Sulfonate photoacid generator, preparation method therefor and use thereof

Abstract

Provided in the present application are a sulfonate photoacid generator, a preparation method therefor and the use thereof. The sulfonate photoacid generator has a structure as shown in general formula (I). The photoacid generator of the present application does not contain fluorine, and the acidity of sulfonic acid generated by photolysis thereof is not weaker than that of traditional fluorine-containing photoacids. The present invention solves the problems of acid groups containing fluorine and fluorine-free acid groups having low acidity of existing sulfonate photoacid generators, and the sulfonate photoacid generator of the present application can improve the photosensitivity and image resolution of photosensitive compositions.

Description

Sulfonate photoacid generator and preparation method and application thereof TECHNICAL FIELD The application belongs to the technical field of photosensitive materials, and relates to a sulfonate photoacid generator and a preparation method and application thereof. BACKGROUND A photoacid generator is one of the key components of a chemical amplification type photoresist, and its structure and performance have a great influence on the lithographic image. With the development of the semiconductor industry, people's demand for high-fineness patterns is growing, and higher requirements are put forward for the expansion of the types of photoacid generators and the performance of photoacid generators, especially the low diffusion, high solubility, high acid yield and other characteristics. Although sulfonate compounds of naphthalene anhydride have been widely known as photo-initiators in the semiconductor field, most of the current resist formulations need to add additives to inhibit acid migration or enhance pattern firmness. CN104822662B provides a photosensitive resin composition, which comprises a resin component and an acid generator. The acid generator is a sulfonimide photoacid generator, and the sulfonimide photoacid generator has the following structure: The molecule of the above-mentioned acid generator contains a sulfonate group, which is directly connected with an imide structure. The structure has photosensitive cleavage, and can produce sulfonic acid under the irradiation of active energy rays. However, the sulfonic acid produced by the above-mentioned structure is fluorine-containing super strong sulfonic acid and non-fluorine-containing sulfonic acid. The fluorine-containing sulfonic acid involves the PFAS (PFAS is a perfluoroalkyl substance, which is used in various consumer and industrial products. PFAS is not easy to decompose, and some types have been proved to accumulate in the environment and people's bodies. Contact with some types of PFAS may have serious health effects) problem, and the non-fluorine-containing sulfonic acid is too weak. CN116249937A provides a photosensitive resin composition, which comprises a resin component and an acid generator. The acid generator is a sulfonimide photoacid generator, and the sulfonimide photoacid generator has the following structure: The molecule of the above-mentioned acid generator contains a sulfonate group, which is directly connected with an imide structure. The structure has photosensitive cleavage, and can produce sulfonic acid under the irradiation of active energy rays. However, the sulfonic acid produced by the above-mentioned structure is fluorine-containing super strong sulfonic acid and non-fluorine-containing sulfonic acid. The fluorine-containing sulfonic acid involves the PFAS problem, and the non-fluorine-containing sulfonic acid is too weak. SUMMARY The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims. In view of the deficiencies of the prior art, the purpose of the present application is to provide a sulfonate photoacid generator and a preparation method and application thereof. The photoacid generator of the present application does not contain fluorine, and the sulfonic acid generated by photolysis is not weaker than the traditional fluorine-containing photoacid. The present application can solve the problem that the existing sulfonate photoacid generator contains fluorine in the acid radical, and the acid radical without fluorine is weak, and the sulfonate photoacid generator of the present application can improve the photosensitivity and resolution of the photosensitive composition. To achieve this purpose, the present application adopts the following technical solutions: In one aspect, the present application provides a sulfonate photoacid generator, which has the following general formula (I): wherein R1 and R2 are each independently selected from a substituted or unsubstituted C2-C 12 (eg C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 or C 12 ) olefin group, C1-C 12 (eg C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 or C 12 ) alkyl group or (aromatic hydrocarbon); R1 and R2 are the same or different; wherein R 11 -R 15 are each independently selected from hydrogen, other halogen atoms except fluorine atom, nitro group, cyano group, substituted or unsubstituted C2-C 25 olefin group, C2-C 25 alkyl group, C2-C 25 alkoxy group, C2-C 25 alkylthio group; or at least one -CH2- in the substituted or unsubstituted C2-C 25 olefin group, C2-C 25 alkyl group, C2-C 25 alkoxy group, C2-C 25 alkylthio group is replaced by -O-, -S-, -CO-, -O-CO- or -COO-; or at least one -CH3 in the substituted or unsubstituted C2-C 25 hydrocarbon group, C2-C 25 alkyl group, C2-C 25 alkoxy group, C2-C 25 alkylthio group is replaced by -SiMe3, -OH, cycloalkyl group; X is -CH2-, a carbonyl or an ester group, m is an integer from 0 to 4 (e.g. 0, 1, 2, 3 or 4); n is an integer from 0 to 2 (e.g. 0, 1 or 2). In the present application, when m is 0, it means The group is a straight chain group without cycloalkyl group, i.e. it is In the present application, the group defines the range of the number of carbon atoms, which means that the number of carbon atoms can be any integer within the defined range, for example, C2-C12 means that it can be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 or C12, and so on. Further, when R1, R2 are independently selected from substituted or unsubstituted C3-C12 alkenyl or C1-C12 alkyl, the C3-C12 alkenyl can be selected from n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl, n-undecenyl and n-dodecenyl, and so on; the C1-C12 alkyl can be selected from methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, iso-propyl, t-butyl, sec-hexyl, and so on. 12 The alkyl group can be selected from methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, iso-propyl, t-butyl, sec-hexyl, and so on. When R1 and R2 are aromatic hydrocarbons, In the present application, R 11 to R 15 The optional number of nitro groups can be an integer from 0 to 4, wherein, other than nitro or cyano, any one can be selected from hydrogen atom, halogen atom other than fluorine atom, substituted or unsubstituted C2-C 25 alkenyl group, C2-C 25 alkyl group, substituted or unsubstituted C2-C 25 alkoxy group, substituted or unsubstituted C2-C 25 alkylthio group; R 11 -R 15 The optional number of cyano groups can be an integer from 0 to 4, wherein, other than nitro or cyano, any one can be selected from hydrogen atom, halogen atom other than fluorine atom, substituted or unsubstituted C2-C 25 alkenyl group, C2-C 25 alkyl group, substituted or unsubstituted C2-C 25 alkoxy group, substituted or unsubstituted C2-C 25 alkylthio group. In the present application, the substituents in the substituted or unsubstituted group are selected from hydrogen, methyl, ethyl, iso-propyl, t-butyl, methoxy, butoxy, nitro or cyano. The sulfonic acid ester photoacid generator of the present application has a sulfonic acid ester group directly connected to an imine structure, which has a photosensitive cleavage property and can undergo N-O bond cleavage to generate different types of sulfonic acids under irradiation of active energy rays. The active energy rays are active energy rays having a wavelength of 300 to 450 nm in the near-ultraviolet region or the visible region, and in particular, active energy rays having a wavelength of 365 nm (i-line). The sulfonic acid ester photoacid generator having the structure of Formula (I) has strong absorption and high sensitivity and solubility to the active energy rays, and is easy to synthesize. When an antireflective agent composition including the sulfonic acid ester photoacid generator and a resin component is used for dissolving a photosensitive composition exposed to light with an alkali developer, an excellent sensitivity and a good contrast can be obtained due to the improvement of the photosensitivity of the sulfonic acid ester photoacid generator, and even when a fine pattern is formed, a resolution and a sensitivity can be sufficiently high. At the same time, the sulfonic acid ester photoacid generator of the present application has improved ultraviolet absorption intensity at 365 nm, sensitivity, solubility, and acid strength compared to conventional naphthalimide sulfonic acid ester photoacids. In one embodiment, R1and R2are alkyl or alkenyl groups, optionally having a carbon chain length of 1 to 4 C lengths (e.g., 1, 2, 3, or 4). In one embodiment, R1and R2are independently selected from the group consisting of n-butyl, In one embodiment, R1and R2are independently selected from the group consisting of methyl, ethyl, vinyl, phenyl, cyano-substituted phenyl, nitro-substituted phenyl, chloro-substituted phenyl, C1-C8 alkyl-substituted phenyl, C1-C8 alkoxy-substituted phenyl, C1-C8 alkylthio-substituted phenyl. In one embodiment, R1and R2are independently selected from the group consisting of methyl, ethyl, vinyl, phenyl, In one embodiment, the sulfonic acid ester photoacid generator is selected from any one of the following compounds In another aspect, the present application provides a method of preparing the sulfonic acid ester photoacid generator as described above, the method comprising the steps of: Step S1, reacting a compound 1 with a cycloalkyl borate compound to produce a compound 2; Step S2, subjecting the compound 2 to a hydroxylamine reaction with a hydroxylamine reagent to produce a hydroxylamine compound 3; Step S3, esterification reaction of hydroxylamine compound 3 with compound 4 to obtain a sulfonic acid ester type photoacid generator; The structural formula of compound 1, compound 2, compound 3 and compound 4 is as follows: Wherein, R1, R2, X, m and n have the same definition as in claim 1. X1is selected from any one of -H and halogen atom. In the above step S1, 4-substituted naphthalene anhydride (compound 1) can be subjected to Suzuki coupling reaction with cycloalkyl borate to obtain 4-substituted naphthalene anhydride (compound 2), wherein the cycloalkyl borate can be prepared by coupling cycloalkyl halide with borate. In one embodiment, the molar ratio of compound 1 to cycloalkyl borate compound in step S1 is 1:1.20-1.30, for example 1:1.2, 1:1.23, 1:1.25, 1:1.28 or 1:1.30. In one embodiment, the temperature of the reaction in step S1 is 75-80℃, for example 75℃, 77℃, 79℃ or 80℃, and the reaction time is 6-8h, for example 6h, 6.5h, 6.8h, 7h, 7.5h, 7.8h or 8h. In one embodiment, the reaction in step S1 is carried out in a solvent selected from any one of toluene, tetrahydrofuran or xylene or a combination of at least two thereof. In the present application, the cycloalkyl borate compound in step S1 is prepared by the following method: Prepared by the following method: Compound A is reacted with compound B to obtain the cycloalkyl borate compound, and the reaction formula is as follows: In one embodiment, the molar ratio of compound A to compound B is 1.00:1.20-1.00:1.30, for example 1:1.20, 1:1.22, 1:1.25, 1:1.28 or 1:1.30. In one embodiment, the reaction of compound A with compound B is carried out in the presence of a basic substance. In one embodiment, the basic substance is selected from any one of potassium acetate, potassium phosphate, ammonium acetate or potassium carbonate or a combination of at least two thereof. In one embodiment, the reaction of compound A with compound B is carried out in the presence of a phosphine ligand and a palladium catalyst. In one embodiment, the phosphine ligand is tris(o-tolyl)phosphine (P-(o-tol)3), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), palladium dichloride bis(triphenylphosphine) (PdCl2(PPh3)2); the palladium catalyst is tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), palladium dichloride bis(triphenylphosphine) (PdCl2(PPh3)2), bis(tris(dibenzylideneacetone)dipalladium (Pd2(dba)3). In one embodiment, the reaction of compound A and compound B is carried out in an organic solvent, preferably toluene. In one embodiment, the reaction of compound A and compound B is carried out at a temperature of 100-120°C, for example 100°C, 105°C, 108°C, 110°C, 115°C, 118°C or 120°C, for a time period of 5-8 hours, for example 5 hours, 6 hours, 7 hours or 8 hours. In one embodiment, the hydroxylamination reaction of step S2 is carried out under basic or acidic conditions. In one embodiment, the hydroxylamination reagent of step S2 is hydroxylamine sulfate or hydroxylamine hydrochloride. In one embodiment, the hydroxylamination reaction of step S2 is carried out at a temperature of 25-100°C, for example 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C or 100°C, further optionally 75-100°C, which is further conducive to improving the efficiency of the hydroxylamination reaction. In one embodiment, in step S3, the esterification reaction of hydroxylamine compound 3 and compound 4 is carried out under basic conditions in an inert solvent. In one embodiment, the basic conditions are carried out in the presence of any one or a combination of at least two of pyridine, N-methylpyrrolidine, ethylenediamine, piperidine or triethylamine. In one embodiment, the inert solvent is selected from any one or a combination of at least two of dichloromethane, n-heptane, n-octane, tetrahydrofuran, ethyl acetate, n-butyl propionate, isopropyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,4-dioxane, acetonitrile or N,N-dimethylformamide. In one embodiment, the esterification reaction of step S3 is carried out at a temperature of -10-60°C, for example -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C, further optionally 0-25°C, which is further conducive to improving the efficiency of the esterification reaction. In one embodiment, the time for the esterification reaction of step S3 is 2-4h, for example 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h. In the present application, compound 4 can be obtained by the following reaction, and compounds C and D can be obtained by commercial purchase. In one embodiment, R1 and R2 are consistent with R1 and R2 described above. In one embodiment, the molar ratio of the compound C and the compound D is 1:1.0-1:1.2, for example 1:1.0, 1:1.1, 1:1.15, 1:1.18 or 1:1.2. In one embodiment, the reaction of the compound C and the compound D is carried out in the presence of a weakly basic substance. In one embodiment, the weakly basic substance is selected from any one or more of triethylamine, diisopropylethylamine, pyridine, DMF or diethylamine. In one embodiment, the time for the reaction of the compound C and the compound D is 0.5-2h, for example 0.5h, 1h, 1.5h or 2h. In one embodiment, the temperature for the reaction of the compound C and the compound D is controlled between -10-60℃, for example -10℃, -5℃, 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃ or 60℃, and further optionally 0-25℃, so as to be more conducive to improving the efficiency of the substitution reaction. In addition, the raw materials and reagents used in the above preparation method are all known compounds in the prior art, which can be obtained by commercial purchase or conveniently prepared by known processes, and will not be described here. The sulfonic acid ester photoacid generator of the present application can be used for any known use of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, resists for MEMS, materials for stereolithography and microstereolithography, etc. Among them, as a photoacid generator in a resist composition, it can be prepared together with a resin having an acid dissociable group and applied to semiconductor lithography as a resist. The present application also provides a resist composition comprising a resin component and an acid generator, and the acid generator is the sulfonic acid ester photoacid generator as described above. The resist composition of the present application can be classified into a positive composition and a negative composition according to the application. In addition to the sulfonic acid ester photoacid generator, the positive composition generally contains a resin component (B1) that increases the solubility to the alkali developer via the action of the acid. In the composition pattern forming process, the acid-labile group protected by the protecting group in the positive resin in the exposed area is deprotected under the action of the acid generated by the photoacid generator upon selective exposure, so as to be soluble to the alkali developer. Therefore, when the alkali developing operation is performed, the unexposed area pattern remains, forming a positive pattern. Unlike the positive composition, the negative composition uses a resin-crosslinker component (B2) that is insoluble in the organic developer upon crosslinking under the action of the acid. The resin and the crosslinker react to form a polymer insoluble in the organic developer under the catalysis of the acid generated by the photoacid generator in the exposed area, so as to remain, while the unexposed area is dissolved and removed by the organic developer, finally forming a negative pattern. The specific resin component (B1), resin-crosslinker component (B2) can refer to the description of the Chinese patent application No. 202011299973.1.

[0046] to

[0076] The specific content disclosed in the section is not repeated here. In the positive / negative resist composition of the present application, the sulfonic acid ester photoacid generator can undergo N-O bond cleavage to generate sulfonic acid under the irradiation of active energy rays, and the difference in solubility to the developer between the exposed area and the unexposed area is realized through the PEB process. The sulfonic acid ester photoacid generator product can be used alone or in a mixture of two or more. Thanks to the performance of the sulfonic acid ester photoacid generator with the general formula I in the present application, when the resist composition including the sulfonic acid ester photoacid generator and the resin component is used for the alkali developer dissolution exposure photosensitive composition, even if a fine pattern is formed, it can also have sufficiently high resolution and sensitivity. At the same time, due to the improvement of the sensitivity, the amount of the photoinitiator in the resist can be reduced. In one embodiment, 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, or a sulfonic acid group; in one embodiment, the content of the acid-labile group is 1-80 wt% (for example 1%, 3%, 5%, 8%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%) of the content of the resin component, preferably 3-70 wt%; in one embodiment, the protecting group includes at least one of the groups represented by formula (a), formula (b): wherein, in formula (a), R 6Selected from one or a combination of at least two of the following: substituted or unsubstituted C1-C20 straight-chain alkyl groups, substituted or unsubstituted C3-C20 branched-chain alkyl groups, and substituted or unsubstituted C3-C20 cycloalkyl groups. Preferred R 6 Selected from any one or a combination of at least two of the following: substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched alkyl, and substituted or unsubstituted C3-C10 cycloalkyl. In one further implementation, R 6 The R8 is selected from any one or more of substituted or unsubstituted C1-C6 straight-chain alkyl groups, substituted or unsubstituted C3-C6 branched alkyl groups, and substituted or unsubstituted C3-C6 cycloalkyl groups. Preferably, when R8 has a substituent, the substituent is selected from any one or a combination of at least two of halogen, hydroxyl, cyano, C1-C4 straight-chain alkyl groups, and C3-C5 branched alkyl groups. Preferably, the substituent is selected from any one or a combination of at least two of fluorine, methyl, and ethyl groups. Preferably, one or more C atoms in R8 can be substituted by any heteroatom selected from O, S, N, or Si. Further, preferably, R8 is selected from methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, benzyloxy, 1-methoxyethoxy, 1-ethoxyethoxy, or... One or at least two of them, In equation (b), R 7 The alkyl group is selected from any one or a combination of at least two of substituted or unsubstituted C1-C20 straight-chain alkyl groups, substituted or unsubstituted C3-C20 branched-chain alkyl groups, and substituted or unsubstituted C3-C20 cycloalkyl groups, and n is 0 or 1. Preferably, R9 is selected from any one or a combination of at least two of substituted or unsubstituted C1-C10 straight-chain alkyl groups, substituted or unsubstituted C3-C10 branched-chain alkyl groups, and substituted or unsubstituted C3-C10 cycloalkyl groups. Further, preferably, R9 is selected from any one or a combination of at least two of substituted or unsubstituted C1-C6 straight-chain alkyl groups, substituted or unsubstituted C3-C6 branched-chain alkyl groups, and substituted or unsubstituted C3-C6 cycloalkyl groups. Further, preferably R... 7 The resin is selected from any one or a combination of at least two of tert-butoxycarbonyl, propoxycarbonyl, adamantoxycarbonyl, and tert-butoxycarbonylmethyl. Preferred resin components of the above types are beneficial for their synergistic effect with sulfonate photoacid generators, resulting in good photolithographic patterns. The amount of the acid generator can be the same as that of a conventional acid generator, and the amount of the acid generator can be 0.01 to 5% by weight, for example, 0.01%, 0.1%, 0.5%, 1%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 4.8%, or 5%, preferably 0.1 to 3% by weight, based on the mass of the solid content of the resist composition, so that a good photosensitivity and development can be obtained. The resist composition preferably further includes a solvent. 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 so as to facilitate film formation. The specific solvent can be the same as that described in the Chinese patent application No. 202011299973.1, and the resist composition can further include a conventional additive in the field, which is not described herein. In another aspect, the present application provides a patterning method, which includes film formation and patterning treatment using the resist composition as described above. When the resist composition of the present application is used, a resin solution dissolved or dispersed in an organic solvent is first applied to a substrate using, for example, a spin coating method, and then heated to volatilize the solvent, so that a resist film is formed on the substrate. Then, light irradiation (i.e., exposure) in a wiring pattern shape is performed, followed by a heating treatment (PEB) after exposure, and then an alkaline development, so that a wiring pattern is formed. The drying conditions of the applied resin solution are different depending on the solvent used, and are preferably performed at 50 to 150°C (50°C, 70°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C) for 1 to 30 minutes (for example, 1 minute, 3 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes), which is appropriately determined by the amount of residual solvent (mass percentage) after drying, and the like. After the resist film is formed on the substrate, light irradiation in a wiring pattern shape is performed. The light irradiation can use 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 halide 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), and the like, and is preferably a high-pressure mercury lamp and an LED lamp. The temperature of the heating treatment (PEB) after exposure is usually 40 to 200°C, and is preferably 60 to 150°C. If it is less than 40°C, the deprotection reaction or the crosslinking reaction cannot be sufficiently performed, and thus the difference in solubility between the exposed portion and the unexposed portion is insufficient, and a pattern cannot be formed. If it is higher than 200°C, there is a problem of reduced productivity. The heating time is usually 0.5 to 30 minutes. The development is carried out with an alkali developing solution, and the alkali developing method includes using an alkali developing agent. The alkali developing agent can be selected from a water solution of 0.1-10% (mass percentage) tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and can further include a water-soluble organic solvent such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methyl pyrrolidone, etc. The developing method can be selected from dipping, spraying and spraying, and the spraying is preferred. The temperature of the developing agent is preferably used at 25-40°C, and the developing time is appropriately determined according to the thickness of the resist film, and finally a pattern corresponding to the mask is obtained. In another aspect, the application also provides a sulfonic acid ester photoacid generator or resist composition as described above for use in the preparation of a protective film, interlayer insulating material or pattern transfer material for electronic components. The above use can specifically include forming an interlayer insulating film of the resist composition for TFT, panel of liquid crystal display device, and can also be used as a protective film for color filter, spacer, and as a PS photoresist, BCS photoresist for pattern transfer. Compared with the prior art, the application has the following beneficial effects: The photoacid generator of the application does not contain fluorine, and the sulfonic acid generated by photolysis is not weaker than the traditional fluorine-containing photoacid. The sulfonic acid ester photoacid generator of the application can improve the photosensitivity and resolution of the photosensitive composition. Other aspects can be apparent after reading and understanding the detailed description. DETAILED DESCRIPTION The technical solutions of the application are further illustrated by specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the application, and should not be regarded as specific limitations on the application. Example 1 The present embodiment provides a sulfonic acid ester photoacid generator, and its preparation process is as follows: Under nitrogen protection, 200g of toluene, bromomethylcyclopropane 17.13g, pinacol diborane 32.23g, Pd2(dba)3 0.58g, potassium acetate 47.36g, x-phos 1.82g were added into a 500mL four-necked flask (with a condenser), and the oil bath was stirred to warm up to 110°C, and then refluxed for 6h. The temperature was lowered to 50°C, 100g of water was added, stirred for 10min, and then the water was removed. Activated carbon (878) 3.0g was added, decolorized, and washed with water twice (100g of water was used each time, and the water washing temperature was 20-30°C). After removing the solvent, 9.55g of cyclopropyl methyl borate was obtained by column. In a 500 mL four-necked flask, 200 g of toluene, 27.71 g of 4-bromo-1,8-naphthalic anhydride (S1), 18.21 g of cyclopropyl methyl borate, 0.22 g of palladium acetate, 0.52 g of triphenylphosphine, 11.13 g of triethylamine, and nitrogen protection were added, stirring was started, and the temperature was raised to 75-80°C, and reaction was carried out for 6 hours. After stopping the stirring, the temperature was lowered to room temperature, 100 mL of n-hexane was added, stirring was carried out for 0.5 hours, filtration was carried out, the filter cake was rinsed once with 20 g of toluene, and the organic phases were combined. The solvent was removed under reduced pressure, 100 g of dichloromethane (DCM) was added to the mixture, 3 g of activated carbon was added, stirring was carried out for decolorization, the solvent was removed, and 22.90 g of intermediate T1-1 was obtained by column chromatography. In a 250 mL four-necked flask, 100 g of water, 19.12 g of intermediate T1-1, 4.17 g of hydroxylamine hydrochloride, and 4.63 g of ammonium acetate were added, stirring was started, and the temperature was raised to 75-80°C, and reaction was carried out for 3 hours. After stopping the stirring, the temperature was slightly lowered, hot filtration was carried out, the filter cake was rinsed with about 100 g of pure water, and 12.95 g of intermediate T1-2 was obtained as a light yellow solid after drying. Under nitrogen protection, N-fluorosulfonamide (10 g, 0.079 mol), NaH (3.16 g, 0.079 mol), THF 50 mL were stirred uniformly in a 250 mL four-necked flask, and ethanesulfonyl chloride (10.2 g, 0.079 mol) was slowly added dropwise. After the dropwise addition was completed, the ice bath was removed, and reaction was carried out at room temperature for 4 hours. After stopping the stirring, 25 mL of a quenching agent was added, and the mixture was extracted with 50 mL of dichloromethane three times. The organic phases were collected, concentrated and dried to obtain 13.4 g of a light transparent oil. Under nitrogen protection, hydroxide (10.00 g, 0.0469 mol), N-fluorobisethyl sulfonamide (14.80 g, 0.0469 mol), 240 mL of dichloromethane were added to a 500 mL four-necked flask, and stirring was carried out at 0-5°C for 2 hours. Na2CO3 aqueous solution (3.00 g, 0.0283 mol) was added dropwise, and reaction was carried out at 0-5°C for 2 hours. HPLC control (methanol: water = 80:20) showed that the reaction was complete. The solid solution was collected by filtration, 250 mL of dichloromethane was added, stirring was carried out for 0.5 hours, the mixture was separated, washed with 0.5N hydrochloric acid once, washed with water three times, decolorized, the filtrate was concentrated to be viscous, 20 mL of methanol was added, and the solid was collected by crystallization to obtain 5.60 g of white solid 18. Referring to the reaction steps of Example 18, Examples 2 to 28 were respectively substituted for the substrates, and the reaction conditions were appropriately adjusted to sequentially obtain other corresponding sulfonate photoacid generators 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, and 28. The numbers of the sulfonate photoacid generators prepared in all examples are shown in Table 1. 1 The H NMR characterization results are shown in Table 1. Table 1 Performance evaluation 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 included molar absorption coefficient, solubility and chemical stability. (1) Molar absorption coefficient The compound was diluted into 0.25 mmol / L by using acetonitrile, and the absorbance of 1 cm cuvette length was measured in the range of 200-600 nm by using a UV-visible spectrophotometer (Youshutong Universal UPG-752). The molar absorption coefficient ε at each wavelength was calculated by the following formula, i.e. ε (L·mol -1 ·cm -1 ) = A / (0.00025 mol / L x 1 cm), wherein A represents the absorbance at each wavelength. (2) Solubility High solubility not only makes the photoacid generator compound easy to purify, but also enables the photoacid generator compound to expand the concentration range of use in photoresists and different solvent systems. 1.0000 g of the photoacid generator compound product was respectively taken, and solvent was gradually added at 25°C until the solid in each test tube was completely dissolved, and the mass of the solvent used was recorded, the solubility = (1 g / solvent mass) x 100%, and the evaluation results are shown in Table 2. Table 2 The non-ionic photoacid generator of Comparative Example 1 is denoted as A*1. The non-ionic photoacid generator of Comparative Example 2 is denoted as A*2. The photoacid generator of Comparative Example 3 is denoted as A*3. The photoacid generator of Comparative Example 4 is denoted as A*4. From the test results in Table 2, it can be seen that the photoacid generator of the present application has a high molar absorption coefficient at 365 nm, strong light absorption capacity, can make full use of light energy, can ensure high utilization rate in resist application, and exhibits good solubility. Examples of resist compositions Referring to the formulations shown in Table 3 for resist composition examples 1-31 and resist composition comparative examples 1-6, each raw material was uniformly dissolved in PGMEA (propylene glycol methyl ether acetate) to obtain a resist composition having a solid content concentration of about 20% (mass percent). Among them, the types and contents of the sulfonate photoacid generator (A), the resin component (B), and the sensitizer (C) are shown in Table 3. Composition example 1 The resin component (B) uses a resin of type B1, which is composed of repeating units shown in formula B 11 , formula B 12 , and formula B 13 . The values on the right and below each repeating unit represent the content of the repeating unit in the resin (mass percent). The weight average molecular weight of the B1 resin is about 10000. The sulfonate photoacid generator (A) is the sulfonate photoacid generator of example 1. Composition examples 2 to 24 The difference from composition example 1 is that the sulfonate photoacid generator (A) uses the sulfonate photoacid generators of examples 2 to 24, respectively. The types and contents of the remaining components are shown in Table 3. Composition example 25 The difference from composition example 18 is that the resin component (B) uses a resin of type B2, which is composed of repeating units shown in formula B 21 , formula B 22 , and formula B 23 . The values on the right and below each repeating unit represent the content of the repeating unit in the resin (mass percent). The weight average molecular weight of the B2 resin is about 10000. Composition example 26 The difference from composition example 18 is that the resin component (B) uses a resin of type B3, which is composed of repeating units shown in formula B 31 , and formula B 32 . The values on the right and below each repeating unit represent the content of the repeating unit in the resin (mass percent). The weight average molecular weight of the B3 resin is about 10000. Composition examples 27-28 The difference from composition example 18 is that the content of the sulfonate photoacid generator is different. Composition Example 29 The difference from Composition Example 18 is that no sensitizer is added. Composition Example 30 The difference from Composition Example 25 is that no sensitizer is added. Composition Example 31 The difference from Composition Example 26 is that no sensitizer is added. Composition Comparative Example 1 The difference from Composition Example 18 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used. Composition Comparative Example 2 The difference from Composition Example 25 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used. Composition Comparative Example 3 The difference from Composition Example 26 is that the sulfonate photoacid generator A*1 of Comparative Example 1 is used. Composition Comparative Example 4 The difference from Composition Comparative Example 1 is that no sensitizer is added. Composition Comparative Example 5 The difference from Composition Comparative Example 2 is that no sensitizer is added. Composition Comparative Example 6 The difference from Composition Comparative Example 3 is that no sensitizer is added. Composition Comparative Examples 7 to 24 The resist compositions of Composition Comparative Examples 7 to 24 are shown in Table 3. The resist compositions of Composition Examples 1 to 31 and Composition Comparative Examples 1 to 24 were evaluated for photosensitivity and resolution by the following methods, and the results are shown in Table 3. (1) Photosensitivity Evaluation On each silicon wafer, the resist composition of each example and comparative example was applied to form a coating film at a film thickness of 1 μm which is a film thickness capable of forming a pattern. The formed coating film was pre-baked at 90°C for 100 seconds. After pre-baking, the coating film was exposed through a mask for pattern formation having a 10 μm diameter hole while gradually changing the exposure amount (exposure wavelength 365 nm), and then developed in a 2.0% aqueous tetramethylammonium hydroxide solution at 25°C for 30 seconds. The minimum exposure required to form a 10 μm diameter hole pattern was determined by the above method. From the minimum exposure value obtained, the sensitivity was evaluated according to the following criteria: "O" indicates that the photosensitivity is -50 mJ / cm 2 "X" indicates that the photosensitivity is -300 mJ / cm 2 or more. (2) Resolution Evaluation Using a mask for forming a hole pattern of 5 μm in diameter, the coating film formation, coating film exposure and development were performed in the same manner as in the photosensitivity evaluation except that exposure was performed at an exposure amount of 100 mJ / cm 2 The resolution was evaluated in terms of the following criteria by observing the coating film after development: "O" indicates that a pattern of 5 μm in diameter can be formed, and "X" indicates that a pattern of 5 μm in diameter cannot be formed. Table 3 As can be seen from the results in Table 3, the resist compositions according to the present application as shown in Composition Examples 1 to 28 have very good photosensitivity and resolution, and are significantly superior to the compositions of Comparative Examples 1 to 3. Composition Examples 29 to 31 show that the photosensitivity is very good even without a sensitizer, but the compositions of Comparative Examples 4 to 6, which do not contain a sensitizer, show only general photosensitivity. The compositions of Comparative Examples 7 to 12 have a general yellow color, and have low solubility of the initiator and poor resolution. The compositions of Comparative Examples 13 to 24 have low solubility of the initiator and poor resolution. As can be seen from the above description, the above-described examples according to the present application achieve the following technical effects: The sulfonic acid ester photoacid generator having the general formula I according to the present application has a sulfonic acid ester group in the molecule, and this sulfonic acid ester group is directly connected to an imine structure. This structure has a photosensitive cleavage property, and can undergo N-O bond cleavage to produce different types of sulfonic acids under irradiation of active energy rays. The above-described active energy rays are active energy rays having a wavelength of 300 to 450 nm in the near-ultraviolet region and the visible region, and in particular, have high sensitivity and strong absorption to active energy rays having a wavelength of 365 nm (i-line). When a resist composition including the sulfonic acid ester photoacid generator and a resin component is used for a photosensitive composition for dissolving the exposed photosensitive composition with an alkali developer, the photosensitivity of the sulfonic acid ester photoacid generator is improved, and thus a pattern having excellent sensitivity and good contrast can be formed. Even when a fine pattern is formed, the pattern can have sufficiently high resolution and sensitivity. At the same time, the sulfonic acid ester photoacid generator according to the present application has significantly improved solubility and ultraviolet absorption at 365 nm compared to conventional p-methoxyphenylacetonitrile-type sulfonic acid ester photoacid generators, and thus the conventional photoresist can be used with a reduced dependence on a sensitizer when used under a 365 nm light source. Acid generating performance: The structures of the acid generators and the pKa values of the acids produced by each acid generator are given below. As can be seen, the resist compositions of the present application as shown in Composition Example 1, Example 6, Example 17, and Example 20 have a pKa similar to that of conventional pentafluorophenyl sulfonate acid and greater than that of p-toluenesulfonate acid. From the above description, it can be seen that the above-described examples of the present application achieve the following technical effects: The sulfonic acid ester photoacid generator of the present application has a sulfonic acid ester group in the molecule, which is directly connected to an imide structure, and the structure has a photosensitive cleavage property, and can undergo N-O bond cleavage under irradiation of active energy rays to produce different types of sulfonic acids. The above-described active energy rays are active energy rays having a wavelength of 300 to 450 nm in the near-ultraviolet light region and the visible light region, and in particular, have high sensitivity and strong absorption to active energy rays having a wavelength of 365 nm (i-line). When the resist composition including the sulfonic acid ester photoacid generator and the resin component is used for an alkali developer to dissolve the photosensitive composition exposed to light, the sensitivity of the sulfonic acid ester photoacid generator is improved, and thus a pattern having excellent sensitivity and good contrast can be formed, and even when a fine pattern is formed, it can have sufficiently high resolution and sensitivity. At the same time, the sulfonic acid ester photoacid generator of the present application has a nitrophenyl group or a cyanophenyl group or an alkoxyphenyl group in the substituent, and the introduction of an electron-withdrawing group into the structure can weaken the bond energy of the N-O bond to enhance the sensitivity, and can strengthen the acidity after the acid generation of the molecule. Thus, it is helpful to reduce the amount of the auxiliary agent in the resist, reduce the diffusion of the photoacid molecule, and improve the firmness of the lithographic pattern. Furthermore, the sulfonic acid ester photoacid generator of the present application does not contain PFAS, is environmentally friendly and easy to degrade, can be widely applied, and is more in line with the needs of the current social and industrial development for the environment. The applicant declares that the sulfonic acid ester photoacid generator of the present application, the preparation method and the application thereof are illustrated by the above-described examples, but the present application is not limited to the above-described examples, and it does not mean that the present application must rely on the above-described examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A sulfonate-based photoacid generator having the structure shown in general formula (I): wherein R1and R2are each independently selected from substituted or unsubstituted C2-C 12 alkenyl, C1-C 12 alkyl or R1and R2are the same or different; wherein R 11 -R 15 each independently is selected from the group consisting of hydrogen, halogen atom other than fluorine atom, nitro group, cyano group, substituted or unsubstituted C2-C 25 olefin group, C2-C 25 alkyl group, C2-C 25 alkoxy group, C2-C 25 alkylthio group; or a group in which at least one -CH2- of the substituted or unsubstituted C2-C 25 olefin group, C2-C 25 alkyl group, C2-C 25 alkoxy group, C2-C 25 alkylthio group is replaced with -O-, -S-, -CO-, -O-CO- or -COO-; or a group in which at least one -CH3 of the substituted or unsubstituted C2-C 25 hydrocarbon group, C2-C 25 alkyl group, C2-C 25 alkoxy group, C2-C 25 alkylthio group is replaced with -SiMe3, -OH, cycloalkyl group; X is -CH2-, a carbonyl group or an ester group, m is an integer from 0 to 4; n is an integer from 0 to 2.

2. The sulfonic acid ester-based photoacid generator according to claim 1, wherein, The substituents in the substituted or unsubstituted groups are selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, butoxy, nitro or cyano.

3. The sulfonic acid ester-based photoacid generator according to claim 1 or 2, wherein, the group is selected from n-butyl, Optionally, R1and R2are each independently selected from methyl, ethyl, vinyl, phenyl, cyano-substituted phenyl, nitro-substituted phenyl, chloro-substituted phenyl, C1-C8 alkyl-substituted phenyl, C1-C8 alkoxy-substituted phenyl, C1-C8 alkylthio-substituted phenyl; Further optionally, R1and R2are each independently selected from the group consisting of methyl, ethyl, ethenyl, phenyl, 4. The sulfonate photoacid generator according to any one of claims 1 to 3, wherein, The sulfonic acid ester photoacid generator is selected from any one of the following compounds:

5. The method for preparing the sulfonic acid ester photoacid generator according to any one of claims 1-4, comprising the following steps: Step S1, reacting compound 1 with a cycloalkylboronate compound carrying out a reaction to generate compound 2; Step S2, carrying out a hydroxylamine reaction of compound 2 with a hydroxylamine reagent to generate a hydroxylamine compound 3; Step S3, carrying out an esterification reaction of the hydroxylamine compound 3 with compound 4 to obtain the sulfonic acid ester photoacid generator; The structural formulas of Compound 1, Compound 2, Compound 3, and Compound 4 are as follows: wherein R1, R2, X, m, n and X1 have the same definitions as in claim 1.

6. The production method according to claim 5, wherein The molar ratio of compound 1 to the cycloalkyl borate compound in step S1 is 1:1.20-1.30; Optionally, the temperature of the reaction in step S1 is 75-80°C, and the reaction time is 6-8h; Optionally, the reaction in step S1 is carried out in a solvent selected from any one or a combination of at least two of toluene, tetrahydrofuran or xylene; Optionally, the hydroxylamine reaction in step S2 is carried out under basic or acidic conditions; Optionally, the hydroxylamine reagent in step S2 is hydroxylamine sulfate or hydroxylamine hydrochloride; Optionally, the temperature of the hydroxylamine reaction in step S2 is 25-100°C, further optionally 75-100°C; Optionally, in step S3, the esterification reaction of the hydroxylamine compound 3 with compound 4 is carried out under basic conditions in an inert solvent; Optionally, the basic conditions are carrying out the reaction in the presence of any one or a combination of at least two of pyridine, N-methyl pyrrolidone, ethylenediamine, piperidine or triethylamine; Optionally, the inert solvent is selected from any one or a combination of at least two of dichloromethane, n-heptane, n-octane, tetrahydrofuran, ethyl acetate, n-butyl propionate, isopropyl alcohol, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, 1,4-dioxane, acetonitrile or N,N-dimethyl formamide; Optionally, the temperature of the esterification reaction in step S3 is controlled at -10-60°C, further optionally 0-25°C; Optionally, the time of the esterification reaction in step S3 is 2-4h.

7. A resist composition comprising a resin component and an acid generator, wherein, The photoacid generator is the sulfonic acid ester photoacid generator according to any one of claims 1-3.

8. The resist composition according to claim 7, wherein, The mass percentage of the sulfonic acid ester photoacid generator is 0.01-5% based on the total mass of 100% of the solid components of the resist composition.

9. A patterning method comprising film forming and patterning processes using the resist composition according to claim 7 or 8.

10. Use of the sulfonic acid ester photoacid generator according to any one of claims 1-3 or the resist composition according to claim 7 or 8 in the preparation of a protective film, an interlayer insulating material or a pattern transfer material for electronic components.

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