CN117658997A - Sulfonate photoacid generator, preparation method thereof, patterning method, resist composition and application thereof - Google Patents

Sulfonate photoacid generator, preparation method thereof, patterning method, resist composition and application thereof Download PDF

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Publication number
CN117658997A
CN117658997A CN202211038021.3A CN202211038021A CN117658997A CN 117658997 A CN117658997 A CN 117658997A CN 202211038021 A CN202211038021 A CN 202211038021A CN 117658997 A CN117658997 A CN 117658997A
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China
Prior art keywords
substituted
unsubstituted
photoacid generator
groups
sulfonate photoacid
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CN202211038021.3A
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Chinese (zh)
Inventor
钱彬
闫超
张学龙
徐丽萍
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Changzhou Qiangli Photoelectric Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Qiangli Photoelectric Material Co ltd
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Application filed by Changzhou Qiangli Photoelectric Material Co ltd, Changzhou Tronly New Electronic Materials Co Ltd, Changzhou Tronly Advanced Electronic Materials Co Ltd filed Critical Changzhou Qiangli Photoelectric Material Co ltd
Priority to CN202211038021.3A priority Critical patent/CN117658997A/en
Priority to PCT/CN2023/115303 priority patent/WO2024041660A1/en
Publication of CN117658997A publication Critical patent/CN117658997A/en
Pending legal-status Critical Current

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    • 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
    • C07D405/06—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
    • 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

Abstract

The invention provides a sulfonate photoacid generator, a preparation method, a patterning method, a resist composition and application thereof. Sulfonate photoacid generators have the general formula (I), wherein R 1 Selected from substituted or unsubstituted C 2 ～C 25 Substituted or unsubstituted C 2 ～C 25 Alkoxy, substituted or unsubstituted C 2 ～C 25 Any one of alkylthio groups in which-CH 2 Optionally interrupted by-O-, -S-, -CO-, -O-CO-, or-COO-substitution,wherein the C atom is optionally substituted by N atom and R 1 Containing at least one substituted or unsubstituted C at the end 2 ～C 10 An epoxy group of (2); r is R 2 Selected from C 1 ～C 20 Alkyl, C of (2) 6 ～C 18 Any one of substituted or unsubstituted aryl, camphoryl, camphorquinone, and azidonadone groups. The sulfonate photoacid generator can reduce photoacid molecule diffusion and improve the firmness of photoetching patterns.

Description

Sulfonate photoacid generator, preparation method thereof, patterning method, resist composition and application thereof
Technical Field
The invention relates to the technical field of photosensitive materials, in particular to a sulfonate photoacid generator, a preparation method, a patterning method, a resist composition and application thereof.
Background
Photoacid generators are one of the key components of chemically amplified photoresists, whose structure and performance have a large impact on lithographic images. With the development of the semiconductor industry, the demand for high-definition patterns is continuously growing, and simultaneously, higher demands are also put on the expansion of applicable types of photoacid generators, and the performances of the photoacid generators, particularly the characteristics of low diffusivity, high solubility, high acid yield and the like. Although sulfonate compounds of naphthalene anhydride are widely known as photoinitiators in the semiconductor field, most of the current resist formulations require addition of auxiliaries to inhibit acid migration or enhance pattern fastness.
Disclosure of Invention
The invention mainly aims to provide a sulfonate photoacid generator, a preparation method thereof, a patterning method, a resist composition and application thereof, so as to solve the problems of acid migration and poor photoetching pattern firmness in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a sulfonate photoacid generator having the following general formula (I):
wherein R is 1 Selected from substituted or unsubstituted C 2 ～C 25 Substituted or unsubstituted C 2 ～C 25 Alkoxy, substituted or unsubstituted C 2 ～C 25 Any one of alkylthio groups in which-CH 2 Optionally interrupted by-O-, -S-, -CO-, -O-CO-, or-COO-substitution, wherein the C atom is optionally substituted by N atom, and substituted or unsubstituted C 2 ～C 25 Substituted or unsubstituted C 2 ～C 25 Alkoxy, substituted or unsubstituted C 2 ～C 25 Containing at least one substituted or unsubstituted C at the end of the alkylthio group 2 ～C 10 An epoxy group of (2); r is R 2 Selected from C 1 ～C 20 Alkyl, C of (2) 6 ～C 18 Any one of substituted or unsubstituted aryl, camphoryl, camphorquinone, and azidonadone groups.
According to another aspect of the present invention, there is provided a method for preparing the above sulfonate photoacid generator, comprising: step S1, compounds 1 and R 1 ' Y reacts to form compound 2; step S2, carrying out hydroxylamine amination reaction on the compound 2 and hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound; step S3, mixing hydroxylamine compound with R 2 SO 2 X 2 Or (R) 2 SO 2 ) 2 O is subjected to esterification reaction to obtain a sulfonate photoacid generator; the structural formulas of the compound 1 and the compound 2 are as follows:
wherein X is 1 Is selected from any one of-H, -OH, -SH and halogen atoms, and Y is selected from-OH, -CH=CH 2 Any one of-C.ident.CH and halogen atoms, X 2 Is a halogen atom, R 1 ' Y and X in Compound 1 1 The substituents react to form R 1 Substituent, when Y is a halogen atom, R 1 ＝R 1 ' when Y is OH, R 1 ＝R 1 ' O-, when Y is-CH=CH 2 When R is 1 ＝R 1’ -ch=ch-, when Y is-c≡ch, R 1 ＝R 1’ -C≡C-，R 1 、R 2 R is as described above 1 、R 2 。
According to still another aspect of the present invention, there is provided a resist composition comprising a resin component and an acid generator which is the above-mentioned sulfonate photoacid generator.
According to still another aspect of the present invention, there is provided a patterning method comprising mixing, film forming and patterning a resist composition, which is the aforementioned resist composition.
According to still another aspect of the present invention, there is provided the use of the aforementioned resist composition, which comprises the use of the resist composition in the preparation of protective films for electronic components, interlayer insulating materials, pattern transfer materials.
By applying the technical scheme of the invention, the molecule of the sulfonate photoacid generator with the general formula I contains sulfonate groups, the sulfonate groups are directly connected with imide structures, the structures have photosensitive cracking characteristics, and N-O bond breakage can occur under the irradiation of active energy rays to generate different types of sulfonic acids. The active energy ray is an active energy ray having a wavelength of 300 to 450nm in the near ultraviolet region and the visible light region, and particularly has high sensitivity and strong absorption to an active energy ray having a wavelength of 365nm (i-line), and when a resist composition comprising the sulfonate photoacid generator and a resin component is used in an alkali developer for dissolution exposure of a photosensitive composition, a pattern having excellent sensitivity and good contrast can be formed due to the improvement of the sensitivity of the sulfonate photoacid generator, and even if a fine pattern is formed, a sufficiently high resolution and sensitivity can be obtained. Meanwhile, the substituent group of the sulfonate photoacid generator contains an epoxy group structure, and the sulfonate photoacid generator can open a loop under the conditions of acidity and high temperature, and does not open a loop under the conditions of neutrality and high temperature, so that the sulfonate photoacid generator is beneficial to reducing the dosage of auxiliary agents in a resist, reducing the diffusion of photoacid molecules and improving the firmness of photoetching patterns.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed by the background art, the prior art has the problems of poor acid migration and poor photoetching pattern firmness, and in order to solve the problems, the invention provides a sulfonate photoacid generator, a preparation method, a patterning method, a resist composition and application thereof.
In one exemplary embodiment of the present application, a sulfonate photoacid generator is provided, having the following general formula (I):
wherein R is 1 Selected from substituted or unsubstituted C 2 ～C 25 Substituted or unsubstituted C 2 ～C 25 Alkoxy, substituted or unsubstituted C 2 ～C 25 Any one of alkylthio groups in which-CH 2 Optionally interrupted by-O-, -S-, -CO-, -O-CO-, or-COO-substitution, wherein the C atom is optionally substituted by N atom, and substituted or unsubstituted C 2 ～C 25 Substituted or unsubstituted C 2 ～C 25 Alkoxy, substituted or unsubstituted C 2 ～C 25 Containing at least one substituted or unsubstituted C at the end of the alkylthio group 2 ～C 10 An epoxy group of (2); r is R 2 Selected from C 1 ～C 20 Alkyl, C of (2) 6 ～C 18 Any one of substituted or unsubstituted aryl, camphoryl, camphorquinone, and azidonadone groups.
The molecule of the sulfonate photoacid generator with the general formula I contains sulfonate groups, the sulfonate groups are directly connected with imide structures, the structures have photosensitive cleavage characteristics, and N-O bond cleavage can be generated under the irradiation of active energy rays to generate different types of sulfonic acids. The active energy ray is an active energy ray having a wavelength of 300 to 450nm in the near ultraviolet region and the visible light region, and particularly has high sensitivity and strong absorption to an active energy ray having a wavelength of 365nm (i-line), and when a resist composition comprising the sulfonate photoacid generator and a resin component is used in an alkali developer for dissolution exposure of a photosensitive composition, a pattern having excellent sensitivity and good contrast can be formed due to the improvement of the sensitivity of the sulfonate photoacid generator, and even if a fine pattern is formed, a sufficiently high resolution and sensitivity can be obtained. Meanwhile, the substituent group of the sulfonate photoacid generator contains an epoxy group structure, and the sulfonate photoacid generator can open a loop under the conditions of acidity and high temperature, and does not open a loop under the conditions of neutrality and high temperature, so that the sulfonate photoacid generator is beneficial to reducing the dosage of auxiliary agents in a resist, reducing the diffusion of photoacid molecules and improving the firmness of photoetching patterns.
In one embodiment of the present application, substituted or unsubstituted C 2 ～C 25 Is selected from the group consisting of substituted and unsubstituted C 2 ～C 25 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 25 Branched alkyl, substituted or unsubstituted C 4 ～C 25 Alkenyl, substituted or unsubstituted C 4 ～C 25 Any one of the alkynyl groups of (a); preferably R 1 Selected from substituted or unsubstituted C 6 ～C 17 Branched alkyl, substituted or unsubstituted C 9 ～C 16 Alkenyl, substituted or unsubstituted C 9 ～C 18 Alkynyl, substituted or unsubstituted C 6 ～C 17 Alkoxy, substituted or unsubstituted C 6 ～C 15 Any one of alkylthio groups of (2);
further, substituted or unsubstituted C is preferred 6 ～C 17 Is selected from branched alkyl groups of Any one of them; preferably substituted or unsubstituted C 9 ～C 16 Alkenyl group of-> Any one of them; preferably substituted or unsubstituted C 9 ～C 18 Alkynyl of (2) is selected from-> Any one of them; preferably substituted or unsubstituted C 6 ～C 17 Alkoxy radicals selected from->Any one of them; preferably substituted or unsubstituted C 6 ～C 15 Alkylthio groups of (2) are selected from-> Wherein "xe" is R 1 And the position connected with the naphthalene ring of the sulfonate photoacid generator.
In order to make the synthesis of the sulfonate photoacid generator easier and to achieve cost, R is preferably selected 1 Selected from substituted or unsubstituted C 9 ～C 16 Alkenyl, substituted or unsubstituted C 9 ～C 18 Alkynyl, substituted or unsubstituted C 6 ～C 17 Any of the alkoxy groups of (2)Meaning one; considering that alkenyl groups are easily yellowing, R is more preferred for transparent systems 1 Selected from substituted or unsubstituted C 9 ～C 18 Alkynyl, substituted or unsubstituted C 6 ～C 17 Any one of the alkoxy groups of (a).
In one embodiment of the present application, the epoxy group is C 2 ～C 5 Preferably selected from the group consisting of epoxy groups Any one of, further, preferably +.>
The number of ring carbon atoms of the epoxy group affects the difficulty of ring opening, and the preferable epoxy group is more favorable for improving the ring opening property of the sulfonate photoacid generator under acidic and high-temperature conditions.
To further improve the structural stability and performance of the sulfonate photoacid generator, R is preferably as defined above 2 In C 1 ～C 20 Is selected from substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted C 3 ～C 20 Any one of cycloalkyl groups of (a); preferably R 2 Selected from C 1 ～C 10 Alkyl, C of (2) 6 ～C 10 Substituted or unsubstituted aryl, substituted or unsubstituted C 3 ～C 10 Any one of cycloalkyl, camphoryl, camphorquinone, azidonaphthyl, and the like; further, R is preferably 2 Selected from substituted or unsubstituted C 1 ～C 8 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 8 Branched alkyl, substituted or unsubstituted C 3 ～C 5 Any one of cycloalkyl, substituted or unsubstituted phenyl, camphoryl, camphorquinone, azidonadone;further, R is preferably 2 The substituent in (a) is a halogen atom, and further, preferably a fluorine atom; further, R is preferably 2 Selected from C 1 ～C 4 Linear perfluoroalkyl groups, C 1 ～C 4 Straight chain alkyl, C 3 ～C 6 Branched perfluoroalkyl, perfluorophenyl, C 1 ～C 4 Perfluoroalkyl-substituted phenyl, C 1 ～C 4 Any one of alkyl-substituted phenyl, camphoryl, camphorquinone, azidonaphthyl, ketone groups; preferably R 2 Any one selected from trifluoromethyl, perfluorobutyl, n-propyl, n-butyl, camphoryl, p-tolyl and o-trifluoromethylphenyl.
In some embodiments of the present application, it is preferred that the sulfonate photoacid generator has a structural formula selected from
Any one or more of these, thereby further improving the excellent performance of the photoresist.
In another exemplary embodiment of the present application, a method ofThe preparation method of the sulfonate photoacid generator comprises the following steps: step S1, compounds 1 and R 1 ' Y reacts to form compound 2; step S2, carrying out hydroxylamine amination reaction on the compound 2 and hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound; step S3, mixing hydroxylamine compound with R 2 SO 2 X 2 Or (R) 2 SO 2 ) 2 O is subjected to esterification reaction to obtain a sulfonate photoacid generator; the structural formulas of the compound 1 and the compound 2 are as follows:
wherein X is 1 Is selected from any one of-H, -OH, -SH and halogen atoms, and Y is selected from-OH, -CH=CH 2 Any one of-C.ident.CH and halogen atoms, X 2 Is a halogen atom, R 1 ' Y and X in Compound 1 1 The substituents react to form R 1 Substituent, when Y is a halogen atom, R 1 ＝R 1 ' when Y is OH, R 1 ＝R 1 ' O-, when Y is-CH=CH 2 When R is 1 ＝R 1’ -ch=ch-, when Y is-c≡ch, R 1 ＝R 1’ -C≡C-，R 1 、R 2 R is as previously described 1 、R 2 。
In the above step S1, R which may be substituted with terminal position is substituted with 4-substituted naphthalene anhydride (Compound 1) 1 ' Y (halohydrocarbon, alkene, alkyne, alcohol, etc.) is subjected to Friedel-crafts reaction, heck coupling reaction, addition reaction or Click reaction to obtain R at 4-position 1 Substituted naphthalene anhydrides (compound 2), wherein R 1 'Y' can be obtained through purchase, and can also be prepared through esterification, etherification, addition and other reactions among primary alcohol, carboxylic acid, terminal alkene, terminal alkyne, halogenated hydrocarbon. In step S2, the 4-position is R 1 The substituted naphthalene anhydride is subjected to hydroxylamine reaction with a hydroxylamine reagent under alkaline or acidic condition to form a hydroxylamine compound, wherein the hydroxylamine reagent can be hydroxylamine sulfate or hydroxylamine hydrochloride, and the hydroxylamine reaction temperature is preferably controlled to be 25-1The temperature of between 00℃is more preferably 75 to 100℃and is more useful for improving the efficiency of the hydroxylation reaction. In the step S3, the hydroxylamine compound and the acylating agent are subjected to esterification reaction in an inert solvent under alkaline conditions to generate a sulfonate compound. The temperature of the esterification reaction is preferably controlled to be between-10 and 60 ℃, and more preferably between 0 and 25 ℃, so that the efficiency of the esterification reaction is more advantageously improved.
In addition, the raw materials and reagents used in the preparation method are all known compounds in the prior art, and can be obtained commercially or conveniently prepared through known processes, and are not described herein.
The sulfonate photoacid generator of the present invention can be used for any known use of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, MEMS resists, stereolithography and microlithography materials, and the like. Among them, as a photoacid generator in a resist composition, a resist can be prepared together with a resin having an acid dissociable group for use in semiconductor lithography.
In yet another exemplary embodiment of the present application, a resist composition is provided that includes a resin component and an acid generator that is the sulfonate photoacid generator described previously.
The resist composition of the present invention can be classified into a positive type composition and a negative type composition according to the application. In addition to the sulfonate photoacid generator, the positive-type composition generally contains a resin component (B1) that increases solubility in an alkali developer by the action of an acid. During patterning of the composition, acid labile groups in the positive resin in the exposed areas, protected by protecting groups, are deprotected by an acid generated by a photoacid generator to render them soluble in an alkaline developer, upon selective exposure. Thus, the unexposed region pattern remains to form a positive pattern when the alkali development operation is performed. Unlike the positive composition, the negative composition uses a resin-crosslinking agent component (B2) that is crosslinked by an acid and is insoluble in an organic developer. The exposed areas react with the cross-linking agent under the catalysis of acid generated by the photoacid generator to form a polymer insoluble in the organic developer, while the unexposed areas are dissolved and removed by the organic developer to finally form a negative pattern, wherein specific resin components (B1) and resin-cross-linking agent components (B2) can be referred to the specific contents disclosed in paragraphs [0046] to [0076] of the Chinese patent application with application number 202011299973.1, and are not repeated here.
In the positive/negative resist composition, the sulfonate photoacid generator can generate N-O bond fracture under the irradiation of active energy rays to generate sulfonic acid, and the difference of solubility of an exposed area and an unexposed area to a developing solution is realized through a PEB process. The sulfonate photoacid generator product can be used singly or in combination.
The resist composition comprising the sulfonate photoacid generator of the general formula I and the resin component can have sufficiently high resolution and sensitivity even when a fine pattern is formed when used in an alkali developer solution-exposed photosensitive composition, thanks to the properties of the sulfonate photoacid generator of the general formula I in the present application. Meanwhile, the dosage of the auxiliary agent in the resist can be reduced, the diffusion of photoacid molecules can be reduced, and the firmness of the photoetching pattern can be improved.
In one embodiment of the present application, the above 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, a sulfonic acid group; preferably, the acid labile groups are present in an amount of 1 to 80%, preferably 3 to 70%, of the resin component; preferably, the protecting group comprises at least one of the groups of formula (a), formula (b):wherein in formula (a), R 3 Selected from substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Substituted or unsubstituted C 3 ～C 20 Any one or more of cycloalkyl groups of (2), preferably R 3 Selected from substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Substituted or unsubstituted C 3 ～C 10 Is a cycloalkyl group of (C)Further, R is preferably any one or more of 3 Selected from substituted or unsubstituted C 1 ～C 6 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 6 Substituted or unsubstituted C 3 ～C 6 Any one or more of cycloalkyl groups of (2), preferably R 3 The substituents, when present, being selected from halogen, hydroxy, cyano, C 1 ～C 4 Straight chain alkyl, C 3 ～C 5 Preferably, the substituent is selected from any one or more of fluorine atom, methyl and ethyl, preferably R 3 One or more C atoms of (C) may be substituted with any heteroatom in O, S, N or Si; further, R is preferably 3 Selected from methoxy, ethoxy, n-propoxy, n-butoxy, t-butoxy, benzyloxy, 1-methoxyethoxy, 1-ethoxyethoxy,/i>Any one or more of (b) wherein R4 is selected from substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Substituted or unsubstituted C 3 ～C 20 And n is 0 or 1, preferably R 4 Selected from substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Substituted or unsubstituted C 3 ～C 10 Any one or more of cycloalkyl groups of (a), further, R is preferable 4 Selected from substituted or unsubstituted C 1 ～C 6 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 6 Substituted or unsubstituted C 3 ～C 6 Any one or more of cycloalkyl groups of (a); further, R is preferably 4 Any one or more selected from tert-butoxycarbonyl, propoxycarbonyl, adamantyloxycarbonyl and tert-butoxycarbonylmethyl.
The resin component of the above type is preferable in that it is advantageous in that it cooperates with the sulfonate photoacid generator to obtain a firm lithographic pattern.
The amount of the acid generator may be referred to the amount of the conventional acid generator in the prior art, and in one embodiment, the weight content of the acid generator is 0.5 to 5%, preferably 1 to 3%, relative to the mass of the solid content of the resist composition, so that good photosensitivity can be exhibited and the developing effect can be improved.
The solvent is used to dissolve each component in the resist composition to form a uniform solution, and is used to adjust the viscosity and coatability thereof so as to facilitate film formation, and specific solvents may be referred to in the chinese patent application No. 202011299973.1, and optionally, the resist composition may further contain adjuvants conventional in the art, and will not be described herein.
In yet another exemplary embodiment of the present application, a patterning process is provided that includes mixing, film forming, and patterning a resist composition that is a resist composition as described above.
When the resist composition of the present invention is applied, a resin solution obtained by dissolving or dispersing an organic solvent is first applied to a substrate by a spin coating method, then the solvent is volatilized by heating to form a resist film on the substrate, light irradiation (i.e., exposure) is then performed in the shape of a wiring pattern, and then alkali development is performed after heat treatment (PEB) is performed after the exposure to form a wiring pattern.
The drying conditions of the resin solution after the application vary depending on the solvent used, and are preferably carried out at 50 to 150℃for 1 to 30 minutes, that is, the amount (mass percent) of the residual solvent after the drying is appropriately determined.
After forming a resist film on a substrate, the wiring pattern shape is irradiated with light. The light irradiation may be performed using a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halogen lamp, an electron beam irradiation device, an X-ray irradiation device, a laser (such as an argon laser, a dye laser, a nitrogen laser, an LED, a helium cadmium laser), or the like, with a high-pressure mercury lamp and an LED lamp being preferred.
The temperature of the post-exposure heat treatment (PEB) is usually 40 to 200℃and preferably 60 to 150 ℃. If the temperature is less than 40 ℃, the deprotection reaction or the crosslinking reaction cannot be sufficiently performed, and therefore the difference in solubility between the exposed portion and the unexposed portion is insufficient, and a pattern cannot be formed; if the temperature is higher than 200 ℃, there is a problem that productivity is lowered. The heating time is usually 0.5 to 30 minutes.
Development is performed with an alkali developer, and the alkali development method includes the use of an alkali developer. The alkaline developer may be selected from aqueous solutions of 0.1 to 10% by mass of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and the alkaline developer may further comprise water-soluble organic solvents such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, etc. The developing method may be selected from the group consisting of dipping, spraying and spraying, preferably spraying. 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.
In yet another exemplary embodiment of the present application, there is provided the use of the above-described resist composition, including the use of the resist composition in the preparation of protective films, interlayer insulating materials, pattern transfer materials for electronic components.
The above-mentioned application may specifically include forming an interlayer insulating film of a resist composition, a TFT for a liquid crystal display device, a panel; the resist can also be used as a protective film for color filters and spacer columns, and also used as PS photoresist and BCS photoresist for pattern transfer.
Such as, but not limited to, liquid crystal display devices, organic EL display devices, micro-LEDs, mini-LEDs, and quantum dot LED display devices.
The beneficial effects of the present application will be described below with reference to specific examples.
Preparation example of sulfonate photoacid generator
Example 1
200g of toluene, 27.71g of 4-bromo-1, 8-naphthalene dicarboxylic anhydride (S1), 20.49g of 3-ethyl-3- ((2- (vinyl) ethoxy) methyl) oxoalkane, 0.22g of palladium acetate, 0.52g of triphenylphosphine and 11.13g of triethylamine are added into a 500mL four-necked flask under the protection of nitrogen, stirring is started, the temperature is raised to 75-80 ℃, and the reaction is carried out for 6 hours under the heat preservation. After stopping stirring and cooling to room temperature, 100mL of n-hexane was added, stirred for 0.5h, filtered, the filter cake rinsed once with 20g of toluene and the organic phases were combined. The solvent was removed under reduced pressure, and the mixture was dissolved in 100g of DCM, 3g of activated carbon was added thereto, followed by decolorizing with stirring, and after removal of the solvent, 30.10g of intermediate T1-1 was obtained by column chromatography.
100g of water, 19.12g of intermediate T1-1, 4.17g of hydroxylamine hydrochloride and 4.63g of ammonium acetate are added into a 250mL four-necked flask, stirring is started, the temperature is raised to 75-80 ℃, and the reaction is carried out for 3 hours under heat preservation. Stirring was stopped, slightly cooled, filtered while hot, and the filtrate was rinsed with approximately 100g of pure water, and dried to give 13.95g of intermediate T1-2 as a pale yellow solid.
200g of methylene dichloride, 13.95g of intermediate T1-2 and 3.33g of pyridine are added into a 250mL four-necked flask under the protection of nitrogen, the temperature is reduced to 0-5 ℃ after uniform stirring, 11.88g of trifluoromethanesulfonic anhydride is slowly dripped, and the temperature is kept for stirring for 3 hours. 50g of pure water was added, the mixture was stirred for 0.5h, the mixture was separated, the organic phase was concentrated at 55℃under normal pressure until no distillation was performed, and 50g of n-hexane was added for crystallization to obtain 15.25g of sulfonate photoacid generator 34 as a pale yellow solid.
Example 2
Into a 500mL four-necked flask, 250g of tetrahydrofuran, 19.82g of 1, 8-naphthalene dicarboxylic anhydride, 26.66g of aluminum trichloride and 16.15g of 3-ethyl-3- (chloromethyl) -oxoalkane were added, stirring was started, and after stirring uniformly, the temperature was raised to 70℃and the mixture was refluxed for 12 hours. The stirring was stopped, the system was cooled to room temperature, the solvent was removed in vacuo, 100g of pure water and 150g of methylene chloride were added, and the mixture was shaken to separate the solution. The organic phase was concentrated to give 15.56g of intermediate T2-1 as a white solid.
T2-2 is prepared with photoacid 1 by reference to the second and third reactions of example 1.
Example 3
The preparation method of the sulfonate photoacid generator 28 can be referred to in example 1.
Example 4
150g of methanol, 17.62g of intermediate T3-1, 0.15g of 5% Pd/C catalyst and 0.5mL of acetic acid are added into a 250mL stainless steel autoclave, after leak detection and sealing, 1-2 MPa of hydrogen is filled, stirring is started, the temperature is raised to 55-65 ℃, and the temperature is kept for reaction for 6 hours. Stopping stirring and cooling to room temperature. The solvent was removed by filtration under reduced pressure, the mixture was dissolved with 100g of DCM, 3g of activated carbon was added, and the mixture was decolorized with stirring, after which the solvent was removed, 16.35g of intermediate T4-1 was obtained as a white solid by column chromatography.
The preparation of T4-2 and sulfonate photoacid generator 8 can be referred to in the second and third reactions of example 1.
Example 5
200g of 3-ethyl-3-oxabutyl cyclic methanol, 27.71g of 4-bromonaphthalene dimethyl anhydride, 41.46g of potassium carbonate and 0.67g of anhydrous copper chloride are added into a 500mL four-necked flask under the protection of nitrogen, and the mixture is heated, refluxed and stirred for 12 hours, and then the heating is stopped. After room temperature was recovered, filtration was performed, 500g of n-hexane was added to the filtrate, and crystallization was performed at 0℃for 0.5h with stirring. The filter cake was collected by filtration and rinsed with 20mL of n-hexane. The filter cake was dissolved with a small amount of DCM, filtered and purified by column chromatography to finally give 21.55g of intermediate T5-1 as a white solid.
The preparation of T5-2 and sulfonate photoacid generator 15 can be referred to in the second and third reactions of example 1.
Example 6
Under the protection of nitrogen, 20g of 3-ethyl-3-oxabutyl ring methanol and 200mL of THF are added into a 500mL four-necked flask, and the temperature is reduced to 0 ℃ after uniform stirring. NaH was added in portions of 4.80g and the reaction temperature was controlled below 5 ℃. After stirring uniformly, maintaining the temperature at 0 ℃, slowly dripping 17.07g of bromopropyne into the reactor, and slowly heating to room temperature for reaction for 3 hours after dripping. The reaction was stopped, the reaction mixture was concentrated after filtration, and purified by column chromatography to obtain 15.20g of 3-ethyl-3-oxa Ding Huangui propyl ether.
Under the protection of nitrogen, 18.50g of 3-ethyl-3-oxa Ding Huangui propyl ether, 27.71g of 4-bromonaphthalene dimethyl anhydride and 300mL of THF are added into a 500mL four-necked flask, and after uniform stirring, 0.95g of cuprous iodide, 2.62g of triphenylphosphine, 0.70g of bis-triphenylphosphine palladium dichloride and 20.24g of triethylamine are added, and the mixture is stirred for 3 hours after heating is stopped. After restoring to room temperature, the solvent was removed by concentration and purification by column chromatography, 29.78g of intermediate T6-1 was finally obtained as a pale yellow solid.
The preparation of T6-2 and sulfonate photoacid generator 35 can be referred to in the second and third reactions of example 1.
Example 7
Preparation of T6-1, T6-2 can be referred to in example 6.
Into a 500mL four-necked flask, 18.27g of T6-2 and 200mL of methylene dichloride were added, 7.59g of triethylamine was added after stirring and dissolution, and the temperature was lowered to 0℃and pre-cooling was performed for 15 minutes. A total of 10.49g of p-toluenesulfonyl chloride was added to the reactor in portions, and the temperature of the system was controlled to not exceed 5 ℃. After stirring and reacting for 3 hours, ammonia water 100mL is slowly added into the system, and after the system is stable, liquid is separated. The organic phase was washed with 50mL of 0.5M hydrochloric acid and twice with 100mL of water each time. The organic phase was concentrated until a solid precipitated, 200mL of n-hexane was added and stirred for crystallization. After filtration and drying, 20.00g of pale yellow solid which is sulfonate photoacid generator 50 is obtained.
Example 8
Preparation of T6-1, T6-2 can be referred to in example 6. Preparation of sulfonate photoacid generator 52 reference may be made to example 7 substituting butane sulfonyl chloride for the para-toluene sulfonyl chloride starting material.
Referring to the reaction steps similar to examples 1 to 8, examples 9 to 21 respectively replace the substrate and adapt the reaction conditions to obtain the other corresponding sulfonate photoacid generator 2, 11, 13, 14, 18, 21, 24, 25, 27, 29, 32, 36, 39 in sequence.
Example 22
Preparation of sulfonate photoacid generator 49 reference may be made to example 7 substituting p-toluenesulfonyl chloride starting material with suspension camphorsulfonyl chloride.
Example 23
Preparation of sulfonate photoacid generator 51 reference may be made to example 7 substituting p-toluenesulfonyl chloride starting material with propane sulfonyl chloride.
Example 24
Preparation of sulfonate photoacid generator 53 reference may be made to example 7 substituting p-toluenesulfonyl chloride starting material with 2-trifluoromethylbenzenesulfonyl chloride.
Numbering and numbering of the sulfonate photoacid generator prepared in all examples 1 The results of the H NMR characterization are shown in Table 1, respectively.
TABLE 1
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Evaluation of Performance
The sulfonate photoacid generators synthesized in examples 1 to 24 and the sulfonate photoacid generator of comparative example 1 were respectively subjected to performance evaluation, and the evaluation indexes include molar absorptivity, solubility, and chemical stability.
(1) Molar absorption coefficient
The compound was diluted to 0.25mmol/L with acetonitrile, and absorbance was measured at a cuvette length of 1cm using an ultraviolet-visible spectrum photometer (universal spectrum UPG-752) in the range of 200 to 600 nm. The molar absorptivity ε, ε (L. Mol), at each wavelength was calculated from the following equation -1 ·cm -1 ) In the formula, a/(0.00025 mol/l×1 cm), a represents absorbance at each wavelength.
(2) Solubility of
The high solubility not only facilitates purification of the photoacid generator compound, but also allows the photoacid generator compound to be used in a wide range of concentrations in photoresists and different solvent systems. The photoacid generator compound product was taken at 1.0000g and gradually added with the solvent at 25 ℃ until all solids in each test tube were dissolved, the mass of the solvent used was recorded, and the solubility= (1 g/solvent mass) ×100% and the evaluation results are shown in table 2.
TABLE 2
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Wherein the nonionic photoacid generator of comparative example 1 isAnd is denoted as a 1.
As shown by the test results in Table 2, the photoacid generator of the invention has higher molar absorptivity at 365nm, has strong absorptivity, can fully utilize light energy, can ensure higher utilization rate in resist application, and shows good solubility.
Examples of resist compositions
With reference to the formulations shown in resist composition examples 1 to 31 and resist composition comparative examples 1 to 6 in table 3, the respective raw materials were uniformly dissolved in PGMEA (propylene glycol methyl ether acetate) to obtain resist compositions having a solid content concentration of about 20% by mass. Wherein the component types and contents of the sulfonate photoacid generator (A), the resin component (B) and the acid-binding agent triethylamine (C) are shown in Table 3.
Composition example 1
The resin component (B) is B 1 Resins of the type, of the formula B 11 B, B 12 And B is a compound 13 The repeating unit constitution shown, the numerical value at the lower right of each repeating unit represents the content (mass percent) of the repeating unit in the resin. B (B) 1 The weight average molecular weight of the resin was about 10000.
B (B) 11 ：B (B) 12 ：/>B (B) 13 ：/>
The sulfonate photoacid generator (a) was the sulfonate photoacid generator of example 1.
Composition examples 2 to 24
The difference from composition example 1 is that: the sulfonate photoacid generators (a) of examples 2 to 24 were used in this order, respectively.
The remaining component types and amounts are shown in table 3.
Composition example 25
The difference from composition example 5 is that: the resin component (B) is B 2 Resins of the type, of the formula B 21 B, B 22 And B is a compound 23 The repeating units shown are constituted, and the numerical value at the lower right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B (B) 2 The weight average molecular weight of the resin was about 10000.
B (B) 21 ：B (B) 22 ：/>B (B) 23 ：/>
Composition example 26
The difference from composition example 5 is that: the resin component (B) is B 3 Resins of the type, of the formula B 31 And B is a compound 32 The repeating units shown are constituted, and the numerical value at the lower right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B (B) 3 The weight average molecular weight of the resin was about 10000.
B (B) 31 ：B (B) 32 ：/>
Composition examples 27 to 28
The difference from composition example 5 is that: the content of the sulfonate photoacid generator is different.
Composition example 29
The difference from composition example 5 is that: no acid binding agent was added.
Composition example 30
The difference from composition example 6 is that: no acid binding agent was added.
Composition example 31
The difference from composition example 7 is that: no acid binding agent was added.
Comparative composition example 1
The difference from composition example 5 is that: sulfonate photoacid generator a 1 of comparative example 1 was used.
Comparative composition example 2
The difference from composition example 6 is that: sulfonate photoacid generator a 1 of comparative example 1 was used.
Comparative composition example 3
The difference from composition example 7 is that: sulfonate photoacid generator a 1 of comparative example 1 was used.
Composition comparative example 4
The difference from comparative composition 1 is that: no acid binding agent was added.
Comparative example 5 of composition
The difference from comparative composition 2 is that: no acid binding agent was added.
Composition comparative example 6
The difference from comparative composition 3 is that: no acid binding agent was added.
The resist compositions prepared in composition examples 1 to 31 and composition comparative examples 1 to 6 were evaluated for sensitivity and resolution by the following methods, and the results are recorded in table 3.
(1) Sensitivity evaluation
The resist compositions of examples and comparative examples were applied to each silicon wafer at a film thickness of 1 μm, which enables patterning, to form a coating film. The formed coating film was prebaked at 90℃for 100 seconds. After prebaking, the exposure amount (exposure wavelength 365 nm) was gradually changed whileThe coating film was exposed to light through a mask for hole pattern formation having a diameter of 10 μm, and then developed with a 2.0% aqueous solution of tetramethylammonium hydroxide at 25℃for 30 seconds. The minimum exposure required to form a 10 μm diameter hole pattern was determined by the method described above. From the minimum exposure value obtained, the sensitivity was evaluated according to the following criteria: "good" indicates a sensitivity of-50 mJ/cm 2 Hereinafter, "×" means that the sensitivity is-300 mJ/cm 2 The above.
(2) Evaluation of resolution
A mask for forming a hole pattern having a diameter of 5 μm was used except for 100mJ/cm 2 The film was formed in the same manner as in the sensitivity evaluation except that the exposure was performed, and the film was exposed and developed. The developed coating film was observed, and the resolution was evaluated according to the following criteria: "good" indicates that a pattern having a diameter of 5 μm could be formed, and "good" indicates that a pattern having a diameter of 5 μm could not be formed.
TABLE 3 Table 3
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As can be seen from the results of Table 3, the resist compositions of the present invention as shown in composition examples 1 to 28 have very good photosensitivity and resolution, which are significantly superior to those of composition comparative examples 1 to 3. Composition examples 29 to 31 showed that the resolution was still very good without the acid-binding agent, but the compositions of comparative examples 4 to 6, which also did not add the acid-binding agent, showed general resolution.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
the molecule of the sulfonate photoacid generator with the general formula I contains sulfonate groups, the sulfonate groups are directly connected with imide structures, the structures have photosensitive cleavage characteristics, and N-O bond cleavage can be generated under the irradiation of active energy rays to generate different types of sulfonic acids. The active energy ray is an active energy ray having a wavelength of 300 to 450nm in the near ultraviolet region and the visible light region, and particularly has high sensitivity and strong absorption to an active energy ray having a wavelength of 365nm (i-line), and when a resist composition comprising the sulfonate photoacid generator and a resin component is used in an alkali developer for dissolution exposure of a photosensitive composition, a pattern having excellent sensitivity and good contrast can be formed due to the improvement of the sensitivity of the sulfonate photoacid generator, and even if a fine pattern is formed, a sufficiently high resolution and sensitivity can be obtained. Meanwhile, the substituent group of the sulfonate photoacid generator contains an epoxy group structure, and the sulfonate photoacid generator can open a loop under the conditions of acidity and high temperature, and does not open a loop under the conditions of neutrality and high temperature, so that the sulfonate photoacid generator is beneficial to reducing the dosage of auxiliary agents in a resist, reducing the diffusion of photoacid molecules and improving the firmness of photoetching patterns.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. The sulfonate photoacid generator is characterized by having the following general formula (I):
wherein R is 1 Selected from substituted or unsubstituted C 2 ～C 25 Substituted or unsubstituted C 2 ～C 25 Alkoxy, substituted or unsubstituted C 2 ～C 25 In alkylthio groups of (C)Of any one of (C), wherein-CH 2 Optionally interrupted by-O-, -S-, -CO-, -O-CO-, or-COO-substitution, wherein the C atom is optionally substituted with an N atom, and the substituted or unsubstituted C 2 ～C 25 Is a hydrocarbon group of (C), said substituted or unsubstituted C 2 ～C 25 Alkoxy, said substituted or unsubstituted C 2 ～C 25 Containing at least one substituted or unsubstituted C at the end of the alkylthio group 2 ～C 10 An epoxy group of (2);
R 2 selected from C 1 ～C 20 Alkyl, C of (2) 6 ～C 18 Any one of substituted or unsubstituted aryl, camphoryl, camphorquinone, and azidonadone groups.
2. The sulfonate photoacid generator of claim 1, wherein the substituted or unsubstituted C 2 ～C 25 Is selected from the group consisting of substituted and unsubstituted C 2 ～C 25 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 25 Branched alkyl, substituted or unsubstituted C 4 ～C 25 Alkenyl, substituted or unsubstituted C 4 ～C 25 Any one of the alkynyl groups of (a);
preferably said R 1 Selected from substituted or unsubstituted C 6 ～C 17 Branched alkyl, substituted or unsubstituted C 9 ～C 16 Alkenyl, substituted or unsubstituted C 9 ～C 18 Alkynyl, substituted or unsubstituted C 6 ～C 17 Alkoxy, substituted or unsubstituted C 6 ～C 15 Any one of alkylthio groups of (2);
further, it is preferable that the substituted or unsubstituted C 6 ～C 17 Is selected from branched alkyl groups of Any one of them;
preferably said substituted or unsubstituted C 9 ～C 16 Alkenyl groups of (2) are selected from Any one of them;
preferably said substituted or unsubstituted C 9 ～C 18 Alkynyl groups of (2) are selected from Any one of them;
preferably said substituted or unsubstituted C 6 ～C 17 Alkoxy groups of (2) are selected fromAny one of them;
preferably said substituted or unsubstituted C 6 ～C 15 Alkylthio of (2) is selected from Wherein "×" is the R 1 And a position connected with the naphthalene ring of the sulfonate photoacid generator.
3. The sulfonate photoacid generator of claim 1, wherein the epoxy group is C 2 ～C 5 Preferably selected from the group consisting of epoxy groupsAny one of, further, preferably +.>
4. A sulfonate photoacid generator according to any one of claims 1 to 3, wherein R 2 In the above, the C 1 ～C 20 Is selected from substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted C 3 ～C 20 Any one of cycloalkyl groups of (a);
preferably said R 2 Selected from C 1 ～C 10 Alkyl, C of (2) 6 ～C 10 Substituted or unsubstituted aryl, substituted or unsubstituted C 3 ～C 10 Any one of cycloalkyl, camphoryl, camphorquinone, azidonaphthyl, and the like;
further, it is preferable that R 2 Selected from substituted or unsubstituted C 1 ～C 8 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 8 Branched alkyl, substituted or unsubstituted C 3 ～C 5 Cycloalkyl, substituted or unsubstituted phenyl, camphoryl, camphorquinone, azido, naphthacene groupAny one of them;
further, it is preferable that R 2 The substituent in (a) is a halogen atom, and further, preferably a fluorine atom; still further, it is preferable that R 2 Selected from C 1 ～C 4 Linear perfluoroalkyl groups, C 1 ～C 4 Straight chain alkyl, C 3 ～C 6 Branched perfluoroalkyl, perfluorophenyl, C 1 ～C 4 Perfluoroalkyl-substituted phenyl, C 1 ～C 4 Any one of alkyl-substituted phenyl, camphoryl, camphorquinone, azidonaphthyl, ketone groups; preferably said R 2 Any one selected from trifluoromethyl, perfluorobutyl, n-propyl, n-butyl, camphoryl, p-tolyl and o-trifluoromethylphenyl.
5. A sulfonate photoacid generator according to any one of claims 1 to 3, wherein the sulfonate photoacid generator has a structural formula selected from
Any one or more of the following.
6. A process for the preparation of a sulfonate photoacid generator as defined in any one of claims 1 to 5, comprising:
step S1, compounds 1 and R 1′ Y reacts to generate a compound 2;
step S2, carrying out hydroxylamine amination reaction on the compound 2 and hydroxylamine hydrochloride or hydroxylamine sulfate to generate a hydroxylamine compound;
step S3, mixing the hydroxylamine compound with R 2 SO 2 X 2 Or (R) 2 SO 2 ) 2 O is subjected to esterification reaction to obtain the sulfonate photoacid generator;
the structural formulas of the compound 1 and the compound 2 are as follows:
wherein X is 1 Is selected from any one of-H, -OH, -SH and halogen atoms, and Y is selected from-OH, -CH=CH 2 Any one of-C.ident.CH and halogen atoms, X 2 Is a halogen atom, R 1′ Y is identical to X in Compound 1 1 The substituents react to form R 1 Substituent, when Y is a halogen atom, R 1 ＝R 1′ When Y is OH, R 1 ＝R 1′ -O-, when Y is-ch=ch 2 When R is 1 ＝R 1’ -ch=ch-, when Y is-c≡ch, R 1 ＝R 1’ -C≡C-，R 1 、R 2 R as claimed in any one of claims 1 to 5 1 、R 2 。
7. A resist composition comprising a resin component and an acid generator, wherein the acid generator is the sulfonate photoacid generator as claimed in any one of claims 1 to 5.
8. The resist composition according to claim 7, wherein the 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, a sulfonic acid group; preferably, the acid labile groups are present in an amount of 1 to 80%, preferably 3 to 70%, of the resin component;
preferably, the protecting group includes at least one of the groups represented by formula (a) and formula (b):
wherein in the formula (a), R 3 Selected from substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Substituted or unsubstituted C 3 ～C 20 Any one or more of cycloalkyl groups of (c), preferably R 3 Selected from substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Substituted or unsubstituted C 3 ～C 10 Any one or more of cycloalkyl groups of (c), further, preferably, said R 3 Selected from substituted or unsubstituted C 1 ～C 6 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 6 Substituted or unsubstituted C 3 ～C 6 Any one or more of cycloalkyl groups of (c), preferably R 3 The substituents, when present, being selected from halogen, hydroxy, cyano, C 1 ～C 4 Straight chain alkyl, C 3 ～C 5 Preferably, the substituent is selected from any one or more of fluorine atom, methyl and ethyl, preferably, the R 3 One or more C atoms of (C) may be substituted with any heteroatom in O, S, N or Si; further, it is preferable that R 3 Selected from methoxy, ethoxy, n-propoxy, n-butoxy, t-butoxy, benzyloxy, 1-methoxyethoxyRadical, 1-ethoxyethoxy,Any one or more of the above,
in the formula (b), R 4 Selected from substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Substituted or unsubstituted C 3 ～C 20 And n is 0 or 1, preferably said R4 is selected from substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Substituted or unsubstituted C 3 ～C 10 Any one or more of cycloalkyl groups of (c), further, preferably, said R 4 Selected from substituted or unsubstituted C 1 ～C 6 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 6 Substituted or unsubstituted C 3 ～C 6 Any one or more of cycloalkyl groups of (a); further, it is preferable that R 4 Any one or more selected from tert-butoxycarbonyl, propoxycarbonyl, adamantyloxycarbonyl and tert-butoxycarbonylmethyl.
9. Resist composition according to claim 7 or 8, characterized in that the weight content of the acid generator is 0.01 to 5%, preferably 0.1 to 3%, relative to the mass of the solid components of the resist composition, preferably the resist composition further comprises a solvent.
10. A patterning process comprising mixing, film forming and patterning a resist composition, wherein the resist composition is as claimed in any one of claims 7 to 9.
11. Use of a resist composition as claimed in any one of claims 7 to 9, comprising the use of the resist composition in the preparation of protective films, interlayer insulating materials, pattern transfer materials for electronic components.
CN202211038021.3A 2022-08-26 2022-08-26 Sulfonate photoacid generator, preparation method thereof, patterning method, resist composition and application thereof Pending CN117658997A (en)

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