Oxime sulfonate photoacid, resist composition containing same, electronic device and application thereof

Abstract

The present invention provides an oxime sulfonate photoacid, an anti-etching composition containing the same, an electronic device and an application. The oxime sulfonate photoacid comprises: a compound represented by formula (A1) and / or a compound represented by formula (A2), wherein L is selected from the following groups, the residue obtained by removing two hydrogen atoms: thiophene, benzothiophene, thienothiophene, pyrrole, pyrrolidine, pyrrolidone, pyridine or phenyl, or a substituent obtained by replacing at least one hydrogen atom in the above residue with a fluorine atom, a C1-C4 alkoxy group or a C1-C4 alkyl group. The oxime sulfonate photoacid containing the compound represented by formula (A1) and / or the compound represented by formula (A2) also has high sensitivity and strong absorption to active energy rays with a wavelength of 300-450nm (especially 385nm-436nm), can produce acid quickly under a lower exposure, and also has good solubility, thermal stability and storage stability. #imgabs0#

Description

Technical Field

[0001] The invention relates to the field of photosensitive materials, and in particular to an oxime sulfonate photoacid, a resist composition containing the same, an electronic device and applications. Background Art

[0002] The process of integrated circuit preparation is inseparable from chemical etching technology. Photoresist is one of the key materials. It is the material with the highest technical barriers among electronic chemicals. It has the characteristics of high purity requirements, complex production processes, large initial investment, and long technology accumulation period. It is highly monopolized by foreign companies and is a capital- and technology-intensive industry. Photoresist is mainly used in the processing and production of fine graphic circuits in the optoelectronic information industry. It is an upstream key material for liquid crystal displays (LCDs) and semiconductor industry chains (photoresist processes before chip processing and packaging processes after processing).

[0003] One typical example of photoresist in the photolithography process is a resin composition containing a resin and a photoacid, wherein the resin may be, for example, a tert-butyl ester of a carboxylic acid or a tert-butyl ether of a phenol, a silyl ether, etc. When irradiated with active energy rays such as ultraviolet rays, the photoacid decomposes to produce a strong acid (which may be further heated after exposure), and under the action of the strong acid, the carboxylic acid derivative or the phenol derivative is deprotected to produce a carboxylic acid or a phenol. After this chemical change, the resin in the exposed part becomes soluble in an alkaline developer, and then reacting it with an alkaline developer can promote the formation of a pattern.

[0004] As a resist for I-line lithography with a wavelength of 365nm, a diazonaphthoquinone (DNQ) resist is usually used, but a chemically amplified resist can have a high sensitivity that a DNQ resist cannot achieve, and is conducive to the production of thick film resists, so the use of chemically amplified I-line lithography has attracted attention. At present, there are many types of photoacids used in chemically amplified resists for I-line, such as naphthylsulfimide derivatives, anthraquinone derivatives, coumarin derivatives, acylphosphine oxide derivatives, oxime ester derivatives, etc., which can be roughly classified into two types: non-ionic and ionic. Among them, ionic photoacids often have insufficient solubility with solvents, resulting in their inability to fully exert their effects in resists; non-ionic photoacids have good compatibility with hydrophobic materials, but existing non-ionic photoacids have the problem of low sensitivity to I-line (resulting in poor acid generation efficiency), and due to insufficient heat resistance, they are easily decomposed in the post-exposure heating (PEB) process, and there is also a problem of narrow margin (DOF).

[0005] In the patent application with application number 202110553209.0, an oxime sulfonate photoacid generator is provided, which includes a compound represented by the general formula (A1), and the general formula (A1) has the following structure:

[0006]

[0007] The above-mentioned oxime sulfonate photoacid generator has high sensitivity and strong absorption to active energy rays with a wavelength of 300-450nm, especially 365nm (I line), 385nm and 405nm (H line), and can generate acid quickly under lower exposure.

[0008] The patent application with application number 202110553214.1 provides an oxime sulfonate compound, which includes a compound represented by the general formula (A2), and the general formula (A2) has the following structure:

[0009]

[0010] The above-mentioned oxime sulfonate photoacid generator also has high sensitivity and strong absorption to active energy rays with a wavelength of 300-450nm, especially 365nm (I line), 385nm and 405nm (H line), and can generate acid quickly under lower exposure.

[0011] Although compared with the existing oxime sulfonate photoacid generators, the above two oxime sulfonate photoacid generators have high sensitivity and strong absorption to active energy rays with a wavelength of 300-450nm, especially 365nm (I line), 385nm and 405nm (H line), their absorption rate and sensitivity to rays with a wavelength of 385nm to 436nm are still not ideal.

[0012] In view of the above problems, it is necessary to provide an oxime sulfonate photoacid generator having high sensitivity and absorptivity to radiation with a wavelength of 385 nm to 436 nm (especially 385 nm and 405 nm). Summary of the invention

[0013] The main purpose of the present invention is to provide an oxime sulfonate photoacid, a resist composition containing the same, an electronic device and an application thereof, so as to solve the problem that the existing oxime sulfonate photoacid has a less than ideal absorption rate and sensitivity to radiation with a wavelength of 385nm to 436nm.

[0014] In order to achieve the above object, the present invention provides an oxime sulfonate photoacid, which comprises: a compound represented by formula (A1) and / or a compound represented by formula (A2),

[0015]

[0016] Among them, R 1 One of the following substituents:

[0017] Hydrogen, nitro, cyano, C 1 ~C 20 A straight or branched alkyl group, C 5~C 6 Cycloalkyl substituted C 1 ~C 4 Alkyl, or -CH in the above groups 2 -substituted by -O- and / or -S-; phenyl, or a hydrogen atom on a phenyl group replaced by C 1 ~C 4 Substituents obtained by alkyl substitution; C 7 ~C 20 Phenylalkyl, and C 7 ~C 20 At least one hydrogen atom on the phenyl group in the phenylalkyl group may be replaced by a C 1 ~C 4 The -CH 2 - is optionally substituted with -O- and / or -S-; R 1 '-CO-, R 1 'Selected from C 1 ~C 4 The alkyl group, phenyl group, or at least one hydrogen atom in the phenyl group is replaced by a C 1 ~C 4 A substituent obtained by substitution of an alkyl group or an alkoxy group; 4 ~C 10 Aromatic heterocyclic group; C 4 ~C 10 An aromatic heterocyclyl alkyl group, and C 4 ~C 10 At least one hydrogen atom on the heterocyclic group of the aromatic heterocyclic alkyl group may be replaced by C 1 ~C 4 The -CH 2 - is optionally substituted by -O-, -S-; C 2 ~C 10 Alkynyl; C 2 ~C 10 Alkenyl; R 2 '-CO-O-, where R 2 'Selected from C 1 ~C 10 A straight chain or branched alkyl group; R 4 '-O-CO-R 5 '-, where R 4 'Selected from C 1 ~C 10 A straight chain or branched alkyl group, R 5 ' means empty or C 1 ~C 4 The alkylene group, and the -CH 2 - is optionally substituted by -O-, -S-; R2 , R 3 , R 4 are independently selected from hydrogen, halogen, cyano, nitro, amine, C 1 ~C 20 Straight or branched alkyl, C 1 ~C 20 Haloalkyl, C 7 ~C 20 Phenylalkyl, C 1 ~C 20 Alkylsulfonyl, C 6 ~C 18 Arylsulfonyl, C 1 ~C 20 Straight or branched chain alkyl or C 1 ~C 20 -CH in haloalkyl 2 - optionally substituted by -S-, -O-, acyl or acyloxy, or C 7 ~C 20 -CH in phenylalkyl 2 - a substituent optionally substituted by -S-, -O-, acyl or acyloxy; R 5 Selected from C 1 ~C 20 Straight or branched alkyl, C 3 ~C 20 Substituted or unsubstituted cycloalkyl, C 6 ~C 20 aryl or camphoryl, or at least one hydrogen atom in the above groups is replaced by a fluorine atom; L is selected from the following residues obtained by removing two hydrogen atoms: thiophene, benzothiophene, thienothiophene, pyrrole, pyrrolidine, pyrrolidone, pyridine or phenyl, or at least one hydrogen atom in the above residues is replaced by a fluorine atom, C 1 ~C 4 Alkoxy or C 1 ~C 4 Substituents obtained by alkyl substitution.

[0018] In order to achieve the above-mentioned object, another aspect of the present invention further provides a resist composition, which comprises the oxime sulfonate photoacid provided in the present application.

[0019] Furthermore, the sum of the amounts of the compound represented by formula (A1) and the compound represented by formula (A2) used is 0.01 to 5 wt %, preferably 0.1 to 3 wt %, based on the weight percentage of the resist composition.

[0020] The third aspect of the present application also provides an electronic device, including any one or more of a protective film, an interlayer insulating material or a pattern transfer material, wherein the protective film, the interlayer insulating material or the pattern transfer material is prepared by a pattern development method using the anti-etching composition provided by the present application.

[0021] The fourth aspect of the present application also provides an application of an oxime sulfonate photoacid or resist composition in the field of photosensitivity.

[0022] By applying the technical solution of the present invention, the compounds shown in formula (A1) and formula (A2) with the above structure belong to non-ionic photoacids, have light-absorbing groups and acid-generating groups, and the sulfonate group is directly connected to the oxime (C=N) structure, and can break the NO bond under the irradiation of active energy rays to produce highly acidic sulfonic acids. At the same time, the above-mentioned specific type of L group belongs to a strong electron-withdrawing group. The introduction of the above group can increase the longest absorption wavelength of the entire compound, which makes the compounds shown in formula (A1) and formula (A2) have high sensitivity and strong absorption to active energy rays with a wavelength of 300 to 450nm (especially 385nm to 436nm), and can produce acid more quickly under a lower exposure. At the same time, it also has good solubility, thermal stability and storage stability. On this basis, the oxime sulfonate photoacid containing the compound represented by the above formula (A1) and / or the compound represented by formula (A2) also has high sensitivity and strong absorption to active energy rays with a wavelength of 300 to 450 nm (especially 385 nm to 436 nm), can produce acid more quickly under lower exposure, and also has good solubility, thermal stability and storage stability. DETAILED DESCRIPTION

[0023] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0024] As described in the background art, the existing oxime sulfonate photoacid has a less than ideal absorption rate and sensitivity to radiation with a wavelength of 385nm to 436nm. In order to solve the above technical problems, the present application provides an oxime sulfonate photoacid, comprising: a compound represented by formula (A1) and / or a compound represented by formula (A2),

[0025]

[0026] Among them, each R 1 Each is independently selected from one of the following substituents:

[0027] Hydrogen, nitro, cyano, C 1 ~C 20 A straight or branched alkyl group, C 5 ~C6 Cycloalkyl substituted C 1 ~C 4 Alkyl, or -CH in the above groups 2 - a substituent obtained by substitution with -O- and / or -S-; or

[0028] Phenyl, or the hydrogen on the phenyl is replaced by C 1 ~C 4 Substituents obtained by substitution with an alkyl group;

[0029] C 7 ~C 20 Phenylalkyl, and C 7 ~C 20 At least one hydrogen atom on the phenyl group in the phenylalkyl group may be replaced by a C 1 ~C 4 The -CH 2 - is optionally substituted with -O- and / or -S-;

[0030] R 1 '-CO-, R 1 'Selected from C 1 ~C 4 The alkyl group, phenyl group, or at least one hydrogen atom in the phenyl group is replaced by a C 1 ~C 4 A substituent obtained by substitution with an alkyl group or an alkoxy group;

[0031] C 4 ~C 10 An aromatic heterocyclic group;

[0032] C 4 ~C 10 An aromatic heterocyclyl alkyl group, and C 4 ~C 10 At least one hydrogen atom on the heterocyclic group of the aromatic heterocyclic alkyl group may be replaced by C 1 ~C 4 The -CH 2 - is optionally substituted by -O-, -S-;

[0033] C 2 ~C 10 Alkyne group;

[0034] C 2 ~C 10 Alkenyl;

[0035] R 2 '-CO-O-, where R 2 'Selected from C 1 ~C 10A straight chain or branched alkyl group;

[0036] R 4 '-O-CO-R 5 '-, where R 4 'Selected from C 1 ~C 10 A straight chain or branched alkyl group, R 5 ' means empty or C 1 ~C 4 The alkylene group, and the -CH 2 - is optionally substituted by -O-, -S-;

[0037] R 2 , R 3 , R 4 are independently selected from hydrogen, halogen, cyano, nitro, amine, C 1 ~C 20 Straight or branched alkyl, C 1 ~C 20 Haloalkyl, C 7 ~C 20 Phenylalkyl, C 1 ~C 20 Alkylsulfonyl, C 6 ~C 18 Arylsulfonyl, C 1 ~C 20 Straight or branched chain alkyl or C 1 ~C 20 -CH in haloalkyl 2 - optionally substituted by -S-, -O-, acyl or acyloxy, or C 7 ~C 20 -CH in phenylalkyl 2 - a substituent optionally substituted with -S-, -O-, acyl or acyloxy;

[0038] R 5 Selected from C 1 ~C 20 Straight or branched alkyl, C 3 ~C 20 Substituted or unsubstituted cycloalkyl, C 6 ~C 20 An aryl group or a camphoryl group, or a substituent formed by replacing at least one hydrogen atom in the above groups with a fluorine atom;

[0039] L is selected from the following residues obtained by removing two hydrogen atoms: thiophene, benzothiophene, thienothiophene, pyrrole, pyrrolidine, pyrrolidone, pyridine or phenyl, or at least one hydrogen atom in the above residues is replaced by a fluorine atom, C 1 ~C 4 Alkoxy or C1 ~C 4 Substituents obtained by alkyl substitution.

[0040] The compounds represented by formula (A1) and formula (A2) with the above structure are non-ionic photoacids, have light-absorbing groups and acid-generating groups, and the sulfonate group is directly connected to the oxime (C=N) structure, and the NO bond can be broken under the irradiation of active energy rays to produce highly acidic sulfonic acids. At the same time, the above-mentioned specific type of L group is a strong electron-withdrawing group. The introduction of the above group can increase the longest absorption wavelength of the entire compound, which makes the compounds represented by formula (A1) and formula (A2) have high sensitivity and strong absorption to active energy rays with a wavelength of 300 to 450nm (especially 385nm to 436nm), and can produce acid more quickly under lower exposure. At the same time, it also has good solubility, thermal stability and storage stability. On this basis, the oxime sulfonate photoacid containing the compound represented by the above formula (A1) and / or the compound represented by formula (A2) also has high sensitivity and strong absorption to active energy rays with a wavelength of 300 to 450 nm (especially 385 nm to 436 nm), can produce acid more quickly under lower exposure, and also has good solubility, thermal stability and storage stability.

[0041] In order to further improve the comprehensive performance of the oxime sulfonate photoacid, the groups in the compound represented by formula (A1) and the compound represented by formula (A2) can be optimized. Preferably,

[0042] R 1 One of the following substituents: hydrogen, nitro, cyano, C 1 ~C 10 A straight or branched alkyl group, C 5 ~C 6 Cycloalkyl substituted C 1 ~C 4 Alkyl, or -CH in the above groups 2 -substituted by -O- and / or -S-; phenyl, or a hydrogen atom on a phenyl group replaced by C 1 ~C 4 Substituents obtained by alkyl substitution; C 7 ~C 10 Phenylalkyl, and C 7 ~C 10 At least one hydrogen atom on the phenyl group in the phenylalkyl group may be replaced by a C 1 ~C 4 Alkyl substitution, C 7 ~C 20 The -CH 2 - is optionally substituted with -O- and / or -S-; R 1'-CO-, R 1 'Selected from C 1 ~C 4 The alkyl group, phenyl group, or at least one hydrogen atom in the phenyl group is replaced by a C 1 ~C 4 substituted by alkyl or alkoxy; thienyl, furyl or pyrrolyl; C substituted by heterocyclic group 1 ~C 3 wherein the heterocyclic group is thienyl, furyl or pyrrolyl, and at least one hydrogen atom on the heterocyclic group is optionally replaced by C 1 ~C 4 substituted by an alkyl group, C 1 ~C 3 -CH in the alkyl group 2 - is optionally substituted by -O-, -S-; C 2 ~C 5 Alkynyl; C 2 ~C 5 Alkenyl; R 2 '-CO-O-, where R 2 'Selected from C 1 ~C 10 A straight chain or branched alkyl group; R 4 '-O-CO-R 5 '-, where R 4 'Selected from C 1 ~C 10 A straight chain or branched alkyl group, R 5 ' means empty or C 1 ~C 4 The alkylene group, and the -CH 2 - is optionally substituted by -O-, -S-; R 2 , R 3 , R 4 are independently selected from hydrogen, halogen, cyano, nitro, amine, C 1 ~C 5 Straight or branched alkyl, C 1 ~C 5 Haloalkyl; R 5 Selected from C 1 ~C 80 Straight-chain or branched alkyl, phenyl or C 1 ~C 3 A phenyl group substituted with an alkyl group, or a substituent formed by replacing at least one hydrogen atom in the above group with a fluorine atom.

[0043] In a preferred embodiment, when L is selected from the following substituents obtained by removing two hydrogen atoms: thiophene, benzothiophene or thienothiophene, the compound represented by formula (A1) is selected from one or more of the following compounds:

[0044]

[0045]

[0046]

[0047] In a preferred embodiment, when L is selected from the residue obtained by removing two hydrogen atoms from the following groups: pyrrole, pyrrolidine or pyridine, the compound represented by formula (A1) is selected from one or more of the following compounds:

[0048]

[0049] In a preferred embodiment, when L is phenylene, the compound represented by formula (A1) is selected from one or more of the following compounds:

[0050]

[0051]

[0052]

[0053] In a preferred embodiment, the compound represented by formula (A2) is selected from one or more of the following compounds:

[0054]

[0055]

[0056]

[0057]

[0058] Since oxime sulfonate photoacid can rapidly generate acid under specific active energy rays, the present invention provides an acid generation method, comprising irradiating the above-mentioned photoacid, ie, oxime sulfonate photoacid, with active energy rays.

[0059] The above-mentioned active energy rays can be electromagnetic waves with wavelengths in the visible light region (visible light), electromagnetic waves with wavelengths in the ultraviolet light region (ultraviolet light), electromagnetic waves with wavelengths in the infrared light region (infrared light), and electromagnetic waves with wavelengths in the non-visible region such as X-rays, etc. However, more preferably, the active energy rays are active energy rays with wavelengths between 300 and 450 nm in the near ultraviolet light region and the visible light region, and particularly preferably active energy rays with wavelengths of 365 nm (I line), 385 nm and 405 nm (H line).

[0060] The photoacid generator of the present invention can be used for any known uses of photoacid generators, such as resist films, liquid resists, negative resists, positive resists, resists for MEMS, materials for stereolithography and microstereolithography, etc. Among them, as a photoacid generator in a resist composition, it can be used in semiconductor lithography together with a resin having an acid dissociable group to prepare a resist.

[0061] The second aspect of the present application also provides a method for preparing the compound represented by formula (A1) and / or the compound represented by formula (A2), comprising:

[0062]

[0063] Among them, R 1 , R 2 , R 3 , R 4 , R 5 and L are defined as above.

[0064] First, thiopyran or pyran is nitrated to obtain nitrothiopyran or nitropyran.

[0065] In the second step, in the presence of a base, the nitrothiopyran / pyran is reacted with The cyanide shown reacts in a polar solvent to produce an oxime compound, the base includes but is not limited to sodium methoxide, sodium hydroxide or potassium hydroxide, and the polar solvent includes but is not limited to methanol, toluene or DMF. The reaction temperature is controlled at -80 to 80°C, preferably -10 to 60°C.

[0066] In the third step, the oxime compound and the acylating agent undergo esterification reaction in the presence of a base in an inert solvent to generate the oxime sulfonate photoacid described in the present application. The acylating agent includes but is not limited to acyl halide or anhydride, and the inert solvent includes but is not limited to diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, dimethylformamide, etc. The base includes but is not limited to triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, cesium carbonate or sodium carbonate, etc.; the reaction temperature is controlled at -10 to 60°C, preferably -5 to 5°C.

[0067] The raw materials used in the above preparation methods are all known compounds in the prior art and can be purchased commercially or conveniently prepared by known synthetic methods such as coupling, esterification, etc.

[0068] The third aspect of the present application also provides a resist composition, which comprises the oxime sulfonate photoacid provided by the present application.

[0069] The oxime sulfonate photoacid containing the compound represented by the above formula (A1) and / or the compound represented by the formula (A2) also has high sensitivity and strong absorption to active energy rays with a wavelength of 300 to 450 nm (especially 385 nm to 436 nm), can produce acid quickly under low exposure, and also has good solubility, thermal stability and storage stability. When it is applied to the anti-corrosion composition, when a protective film, interlayer insulating material or pattern transfer material is formed by a pattern development method, the corresponding electronic device can have better comprehensive performance.

[0070] The resist composition of the present invention is divided into a positive composition and a negative composition according to the application. In addition to the oxime sulfonate photoacid, the positive composition contains a resin component (B1) that increases solubility in an alkaline developer solution through the action of an acid. In the composition pattern formation process, after selective exposure, the acid-labile group protected by a protecting group in the positive resin in the exposure area will be deprotected under the action of an acid generated by a photoacid generator, making it soluble in an alkaline developer solution. Therefore, when performing an alkaline development operation, the unexposed area pattern is retained to form a positive pattern. Different from the positive composition, in addition to the oxime sulfonate photoacid, the negative composition uses a resin-crosslinker component (B2) that is crosslinked under the action of an acid and is insoluble in an organic developer solution. Under the acid catalysis generated by the photoacid generator, the resin reacts with the crosslinker in the exposure area to form a polymer that is insoluble in an organic developer solution and is retained, while the unexposed area is dissolved and removed by the organic developer solution, and finally forms a negative pattern.

[0071] In the above-mentioned resist composition, the oxime sulfonate photoacid provided in the present application can break the NO bond under the irradiation of active energy rays to generate sulfonic acid, and after the PEB process (post-exposure heating process), the difference in solubility in developer between the exposed area and the unexposed area is achieved. And it has high sensitivity and strong absorption to active energy rays with a wavelength of 300 to 450 nm, especially 385 nm to 436 nm.

[0072] In a preferred embodiment, the sum of the amount of the compound represented by formula (A1) and the compound represented by formula (A2) is 0.01 to 5 wt %, preferably 0.1 to 3 wt %, based on the weight percentage of the resist composition. When the sum of the amount of the compound represented by formula (A1) and the compound represented by formula (A2) is limited to this range, it is not only beneficial to further improve its sensitivity to active energy rays of a specific wavelength, but also beneficial to exert its physical properties of the insoluble part of the alkaline developer and improve its development effect.

[0073] The above-mentioned resist composition also includes a solvent, which can be a type commonly used in the art. Optionally, ester solvents include but are not limited to one or more of γ-butyrolactone (GBL), ethyl acetate, butyl acetate, ethyl lactate, and methyl pyruvate; ketone solvents include but are not limited to one or more of acetone, butanone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ether solvents include but are not limited to one or more of methyl ether, ethyl ether, propyl ether, butyl ether, anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, and butyl phenyl ether; polyol and derivative solvents include but are not limited to ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, One or more of esters, ethylene glycol monopropionate, diethylene glycol monopropionate, propylene glycol monopropionate, dipropylene glycol monopropionate, propylene glycol monomethyl ether and propylene glycol methyl ether acetate (PGMEA); aromatic organic solvents include but are not limited to one or more of toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, methyl isopropylbenzene and mesitylene; nitrogen-containing polar solvents include but are not limited to one or more of N,N,N',N'-tetramethylurea, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone and 2-trimethylpropionamide. The above organic solvents can be used alone or as a mixed solvent of two or more.

[0074] The solvent is used to dissolve the components in the resist composition to form a uniform solution for adjusting the viscosity and coating properties. Preferably, the solvent includes but is not limited to one or more of the group consisting of propylene glycol methyl ether acetate PGMEA, cyclohexanone and gamma-butyrolactone GBL. In a preferred embodiment, the amount of solvent is selected so that the concentration of the solid component in the resist composition is 5-30wt%.

[0075] Positive resist composition

[0076] In addition to the oxime sulfonate photoacid provided in the present application, the positive type composition contains a resin component (B1) whose solubility in an alkaline developer is increased by the action of an acid. During the pattern formation of the composition, after selective exposure, the acid-labile groups protected by the protecting groups in the positive type resin in the exposed area are deprotected by the acid action generated by the photoacid, making them soluble in an alkaline developer. Therefore, during alkaline development, the pattern in the unexposed area remains, forming a positive type pattern.

[0077] In a preferred embodiment, when the resist composition is a positive resist composition, the resin component (B1) can be obtained by vinyl polymerization of a vinyl monomer containing an alkali-soluble acidic group and a vinyl monomer containing a hydrophobic group as required, wherein a part or all of the hydrogen atoms of the alkali-soluble acidic group are substituted by an acid-dissociable group as a protecting group. The alkali-soluble acidic group can be a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group, and the acid-dissociable group can be dissociated in the presence of a strong acid, and the strong acid is generated by an oxime sulfonate photoacid.

[0078] For ease of description, the unit structure formed by polymerization of the vinyl monomer containing an alkali-soluble acidic group is defined as an acid-based resin, and the unit structure formed by polymerization of the acid-based resin and the vinyl monomer containing a hydrophobic group together constitute the resin component (B1). The acid-based resin itself is alkali-insoluble or poorly alkali-soluble.

[0079] Preferably, the above-mentioned protecting group comprises at least one of the following groups:

[0080]

[0081] Where R 8 , R 9 , R 10 Each independently represents a C 1 ~C 6 Alkyl, C 1 ~C 10 Any one of the fluorinated alkyl groups of 8 , R 9 , R 10 Any two of them can be bonded to form a ring; 11 , R 12 and R 13 Each independently represents C 1 ~C 20 The hydrocarbon group, and R 11 , R 12 , R 13 Any two of R can be bonded to each other to form a ring; 14 Indicates that it has C 1 ~C 6 Straight chain alkyl, C 1 ~C 6 Branched alkyl, C 1 ~C 6 and n is 0 or 1.

[0082] Specifically, in formula (a), when R 8 , R 9 and R 10When R is an alkyl group, it can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, etc.; when R 8 , R 9 and R 10 When any two groups in are bonded to each other to form a ring, preferably C 5 ~C 20 Monocyclic or polycyclic aliphatic hydrocarbons, exemplarily selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, tricyclodecane, tetracyclodecane, etc.; by combining R 8 , R 9 and R 10 The ring formed by any two groups in may have a substituent, such as a hydroxyl group, a cyano group and an oxygen atom (=O), as well as a C 1 ~C 4 Preferably, the protecting group represented by formula (a) can be selected from the following molecular formula (formula a) 1 -Formula A 6 )

[0083] Formula a 1 : Formula a 2 : Formula a 3 : Formula a 4 : Formula a 5 : Formula a 6 :

[0084] Specifically, in formula (b), R 11 , R 12 and R 13 For C 1 ~C 20 aliphatic or / and aromatic hydrocarbon group. 11 , R 12 and R 13 When it is an aliphatic hydrocarbon group, it can be a straight chain structure or a cyclic structure. The straight chain structure can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl and n-undecyl; the cyclic structure can be selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the polycyclic groups of the following molecular formula (Formula b) 1 -Formula b 8 );

[0085] Formula b 1 : Formula b 2 : Formula b 3 : Formula b 4 :

[0086] Formula b 5 : Formula b 6 : Formula b 7 : Formula b 8 :

[0087] In formula (b), when R 11 , R 12 and R 13 When R is an aromatic hydrocarbon group, it can be selected from phenyl, naphthyl, anthracenyl, biphenyl, phenanthrenyl and fluorenyl. 11 , R 12 and R 13 When the aliphatic and aromatic groups are present at the same time, they can be selected from benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl and 2-(β-naphthyl)ethyl. The aromatic ring can be substituted or partially substituted, and the substituents are selected from halogen atoms, hydroxyl groups, C 1 ~C 10 Alkyl or alkoxy, C 2 ~C 10 In formula (b), R 11 Preferably, a hydrogen atom, R 12 Preferably, methyl, R 13 Preferably, ethyl, isobutyl, cyclohexyl, 2-ethyl-n-hexyl or octadecyl; when R 12 and R 13 When bonded to each other to form a ring, preferably C 4 ~C 6 Heterocyclic ring; when R 11 and R 12 When they are bonded to each other to form a ring, preferably C 3 ~C 12 A saturated aliphatic hydrocarbon ring.

[0088] Preferably, the protecting group represented by formula (b) may preferably be of the following molecular formula (Formula b 9 -Formula b 14 ) group:

[0089] Formula b 9 : Formula b10 : Formula b 11 : Formula b 12 : Formula b 13 : Formula b 14 :

[0090] Specifically, the protecting group represented by formula (c) may be selected from tert-butyloxycarbonyl and tert-butyloxycarbonylmethyl.

[0091] The alkali-soluble acidic group in the resin component (B1) may be a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group.

[0092] The resin containing phenolic hydroxyl groups (B1-1) includes but is not limited to novolac resin, polymers having hydroxyl styrene (polyhydroxystyrene resin), phenol-benzenedimethanol condensation resin, cresol-benzenedimethanol condensation resin, polyimide containing phenolic hydroxyl groups, polyamic acid containing phenolic hydroxyl groups, and one or more of phenol-dicyclopentadiene condensation resins, wherein the polyhydroxystyrene resin includes but is not limited to copolymers of polyhydroxystyrene-hydroxystyrene, copolymers of hydroxystyrene-styrene, copolymers of hydroxystyrene-styrene and (meth) acrylic acid derivatives. More preferably, the resin containing phenolic hydroxyl groups (B1-1) is one or more of novolac resin, polyhydroxystyrene resin and phenol-benzenedimethanol condensation resin.

[0093] The hydroxystyrene resin is preferably a copolymer of a hydroxystyrene compound and a styrene compound, which can be selected from styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, etc. And the molecular weight of the hydroxystyrene resin is preferably 1000-50000. A resin in which at least a portion of the hydroxyl groups of the hydroxystyrene resin are protected by a protective group is used in the resin component. As described above, the polyhydroxystyrene resin can introduce a crosslinking group as needed. A crosslinking group is a functional group that can be thermally crosslinked when the patterned film to be formed is post-baked. A group suitable for crosslinking can be selected from an epoxy group, an oxetane group, and a group containing an unsaturated double bond [such as a (meth) acryloyl group]. In the resin component, the content of the crosslinking agent is preferably 20-70wt%, within which a film with excellent mechanical properties and chemical resistance can be formed by thermal crosslinking between crosslinking groups during PEB (post-exposure heat treatment).

[0094] The above-mentioned (meth)acrylamide includes (meth)acrylamide, (meth)N-alkyl(meth)acrylamide, (meth)N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl(meth)acrylamide, etc. Allyl compounds include allyl acetate, allyl caproate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc. Vinyl ethers include hexyl vinyl ether, octyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether and benzyl vinyl ether, etc.

[0095] The novolac resin mentioned in the present application is obtained by adding and condensing an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenol") with an aldehyde in the presence of an acid catalyst, wherein the phenolic organic matter is mainly selected from alkylphenols and / or aromatic phenols, including but not limited to phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5- The present invention relates to one or more of phenol-formaldehyde condensation phenol-formaldehyde varnish resin, cresol-formaldehyde condensation phenol-formaldehyde varnish resin, and phenol-naphthol-formaldehyde condensation phenol-formaldehyde varnish resin.

[0096] The molecular weight of the resin containing phenolic hydroxyl groups is preferably 1000-50000. As mentioned above, crosslinking groups can be introduced into the resin containing phenolic hydroxyl groups as needed, such as carboxyl groups, alcoholic hydroxyl groups and cyclic ether groups combined with aromatic groups.

[0097] In a preferred embodiment, the carboxyl groups in the acid-based resin can be provided by the following organic acids: unsaturated monocarboxylic acids include but are not limited to one or more of (meth) acrylic acid, crotonic acid and cinnamic acid; unsaturated polycarboxylic acids include but are not limited to one or more of (anhydrous) maleic acid, itaconic acid, fumaric acid and citraconic acid; unsaturated polycarboxylic acid alkyl (C 1 ~C 10) esters include but are not limited to one or more of monoalkyl maleate, monoalkyl fumarate and monoalkyl citraconic acid, or salts corresponding to the above organic acids, such as alkali metal salts (sodium salt, potassium salt), alkaline earth metal salts (calcium salt, magnesium salt), amine salts and ammonium salts. More preferably, the above carboxyl group is provided by (meth) acrylic acid.

[0098] In a preferred embodiment, the acrylic resin is preferably a resin obtained by copolymerizing (meth) acrylic acid with other monomers having unsaturated bonds. The monomer copolymerized with (meth) acrylic acid can be selected from unsaturated carboxylic acids, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, etc. except (meth) acrylic acid. Among them, the unsaturated carboxylic acid is preferably a monocarboxylic acid of (meth) acrylic acid and a dicarboxylic acid of maleic acid. Straight or branched (meth) acrylic acid esters can be selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, tert-octyl (meth) acrylate, etc. Among (meth) acrylic acid esters without epoxy groups, (meth) acrylic acid esters with alicyclic skeletons are preferred. In (meth) acrylic acid esters with alicyclic skeletons, alicyclic groups can be monocyclic or polycyclic, monocyclic alicyclic groups can be selected from cyclopentyl and cyclohexyl, and polycyclic alicyclic groups can be selected from norbornyl, isobornyl, tricyclononyl, etc.

[0099] In a preferred embodiment, the sulfonic acid groups in the acid-based resin can be provided by the following types of sulfonic acids: vinyl sulfonic acid, (methyl) allyl sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, 2-(methyl) acrylamido-2-methylpropane sulfonic acid and salts corresponding to the above organic sulfonic acids, such as alkali metal salts (sodium salts, potassium salts), alkaline earth metal salts (calcium salts, magnesium salts), first to third grade amine salts, ammonium salts and quaternary ammonium salts, etc.

[0100] The hydrophilicity-lipophilicity balance (HLB) value of the alkali-soluble group-containing resin varies depending on the resin skeleton of the alkali-soluble resin, and is generally 4 to 19. When the HLB value of the alkali-soluble group-containing resin is ≥ 4, the developability of the resist composition is better, and when the HLB value is ≤ 19, the water resistance of the cured product of the resist composition after curing is better. More preferably, the HLB value of the alkali-soluble group-containing resin is 6 to 17.

[0101] In order to further improve the developing performance of the resist composition, preferably, the content of the above acid-based resin accounts for 1 to 80% of the content of the resin component (B1), and more preferably 10 to 70%.

[0102] Preferably, the hydrophobic group-containing vinyl monomers include, but are not limited to, (meth)acrylates and aromatic hydrocarbon monomers.

[0103] Further preferably, the above (meth)acrylate includes but is not limited to C1 ~C 20 Alkyl (meth) acrylate and / or alicyclic (meth) acrylate. 1 ~C 20 Alkyl (meth)acrylates include, but are not limited to, one or more of the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic (meth)acrylates include, but are not limited to, one or more of the group consisting of dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate.

[0104] Further preferably, the aromatic hydrocarbon monomer includes but is not limited to alkanes and aromatic hydrocarbons having a styrene skeleton, such as one or more of styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene and vinylnaphthalene.

[0105] In order to further improve the water resistance of the developed pattern formed after curing of the resist composition and improve its developing effect, preferably, the content of the unit structure formed by polymerization of the above-mentioned hydrophobic group-containing vinyl monomer in the resin component (B1) is more preferably 15 to 75%.

[0106] Preferably, the acid-dissociable groups as protecting groups in the positive resist composition include, but are not limited to, one or more of substituted methyl, 1-substituted ethyl, 1-branched alkyl, silane, germyl, alkoxycarbonyl, acyl and cyclic acid-dissociable groups.

[0107] In the actual preparation process, the type of acidic protecting group needs to be further optimized from multiple aspects such as the difficulty of synthesizing the resin component (B1), the ease of dissociation of the protecting group, and the water resistance of the resist composition.

[0108] In a preferred embodiment, the substituted methyl radicals include but are not limited to methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzylthiomethyl, phenacyl, bromophenacyl, methoxyphenacyl, methylthiophenacyl, α-methylphenacyl, cyclopropylmethyl, benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl, piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl or tert-butoxycarbonylmethyl.

[0109] In a preferred embodiment, the 1-substituted ethyl group includes but is not limited to 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, 1-ethylthioethyl, 1,1-diethoxyethyl, 1-ethoxypropyl, 1-propoxyethyl, 1-cyclohexyloxyethyl, 1-phenoxyethyl, 1-phenylthioethyl, 1,1-diphenoxyethyl, 1-benzyloxyethyl, 1-benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1,1-diphenylethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-n-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-n-butoxycarbonylethyl or 1-tert-butoxycarbonylethyl.

[0110] In a preferred embodiment, the 1-branched alkyl group includes but is not limited to isopropyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, 1-methylbutyl or 1,1-dimethylbutyl.

[0111] In a preferred embodiment, the above-mentioned silane group includes but is not limited to trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, methyldi-tert-butylsilyl, tri-tert-butylsilyl, phenyldimethylsilyl, methyldiphenylsilyl or triphenylsilyl.

[0112] In a preferred embodiment, the above-mentioned germanyl group includes but is not limited to trimethylgermanyl, ethyldimethylgermanyl, methyldiethylgermanyl, triethylgermanyl, isopropyldimethylgermanyl, methyldiisopropylgermanyl, triisopropylgermanyl, tert-butyldimethylgermanyl, methyldi-tert-butylgermanyl, tri-tert-butylgermanyl, phenyldimethylgermanyl, methyldiphenylgermanyl or triphenylgermanyl.

[0113] In a preferred embodiment, the alkoxycarbonyl group includes but is not limited to methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl or tert-butoxycarbonyl.

[0114] In a preferred embodiment, the acyl group includes but is not limited to acetyl, propionyl, butyryl, heptanoyl, caproyl, valeryl, pivaloyl, isovaleryl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl, adipoyl, pimeloyl, suberoyl, azelayl, sebacoyl, acryloyl, propioloyl, methacryloyl, butenoyl, oleoyl, maleoyl, fumaroyl, mesoconoyl, camphenoyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroatropoyl, atropoyl, cinnamoyl, furoyl, thenoyl, nicotinoyl, isonicotinoyl or toluenesulfonylmethylsulfonyl.

[0115] In a preferred embodiment, the above-mentioned cyclic acid-dissociable groups include but are not limited to cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl, 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl or 3-tetrahydrothiophene-1,1-dioxide.

[0116] In a preferred embodiment, the acid-dissociable groups include but are not limited to tert-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl or tetrahydrothiofuranyl.

[0117] The developing effect of the resist composition can be adjusted by adjusting the content of the acidic dissociative groups. In order to further improve its developing effect, preferably, the introduction rate of the acidic dissociative groups in the acid-based resin (the ratio of the number of acidic dissociative groups to the sum of the unprotected acidic groups and the acidic dissociative groups in B1) is 15 to 100%.

[0118] In a preferred embodiment, the average molecular weight of the acid-based resin is 1,000 to 150,000. The average molecular weight of the acid-based resin includes but is not limited to the above range, and limiting it within the above range is beneficial to improving its water resistance, thereby improving the developing effect of its developing pattern. More preferably, the average molecular weight of the acid-based resin (B1) is 3,000 to 100,000.

[0119] Negative resist composition

[0120] When the resist composition includes a mixture of a second resin and a crosslinking agent that are crosslinked under the action of an acid and are insoluble in an organic developer, a photoacid generator, and a solvent, the resist is a negative composition. Under the catalysis of the acid generated by the photoacid, the resin and the crosslinking agent react to form a polymer that is insoluble in an organic developer and remain, while the unexposed area is dissolved and removed by the organic developer, finally forming a negative photoresist pattern.

[0121] In the negative resist composition provided by the present application, the negative resin mainly comprises a phenolic hydroxyl-containing resin (B2-1) and a crosslinking agent (B2-2). The phenolic hydroxyl-containing resin (B2-1) can be the same as B1-1 described above.

[0122] In a preferred embodiment, the weight percentage of the phenolic hydroxyl-containing resin B2-1 in the solid content of the negative resist composition is 30 to 90% (w / w), more preferably 40 to 80% (w / w).

[0123] The crosslinking agent (B2-2) is a compound that crosslinks and polymerizes the phenolic hydroxyl group-containing resin under the catalysis of the acid generated by the photoacid generator (A). In a preferred embodiment, the crosslinking agent (B2-2) includes but is not limited to bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, soluble phenolic resin epoxy compounds, poly (hydroxystyrene) epoxy compounds, oxetane compounds, hydroxymethyl-containing melamine compounds, hydroxymethyl-containing benzoguanamine compounds, hydroxymethyl-containing urea compounds, hydroxymethyl-containing phenol compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing phenol compounds, carboxymethyl-containing melamine resins, carboxymethyl-containing benzoguanamine resins, carboxymethyl-containing urea resins, carboxymethyl-containing phenol resins, carboxymethyl-containing melamine compounds, carboxymethyl-containing benzoguanamine compounds, carboxymethyl-containing urea compounds and carboxymethyl-containing phenol compounds. One or more. More preferably, the crosslinking agent (B2-2) is one or more of a methoxymethyl-containing melamine compound (e.g., hexamethoxymethyl melamine), a methoxymethyl-containing glycoluril compound, and a methoxymethyl-containing urea compound. Methoxymethyl-containing melamine compounds are commercially available under trade names such as CYMEL 300, CYMEL 301, CYMEL 303, and CYMEL 305 (manufactured by Mitsui Cyanamide Co., Ltd.), and methoxymethyl-containing glycoluril compounds are commercially available under trade names such as CYMEL 1174 (manufactured by Mitsui Cyanamide Co., Ltd.); and methoxymethyl-containing urea compounds are commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

[0124] In order to reduce the residual film rate during the graphic development process and improve the resolution of the developed pattern, the content of the crosslinking agent (B2-2) is usually 10 mol to 50 mol%, preferably 15 mol to 40 mol%, relative to all acidic functional groups in the phenolic hydroxyl-containing resin (B2-1).

[0125] Preferably, the above (positive / negative) resist composition further comprises an aromatic carboxylic acid compound (C), i.e., at least one carboxyl group is bonded to an aromatic group, and the aromatic group can be an aromatic hydrocarbon group and an aromatic heterocyclic group. The addition of the aromatic carboxylic acid compound is beneficial to increase the deprotection reaction rate of the negative resin component in the resist composition after being exposed to the acid group.

[0126] The aromatic carboxylic acid compound can be selected from at least one of a low molecular weight aromatic carboxylic acid compound or a high molecular weight aromatic carboxylic acid compound. Preferably, the low molecular weight aromatic carboxylic acid compound is a monocarboxylic acid compound and / or a polycarboxylic acid compound including at least two carboxyl groups and / or substituents; the high molecular weight aromatic carboxylic acid compound is a high molecular weight compound including a carboxyl group bonded to an aromatic group and an unsaturated double bond.

[0127] In the aromatic carboxylic acid compound, in addition to the carboxyl group, there may be more than one substituent, which may be selected from halogen, hydroxyl, mercapto, sulfide group, silyl, silanol group, nitro, nitroso, sulfonate, phosphinyl or phosphonate; when the substituent on the aromatic group is an organic group, it may be selected from alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or aralkyl; the organic group may contain bonds or substituents other than hydrocarbon groups, such as heteroatoms such as O, Si, N, and the bonds of heteroatoms may include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, carbamate bonds and imino bonds, carbonate bonds, sulfonyl bonds, sulfinyl bonds and azo bonds. The organic group may be linear, branched or cyclic. As the substituent on the aromatic group, preferably having C 1 ~C 12 of alkyl, aryl, alkoxy and halogen.

[0128] The above aromatic carboxylic acid compound may be a low molecular weight compound, such as benzoic acid or naphthoic acid, or a high molecular weight compound having a carboxyl group bonded to an aromatic group, specifically as follows: The low molecular weight aromatic carboxylic acid compound may be a monocarboxylic acid compound or a polyvalent carboxylic acid compound having two or more carboxyl groups. The aromatic group contained in the low molecular weight aromatic carboxylic acid compound may have a substituent other than the carboxyl group.

[0129] Preferably, the low molecular weight aromatic carboxylic acid compound can be selected from the following carboxylic acids: benzoic acid; hydroxybenzoic acids include but are not limited to salicylic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid, etc.; alkylbenzoic acids include but are not limited to o-methylbenzoic acid, m-methylbenzoic acid and p-methylbenzoic acid; halogenated benzoic acids include but are not limited to o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid and p-bromobenzoic acid; alkoxybenzoic acids include but are not limited to o-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, o-ethoxybenzoic acid, m-ethoxybenzoic acid and p-ethoxybenzoic acid; aminobenzoic acids include but are not limited to o-aminobenzoic acid, m-aminobenzoic acid and p-aminobenzoic acid; acyloxybenzoic acids include but are not limited to o-acetoxybenzoic acid. The hydroxynaphthoic acids include, but are not limited to, 1-hydroxy-2-naphthoic acid, 1-hydroxy-3-naphthoic acid, 1-hydroxy-4-naphthoic acid, 1-hydroxy-5-naphthoic acid, 1-hydroxy-6-naphthoic acid, 1-hydroxy-7-naphthoic acid, 1-hydroxy-8-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-4-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-7-naphthoic acid and 2-hydroxy-8-naphthoic acid; the aminonaphthoic acids include, but are not limited to, 1-amino-2-naphthoic acid, 1-amino-3-naphthoic acid, 1-amino-4-naphthoic acid The alkoxy naphthoic acids include, but are not limited to, 1-methoxy-2-naphthoic acid, 1-methoxy-3-naphthoic acid, 1-methoxy-4-naphthoic acid, 1-methoxy-5-naphthoic acid, 1-methoxy-6-naphthoic acid, 1-methoxy-7-naphthoic acid, 1-methoxy-8-naphthoic acid, 2-methoxy-1-naphthoic acid, 2-methoxy-3-naphthoic acid, 2-methoxy-4-naphthoic acid, 2-amino-5-naphthoic acid, 2-amino-6-naphthoic acid, 2-amino-7-naphthoic acid and 2-amino-8-naphthoic acid; the alkoxy naphthoic acids include, but are not limited to, 1-methoxy-2-naphthoic acid, 1-methoxy-3-naphthoic acid, 1-methoxy-4-naphthoic acid, 1-methoxy-5-naphthoic acid, 1-methoxy-6-naphthoic acid, 1-methoxy-7-naphthoic acid, 1-methoxy-8-naphthoic acid, 2-methoxy-1-naphthoic acid, 2-methoxy-3-naphthoic acid, 2-methoxy-4-naphthoic acid Acid, 2-methoxy-5-naphthoic acid, 2-methoxy-6-naphthoic acid, 2-methoxy-7-naphthoic acid, 2-methoxy-8-naphthoic acid, 1-ethoxy-2-naphthoic acid, 1-ethoxy-3-naphthoic acid, 1-ethoxy-4-naphthoic acid, 1-ethoxy-5-naphthoic acid, 1-ethoxy-6-naphthoic acid, 1-ethoxy-7-naphthoic acid, 1-ethoxy-8-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2-ethoxy-3-naphthoic acid, 2-ethoxy-4-naphthoic acid, 2-ethoxy-5-naphthoic acid, 2-ethoxy-6-naphthoic acid, 2-ethoxy-7-naphthoic acid and 2-ethoxy-8-naphthoic acid, etc.; phthalic acid includes but is not limited to phthalic acid, terephthalic acid and isophthalic acid;Naphthalene dicarboxylic acids include but are not limited to 1,2-naphthalene dicarboxylic acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid; biphenyl carboxylic acids include but are not limited to 1,1′-biphenyl-4-carboxylic acid, 1,1′-biphenyl-3-carboxylic acid and 1,1′-biphenyl-2-carboxylic acid; Biphenyl dicarboxylic acids include, but are not limited to, 1,1′-biphenyl-4,4′-dicarboxylic acid, 1,1′-biphenyl-3,3′-dicarboxylic acid, 1,1′-biphenyl-2,2′-dicarboxylic acid, 1,1′-biphenyl-3,4′-dicarboxylic acid, 1,1′-biphenyl-2,4′-dicarboxylic acid, and 1,1′-biphenyl-2,3′-dicarboxylic acid; trivalent or higher valent aromatic polycarboxylic acids include, but are not limited to, pyromellitic acid, trimellitic acid, and trimellitic acid; hydroxy The benzoic acid includes but is not limited to 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid and 2-hydroxyisophthalic acid; the dihydroxybenzoic acid includes but is not limited to 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid and 3,4-dihydroxyphthalic acid; the pyridinecarboxylic acid includes but is not limited to pyridine-2-carboxylic acid, pyridine-3-carboxylic acid and pyridine-4-carboxylic acid; the pyridinedicarboxylic acid includes but is not limited to pyridine-2,5-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid and pyridine-2,4-dicarboxylic acid; the pyrimidinecarboxylic acid includes but is not limited to pyrimidine-2-carboxylic acid, pyrimidine-4-carboxylic acid, pyrimidine-5-carboxylic acid and pyrimidine-6-carboxylic acid; and the pyrimidinedicarboxylic acid includes but is not limited to 2,6-pyrimidinedicarboxylic acid and 2,5-pyrimidinedicarboxylic acid. These low molecular weight aromatic carboxylic acid compounds can be used alone or in combination of two or more. ;

[0130] Preferably, the high molecular weight aromatic carboxylic acid compound is a polymer compound having a carboxyl group bonded to an aromatic group. The comonomer has a carboxyl group and an unsaturated double bond bonded to an aromatic group, and does not include an acid-labile group protected by a protecting group. As a preferred copolymerization component, together with a monomer having a carboxyl group and an unsaturated double bond bond bonded to an aromatic group, the above-mentioned (meth) acrylic acid as a monomer for preparing acrylic resin can be used, such as unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters and styrene.

[0131] The photosensitive composition further comprises a bridging compound, and the bridging compound contains at least one cross-linking group, and the cross-linking group comprises an epoxy group and / or an oxetane group. The bridging compound comprises: a bridging low molecular weight compound (an epoxy-containing resin with a weight average molecular weight of less than 5,000), a bridging high molecular weight compound (an epoxy-containing resin with a weight average molecular weight of 5,000 to 15,000, and / or a resin with an ethylenically unsaturated group with a weight average molecular weight of 2,000 to 30,000).

[0132] The bridging low molecular compound comprises at least one of a bifunctional or multifunctional epoxy compound with a functionality greater than 2 and a polyoxetane compound.

[0133] Alternatively, the multifunctional epoxy compound can be selected from difunctional epoxy resins, such as dialdehyde A-type epoxy resins and bisphenol S-type epoxy resins, etc.; glycidyl ester type epoxy resins, such as dimer acid glycidyl ester and triglycidyl ester, etc.; glycidyl amine type epoxy resins, such as tetraglycidyl aminodiphenylmethane and tetraglycidyl bisaminomethylcyclohexane, etc.; heterocyclic epoxy resins, such as triglycidyl isocyanurate, etc.; multifunctional epoxy resins, such as phloroglucinol triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether, etc. Alicyclic epoxy compounds are also preferred as multifunctional epoxy compounds, which are easy to form highly transparent films. Alternatively, the multifunctional oxetane compound may be selected from 3,3′-(oxybismethylene)bis(3-ethyloxetane), 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl and 3,7-bis(3-oxetanyl)-5-oxanonane, and the like.

[0134] The above-mentioned bridging polymer compound includes: at least one of an epoxy-containing resin and an unsaturated double bond-containing resin. The epoxy-containing resin can be polymerized from an epoxy-containing monomer or a monomer mixture, and can be selected from novolac epoxy resins, such as phenol novolac epoxy resins, brominated phenol novolac epoxy resins, etc.; alicyclic epoxy resins, such as epoxidized products of dicyclopentadiene phenolic resins; and aromatic epoxy resins, such as epoxidized products of naphthalene phenolic resins.

[0135] In addition, according to functional requirements, the photosensitive resin composition of the present application may further include the following auxiliary raw materials: a dissolution control agent, a dissolution inhibitor, an alkaline compound, a surfactant, a storage stabilizer, and a defoaming agent.

[0136] In order to improve the combined performance of the resist composition, the resist composition may further include some other auxiliary agents, and the types of the auxiliary agents may be selected from the commonly used substances in the resist composition, which will not be described in detail here.

[0137] The coating method of the resist composition provided in the present application includes: using a spin coating method, dissolving the resist composition (when it contains inorganic microparticles, dissolving and dispersing) in a predetermined organic solvent to form a resin solution, then coating it on a substrate, and finally volatilizing the solvent by heating.

[0138] The drying conditions of the resin solution after coating vary depending on the solvent used, and are preferably carried out at 50°C to 150°C for 1 to 30 minutes, and are appropriately determined by the amount of residual solvent (weight %) after drying, etc. After forming a resist film on the substrate, light irradiation in the shape of a wiring pattern is performed. Then, after post-exposure heating (PEB), alkaline development is performed to form a wiring pattern.

[0139] After forming the resist film on the substrate, the wiring pattern shape is irradiated with light. Actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium cadmium lasers), preferably high-pressure mercury lamps and LED lamps.

[0140] The temperature of the post-exposure heating (PEB) is usually 40°C to 200°C, preferably 60°C to 150°C. If the temperature is lower than 40°C, the deprotection reaction or cross-linking reaction cannot be fully carried out, so the difference in solubility between the ultraviolet irradiated part and the ultraviolet non-irradiated part is insufficient and a pattern cannot be formed; if the temperature is higher than 200°C, there is a problem of reduced productivity. Preferably, the heating time is usually 0.5 min to 30 min.

[0141] The development is performed with an alkaline developer, and the alkaline development method includes using an alkaline developer to dissolve and remove the wiring pattern shape. Preferably, the alkaline developer includes but is not limited to 0.1-10wt% aqueous solution of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and sodium bicarbonate, and these alkaline developers may contain water-soluble organic solvents such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, etc. The development method includes but is not limited to immersion method, spray method and spray method, preferably spray method; the temperature of the developer is preferably used at 25-40°C, and the development time is appropriately determined according to the thickness of the resist, and finally a resist pattern faithful to the mask pattern is obtained.

[0142] Among them, the wavelength used for exposure can be selected from h, i line, ArF excimer laser (wavelength 193nm), KrF excimer laser (wavelength 248nm), F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, and soft X-ray, etc. can be used for exposure. Among them, h, i line is preferred.

[0143] The fourth aspect of the present application also provides an electronic device, including any one or more of a protective film, an interlayer insulating material or a pattern transfer material, and the protective film, the interlayer insulating material or the pattern transfer material is prepared by a pattern development method using the anti-etching composition provided by the present application.

[0144] The oxime sulfonate photoacid containing the compound represented by the above formula (A1) and / or the compound represented by the formula (A2) also has high sensitivity and strong absorption to active energy rays with a wavelength of 300-450nm (especially 385nm-436nm), can produce acid quickly under low exposure, and also has good solubility, thermal stability and storage stability. When it is applied to the anti-corrosion composition, when a protective film, interlayer insulating material or pattern transfer material is formed by a pattern development method, the corresponding electronic device can have better comprehensive performance.

[0145] The above application may specifically include forming the photosensitive composition into an interlayer insulating film for use in TFT and panel of liquid crystal display devices; it may also be used as a protective film for color filters and spacers, and as PS photoresist and BCS photoresist for pattern transfer. The above electronic components include, but are not limited to, liquid crystal display devices, organic EL display devices, Micro-LED, Mini-LED and quantum dot LED display devices and other electronic components.

[0146] The fifth aspect of the present application also provides an application of the above-mentioned oxime sulfonate photoacid or resist composition in the photosensitive field.

[0147] Since the oxime sulfonate photoacid provided in the present application has very excellent photosensitivity and thermal stability, solubility and storage stability, its application in the field of photosensitivity can achieve more excellent results.

[0148] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0149] Example 1

[0150] Preparation of compound 3

[0151]

[0152] Place glacial acetic acid in a flask, cool it in a water bath, and slowly add fuming nitric acid to prepare a 50% nitric acid glacial acetic acid solution, which is a light red fuming liquid. Dissolve 2-methyldihydrothiopyran in dichloromethane at a ratio of 2:1 (w / w) to prepare a dihydropyran dichloromethane solution.

[0153] Add 138.29g of acetic anhydride to a four-necked flask, cool to about 2°C in an ice bath, and simultaneously add 164.44g of 2-methylthiopyran solution and 149.15g of nitric acid glacial acetic acid solution in batches, control the nitric acid ratio to 10%, and control the temperature at 5-10°C. After the addition is complete, continue stirring for 2h until the reaction is complete; pour the reaction solution into ice water, stir for 30min, and stand for stratification; dilute the aqueous layer with 500mL of water, and extract three times with 300mL of dichloromethane, combine the organic layers, filter and wash three times with water; concentrate the organic layer to obtain a dark oil; extract the oil with n-hexane reflux for 3 times, 250g of n-hexane each time, combine the extract phases, cool and crystallize to obtain 65.82 solids.

[0154] 32.56 g of sodium methoxide solution (28%), 500 g of toluene and 32.77 g of 2-(5-ethylthiophen-2-yl)acetonitrile were added in sequence, the temperature was lowered to -10-5°C, stirring was continued, 30.36 g of the obtained solid was prepared into a toluene solution, and below 0°C, it was added dropwise to the reaction system, the color turned into dark red, and kept warm at -5-0°C for 1 h. Sampling was performed for central control, and the raw material was <2%, and the reaction was completed; 300 mL of water was added dropwise, heat was slightly released, and 2% hydrochloric acid was added dropwise at 10-15°C to a pH of 4-5; after stirring and standing to separate the organic phase, all the organic phases were combined, decolorized with activated carbon for 30 min and filtered; the filtrate was washed with water until neutral, and the solvent was evaporated under reduced pressure to obtain a dark oily substance; toluene was added for recrystallization to obtain 21.55 g of solid powder.

[0155] 21.57g of solid, 153.15g of dichloromethane and 8.10g of triethylamine were put into a four-necked flask, stirring was started, the kettle temperature was controlled at -5-5°C, 21.65g of trifluoromethanesulfonic anhydride was slowly added dropwise, and then stirred at 10-15°C for 1h. The reaction was stopped when the raw material was less than 1%. Washed with water 3 times, 12.50g of silica gel (200 mesh) was added to the organic layer and the temperature was raised to about 25±5°C and stirred for 1h, filtered and washed with a small amount of dichloromethane, the filtrate was distilled at atmospheric pressure until no dichloromethane was distilled out, 126.18g of membrane filtration n-hexane was added, and when solid appeared, it was placed in a 0-5°C low temperature tank, stirred for 0.5h, filtered, rinsed with 10.00g of n-hexane, dried, and vacuum dried to obtain 25.69g of solid powder. This is the compound shown in (3).

[0156] pass 1 The product structure was characterized by H-NMR, and the results are as follows:

[0157] 1 H NMR (400 MHz, CDCl 3)δ7.34(d,J=7.5Hz,1H),6.88–6.82(m,2H),6.80(d,J=10.9Hz,1H),4.73(d,J=1.8Hz,1H),2.84(qd,J=8.0,4.8Hz,2H),1.50–1.32(m,6H).

[0158] Embodiment 2-9

[0159] Referring to the method of Example 1, the corresponding raw materials were replaced to synthesize other compounds shown in the following Table 1.

[0160] Table 1

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167] Compound

[0168] Comparative Example 1

[0169] Non-ionic photoacid (A*1)

[0170]

[0171] Comparative Example 2

[0172] Non-ionic photoacid (A*2)

[0173]

[0174] Comparative Example 3

[0175] Non-ionic photoacid (A*3)

[0176]

[0177] Performance Evaluation

[0178] The performance of the photoacid compounds synthesized in Examples 1-9 and the comparative example compounds A*1-A*3 was evaluated respectively, and the evaluation indicators included molar absorption coefficient, solubility and resist hardening property.

[0179] (1) Molar absorptivity

[0180] The compound was diluted to 0.25 mmol / L with acetonitrile, and the absorbance of the cuvette length of 1 cm was measured in the range of 200-500 nm using a UV-visible spectrophotometer (UPG-752). The molar absorption coefficient at each wavelength was calculated by the following formula.

[0181] ε(L·mol -1 cm -1 )=A / (0.00025mol / L×1cm), where A represents absorbance.

[0182] The results are shown in Table 2.

[0183] Table 2

[0184]

[0185]

[0186] (2) Solvent solubility

[0187] Take 1.0000g of photoacid generating compound respectively, add solvent (butyl acetate, cyclohexanone and PMA) at 25℃ until the compound in each test tube is completely dissolved and clarified, record the mass of organic solvent used, and the solubility is expressed by the following formula.

[0188]

[0189] (3) Hardening of the resist

[0190] A resin solution of 75 parts of p-hydroxystyrene resin (Maruzen Chemical: MarukaLINKER S-2P), 25 parts of melamine curing agent (Beinock Biotech), 1 part of photoacid and 200 parts of propylene glycol monomethyl ether acetate (PGMEA) was applied to a glass substrate (diameter 10 cm) using a spin coater at 100 rpm / 10 s. Then, vacuum drying was performed at 25°C for 5 minutes, and then drying was performed on a hot plate at 80°C for 3 minutes to form a resist film with a thickness of about 3 μm. The resist film was exposed using an ultraviolet irradiation device (IWATA UV-100D) equipped with a filter. The cumulative exposure amount was measured at a wavelength of 365 nm. Then, post-exposure heating (PEB) was performed in a dryer at 120°C for 10 minutes, and then, immersion in 0.5% potassium hydroxide for 30 seconds was used for development, and then washing and drying were performed immediately. The film thickness of the resist was measured using a shape measurement microscope (Keyence VK-8500). The resist curability was evaluated based on the following criteria from the minimum exposure amount at which the resist film thickness change before and after development was within 10%.

[0191] ⊙: Minimum exposure is 100mJ / cm 2 the following;

[0192] ○: Minimum exposure is greater than 100mJ / cm 2 And at 150mJ / cm 2 the following;

[0193] ×: Minimum exposure greater than 150mJ / cm 2 .

[0194] The evaluation results are listed in Table 3.

[0195] Table 3

[0196]

[0197]

[0198] As shown in Table 2 and Table 3, the photoacid of the present invention has a high molar absorption coefficient at 365nm, 385nm, 405nm and even 436nm, and the light absorption capacity is much higher than that of Comparative Examples 1 to 3. At the same time, the photoacid of the present invention has good solubility, can meet the requirements of resist compositions with different proportions, and can be applied to various fields; in terms of resist hardening, it can also be selected according to the light source, which is more advantageous than the comparative example.

[0199] Industrial Applicability

[0200] The photoacid having the structure shown in the general formula (A) of the present invention has high sensitivity to I-line, H-line and G-line, and can be used for resist films, liquid resists, negative resists, positive resists, resists for MEMS, negative photosensitive materials, materials for stereolithography and micro-stereolithography, etc. with a wavelength range of 300nm-450nm.

[0201] The industrial applicability of the above-mentioned is described below in conjunction with composition examples and comparative examples.

[0202] Examples of photosensitive compositions

[0203] The raw materials of the photosensitive composition were uniformly dissolved in 100% PGMEA (propylene glycol methyl ether acetate) to obtain a photosensitive composition with a solid content concentration of 20 wt %. The oxime sulfonate photoacid (A), resin component (B), aromatic carboxylic acid compound (C) and their contents are shown in Table 4.

[0204] Composition Example 1

[0205] The resin component B is B 1 The structural formulas of the components are as follows: 11 -Formula B 13As shown, the numerical value at the lower right of each repeating unit represents the content (mass %) of the repeating unit in the resin.

[0206] Formula B 11 : Formula B 12 : Formula B 13 :

[0207] The molecular structure of oxime sulfonate photoacid generator is:

[0208] Formula 3:

[0209] Aromatic carboxylic acid compounds (C 1 ) is an aromatic diol (C ′ ) is obtained by reacting with 2,3,3′,4′-biphenyltetracarboxylic dianhydride.

[0210] Formula C ′ :

[0211] Composition Example 2

[0212] The difference between Composition Example 2 and Composition Example 1 is that the oxime sulfonate photoacid generator (A1) adopts an oxime ester photoacid of Formula 5, and its molecular formula structure is:

[0213] Formula 5:

[0214] (2) The types and contents of the remaining components are shown in Table 4.

[0215] Composition Example 3

[0216] The difference between Composition Example 3 and Composition Example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of Formula 7, and its molecular formula structure is:

[0217] Formula 7:

[0218] (2) The types and contents of the remaining components are shown in Table 4.

[0219] Composition Example 4

[0220] The difference between composition example 4 and composition example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of formula 13, and its molecular formula structure is:

[0221] Formula 13:

[0222] (2) The types and contents of the remaining components are shown in Table 4.

[0223] Composition Example 5

[0224] The difference between Composition Example 5 and Composition Example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of Formula 18, and its molecular formula structure is:

[0225] Formula 18:

[0226] (2) The types and contents of the remaining components are shown in Table 4.

[0227] Composition Example 6

[0228] The difference between Composition Example 6 and Composition Example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of Formula 20, and its molecular formula structure is:

[0229] Formula 20:

[0230] (2) The types and contents of the remaining components are shown in Table 4.

[0231] Composition Example 7

[0232] The difference between Composition Example 7 and Composition Example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of Formula 22, and its molecular formula structure is:

[0233] Formula 22:

[0234] (2) The types and contents of the remaining components are shown in Table 4.

[0235] Composition Example 8

[0236] The difference between Composition Example 8 and Composition Example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of Formula 28, and its molecular formula structure is:

[0237] Formula 28:

[0238] (2) The types and contents of the remaining components are shown in Table 4.

[0239] Composition Example 9

[0240] The difference between Composition Example 9 and Composition Example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of Formula 49, and its molecular formula structure is:

[0241] Formula 49:

[0242] (2) The types and contents of the remaining components are shown in Table 4.

[0243] Composition Example 10

[0244] The difference between composition example 10 and composition example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of formula 66, and its molecular formula structure is:

[0245] Formula 66:

[0246] (2) The types and contents of the remaining components are shown in Table 4.

[0247] Composition Example 11

[0248] The difference between composition example 11 and composition example 1 is that the oxime sulfonate photoacid (A1) is an oxime ester photoacid of formula 72, and its molecular formula structure is:

[0249] Formula 72:

[0250] (2) The types and contents of the remaining components are shown in Table 4.

[0251] Composition Example 12

[0252] The difference between composition example 12 and composition example 1 is that the oxime sulfonate photoacid (A2) is an oxime ester photoacid of formula 74, and its molecular formula structure is:

[0253] Formula 74:

[0254] (2) The types and contents of the remaining components are shown in Table 4.

[0255] Composition Example 13

[0256] The difference between composition example 13 and composition example 1 is that the oxime sulfonate photoacid (A2) is an oxime ester photoacid of formula 75, and its molecular formula structure is:

[0257] Formula 75:

[0258] (2) The types and contents of the remaining components are shown in Table 4.

[0259] Composition Example 14

[0260] The difference between composition example 14 and composition example 1 is that the oxime sulfonate photoacid (A2) is an oxime ester photoacid of formula 81, and its molecular formula structure is:

[0261] Formula 81:

[0262] (2) The types and contents of the remaining components are shown in Table 4.

[0263] Composition Example 15

[0264] The difference between composition example 15 and composition example 1 is that,

[0265] Resin component B adopts B 2 The structural formulas of the components of the resin are as follows: 21 -Formula B 23 As shown, the numerical value at the lower right of each repeating unit represents the content (mass %) of the repeating unit in the resin.

[0266] Formula B 21 : Formula B 22 : Formula B 23 :

[0267] The types and contents of other components are shown in Table 4.

[0268] Composition Example 16

[0269] The difference between composition example 16 and composition example 1 is that,

[0270] Resin component B adopts B 3 The structural formulas of the components of the resin are as follows: 31 -Formula B 32 As shown, the numerical value at the lower right of each repeating unit represents the content (mass %) of the repeating unit in the resin.

[0271] Formula B 31 : Formula B 32 :

[0272] The types and contents of other components are shown in Table 4.

[0273] Composition Example 17

[0274] The difference between composition example 17 and composition example 1 is that

[0275] (1) The content of the photoacid of the type 3 is different.

[0276] (2) The types and contents of the remaining components are shown in Table 4.

[0277] Composition Example 18

[0278] The difference between composition example 11 and composition example 1 is that,

[0279] (1) The content of the sulfonate photoacid generator of formula 3 is different.

[0280] (2) The types and contents of the remaining components are shown in Table 4.

[0281] Composition Comparative Example 1

[0282] The resin component B is B 1 The structural formulas of the components are as follows: 11 -Formula B 13 As shown, the numerical value at the lower right of each repeating unit represents the content (mass %) of the repeating unit in the resin.

[0283] Formula B 11 : Formula B 12 : Formula B 13 :

[0284] The molecular structure of oxime sulfonate photoacid is:

[0285] Formula 3:

[0286] The types and contents of other components are shown in Table 4.

[0287] Composition Comparative Example 2

[0288] The difference between the composition comparative example 2 and the composition example 1 is that the photoacid (A) is an imide sulfonate photoacid, and its molecular formula structure is:

[0289] Formula A*1:

[0290] The types and contents of other components are shown in Table 3.

[0291] (2) The types and contents of the remaining components are shown in Table 4.

[0292] Composition Comparative Example 3

[0293] The difference between the comparative example 3 and the example 1 is that:

[0294] (1) The photoacid (A) is an oxime ester photoacid having the following molecular formula:

[0295] Formula A*2:

[0296] (2) The types and contents of the remaining components are shown in Table 4.

[0297] Composition Comparative Example 4

[0298] The difference between the composition comparative example 4 and the composition example 1 is that,

[0299] (1) The photoacid (A) is an oxime ester photoacid having the following molecular formula:

[0300] Formula A*3:

[0301] (2) The types and contents of the remaining components are shown in Table 4.

[0302] Composition Comparative Example 5

[0303] The difference between the composition comparative example 5 and the composition example 1 is that,

[0304] (1) Using aromatic diol (B ′ ) and tetrahydrophthalic anhydride in a molar ratio of 1:1 to obtain a non-aromatic carboxylic acid compound B 2 .

[0305] (2) The types and contents of the remaining components are shown in Table 4.

[0306] Composition Comparative Example 6

[0307] The difference between the composition comparative example 6 and the composition example 1 is that,

[0308] (1) Using non-aromatic carboxylic acid compound polymethacrylic acid (B 3 ).

[0309] (2) 1 part by mass of 2-isopropylthioxanthone was added as a photosensitizer.

[0310] (3) The types and contents of the remaining components are shown in Table 4.

[0311] The photosensitive compositions prepared from Composition Examples 1-18 and Composition Comparative Examples 1-6 were evaluated for sensitivity and resolution by the following methods. The results are recorded in Table 4.

[0312] (1) Sensitivity evaluation method

[0313] On each silicon wafer, the photosensitive composition of each embodiment and comparative example was applied to form a coating film with a film thickness of 3 μm 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 forming a hole pattern with a diameter of 10 μm while gradually changing the exposure amount, and then developed for 30 seconds at 25°C with a 2.0% tetramethylammonium hydroxide aqueous solution. The minimum exposure required to form a hole pattern with a diameter of 10 μm was determined by the above method. From the minimum exposure value obtained, the sensitivity was evaluated according to the following standard. (○-50mJ / cm 2 Below, X-300mJ / cm 2 above)

[0314] (2) Resolution evaluation

[0315] A mask for forming a hole pattern with a diameter of 5 μm was used, except that the 2 Except for exposure at an exposure amount of , the coating film formation, coating film exposure and development were performed in the same manner as the sensitivity evaluation. The coating film after development was observed and the resolution was evaluated according to the following criteria. (○-can form a pattern with a diameter of 5μm, X-cannot form a pattern with a diameter of 5μm)

[0316] Table 4

[0317]

[0318]

[0319] From the test results in Table 4, it can be seen that the photoacid of the present invention has a molar absorption coefficient of more than 20,000 at 385-405 nm, has a strong H-line absorption capacity, can fully utilize light energy, can ensure a high utilization rate in resist applications, and exhibits good resist hardening properties.

[0320] As shown in Table 4, oxime sulfonate A having a predetermined structure, resin component B having an acid group protected by a protecting group, and aromatic carboxylic acid compound C having a carboxyl group bonded to an aromatic group, when mixed in a solvent to form a photosensitive composition containing the derivative, can form a pattern with excellent sensitivity and resolution.

[0321] It can be seen from composition examples 1 to 18 that when the photosensitive composition comprises the oxime sulfonate photoacid of the present invention, the photosensitive composition can obtain the desired sensitivity.

[0322] It can be seen from Composition Example 1 and Composition Comparative Examples 5 and 6 that even if the photosensitive composition contains a compound having a carboxyl group, when the compound does not have a carboxyl group bonded to an aromatic group, the resolution of the photosensitive composition cannot meet the requirements.

[0323] In summary, the photosensitive composition of the present invention can be used as a positive and negative photosensitive composition, the difference between the opening width of the pattern mask and the pattern width is small, fine patterns can be formed, the pattern after development is suppressed from generating undercuts, and the sensitivity is excellent. The photosensitive composition can be used as a protective film or interlayer insulating material for electronic components such as radio frequency devices, liquid crystal display devices, organic EL display devices, Micro-LED, Mini-LED and quantum dot LED display devices; and pattern transfer materials in semiconductor chips.

[0324] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example.

[0325] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An oxime sulfonate photoacid, characterized in that The oxime sulfonate photoacid is: a compound represented by formula (A1) and / or a compound represented by formula (A2), Wherein, R1 is selected from one of the following substituents: Hydrogen, nitro, cyano, C1~C 20 A straight-chain or branched alkyl group, a C1-C4 alkyl group substituted with a C5-C6 cycloalkyl group, or a substituent obtained by replacing -CH2- in the above groups with -O- and / or -S-; Phenyl, or a substituent obtained by replacing hydrogen on the phenyl with a C1-C4 alkyl group; C7~C 20 The C7~C 20 At least one hydrogen atom on the phenyl group in the phenylalkyl group is optionally substituted by a C1-C4 alkyl group, and the -CH2- in the alkyl group connected to the carbon number 1 of the benzene ring is optionally substituted by -O- and / or -S-; R1'-CO-, R1' is selected from a C1-C4 alkyl group, a phenyl group, or a substituent obtained by replacing at least one hydrogen atom in the phenyl group with a C1-C4 alkyl group or an alkoxy group; C4~C 10 An aromatic heterocyclic group; C4~C 10 The aromatic heterocyclic alkyl group, and the C4~C 10 At least one hydrogen atom on the heterocyclic group of the aromatic heterocyclic alkyl group may be optionally replaced by a C1-C4 alkyl group, and the -CH2- in the alkyl group connected to the carbon number 1 of the benzene ring may be optionally replaced by -O- or -S-; C2~C 10 Alkyne group; C2~C 10 Alkenyl; R2'-CO-O-, wherein R2' is selected from C1~C 10 A straight chain or branched alkyl group; R4'-O-CO-R5'-, wherein R4' is selected from C1~C 10 A straight or branched alkyl group, R5' represents a space or a C1-C4 alkylene group, and the -CH2- in the alkylene group may be optionally substituted by -O- or -S-; R2, R3, and R4 are independently selected from hydrogen, C1-C5 straight or branched alkyl; R5 is selected from C1~C 20 Straight or branched alkyl, C3~C 20 Substituted or unsubstituted cycloalkyl, C6~C 20 An aryl group or a camphoryl group, or a substituent formed by replacing at least one hydrogen atom in the above groups with a fluorine atom; The L is selected from the following residues obtained by removing two hydrogen atoms: thiophene, benzothiophene, thienothiophene, pyrrole, pyrrolidine, pyrrolidone, pyridine or phenyl, or a substituent obtained by replacing at least one hydrogen atom in the above residues with a fluorine atom, a C1-C4 alkoxy group or a C1-C4 alkyl group.

2. The oxime sulfonate photoacid according to claim 1, characterized in that The R1 is selected from one of the following substituents: Hydrogen, nitro, cyano, C1~C 10 A straight-chain or branched alkyl group, a C1-C4 alkyl group substituted with a C5-C6 cycloalkyl group, or a substituent obtained by replacing -CH2- in the above groups with -O- and / or -S-; Phenyl, or a substituent obtained by replacing hydrogen on the phenyl with a C1-C4 alkyl group; C7~C 10 The C7~C 10 At least one hydrogen atom on the phenyl group in the phenylalkyl group is optionally substituted by a C1-C4 alkyl group, and the -CH2- in the alkyl group connected to the carbon number 1 of the benzene ring is optionally substituted by -O- and / or -S-; R1'-CO-, R1' is selected from a C1-C4 alkyl group, a phenyl group, or a substituent obtained by replacing at least one hydrogen atom in the phenyl group with a C1-C4 alkyl group or an alkoxy group; thienyl, furanyl or pyrrolyl; A C1-C3 alkyl group substituted with a heterocyclic group, wherein the heterocyclic group is a thienyl group, a furyl group or a pyrrolyl group, at least one hydrogen atom on the heterocyclic group is optionally substituted with a C1-C4 alkyl group, and the -CH2- in the C1-C3 alkyl group is optionally substituted with -O- or -S-; C2-C5 alkynyl; C2-C5 alkenyl; R2'-CO-O-, wherein R2' is selected from C1~C 10 A straight chain or branched alkyl group; R4'-O-CO-R5'-, wherein R4' is selected from C1~C 10 A straight or branched alkyl group, R5' represents a space or a C1-C4 alkylene group, and the -CH2- in the alkylene group may be optionally substituted by -O- or -S-; R2, R3, and R4 are independently selected from hydrogen, C1-C5 straight or branched alkyl; R5 is selected from C1~C 20 A straight-chain or branched alkyl group, a phenyl group, or a phenyl group substituted with a C1-C3 alkyl group, or a substituent formed by replacing at least one hydrogen atom in the above groups with a fluorine atom.

3. The oxime sulfonate photoacid according to claim 1 or 2, characterized in that When L is selected from the following substituents obtained by removing two hydrogen atoms: thiophene, benzothiophene or thienothiophene, the compound represented by formula (A1) is selected from one or more of the following compounds:

4. The oxime sulfonate photoacid according to claim 1 or 2, characterized in that When L is selected from the residue obtained by removing two hydrogen atoms from the following groups: pyrrole, pyrrolidine or pyridine, the compound represented by formula (A1) is selected from one or more of the following compounds:

5. The oxime sulfonate photoacid according to claim 1, characterized in that When L is phenylene, the compound represented by formula (A1) is selected from one or more of the following compounds:

6. The oxime sulfonate photoacid according to any one of claims 1 to 5, characterized in that The compound represented by formula (A2) is selected from one or more of the following compounds:

7. A resist composition, characterized in that The resist composition comprises the oxime sulfonate photoacid according to any one of claims 1 to 6.

8. The resist composition according to claim 7, characterized in that Calculated by weight percentage of the resist composition, the sum of the amounts of the compound represented by formula (A1) and the compound represented by formula (A2) is 0.01 to 5 wt %.

9. The resist composition according to claim 8, characterized in that The total amount of the compound represented by formula (A1) and the compound represented by formula (A2) is 0.1 to 3 wt %.

10. An electronic device comprising any one or more of a protective film, an interlayer insulating material or a pattern transfer material, characterized in that: The protective film, the interlayer insulating material or the pattern transfer material is prepared by using the resist composition according to any one of claims 7 to 9 through a pattern developing method.

11. Use of the oxime sulfonate photoacid according to any one of claims 1 to 6 or the resist composition according to claim 7 in the field of photosensitivity.

Images