Imidosulfonate photoacid, resist composition, electronic device and application

Abstract

The present invention provides an imide sulfonate photoacid, an anti-corrosion composition, an electronic device and an application thereof. The imide sulfonate photoacid has the following structure, R 3 Selected from C 1 ‑C 20 A straight or branched alkyl group, C 1 ‑C 20 A straight or branched fluoroalkyl group, C 3 ‑C 20 Cycloalkyl, C 3 ‑C 20 Fluorinated cycloalkyl, C 6 ‑C 18 A substituted or unsubstituted aryl or camphor group. 3 The introduction of the group makes the imide sulfonate photoacid provided in the present application have higher photosensitivity and sensitivity, better thermal stability and chemical stability (such as amine stability) compared to the existing imide sulfonate photoacid, and has better compatibility with other components during the application process.

Description

Technical Field

[0001] The invention relates to the field of photoacids, and in particular to an imidosulfonate photoacid, a resist composition, an electronic device and applications. Background Art

[0002] The semiconductor integrated circuit industry has developed by finding new application areas and is the basis of all current electronic devices. Chemical etching technology is indispensable in the preparation of integrated circuits. Photoresist is one of the key materials and is the material with the highest technical barriers among electronic chemicals. It has the characteristics of high purity requirements, complex production processes, large initial investments, and long technology accumulation periods. 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 a photoresist in a 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 (optionally, further heating (PEB) may be performed 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] It is widely known that sulfonyl imide photoacid generators are used as photoinitiators in the semiconductor field. However, existing research on sulfonyl imide photoacid generators focuses on sensitivity, system compatibility, etc., and pays insufficient attention to chemical stability. However, with the improvement of industrialization level and the expansion of application fields, the chemical stability of photoacid generators has become an important factor affecting the overall application performance of photoresist compositions.

[0005] The present invention intends to further explore photoacid generator products with high sensitivity, solubility, thermal stability and chemical stability on the basis of the existing technology (such as CN112558409A) to meet higher application requirements. Summary of the invention

[0006] The main purpose of the present invention is to provide an imide sulfonate photoacid, a resist composition, an electronic device and an application thereof, so as to solve the problems that the existing photoacid generator has low sensitivity to active energy rays with a wavelength of 300 to 450 nm (especially 365 nm), and has poor compatibility and chemical stability during application.

[0007] In order to achieve the above object, the present invention provides an imidosulfonate photoacid on the one hand, wherein the imidosulfonate photoacid has the following structure:

[0008]

[0009] R 1 Selected from hydrogen, nitro, cyano, C 1 -C 20 A straight or branched alkyl group, C 3 -C 20 Cycloalkyl, C 2 -C 7 A straight-chain, branched-chain or cyclic aliphatic acyl group, C 2 -C 20 A straight-chain or branched alkynyl group, C 2 -C 20 A straight-chain or branched alkenyl group, C 6 -C 10 Aryl acyl, C 6 -C 18 A substituted or unsubstituted aryl group, C 2 -C 20 A straight or branched alkyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, C 2 -C 20 A straight or branched alkenyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, or R 1 Connected to the carbon on the fluorene ring to form a ring;

[0010] R 2 , R 2 'Independently selected from: C 1 -C 20 A straight or branched alkyl group, C 2 -C 20 A straight or branched alkyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, C 2 -C 20 A straight-chain or branched alkenyl group, C 2 -C 20 A straight-chain or branched alkynyl group, C 6 -C 18 A substituted or unsubstituted aryl group, C 1 -C 10 Alkyl substituted C 3 -C 12 A cycloalkyl group, or R 2 , R 2 'Connected to each other in a ring;

[0011] R 3 Selected from C 1 -C 20 A straight or branched alkyl group, C 1 -C 20 A straight or branched fluoroalkyl group, C 3 -C 20 Cycloalkyl, C 3 -C 20 Fluorinated cycloalkyl, C 6 -C 18 a substituted or unsubstituted aryl group or a camphor group.

[0012] Furthermore, when R 2 , R 2 'When connected to each other to form a ring, R 2 and R 2 'Connected to each other to form Among them, R 4 , R 4 'are independently selected from C 1 -C 8 A straight chain or branched chain alkyl group.

[0013] Furthermore, R 2 and R 2 'are independently selected from C 1 -C 12 A straight or branched alkyl group, C 1 -C 6 Alkyl substituted C 3 -C 8 Cycloalkyl, C 2 -C 12 A straight or branched alkyl group is interrupted by one or more -O- or -S- to form a substituent, C 2 -C 12 A straight-chain or branched alkenyl group, C 2 -C 8 A straight-chain or branched alkynyl group, C 6 -C 13 Aryl, C 1 -C 4 Alkyl substituted C 6 -C 13 Aryl or C 1 -C 4 Alkoxy substituted C 6 -C 13 Aryl.

[0014] Furthermore, R 3 Selected from C 1 -C 10A straight or branched alkyl group, C 3 -C 10 Cycloalkyl, C 1 -C 8 A straight or branched fluoroalkyl group, C 3 -C 10 Fluorinated cycloalkyl, fluorophenyl, C 1 -C 4 phenyl substituted with alkyl or fluoroalkyl, or camphoryl.

[0015] Furthermore, R 1 Selected from hydrogen, nitro, cyano, C 1 -C 10 A straight or branched alkyl group, C 3 -C 8 Cycloalkyl, C interrupted by one or more -O- or -S- 2 -C 7 A straight or branched alkyl group, C 2 -C 7 A straight-chain or branched aliphatic acyl group, C 2 -C 8 A straight-chain or branched alkenyl group, interrupted by one or more -O-, -S-, -O-CO- or -CO-O- 2 -C 8 A straight-chain or branched alkenyl group, C 2 -C 8 A straight-chain or branched alkynyl group, C 6 -C 10 Aryl acyl, C 6 -C 18 a substituted or unsubstituted aryl group, or

[0016] Furthermore, when R 1 When connected to the carbon on the fluorene ring to form a ring, the cyclic group formed is selected from R 1 'for

[0017] In order to achieve the above object, another aspect of the present invention further provides a resist composition, comprising a photoacid generator, wherein the photoacid generator comprises the imidosulfonate photoacid provided in the present application.

[0018] Another 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 above-mentioned protective film, interlayer insulating material or pattern transfer material are all prepared by a pattern development method using the anti-etching composition provided by the present application.

[0019] Another aspect of the present application also provides the use of the imidosulfonate photoacid provided by the present application in the field of photosensitivity.

[0020] By applying the technical solution of the present invention, the sulfonate group in the compound represented by the general formula (A) is directly connected to the imide structure, and the structure has a photosensitive decomposition property and can be rapidly photolyzed to produce sulfonic acid under the irradiation of active energy rays; at the same time, due to the substituted fluorene group and R 3 The introduction of the group makes the imide sulfonate photoacid provided in the present application have higher photosensitivity and sensitivity, better thermal stability and chemical stability (such as amine stability) compared to the existing imide sulfonate photoacid, and has better compatibility with other components during the application process. DETAILED DESCRIPTION

[0021] 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.

[0022] As described in the background technology, the existing photoacid generators are not very sensitive to active energy rays with a wavelength of 300 to 450 nm (especially 365 nm), and have problems such as poor compatibility and chemical stability during application. In order to solve the above technical problems, the present application provides an imide sulfonate photoacid, which has the following structure:

[0023]

[0024] R 1 Selected from hydrogen, nitro, cyano, C 1 -C 20 A straight or branched alkyl group, C 3 -C 20 Cycloalkyl, C 2 -C 7 A straight-chain, branched-chain or cyclic aliphatic acyl group, C 2 -C 20 A straight-chain or branched alkynyl group, C 2 -C 20 A straight-chain or branched alkenyl group, C 6 -C 10 Aryl acyl, C 6 -C 18 A substituted or unsubstituted aryl group, C 2 -C 20 A straight or branched alkyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, C 2 -C 20A straight or branched alkenyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, or R 1 Connected to the carbon on the fluorene ring to form a ring;

[0025] R 2 , R 2 'Independently selected from: C 1 -C 20 A straight or branched alkyl group, C 2 -C 20 A straight or branched alkyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, C 2 -C 20 A straight-chain or branched alkenyl group, C 2 -C 20 A straight-chain or branched alkynyl group, C 6 -C 18 A substituted or unsubstituted aryl group, C 1 -C 10 Alkyl substituted C 3 -C 12 A cycloalkyl group, or R 2 , R 2 'Connected to each other in a ring;

[0026] R 3 Selected from C 1 -C 20 A straight or branched alkyl group, C 1 -C 20 A straight or branched fluoroalkyl group, C 3 -C 20 Cycloalkyl, C 3 -C 20 Fluorinated cycloalkyl, C 6 -C 18 a substituted or unsubstituted aryl group or a camphor group.

[0027] In the compound represented by the general formula (A), the sulfonate group is directly connected to the imide structure, which has a photosensitive decomposition property and can be rapidly photolyzed to produce sulfonic acid under the irradiation of active energy rays; at the same time, due to the substitution of the fluorene group and R 3 The introduction of the group makes the imide sulfonate photoacid provided in the present application have higher photosensitivity and sensitivity, better thermal stability and chemical stability (such as amine stability) compared to the existing imide sulfonate photoacid, and has better compatibility with other components during the application process.

[0028] The active energy ray can be, without limitation, an electromagnetic wave with a wavelength in the visible light region (visible light), an electromagnetic wave with a wavelength in the ultraviolet light region (ultraviolet light), an electromagnetic wave with a wavelength in the infrared light region (infrared light), and an electromagnetic wave with a wavelength in the non-visible region such as X-rays, etc. However, preferably, the active energy ray is an active energy ray with a wavelength between 300-450nm in the near ultraviolet light region and the visible light region, and particularly preferably an active energy ray with a wavelength of 365nm (I line).

[0029] In order to further improve the comprehensive performance of the imide sulfonate photoacid represented by the general formula (A), the substituents contained therein may be optimized.

[0030] In a preferred embodiment, when R 2 , R 2 'When connected to each other to form a ring, R 2 and R 2 'Connected to each other to form Among them, R 4 , R 4 'are independently selected from C 1 -C 8 A straight chain or branched chain alkyl group.

[0031] In a preferred embodiment, R 2 and R 2 'are independently selected from C 1 -C 12 A straight or branched alkyl group, C 1 -C 6 Alkyl substituted C 3 -C 8 Cycloalkyl, C 2 -C 12 A straight or branched alkyl group is substituted by one or more -O- or -S- groups. 2 -C 12 A straight-chain or branched alkenyl group, C 2 -C 8 A straight-chain or branched alkynyl group, C 6 -C 13 Aryl, C 1 -C 4 Alkyl substituted C 6 -C 13 Aryl or C 1 -C 4 Alkoxy substituted C 6 -C 13 Aryl.

[0032] In a preferred embodiment, R 3 Selected from C1 -C 10 A straight or branched alkyl group, C 3 -C 10 Cycloalkyl, C 1 -C 8 A straight or branched fluoroalkyl group, C 3 -C 10 Fluorinated cycloalkyl, fluorophenyl, C 1 -C 4 phenyl substituted with alkyl or fluoroalkyl, or camphoryl.

[0033] In a preferred embodiment, R 1 Selected from hydrogen, nitro, cyano, C 1 -C 10 A straight or branched alkyl group, C 3 -C 8 Cycloalkyl, C interrupted by one or more -O- or -S- 2 -C 7 A straight or branched alkyl group, C 2 -C 7 A straight-chain or branched aliphatic acyl group, C 2 -C 8 A straight-chain or branched alkenyl group, interrupted by one or more -O-, -S-, -O-CO- or -CO-O- 2 -C 8 A straight-chain or branched alkenyl group, C 2 -C 8 A straight-chain or branched alkynyl group, C 6 -C 10 Aryl acyl, C 6 -C 18 A substituted or unsubstituted aryl group or

[0034] In a preferred embodiment, when R 1 When connected to the carbon on the fluorene ring to form a ring, the cyclic group formed is selected from R 1 'for

[0035] In order to further improve the sensitivity of the imide sulfonate photoacid to energy rays, thermal stability and chemical stability, and compatibility with other components during application, in a preferred embodiment, the imide sulfonate photoacid is selected from one or more of the following organic substances:

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] The second aspect of the present application provides a method for preparing the above-mentioned imide sulfonate photoacid, comprising:

[0044] (1) halogenated phthalic anhydride undergoes alcoholysis reaction with Y-OH to obtain an esterified product;

[0045] (2) reacting the esterified product of step (1) with biboric acid pinacol ester to obtain a boron reagent;

[0046] (3) the boron reagent in step (2) undergoes a Suzuki coupling reaction with the substituent to obtain a coupling product;

[0047] (4) hydrolyzing the ester group of the coupling product of step (3) and then dehydrating it to obtain an anhydride;

[0048] (5) the anhydride generated in step (4) undergoes an oximation reaction with (hydrochloric acid or sulfuric acid) hydroxylamine to obtain a hydroxylation product;

[0049] (6) the hydroxylation product of step (5) and sulfonic anhydride (R 3 -SO 2 ) 2 O or sulfonyl chloride R 3 -SO 2 -Cl was subjected to esterification reaction to obtain the target compound.

[0050] The synthetic route is as follows:

[0051]

[0052] Wherein, X is halogen; Y is C 1 -C 12 Straight or branched chain alkanes, cycloalkanes or C 6 -C 12 Aromatic hydrocarbons; R 1 , R 2 , R 2 ' and R 3 The definition of is as described above.

[0053] In view of this, the present invention provides an acid generation method, wherein the above-mentioned photoacid, i.e., the compound of the general formula (A), is irradiated with active energy rays. In a non-limiting manner, the active energy rays may 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. However, preferably, the active energy rays are active energy rays with wavelengths between 300-450nm in the near ultraviolet light region and the visible light region, and particularly preferably, active energy rays with wavelengths of 365nm (I-line) and 385nm.

[0054] 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.

[0055] The third aspect of the present application also provides a resist composition, comprising a photoacid generator, wherein the photoacid generator comprises the imidosulfonate photoacid provided in the present application.

[0056] In the above-mentioned resist composition, the imide sulfonate photoacid generator provided in the present application can break the NO bond under the irradiation of active energy rays to produce sulfonic acid, and after the PEB 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 365 nm (I line). The addition of aromatic carboxylic acid compounds is beneficial to increasing the deprotection reaction rate of the negative resin component in the resist composition after being exposed to acid groups. Therefore, it is beneficial to improve the development effect when using the above-mentioned resist for patterning operations.

[0057] In a preferred embodiment, the content of the imidosulfonate is 0.01-5%, preferably 0.1-3% (w / w) relative to the weight of the solid content of the resist composition. When the amount of the imidosulfonate is limited to this range, it is not only beneficial to further improve its sensitivity to ultraviolet rays, but also beneficial to exert its physical properties of the insoluble part in the alkaline developer, thereby improving its development effect.

[0058] The solvent in the above-mentioned resist composition can be one 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, and propylene 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.

[0059] The solvent is used to dissolve the components in the resist composition to form a uniform solution for adjusting the viscosity and coating properties. 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 of the resist composition is 5-30% (w / w).

[0060] Positive resist composition

[0061] In addition to the imide sulfonate photoacid generator (A), 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, when selective exposure is performed, the acid-labile groups protected by the protecting groups in the positive type resin in the exposed area are deprotected by the acid generated by the photoacid, making them soluble in an alkaline developer. Therefore, when alkaline development is performed, the pattern in the unexposed area remains, forming a positive type pattern.

[0062] 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 with 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 generated by the photoacid generator (A).

[0063] 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.

[0064] Preferably, the above-mentioned protecting group comprises at least one of the following groups:

[0065]

[0066] 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 are suitable for bonding to each other 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 are suitable to 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 wherein n is 0 or 1.

[0067] Specifically, in formula (a), when R 8 , R 9 and R 10When it is an alkyl group, it can be optionally 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 and the like.

[0068] When R 8 , R 9 and R 10 When any two groups in are bonded to each other to form a ring, preferably 5 -C 20 A monocyclic or polycyclic aliphatic hydrocarbon; optionally, 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 A straight chain or branched chain alkyl group.

[0069] Preferably, formula (a) can be selected from the following molecular formula (formula a 1 -Formula A 6 )

[0070]

[0071] 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 );

[0072]

[0073] And, in formula (b), when R 11 , R 12 and R 13When 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 or 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.

[0074] Preferably, formula (b) may preferably be the following molecular formula (Formula b 9 -Formula b 14 ) group:

[0075]

[0076] Specifically, the formula (c) can be selected from tert-butyloxycarbonyl and tert-butyloxycarbonylmethyl.

[0077] The alkali-soluble acidic group in the resin component (B1) may be a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group.

[0078] Among them, the resin containing phenolic hydroxyl groups (B1-1) includes but is not limited to novolac resin, a polymer 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, and polyhydroxystyrene resins include but are 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.

[0079] 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. 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 protecting group is used in the resin component. As described above, the polyhydroxystyrene resin can introduce a crosslinking group as needed. The crosslinking group is a functional group that can be thermally crosslinked when the patterned film to be formed is post-baked. Groups suitable for use as crosslinking groups can be selected from epoxy groups, oxetane groups, and groups containing unsaturated double bonds [such as (meth) acryloyl groups]. In the resin component, the content of the crosslinking group is preferably 20-70% (w / w), within which a film with excellent mechanical properties and chemical resistance can be formed by thermal crosslinking between crosslinking groups during PEB.

[0080] The above-mentioned (meth)acrylamide includes but is not limited to (meth)acrylamide, (meth)N-alkyl(meth)acrylamide, (meth)N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide or N-hydroxyethyl-N-methyl(meth)acrylamide, etc. Allyl compounds include but are not limited to allyl acetate, allyl caproate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate or 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.

[0081] The novolac resin mentioned in the present application is obtained by condensing an aromatic compound having a phenolic hydroxyl group (hereinafter referred to as "phenol") with an aldehyde under 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-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, pyrogallol, hydroxydiphenyl, bisphenol A, gallic acid, α-naphthol, β-naphthol and one or more thereof. Aldehydes include but are not limited to formaldehyde, trioxymethylene, acetaldehyde, furfural, benzaldehyde and nitrobenzaldehyde, etc. In a preferred embodiment, the novolac resin includes but is not limited to one or more of phenol-formaldehyde condensation novolac resin, cresol-formaldehyde condensation novolac resin, and phenol-naphthol-formaldehyde condensation novolac resin.

[0082] The molecular weight of the above resin containing phenolic hydroxyl groups is preferably about 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] In order to further improve the developing performance of the resist composition, preferably, the content of the acid-based resin accounts for 1 to 80% of the content of the resin component (B1), more preferably 10 to 70%. Preferably, the hydrophobic vinyl monomer includes but is not limited to (meth)acrylate and aromatic hydrocarbon monomer.

[0088] Further preferably, the above (meth)acrylate includes but is not limited to C 1 -C 20 Alkyl (meth) acrylate and / or alicyclic (meth) acrylate. 1 -C 20Alkyl (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.

[0089] 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.

[0090] 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%.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] In a preferred embodiment, the alkoxycarbonyl group includes but is not limited to methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl or tert-butoxycarbonyl.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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%.

[0103] 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.

[0104] Negative resist composition

[0105] 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.

[0106] 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.

[0107] 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).

[0108] 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.).

[0109] 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).

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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. ;

[0115] 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.

[0116] 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).

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] The pattern is developed 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 0.1-10% (w / w) 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, spraying and spraying, preferably spraying; 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.

[0127] 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.

[0128] 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, 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.

[0129] Since the resist composition provided by the present application 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)), acid can be generated quickly under a lower exposure amount, and it also has good solubility, thermal stability and storage stability. Therefore, when the above-mentioned resist composition is used to form a protective film, an interlayer insulating material or a pattern transfer material through a pattern development method, the corresponding electronic device can have better comprehensive performance.

[0130] 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.

[0131] As a photoacid generator, the fifth aspect of the present application also provides an application of the imidosulfonate provided by the present application in the field of photosensitization.

[0132] Since the imide sulfonate provided in the present application has very excellent photosensitivity and thermal stability, solubility and storage stability, it can also be applied to other photosensitive fields.

[0133] 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.

[0134] Example 1

[0135] Preparation of compound 7

[0136]

[0137] Add 50mL of pure water to a 200ml beaker, then add 40.00g of sodium hydroxide under stirring, dissolve and place at room temperature. Add 30.00g of 2-bromofluorene and 0.32g of 4-butylammonium bromide to a four-necked flask, add 200.09g of DMSO, start stirring and cool to -5-0°C, slowly drop the sodium hydroxide solution into the flask, then drop 70.45g of 1-bromobutane into the system, heat to room temperature and stir for 20h to obtain 39.80g of 2-bromo-9,9-dibutylfluorene.

[0138] Under water bath cooling, slowly add fuming nitric acid to prepare 50% (w / w) nitric acid glacial acetic acid solution, which is a light red fuming liquid. Add 17.11g of acetic anhydride to a four-necked flask, and when the ice bath is cooled to about 2°C, add 39.80g of 2-bromo-9,9-dibutylfluorene and 17.56g of nitric acid glacial acetic acid solution in batches at the same time, 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 completed; pour the reaction solution into ice water, stir for 30min, and stand for stratification; dilute the water layer with 500mL of water, and extract three times with 60mL of dichloromethane, combine the organic layers, filter and wash three times with water; concentrate the organic layer to obtain a dark oil; the oil is reflux extracted with n-hexane 3 times, 30g of n-hexane each time, combine the extract phases, cool and crystallize to obtain 34.05g of solid.

[0139] Add 100.02g 4-bromophthalic anhydride, 100.27g concentrated sulfuric acid and 500.02g n-butanol to a 1000ml four-necked flask (with a water separator), stir in an external oil bath and heat to 90°C, stir for 6h, stop stirring when the main peak is ≥93.00% in the central control, and cool to 10-20°C. Add 400g pure water to the four-necked flask, stir for 5min, let stand for 10min, and separate the water layer. Add 200g pure water to the organic layer, stir for 5min, refine for 10min, and separate the water layer. Add 500.0g dichloromethane to the organic layer, add 200g pure water, stir for 5min, refine for 10min, and separate the water layer. Wash the organic layer to a neutral PH = 7 (estimated to wash three times) (water washing temperature 20-30°C). After washing the organic layer with water, add 1.0g anhydrous sodium sulfate and filter with suction. The organic layer was added into a 1000 ml four-necked flask and distilled at 120° C. under reduced pressure (vacuum degree ≥ -0.090 MPa) until no more distillate was produced to obtain 128.48 g of a light yellow oily liquid.

[0140] 700.15g toluene, 86.21g n-butyl 4-bromophthalate, 55.66g pinacol diborane, 1.21g Pd(dba)2, 63.88g potassium acetate, 2.11g x-phos (2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl) were added to a 2000ml four-necked flask (with a condenser), and the temperature was raised to 110°C with stirring in an oil bath, the internal temperature was 105°C, and the temperature was kept under reflux for 2 hours: n-butyl ester peak ≤ 0.50%. The temperature was lowered to 50°C, 100g water was added, stirred for 10min, the water was separated, 3.0g activated carbon (878 type) was added, decolorized, washed twice with water (100g water each time, the washing temperature was 20-30°C), and toluene was removed under reduced pressure to obtain 85.05g of dark red oily liquid.

[0141] In a 1000 ml four-necked flask (with a condenser), 250 g of toluene, 30.03 g of 4-boronate phthalic acid n-butyl ester, 31.41 g of 2-bromo-7-nitro-9,9-dibutylfluorene, 1.56 g of Pd(PPh 3 ) 2 Cl 2 , 39.39g of tripotassium phosphate, stir in an oil bath and heat to an internal temperature of 90°C, keep reflux, and stop the reaction when 4-boric acid ester butyl phthalate ≤3.00% and 2-bromo-7-nitro-9,9-dibutylfluorene ≤1.00%. Cool the reaction system to 30°C, add 100g of water, stir for 10min, then separate and remove the water phase, add 3.0g of activated carbon (878) for decolorization, and then wash twice (30g of water each time, washing temperature 20-30°C). Remove toluene under reduced pressure, pass through a column (dichloromethane, 200-300 mesh silica gel), and obtain 31.33g of dark oily liquid.

[0142] Take 30.05g of 4-(7-nitro-9,9-dibutylfluorene)phthalic acid n-butyl ester and dissolve it in anhydrous ethanol, stir it evenly to prepare solution A. Take 6.02g of sodium hydroxide and dissolve it in pure water, stir it evenly to prepare solution B. Mix solutions A and B evenly, add them into a 500ml four-necked flask, stir in a water bath and heat to 52°C, the internal temperature is 50°C, and keep reflux. HPLC control: no 4-(7-nitro-9,9-dibutylfluorene)phthalic acid n-butyl ester remains, 4-(7-nitro-9,9-dibutylfluorene)phthalic acid sodium ≥94%, stop the reaction. Distill under reduced pressure at 60°C and -0.9MPa until no product is distilled out, add water repeatedly, extract and separate with dichloromethane until both phases are clear. Concentrated hydrochloric acid was added dropwise to the aqueous phase until the pH value was 1-2, and the solution changed from clear to yellow suspension. It was stirred in an ice-water bath for 10 minutes, filtered and dried to obtain 22.46 g of product.

[0143] Add 22.45g 4-(7-nitro-9,9-dibutylfluorene)phthalic acid and 56.13g acetic anhydride to a 250ml four-necked flask, stir in an oil bath and heat to 70°C, keep warm and stir for 2h, stop stirring when the central control system no longer changes, cool to 10-20°C. Cool the reacted solution to ≤5°C in an ice-water bath, and let stand in an ice-water bath to precipitate 11.78g of product.

[0144] Add 100.12g methanol, 11.50g 4-(7-nitro-9,9-dibutylfluorene)phthalic anhydride, 2.36g hydroxylamine hydrochloride, and 3.01g triethylamine to a 500ml four-necked flask (with a condenser), stir in an oil bath, heat to 80°C, internal temperature 68°C, keep warm and reflux for 6h, control: when the product peak no longer increases, stop the reaction. Cool to 20-40°C, add 2.0g activated carbon (878), decolorize, add 10.0g water, 40.0g dichloromethane, wash twice with water at room temperature (10.0g water each time), distill methanol, crystallize at low temperature and filter to obtain a red solid, dissolve with dichloromethane, adjust pH to 2 with hydrochloric acid, and filter to obtain 4.69g yellow solid product.

[0145] To a 500ml four-necked flask, add 200.12g of dichloromethane, 4.69g of 4-(7-nitro-9,9-dibutylfluorene)phthalimide, and 0.80g of pyridine. Place in an ice-water bath, cool to 0-3°C, internal temperature 0-2°C, begin to dropwise add 2.88g of trifluoromethylsulfonic anhydride, control the internal temperature at 0-5°C, after the addition is complete, stir at this temperature for 0.5h, control: imide peak ≤1.00%. Cool to 20-40°C, add 2.0 g of activated carbon (878), decolorize, wash twice with water at room temperature (60.0 g each time), adjust pH to 2 with hydrochloric acid (35.0%), wash twice with water at room temperature (60.0 g each time), adjust pH to 8 with aqueous ammonia, wash to pH 7, distill at 60°C, cool to below 40°C, pass through a 200-300 mesh silica gel column, distill the distillate at normal pressure until no dichloromethane is distilled out, add 30.35 g of membrane-filtered n-hexane, wait until solid appears, put into 0-5°C low-temperature tank, stir for 0.5 h, filter, rinse with 10.00 g of n-hexane, drain, and vacuum dry to obtain 2.96 g of a light yellow solid product. This is the compound shown in (7).

[0146] pass 1 The product structure was characterized by H-NMR, and the results are as follows:

[0147] 1 H NMR (400 MHz, CDCl 3 )δ8.23(dd,J=7.4,1.6Hz,1H),8.18(d,J=1.5Hz,1H),8.09–8.04(m,2H),7.88-7.51(dd,J=7.5,1.5Hz,4H),7.35( d,J=1.5Hz,1H),1.94-1.84(dt,J=12.5,7.0Hz,4H),1.56–1.44(m,4H),1.43–1.31(m,4H),0.88(t,J=7.9Hz,6H).

[0148] Example 2-21

[0149] Referring to the method of Example 1, the corresponding raw materials were replaced to synthesize other compounds shown in the following Table 1.

[0150] Table 1

[0151]

[0152]

[0153]

[0154]

[0155]

[0156] Compound

[0157] Comparative Example 1

[0158] Non-ionic photoacid (A*1)

[0159]

[0160] Comparative Example 2

[0161] Non-ionic photoacid (A*2)

[0162]

[0163] Performance Evaluation

[0164] The performance of the photoacid compounds synthesized in Examples 1-31 and the comparative example compounds A*1 and A*2 was evaluated respectively, and the evaluation indicators included molar absorption coefficient, solubility, resist hardenability and chemical stability.

[0165] (1) Molar absorptivity

[0166] The compound was diluted to 0.25 mmol / L with acetonitrile, and the absorbance was measured in the range of 200 to 500 nm with a cuvette length of 1 cm using a UV-visible spectrophotometer (UPG-752). The molar absorption coefficient at each wavelength was calculated using the following formula.

[0167] E(L·mol -1 cm -1 )=A / (0.00025mol / L×1cm)

[0168] Where A represents absorbance.

[0169] The results are shown in Table 2.

[0170] Table 2

[0171]

[0172]

[0173] (2) Solvent solubility

[0174] Take 1.0000g of photoacid generating compound respectively, add solvent (butyl acetate, cyclohexanone and PMA) at 25°C until the compound in each test tube is completely dissolved and clear, record the mass of organic solvent used, and the solubility is expressed by the following formula.

[0175]

[0176] (3) Hardening of the resist

[0177] 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%.

[0178] ⊙: Minimum exposure is 200mJ / cm 2 the following;

[0179] ○: Minimum exposure is greater than 200mJ / cm 2 And at 250mJ / cm 2 the following;

[0180] ×: Minimum exposure greater than 250mJ / cm 2 .

[0181] The evaluation results are listed in Table 3.

[0182] (4) Chemical stability

[0183] In the formulation composition containing the photoacid generator, a variety of auxiliary agents are contained to achieve the storage stability of the composition and meet the conditions of the subsequent process. This requires that the photoacid generator not only cannot affect the auxiliary agents in the composition, but also must exist stably in it without any chemical reaction. Triethylamine was used as the auxiliary agent for investigation, and the addition amount of 10% photoacid generator (w / w) was dissolved in PGMEA together with the photoacid generator, and then stored at room temperature for 168 hours after sealing. The storage stability of the photoacid generator was investigated by HPLC.

[0184] The results are graded as follows:

[0185] ◎-HPLC content ≥95.00%;

[0186] ○-HPLC content 85.00-95.00%;

[0187] ×-HPLC content <85.00%.

[0188] Table 3

[0189]

[0190] As shown in Table 2 and Table 3, the photoacid of the present invention has a high molar absorption coefficient at 365nm, 385nm and even 405nm, and the light absorption capacity is much higher than that of Comparative Example 1 and Comparative Example 2. At the same time, the photoacid of the present invention has good solubility and chemical stability in PMA, can meet the requirements of resist compositions with different ratios, and can be applied in 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.

[0191] Industrial Applicability

[0192] The photoacid having the structure shown in the general formula (A) of the present invention has a high sensitivity to I-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.

[0193] The industrial applicability of the above-mentioned is described below in conjunction with composition examples and comparative examples.

[0194] Examples of photosensitive compositions

[0195] The raw materials of the photosensitive composition are uniformly dissolved in 100% PGMEA (propylene glycol methyl ether acetate) to obtain a photosensitive composition with a solid content concentration of 20% (w / w). The imide sulfonate photoacid (A), resin component (B), aromatic carboxylic acid compound (C) and their contents are shown in Table 4.

[0196] Composition Example 1

[0197] 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.

[0198]

[0199] The molecular structure of the imide sulfonate photoacid generator is:

[0200]

[0201] Aromatic carboxylic acid compounds (C 1 ) is obtained by reacting an aromatic diol (C) with 2,3,3′,4′-biphenyltetracarboxylic dianhydride in a molar ratio of 1:1.

[0202]

[0203] Composition Example 2

[0204] The difference between composition example 2 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 10, whose molecular formula structure is:

[0205]

[0206] The types and contents of other components are shown in Table 4.

[0207] Composition Example 3

[0208] The difference between composition example 3 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 12, whose molecular formula structure is:

[0209]

[0210] The types and contents of other components are shown in Table 4.

[0211] Composition Example 4

[0212] The difference between composition example 4 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 14, whose molecular formula structure is:

[0213]

[0214] The types and contents of other components are shown in Table 4.

[0215] Composition Example 5

[0216] The difference between composition example 5 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 17, whose molecular formula structure is:

[0217]

[0218] The types and contents of other components are shown in Table 4.

[0219] Composition Example 6

[0220] The difference between composition example 6 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 20, whose molecular formula structure is:

[0221]

[0222] The types and contents of other components are shown in Table 4.

[0223] Composition Example 7

[0224] The difference between composition example 7 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 26, whose molecular formula structure is:

[0225]

[0226] The types and contents of other components are shown in Table 4.

[0227] Composition Example 8

[0228] The difference between composition example 8 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 28, whose molecular formula structure is:

[0229]

[0230] The types and contents of other components are shown in Table 4.

[0231] Composition Example 9

[0232] The difference between composition example 9 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 29, whose molecular formula structure is:

[0233]

[0234] The types and contents of other components are shown in Table 4.

[0235] Composition Example 10

[0236] The difference between composition example 10 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 31, whose molecular formula structure is:

[0237]

[0238] The types and contents of other components are shown in Table 4.

[0239] Composition Example 11

[0240] The difference between composition example 11 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 46, whose molecular formula structure is:

[0241]

[0242] The types and contents of other components are shown in Table 4.

[0243] Composition Example 12

[0244] The difference between composition example 12 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 47, whose molecular formula structure is:

[0245]

[0246] The types and contents of other components are shown in Table 4.

[0247] Composition Example 13

[0248] The difference between composition example 13 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 57, whose molecular formula structure is:

[0249]

[0250] The types and contents of other components are shown in Table 4.

[0251] Composition Example 14

[0252] The difference between composition example 14 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 59, whose molecular formula structure is:

[0253]

[0254] The types and contents of other components are shown in Table 4.

[0255] Composition Example 15

[0256] The difference between composition example 15 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 60, whose molecular formula structure is:

[0257]

[0258] The types and contents of other components are shown in Table 4.

[0259] Composition Example 16

[0260] The difference between composition example 16 and composition example 1 is that the imide sulfonate photoacid generator (A) adopts the photoacid generator compound 62, whose molecular formula structure is:

[0261]

[0262] The types and contents of other components are shown in Table 4.

[0263] Composition Example 17

[0264] The difference between composition example 17 and composition example 1 is that:

[0265] The resin component (B) is a B2 type resin, which is composed of repeating units represented by formula B21, B22 and B23. The value at the bottom right of each repeating unit represents the content (mass %) of the repeating unit in the resin. The weight average molecular weight of the B2 resin is about 10,000.

[0266]

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

[0268] Composition Example 18

[0269] The difference between composition example 18 and composition example 1 is:

[0270] The resin component (B) is a B3 type resin, which is composed of repeating units represented by formula B31 and formula B32. The value at the lower right of each repeating unit represents the content (mass %) of the repeating unit in the resin. The weight average molecular weight of the B3 resin is about 10,000.

[0271]

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

[0273] Composition Example 19

[0274] The difference between composition example 19 and composition example 1 is that the content of the imide sulfonate photoacid generator shown in photoacid generator example 1 is different. The types and contents of the remaining components are shown in Table 4.

[0275] Composition Example 20

[0276] The difference between composition example 20 and composition example 1 is that the content of the imide sulfonate photoacid generator shown in photoacid generator example 1 is different. The types and contents of the remaining components are shown in Table 4.

[0277] Composition Comparative Example 1

[0278] The difference between the comparative example 1 and the example 1 is that the aromatic carboxylic acid compound (C) is not contained. The component types and contents are shown in Table 4.

[0279] Composition Comparative Example 2

[0280] The difference between the comparative example 2 and the example 1 is that the imide sulfonate photoacid generator (A) is the imide sulfonate photoacid generator shown in A*1. The component types and contents are shown in Table 4.

[0281] Composition Comparative Example 3

[0282] The difference between the comparative example 3 and the example 1 is that the imide sulfonate photoacid generator (A) is the imide sulfonate photoacid generator shown in A*2. The component types and contents are shown in Table 4.

[0283] Composition Comparative Example 4

[0284] The difference between the composition comparative example 4 and the composition example 1 is that,

[0285] (1) An aromatic carboxylic acid compound C2 is obtained by reacting an aromatic diol (C') with tetrahydrophthalic anhydride at a molar ratio of 1:1.

[0286] (2) The types and contents of the remaining components are shown in Table 4.

[0287] Composition Comparative Example 5

[0288] The difference between the composition comparative example 5 and the composition example 1 is that,

[0289] (1) Using the non-aromatic carboxylic acid compound polymethacrylic acid (C3).

[0290] (2) 1 part by mass of 2-isopropylthioxanthone was added as a photosensitizer.

[0291] (3) The types and contents of the remaining components are shown in Table 4.

[0292] The photosensitive compositions prepared from Composition Examples 1-20 and Composition Comparative Examples 1-5 were evaluated for sensitivity and resolution by the following methods. The results are recorded in Table 4.

[0293] (1) Sensitivity evaluation method

[0294] 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)

[0295] (2) Resolution evaluation

[0296] A mask for forming a hole pattern with a diameter of 5 μm was used, except that the irradiation rate was 100 mJ / cm 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)

[0297] Table 4

[0298]

[0299]

[0300] 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 365 nm, has a strong light absorption capacity, can fully utilize light energy, can ensure a high utilization rate in resist applications, and exhibits good resist hardening properties.

[0301] As can be seen from Table 4, the photosensitive composition containing the derivative formed by mixing the imide sulfonate A having a predetermined structure, the resin component B having an acid group protected by a protecting group, and the aromatic carboxylic acid compound C having a carboxyl group bonded to an aromatic group in a solvent can form a pattern with excellent sensitivity and resolution.

[0302] It can be seen from composition examples 1 to 20 that when the photosensitive composition comprises the imide sulfonate photoacid of the present invention, the photosensitive composition can obtain the desired sensitivity.

[0303] It can be seen from Composition Example 1 and Composition Comparative Examples 4 and 5 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.

[0304] In summary, 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.

[0305] 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.

[0306] 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 imide sulfonate photoacid, It is characterized in that The imidosulfonate photoacid has the following structure: R 1 Selected from hydrogen, nitro, cyano, C 1 -C 20 A straight or branched alkyl group, C 3 -C 20 Cycloalkyl, C 2 -C 7 A straight-chain, branched-chain or cyclic aliphatic acyl group, C 2 -C 20 A straight-chain or branched alkynyl group, C 2 -C 20 A straight-chain or branched alkenyl group, C 6 -C 10 Aryl acyl, C 6 -C 18 Aryl, C 2 -C 20 A straight or branched alkyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, C 2 -C 20 A straight or branched alkenyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, or the R 1 Connected to the carbon on the fluorene ring to form a ring; R 2 , R 2 'Independently selected from: C 1 -C 20 A straight or branched alkyl group, C 2 -C 20 A straight or branched alkyl group is interrupted by at least one -O-, -S-, -O-CO- or -CO-O- to form a substituent, C 2 -C 20 A straight-chain or branched alkenyl group, C 2 -C 20 A straight-chain or branched alkynyl group, C 6 -C 13 Aryl, C 1 -C 4 Alkyl substituted C 6 -C 13 Aryl, C 1 -C 4 Alkoxy substituted C 6 -C 13 Aryl, C 1 -C 10 Alkyl substituted C 3 -C 12 A cycloalkyl group, or R 2 , R 2 'Connected to each other in a ring; R 3 Selected from C 1 -C 20 A straight or branched alkyl group, C 1 -C 20 A straight or branched fluoroalkyl group, C 3 -C 20 Cycloalkyl, C 3 -C 20 Fluorinated cycloalkyl, C 6 -C 18 unsubstituted aryl or camphoryl, replaced by C 1 -C 4 Phenyl substituted with alkyl or fluoroalkyl; When the R 1 When connected to the carbon on the fluorene ring to form a ring, the cyclic group formed is selected from R 1 'for When the R 2 , the R 2 'When connected to each other to form a ring, the R 2 and the R 2 'Connected to each other to form Among them, R 4 , R 4 'are independently selected from C 1 -C 8 A straight chain or branched chain alkyl group.

2. The imide sulfonate photoacid according to claim 1, It is characterized in that The R 2 and the R 2 'are independently selected from C 1 -C 12 A straight or branched alkyl group, C 1 -C 6 Alkyl substituted C 3 -C 8 Cycloalkyl, C 2 -C 12 A straight or branched alkyl group is interrupted by one or more -O- or -S- to form a substituent, C 2 -C 12 A straight-chain or branched alkenyl group, C 2 -C 8 A straight-chain or branched alkynyl group, C 6 -C 13 Aryl, C 1 -C 4 Alkyl substituted C 6 -C 13 Aryl or C 1 -C 4 Alkoxy substituted C 6 -C 13 Aryl.

3. The imide sulfonate photoacid according to claim 1 or 2, It is characterized in that The R 3 Selected from C 1 -C 10 A straight or branched alkyl group, C 3 -C 10 Cycloalkyl, C 1 -C 8 A straight-chain or branched fluoroalkyl group, C 3 -C 10 The fluorinated cycloalkyl, C 1 -C 4 phenyl substituted with alkyl or fluoroalkyl, or camphoryl.

4. The imide sulfonate photoacid according to claim 3, It is characterized in that The R 1 Selected from hydrogen, nitro, cyano, C 1 -C 10 A straight or branched alkyl group, C 3 -C 8 Cycloalkyl, C interrupted by one or more -O- or -S- 2 -C 7 A straight or branched alkyl group, C 2 -C 7 A straight-chain or branched aliphatic acyl group, C 2 -C 8 A straight-chain or branched alkenyl group, interrupted by one or more -O-, -S-, -O-CO- or -CO-O- 2 -C 8 A straight-chain or branched alkenyl group, C 2 -C 8 A straight-chain or branched alkynyl group, C 6 -C 10 Aryl acyl, C 6 -C 18 Aryl, or 5. An imide sulfonate photoacid, It is characterized in that The imide sulfonate photoacid is selected from one or more of the following organic substances:

6. A resist composition comprising a photoacid generator, It is characterized in that The photoacid generator includes the imide sulfonate photoacid according to any one of claims 1 to 5.

7. An electronic device comprising any one or more of a protective film, an interlayer insulating material or a pattern transfer material, It is characterized in that The protective film, the interlayer insulating material or the pattern transfer material is prepared by using the resist composition described in claim 6 through a pattern developing method.

8. Use of the imide sulfonate photoacid according to any one of claims 1 to 5 in the field of photosensitization.

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