环，从而有助于减少抗蚀剂中助剂的用量，减少光酸分子扩散，提高光刻图案的牢固性。
在本申请的一种实施例中，取代或未取代的C2～C25的烃基选自取代或未取代的C2～C25的直链烷基、取代或未取代的C3～C25的支链烷基、取代或未取代的C4～C25的烯基、取代或未取代的C4～C25的炔基中的任意一种；优选R1选自取代或未取代的C6～C17的支链烷基、取代或未取代的C9～C16的烯基、取代或未取代的C9～C18的炔基、取代或未取代的C6～C17的烷氧基、取代或未取代的C6～C15的烷硫基中的任意一种；
进一步地，优选取代或未取代的C6～C17的支链烷基选自 中的任意一种；优选取代或未取代的C9～C16的烯基选自 中的任意一种；优选取代或未取代的C9～C18的炔基选自 中的任意一种；优选取代或未取代的C6～C17的烷氧基选自中的任意一种；优选取代或未取代的C6～C15的烷硫基选自 其中，“*”为R1与磺酸酯类光产酸剂的萘环相连的位置。
为了更容易合成上述磺酸酯类光产酸剂并兼顾成本，优选R1选自取代或未取代的C9～C16的烯基、取代或未取代的C9～C18的炔基、取代或未取代的C6～C17的烷氧基中的任意一种；考虑到烯基易黄变，对于透明体系，更优选R1选自取代或未取代的C9～C18的炔基、取代或未取代的C6～C17的烷氧基中的任意一种。
在本申请的一种实施例中，上述环氧基为C2～C5的环氧基，优选环氧基选自 中的任意一种，进一步地，优选为
环氧基的环碳原子数会影响其开环的难以程度，优选的上述环氧基更有利于提高磺酸酯类光产酸剂在酸性、高温条件下的开环性。
为进一步地提高磺酸酯类光产酸剂的结构稳定性和性能，优选上述R2中，C1～C20的烷基选自取代或未取代的C1～C20的直链烷基、取代或未取代的C3～C20的支链烷基、取代或未取代的C3～C20的环烷基中的任意一种；优选R2选自C1～C10的烷基、C6～C10的取代或未取代的芳基、取代或未取代的C3～C10的环烷基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种；进一步地，优选R2选自取代或未取代的C1～C8的直链烷基、取代或未取代的C3～C8的支链烷基、取代或未取代的C3～C5的环烷基、取代或未取代的苯基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种；进一步地，优选R2中的取代基为卤素原子，进一步地，优选为氟原子；更进一步地，优选R2选自C1～C4的直链全氟代烷基、C1～C4的直链烷基、C3～C6的支链全氟代烷基、全氟代苯基、C1～C4的全氟代烷基取代的苯基、C1～C4的烷基取代的苯基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种；优选R2选自三氟甲基、全氟丁基、正丙基、正丁基、樟脑基、对甲苯基、邻三氟甲基苯基中的任意一种。
在本申请的一些实施例中，优选上述磺酸酯类光产酸剂的结构式选自



中的任意一种或多种，从而进一步地提高光致
抗蚀剂的优良性能。
在本申请的另一种典型的实施方式中，提供了一种前述的磺酸酯类光产酸剂的制备方法，该制备方法包括：步骤S1，将化合物1与R1′Y进行反应，生成化合物2；步骤S2，将化合物2与盐酸羟胺或硫酸羟胺进行羟胺化反应，生成羟胺化合物；步骤S3，将羟胺化合物与R2SO2X2或(R2SO2)2O进行酯化反应，得到磺酸酯类光产酸剂；化合物1与化合物2的结构式如下：
其中，X1选自-H、-OH、-SH、卤素原子中的任意一种，Y选自-OH、-CH＝CH2、-C≡CH、卤素原子中的任意一种，X2为卤素原子，R1′Y与化合物1中的X1取代基反应生成R1取代基，当Y为卤素原子时，R1＝R1′，当Y为OH时，R1＝R1′-O-，当Y为-CH＝CH2时，R1＝R1’-CH＝CH-，当Y为-C≡CH时，R1＝R1’-C≡C-，R1、R2同前述的R1、R2。
上述步骤S1中，4-位取代萘酐(化合物1)可与端位取代的R1′Y(卤代烃、烯烃、炔烃、醇等物质)经过傅克反应、Heck偶联反应、加成反应或Click反应等不同类型的反应，得到4-位为R1取代的萘酐(化合物2)，其中R1′Y可以通过购买获得，也可以通过伯醇、羧酸、端烯、端炔、卤代烃之间的酯化、醚化及加成等反应制备得到。步骤S2中，4-位为R1取代的萘酐在碱性或酸性条件下与羟胺化试剂发生羟胺化反应，生成羟胺化合物，其中，羟胺化试剂可为硫酸羟胺或盐酸羟胺，优选将羟胺化反应温度控制在25～100℃之间，进一步地优选为75～100℃，更有助于提高羟胺化反应的效率。步骤S3中，羟胺化合物与酰化试剂在碱性条件下于惰性溶剂中发生酯化反应，生成磺酸酯类化合物。优选将酯化反应的温度控制在-10～60℃之间，进一步地优选为0～25℃，从而更有利于提高酯化反应的效率。
此外，上述制备方法中使用的原料和试剂均为现有技术中的已知化合物，可通过商购获得或经已知工艺方便地制得，在此不再赘述。
本发明的磺酸酯类光产酸剂可用于光产酸剂的已知任意用途，例如抗蚀膜、液态抗蚀剂、负型抗蚀剂、正型抗蚀剂、MEMS用抗蚀剂、立体光刻和微立体光刻用材料等。其中，作为抗蚀剂组合物中的光产酸剂，可与具有酸解离性基团的树脂一并制备抗蚀剂应用于半导体光刻。
在本申请的又一种典型的实施方式中，提供了一种抗蚀剂组合物，包括树脂组分和产酸剂，该产酸剂为前述的磺酸酯类光产酸剂。
本发明的抗蚀剂组合物可根据应用分为正型组合物和负型组合物。除磺酸酯类光产酸剂外，正型组合物一般含有经由酸的作用而增大对碱显影液溶解性的树脂成分(B1)。在组合物图型形成过程中，经选择性曝光，曝光区域中的正型树脂中由保护基保护的酸不稳定基团，会在由光产酸剂产生的酸作用下脱保护，使其对碱显影液可溶。因此进行碱显影操作时，未曝光区域图型留存，形成正型图型。与正型组成物不同，负型组合物使用在酸的作用下发生交联而不溶于有机系显影液的树脂-交联剂成分(B2)。曝光区域在由光产酸剂产生的酸催化下，树脂与交联剂反应形成不溶于有机系显影液的聚合物而留存，而未曝光区域被有机系显影液溶解、去除，最后形成负型图型，其中，具体的树脂成分(B1)、树脂-交联剂成分(B2)可参考申请号为202011299973.1的中国专利申请的说明书第[0046]至[0076]段公开的具体内容，在此不再赘述。
本发明的正/负型抗蚀剂组合物中，磺酸酯类光产酸剂在活性能量射线照射下能够发生N-O键断裂而产生磺酸，经过PEB工艺，实现曝光区域和未曝光区域对显影液溶解性的差异。磺酸酯类光产酸剂产品可以单独一种使用，也可以两种以上混合使用。
得益于本申请中具有通式I的磺酸酯类光产酸剂的性能，将包括该磺酸酯类光产酸剂和树脂组分的抗蚀剂组合物用于碱显影液溶解曝光的感光性组合物时，即使是形成精细图案，也可以具有足够高的分辨率和灵敏度。与此同时，可以减少抗蚀剂中助剂的用量，减少光酸分子扩散，并提高光刻图案的牢固性。
在本申请的一种实施例中，上述树脂组分具有被保护基团保护的酸不稳定基团，且酸不稳定基团选自羧基、酚羟基、磺酸基中的至少一种；优选酸不稳定基团的含量占树脂组分含量的1～80％，优选为3～70％；优选保护基团包括式(a)、式(b)所示基团中的至少一种：
其中，式(a)中，R3选自取代或非取代的C1～C20的直链烷基、取代或非取代的C3～C20的支链烷基、取代或非取代的C3～C20的环烷基中的任意一种或多种，优选R3选自取代或非取代的C1～C10的直链烷基、取代或非取代的C3～C10的支链烷基、取代或非取代的C3～C10的环烷基中的任意一种或多种，进一步地，优选R3选自取代或非取代的C1～C6的直链烷基、取代或非取代的C3～C6的支链烷基、取代或非取代的C3～C6的环烷基中的任意一种或多种，优选R3有取代基时所述取代基选自卤素、羟基、氰基、C1～C4的直链烷基、C3～C5的支链烷基中的任意一种或多种，优选取代基选自氟原子、甲基、乙基中的任意一种或多种，优选R3中的一个或多个C原子可被O、S、N或Si中的任意杂原子取代；进一步地，优选R3选自甲氧基、乙氧基、正丙氧基、正丁氧基、叔丁氧基、苯甲氧基、1-甲氧基乙氧基、1-乙氧基乙氧基、中的任意一种或多种，式(b)中，R4选自取代或非取代的C1～C20的直链烷基、取代或非取代的C3～C20的支链烷基、取代或非取代的C3～C20的环烷基中的任意一种或多种，且n为0或1，优选R4选自取代或非取代的C1～C10的直链烷基、取代或非取代的C3～C10的支链烷基、取代或非取代的C3～C10的环烷基中的任意一种或多种，进一步地，优选R4选自取代或非取代的C1～C6的直链烷基、取代或非取代的C3～C6的支链烷基、取代或非取代的C3～C6的环烷基中的任意一种或多种；进一步地，优选R4选自叔丁氧基羰基、丙氧羰基、金刚烷氧羰基、叔丁氧基羰基甲基中的任意一种或多种。
优选上述种类的树脂组分有利于其与磺酸酯类光产酸剂的协同作用，得到牢固的光刻图案。
上述产酸剂的用量，可以参考现有技术中常规产酸剂的用量，在一种实施例中，相对于抗蚀剂组合物固成分的质量，产酸剂的重量含量为0.5～5％，优选为1～3％，从而可以发挥出良好的感光度，提高显影效果。
溶剂用于溶解抗蚀剂组合物中的各个组分，形成均匀的溶液，用于调节其黏度和涂布性，从而以利于成膜，具体的溶剂可参考申请号为202011299973.1的中国专利申请，任选地，抗蚀剂组合物中还可包含该领域中的常规助剂，在此不再赘述。
在本申请的又一种典型的实施方式中，提供了一种图形化方法，包括对抗蚀剂组合物进行混合、成膜和图形化处理，该抗蚀剂组合物为上述的抗蚀剂组合物。
应用本发明的抗蚀剂组合物时，首先可使用例如旋转涂布的方法将溶解或分散于有机溶剂而成的树脂溶液涂布于基板上，然后加热使溶剂挥发，从而在基板上形成抗蚀膜，然后进行配线图案形状的光照射(即曝光)，接着在进行曝光后的加热处理(PEB)后，进行碱性显影，形成配线图案。
涂布后的树脂溶液的干燥条件根据所使用的溶剂而不同，优选于50～150℃下、在1～30min的范围内实施，即由干燥后的残留溶剂量(质量百分比)等来适当决定。
在基板上形成抗蚀膜之后，用光照射配线图案形状。光照射可使用低压汞灯、中压汞灯、高压汞灯、超高压汞灯、氙气灯、金属卤素灯、电子束辐照装置、X射线辐照装置、激光(如氩激光、染料激光、氮气激光、LED、氦气镉激光器)等，优选高压汞灯和LED灯。
曝光后加热处理(PEB)的温度通常为40～200℃，优选为60～150℃。若小于40℃，则无法充分进行脱保护反应或交联反应，因此曝光部与未曝光部的溶解性的差异不足而无法形成图案；若高于200℃，则存在生产性降低的问题。上述加热时间，通常为0.5～30min。
用碱显影液进行显影，碱显影方法包括使用碱显影剂。碱性显影剂可选自0.1～10％(质量百分比)的氢氧化四甲基铵、氢氧化钠、氢氧化钾、碳酸氢钠的水溶液，碱性显影剂还可包含水溶性有机溶剂，如甲醇、乙醇、异丙醇、四氢呋喃、N-甲基吡咯烷酮等。显影方法可选自浸渍法、喷淋法和喷雾法，优选喷雾法。显影剂的温度优选在25～40℃下使用，显影时间根据抗蚀膜的厚度适当确定，最后以获得对应于掩模的图案。
在本申请又一种典型的实施方式中，提供了一种上述的抗蚀剂组合物的应用，该应用包括将抗蚀剂组合物应用于电子组件的保护膜、层间绝缘材料、图型转移材料的制备中。
上述应用可具体包括将抗蚀剂组合物形成层间绝缘膜，用于液晶显示装置的TFT、面板；也可作为保护膜用于滤色器、间隔柱，还作为PS光刻胶、BCS光刻胶用于图型转移。
上述电子组件例如但不限于液晶显示装置、有机EL显示装置，Micro-LED、Mini-LED和量子点LED显示装置等电子组件。
以下将结合具体实施例，对本申请的有益效果进行说明。
磺酸酯类光产酸剂的制备实施例
实施例1
氮气保护下，在500mL的四口烧瓶中，加入甲苯200g，4-溴-1，8-萘二甲酸酐(S1)27.71g，3-乙基-3-((2-(乙烯基)乙氧基)甲基)氧代烷20.49g，醋酸钯0.22g，三苯基膦0.52g，三乙胺11.13g，开启搅拌并升温至75～80℃，保温反应6h。停止搅拌，降至室温后，加入100mL正己烷，搅拌0.5h，过滤，滤饼用20g甲苯漂洗一次，合并有机相。减压除去溶剂，再用100g DCM溶解混合体系，加入活性炭3g，搅拌脱色，除去溶剂后通过柱色谱法得到30.10g的中间体T1-1。
在250mL的四口烧瓶中，加入水100g，19.12g的中间体T1-1，盐酸羟胺4.17g，乙酸铵4.63g，开启搅拌并升温至75～80℃，保温反应3h。停止搅拌，稍微冷却后趁热过滤，滤固用100g左右纯水漂洗，烘干后得到13.95g的中间体T1-2，其为淡黄色固体。
氮气保护下，在250mL的四口烧瓶中，加入二氯甲烷200g，中间体13.95g的T1-2，吡啶3.33g，搅拌均匀后降温至0～5℃，缓慢滴入三氟甲磺酸酐11.88g，保持温度搅拌3h。加入纯水50g，搅拌0.5h后分液，55℃常压浓缩有机相至无馏出，加入正己烷50g析晶，得到15.25g的磺酸酯类光产酸剂34，其为淡黄色固体。
实施例2
在500mL的四口烧瓶中，加入四氢呋喃250g，1，8-萘二甲酸酐19.82g，三氯化铝26.66g，3-乙基-3-(氯甲基)-氧代烷16.15g，开启搅拌，搅拌均匀后升温至70℃回流12h。停止搅拌，体系降至室温，真空除去溶剂，加入纯水100g、二氯甲烷150g，摇匀分液。浓缩有机相，得到15.56g的中间体T2-1，其为白色固体。
T2-2与光酸1的制备，可参考实施例1中第二、第三个反应。
实施例3
磺酸酯类光产酸剂28的制备方法可参考实施例1。
实施例4
在250mL的不锈钢加压釜中，加入甲醇150g，17.62g的中间体T3-1，5％的Pd/C催化剂0.15g，醋酸0.5mL，检漏密封后，充入氢气1～2MPa，开启搅拌并升温至55～65℃，保温反应6h。停止搅拌，降至室温。过滤，减压除去溶剂，再用100g的DCM溶解混合体系，加入活性炭3g，搅拌脱色，除去溶剂后通过柱色谱法得到16.35g的中间体T4-1，其为白色固体。
T4-2与磺酸酯类光产酸剂8的制备，可参考实施例1中第二、第三个反应。
实施例5
氮气保护下，在500mL的四口烧瓶中，加入3-乙基-3-氧杂丁环甲醇200g，4-溴萘二甲酸酐27.71g，碳酸钾41.46g，无水氯化铜0.67g，升温回流搅拌12h，停止加热。恢复室温后，过滤，向滤液中加入正己烷500g，0℃搅拌析晶0.5h。过滤，收集滤饼，用20mL正己烷漂洗。用少量DCM溶解滤饼，过滤后经柱色谱法提纯，最终得到21.55g的中间体T5-1，为白色固体。
T5-2与磺酸酯类光产酸剂15的制备，可参考实施例1中第二、第三个反应。
实施例6
氮气保护下，在500mL的四口烧瓶中加入3-乙基-3-氧杂丁环甲醇20g，THF 200mL，搅拌均匀后降温至0℃。批加NaH共4.80g，控制反应温度低于5℃。搅拌均匀后维持0℃温度，向反应器中缓慢滴加溴丙炔17.07g，滴加完后缓慢升至室温反应3h。停止反应，将反应液过滤后浓缩，通过柱色谱法提纯后得到3-乙基-3-氧杂丁环炔丙醚15.20g。
氮气保护下，在500mL的四口烧瓶中，加入3-乙基-3-氧杂丁环炔丙醚18.50g，4-溴萘二甲酸酐27.71g，THF 300mL，搅拌均匀后加入碘化亚铜0.95g，三苯基膦2.62g，双三苯基膦二氯化钯0.70g，三乙胺20.24g，升至70℃搅拌3h，停止加热。恢复室温后，浓缩除去溶剂，经柱色谱法提纯，最终得到29.78g的中间体T6-1，为淡黄色固体。
T6-2与磺酸酯类光产酸剂35的制备，可参考实施例1中第二、第三个反应。
实施例7
T6-1、T6-2的制备，可参考实施例6。
在500mL四口烧瓶中，加入18.27g T6-2、200mL二氯甲烷，搅拌溶解后加入三乙胺7.59g，降温至0℃预冷15min。向反应器内分批次加入对甲苯磺酰氯共10.49g，控制体系温度不超过 5℃。搅拌反应3h后，向体系内缓慢加氨水100mL，待体系稳定后分液。有机相用0.5M盐酸50mL洗涤，再用纯水洗涤两次，每次用水100mL。浓缩有机相至固体析出，加正己烷200mL搅拌析晶。过滤、干燥后得到淡黄色固体20.00g，为磺酸酯类光产酸剂50。
实施例8
T6-1、T6-2的制备，可参考实施例6。磺酸酯类光产酸剂52的制备，可参考实施例7，将对甲苯磺酰氯原料替换为丁烷磺酰氯。
参照类似实施例1至8的反应步骤，实施例9至21分别替换底物并适应调整反应条件，依次得到其它相应的磺酸酯类光产酸剂2、11、13、14、18、21、24、25、27、29、32、36、39。
实施例22
磺酸酯类光产酸剂49的制备，可参考实施例7，将对甲苯磺酰氯原料替换为混悬樟脑磺酰氯。
实施例23
磺酸酯类光产酸剂51的制备，可参考实施例7，将对甲苯磺酰氯原料替换为丙烷磺酰氯。
实施例24
磺酸酯类光产酸剂53的制备，可参考实施例7，将对甲苯磺酰氯原料替换为2-三氟甲基苯磺酰氯。
将所有实施例制备得到的磺酸酯类光产酸剂的编号和1HNMR表征结果分别列于表1。
表1




性能评价
分别对实施例1至24合成的磺酸酯类光产酸剂和对比例1的磺酸酯类光产酸剂进行性能评价，评价指标包括摩尔吸光系数、溶解性和化学稳定性。
(1)摩尔吸光系数
利用乙腈将化合物稀释成0.25mmol/L，使用紫外可见光谱光度计(优谱通用UPG-752)在200～600nm的范围测定1cm的比色皿长度的吸光度。由下述公式算出各波长下的摩尔吸光系数ε，即ε(L·mol-1·cm-1)＝A/(0.00025mol/L×1cm)，式中，A表示各波长下的吸光度。
(2)溶解性
高溶解度不仅使光产酸剂化合物纯化容易，且可以使光产酸剂化合物能够在光阻及不同溶剂系统中扩大使用的浓度范围。分别取光产酸剂化合物产品1.0000g，25℃下逐渐加入溶剂，直至各试管内固体全部溶清，记录所用溶剂的质量，溶解度＝(1g/溶剂质量)×100％，评价结果如表2中所示。
表2

其中对比例1的非离子光产酸剂为记为A*1。
通过表2的测试结果可知，本发明的光产酸剂在365nm处具有较高的摩尔吸光系数，吸光能力强，可充分利用光能，能够确保在抗蚀剂应用中具有较高的利用率，且表现出了良好的溶解性。
抗蚀剂组合物的实施例
参照表3中抗蚀剂组合物实施例1～31、抗蚀剂组合物对比例1～6所示配方，将各原料均匀溶解在PGMEA(丙二醇甲醚乙酸酯)中，得到固体成分浓度约为20％(质量百分比)的抗蚀剂组合物。其中，磺酸酯类光产酸剂(A)、树脂组分(B)、缚酸剂三乙胺(C)的组分类型及含量如表3中所示。
组合物实施例1
树脂组分(B)采用B1类型的树脂，由式B11、式B12和式B13所示的重复单元构成，各重复单元右下的数值表示该重复单元在树脂中的含量(质量百分比)。B1树脂的重均分子量约为10000。
磺酸酯类光产酸剂(A)为实施例1的磺酸酯类光产酸剂。
组合物实施例2至24
与组合物实施例1的区别在于：磺酸酯类光产酸剂(A)分别依次采用实施例2至24的磺酸酯类光产酸剂。
其余组分类型和含量如表3中所示。
组合物实施例25
与组合物实施例5的区别在于：树脂组分(B)采用B2类型的树脂，由式B21、式B22和式B23所示的重复单元构成，各重复单元右下的数值表示该重复单元在树脂中的含量(质量％)。B2树脂的重均分子量约为10000。
组合物实施例26
与组合物实施例5的区别在于：树脂组分(B)采用B3类型的树脂，由式B31和式B32所示的重复单元构成，各重复单元右下的数值表示该重复单元在树脂中的含量(质量％)。B3树脂的重均分子量约为10000。
组合物实施例27～28
与组合物实施例5的区别在于：磺酸酯类光产酸剂的含量不同。
组合物实施例29
与组合物实施例5的区别在于：没有添加缚酸剂。
组合物实施例30
与组合物实施例6的区别在于：没有添加缚酸剂。
组合物实施例31
与组合物实施例7的区别在于：没有添加缚酸剂。
组合物对比例1
与组合物实施例5的区别在于：采用对比例1的磺酸酯类光产酸剂A*1。
组合物对比例2
与组合物实施例6的区别在于：采用对比例1的磺酸酯类光产酸剂A*1。
组合物对比例3
与组合物实施例7的区别在于：采用对比例1的磺酸酯类光产酸剂A*1。
组合物对比例4
与组合物对比例1的区别在于：没有添加缚酸剂。
组合物对比例5
与组合物对比例2的区别在于：没有添加缚酸剂。
组合物对比例6
与组合物对比例3的区别在于：没有添加缚酸剂。
将组合物实施例1～31、组合物对比例1～6制备的抗蚀剂组合物通过以下方法评价感光度和解像性，结果记录在表3中。
(1)感光度评价
在各硅片上，以能够形成图案的膜厚为1μm的膜厚涂布各实施例和对比例的抗蚀剂组合物，形成涂膜。将形成的涂膜在90℃下预烘烤100秒。预烘烤后，一边逐渐改变曝光量(曝光波长365nm)，一边通过直径10μm的孔图案形成用掩模对涂膜进行曝光，然后在25℃下2.0％的氢氧化四甲铵水溶液显影30秒。通过上述方法确定形成10μm直径的孔图案所需的最小曝光。从获得的最小曝光值，根据以下标准评估灵敏度：“○”表示感光度为-50mJ/cm2以下，“×”表示感光度为-300mJ/cm2以上。
(2)解像性评价
使用用于形成直径为5μm的孔图案的掩模，除了以100mJ/cm2的曝光量进行曝光以外，以与感光度评价相同的方式进行涂膜形成，涂膜曝光和显影。观察显影后的涂膜，并根据以下标准评价分辨率：“○”表示可以形成直径为5μm的图案，“○”表示不能形成直径为5μm的图案。
表3

由表3的结果可以看到，本发明的如组合物实施例1～28所示的抗蚀剂组合物具有非常好的感光度和解像性，明显优于组合物对比例1～3。组合物实施例29～31显示，在没有缚酸剂的 情况下，解像性依然非常好，但是同样不添加缚酸剂的组合物对比例4～6，则显示出一般的解像性。
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
本申请中具有通式I的磺酸酯类光产酸剂的分子中含有磺酸酯基，该磺酸酯基与酰亚胺结构直接相连，该结构具有感光裂解特性，在活性能量射线照射下能够发生N-O键断裂而产生不同类型的磺酸。上述活性能量射线是近紫外光区域、可见光区域的波长在300～450nm之间的活性能量射线，特别是对波长365nm(i线)的活性能量射线具有高灵敏度和较强吸收，将包括该磺酸酯类光产酸剂和树脂组分的抗蚀剂组合物用于碱显影液溶解曝光的感光性组合物时，由于磺酸酯类光产酸剂感光度的提升，从而可以形成具有优异的灵敏度和良好对比度的图案，即使是形成精细图案，也可以具有足够高的分辨率和灵敏度。与此同时，本发明的磺酸酯类光产酸剂的取代基中含有环氧基结构，在酸性、高温条件下可开环，中性、高温条件下不开环，从而有助于减少抗蚀剂中助剂的用量，减少光酸分子扩散，提高光刻图案的牢固性。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (11)

  1. 一种磺酸酯类光产酸剂，其特征在于，所述磺酸酯类光产酸剂具有如下通式(I)：
    其中，R1选自取代或未取代的C2～C25的烃基、取代或未取代的C2～C25的烷氧基、取代或未取代的C2～C25的烷硫基中的任意一种，其中的-CH2-可任选地被-O-、-S-、-CO-、-O-CO-或-COO-取代，其中的C原子也可任选地被N原子取代，且所述取代或未取代的C2～C25的烃基、所述取代或未取代的C2～C25的烷氧基、所述取代或未取代的C2～C25的烷硫基中的末端至少含有一个取代或未取代的C2～C10的环氧基；
    R2选自C1～C20的烷基、C6～C18的取代或未取代的芳基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种。
  2. 根据权利要求1所述的磺酸酯类光产酸剂，其特征在于，所述取代或未取代的C2～C25的烃基选自取代或未取代的C2～C25的直链烷基、取代或未取代的C3～C25的支链烷基、取代或未取代的C4～C25的烯基、取代或未取代的C4～C25的炔基中的任意一种；
    优选所述R1选自取代或未取代的C6～C17的支链烷基、取代或未取代的C9～C16的烯基、取代或未取代的C9～C18的炔基、取代或未取代的C6～C17的烷氧基、取代或未取代的C6～C15的烷硫基中的任意一种；
    进一步地，优选所述取代或未取代的C6～C17的支链烷基选自 中的任意一种；
    优选所述取代或未取代的C9～C16的烯基选自 中的任意一种；
    优选所述取代或未取代的C9～C18的炔基选自 中的任意一种；
    优选所述取代或未取代的C6～C17的烷氧基选自中的任意一种；
    优选所述取代或未取代的C6～C15的烷硫基选自 其中，“*”为所述R1与所述磺酸酯类光产酸 剂的萘环相连的位置。
  3. 根据权利要求1所述的磺酸酯类光产酸剂，其特征在于，所述环氧基为C2～C5的环氧基，优选所述环氧基选自中的任意一种，进一步地，优选为
  4. 根据权利要求1至3中任一项所述的磺酸酯类光产酸剂，其特征在于，所述R2中，所述C1～C20的烷基选自取代或未取代的C1～C20的直链烷基、取代或未取代的C3～C20的支链烷基、取代或未取代的C3～C20的环烷基中的任意一种；
    优选所述R2选自C1～C10的烷基、C6～C10的取代或未取代的芳基、取代或未取代的C3～C10的环烷基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种；
    进一步地，优选所述R2选自取代或未取代的C1～C8的直链烷基、取代或未取代的C3～C8的支链烷基、取代或未取代的C3～C5的环烷基、取代或未取代的苯基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种；
    进一步地，优选所述R2中的取代基为卤素原子，进一步地，优选为氟原子；更进一步地，优选所述R2选自C1～C4的直链全氟代烷基、C1～C4的直链烷基、C3～C6的支链全氟代烷基、全氟代苯基、C1～C4的全氟代烷基取代的苯基、C1～C4的烷基取代的苯基、樟脑基、樟脑醌基、叠氮萘酮基中的任意一种；优选所述R2选自三氟甲基、全氟丁基、正丙基、正丁基、樟脑基、对甲苯基、邻三氟甲基苯基中的任意一种。
  5. 根据权利要求1至3中任一项所述的磺酸酯类光产酸剂，其特征在于，所述磺酸酯类光产酸剂的结构式选自
    中的任意一种或多种。
  6. 一种权利要求1至5中任一项所述的磺酸酯类光产酸剂的制备方法，其特征在于，所述制备方法包括：
    步骤S1，将化合物1与R1′Y进行反应，生成化合物2；
    步骤S2，将所述化合物2与盐酸羟胺或硫酸羟胺进行羟胺化反应，生成羟胺化合物；
    步骤S3，将所述羟胺化合物与R2SO2X2或(R2SO2)2O进行酯化反应，得到所述磺酸酯类光产酸剂；
    化合物1与化合物2的结构式如下：
    其中，X1选自-H、-OH、-SH、卤素原子中的任意一种，Y选自-OH、-CH＝CH2、-C ≡CH、卤素原子中的任意一种，X2为卤素原子，R1′Y与化合物1中的X1取代基反应生成R1取代基，当Y为卤素原子时，R1＝R1′，当Y为OH时，R1＝R1′-O-，当Y为-CH＝CH2时，R1＝R1’-CH＝CH-，当Y为-C≡CH时，R1＝R1’-C≡C-，R1、R2同权利要求1至5中任一项所述的R1、R2。
  7. 一种抗蚀剂组合物，包括树脂组分和产酸剂，其特征在于，所述产酸剂为权利要求1至5中任一项所述的磺酸酯类光产酸剂。
  8. 根据权利要求7所述的抗蚀剂组合物，其特征在于，所述树脂组分具有被保护基团保护的酸不稳定基团，且所述酸不稳定基团选自羧基、酚羟基、磺酸基中的至少一种；优选所述酸不稳定基团的含量占所述树脂组分含量的1～80％，优选为3～70％；
    优选所述保护基团包括式(a)、式(b)所示基团中的至少一种：
    其中，所述式(a)中，R3选自取代或非取代的C1～C20的直链烷基、取代或非取代的C3～C20的支链烷基、取代或非取代的C3～C20的环烷基中的任意一种或多种，优选所述R3选自取代或非取代的C1～C10的直链烷基、取代或非取代的C3～C10的支链烷基、取代或非取代的C3～C10的环烷基中的任意一种或多种，进一步地，优选所述R3选自取代或非取代的C1～C6的直链烷基、取代或非取代的C3～C6的支链烷基、取代或非取代的C3～C6的环烷基中的任意一种或多种，优选所述R3有取代基时所述取代基选自卤素、羟基、氰基、C1～C4的直链烷基、C3～C5的支链烷基中的任意一种或多种，优选所述取代基选自氟原子、甲基、乙基中的任意一种或多种，优选所述R3中的一个或多个C原子可被O、S、N或Si中的任意杂原子取代；进一步地，优选所述R3选自甲氧基、乙氧基、正丙氧基、正丁氧基、叔丁氧基、苯甲氧基、1-甲氧基乙氧基、1-乙氧基乙氧基、中的任意一种或多种，
    所述式(b)中，R4选自取代或非取代的C1～C20的直链烷基、取代或非取代的C3～C20的支链烷基、取代或非取代的C3～C20的环烷基中的任意一种或多种，且n为0或1，优选所述R4选自取代或非取代的C1～C10的直链烷基、取代或非取代的C3～C10的支链烷基、取代或非取代的C3～C10的环烷基中的任意一种或多种，进一步地，优选所述R4选自取代或非取代的C1～C6的直链烷基、取代或非取代的C3～C6的支链烷基、取代或非取代的C3～C6的环烷基中的任意一种或多种；进一步地，优选所述R4选自叔丁氧基羰基、丙氧羰基、金刚烷氧羰基、叔丁氧基羰基甲基中的任意一种或多种。
  9. 根据权利要求7或8所述的抗蚀剂组合物，其特征在于，相对于所述抗蚀剂组合物的固成分的质量，所述产酸剂的重量含量为0.01～5％，优选为0.1～3％，优选所述抗蚀剂组合物还包括溶剂。
  10. 一种图形化方法，包括对抗蚀剂组合物进行混合、成膜和图形化处理，其特征在于，所述抗蚀剂组合物为权利要求7至9中任一项所述的抗蚀剂组合物。
  11. 一种权利要求7至9中任一项所述的抗蚀剂组合物的应用，所述应用包括将所述抗蚀剂组合物应用于电子组件的保护膜、层间绝缘材料、图型转移材料的制备中。
PCT/CN2023/115303 2022-08-26 2023-08-28 磺酸酯类光产酸剂及其制备方法、图形化方法、抗蚀剂组合物及其应用 WO2024041660A1 (zh)

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