CN115611782A - High-acid-production oxime sulfonate photoacid generator and application of resist composition thereof - Google Patents
High-acid-production oxime sulfonate photoacid generator and application of resist composition thereof Download PDFInfo
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- CN115611782A CN115611782A CN202211266580.XA CN202211266580A CN115611782A CN 115611782 A CN115611782 A CN 115611782A CN 202211266580 A CN202211266580 A CN 202211266580A CN 115611782 A CN115611782 A CN 115611782A
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- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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Abstract
The invention discloses an I-line high-acid-production oxime sulfonate photoacid generator and application of a resist composition thereof, wherein the high-acid-production oxime sulfonate photoacid generator has high light sensitivity and more advantages in solubility, thermal stability and chemical stability, and has a structure shown in a general formula (I):
Description
Technical Field
The invention belongs to the technical field of photosensitive materials, and particularly relates to an oxime sulfonate photoacid generator capable of highly generating acid within a wavelength range of 300-450nm and application of a resist composition thereof.
Background
Photoacid generators are one of the key components of chemically amplified photoresists, and their structure and performance have a large impact on the lithographic image. The nonionic i-line photoacid generators are primarily sulfonates. Among them, oxime sulfonate photoacid generators are widely known as photoinitiators in the semiconductor field, and various oxime sulfonate photoacid generators are disclosed in patent documents such as JP2000066385A, JP2016169173A, CN1989455B, CN101473268A, CN112010788A, and the like. Few of these techniques can cover the light sensitive region over the i-g line, or the acid yield at the i-g line is low. With the requirement for high-precision patterns, the photoacid generator must have the conditions of high solubility, high acid production rate, good thermal stability matching and chemical stability, and the like.
Disclosure of Invention
The invention aims to provide a photoacid generator for highly producing an oxime sulfonate and a resist composition application thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided an oxime sulfonate photoacid generator having a structure represented by the following general formula (I):
wherein the content of the first and second substances,
R 1 is represented by C 1 -C 20 Straight or branched alkyl of (2), C 3 -C 20 Cycloalkyl of (C) 1 -C 20 Straight or branched fluoroalkyl of (2), C 3 -C 20 Fluorocycloalkyl group of (C) 6 -C 18 Is gotA substituted or unsubstituted aryl, camphoryl, camphorquinone or azidonaphthalenone group;
R 2 and R 2 ' may be the same or different and are each independently selected from the group consisting of: hydrogen, halogen, C 1 -C 20 Linear or branched alkyl of (2), C 3 -C 20 Cycloalkyl of, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (2), C 1 -C 20 Linear or branched alkoxy of (2), C 1 -C 20 Linear or branched alkylthio of (A), C 1 -C 20 Straight or branched haloalkyl of (1), C 1 -C 20 Linear or branched hydroxy-substituted alkyl of (1), C 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 Alkyl, C interrupted by more than 1-O-, -S-, -O-CO-or-CO-O-) 2 -C 20 Linear or branched alkyl or alkoxy, substituted or unsubstituted C 6 -C 10 Aryl radical, C 6 -C 20 Arylthio of (a), a C2-C20 heterocyclic group containing N, O and/or S; or two R 2 Are linked to each other to form a ring;
R 3 selected from the following groups: hydrogen, nitro, cyano, or a salt thereof,
hydroxy, halogen, C 1 -C 20 The alkyl group may have a halogen atom or a hydroxyl group as a hydrogen atom, a linear or branched C2-C20 alkenyl group, or a branched C2-C20 alkenyl group 2 -C 20 Straight-chain or branched alkynyl group of (2), C 1 -C 20 Linear or branched alkyl of (2), or C 1 -C 20 In the straight-chain or branched alkyl group, -CH 2 -is substituted by-O-, -S-, -CO-),
-COO-or-OCO-substituted; c 3 -C 30 Wherein the hydrogen atom may be replaced by halogen, C 1 -C 20 Or a linear or branched alkyl group, is formed by more than 1-O-) -S-, C interrupted by-OCO-or-COO- 2 -C 20 Substituted with a linear or branched alkyl group; bridged cycloalkyl radicals in which the hydrogen atoms may be replaced by halogen, C 1 -C 20 Is a straight-chain or branched alkyl group, is formed by more than 1-O-) -S-, C interrupted by-OCO-or-COO- 2 -C 20 Linear or branched alkyl groups; c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom in the phenyl radical of an aryl group being bound by C 1 -C 20 Linear or branched alkyl of (2), C 1 -C 20 Linear or branched alkoxy of (2), C 6 -C 20 Aryl-substituted C of 1 -C 20 Alkoxy radical, C 1 -C 20 Straight-chain or branched alkylthio of (A) or (B) 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with the formed substituent group; c containing N, O and/or S 2 -C 20 Wherein the hydrogen atom may be replaced by a halogen atom or a hydroxyl group, C 2 -C 20 Straight or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (1), C 1 -C 20 Linear or branched alkyl of (2), or C 1 -C 20 wherein-CH 2-in the straight-chain or branched-chain alkyl group is-O-, -S-, -CO-),
-COO-or-OCO-substituted;
R 3 can be
，R 4 Selected from the following groups: c 1 -C 20 Linear or branched alkyl, haloalkyl or hydroxy-substituted alkyl of (A), C 3 -C 20 Cycloalkyl of, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (2), C 1 -C 20 Linear or branched alkoxy or alkylthio of (A), C 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of (A) by C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 An alkyl group, a carboxyl group, is substituted by 1 or more of-O-, -S-, -O-CO-or-CO-O-interrupted C 2 -C 20 The linear or branched alkyl group of (1); c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom in the phenyl radical of an aryl group being bound by C 1 -C 20 Straight-chain or branched alkyl, alkoxy or alkylthio of 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with the formed substituent group; c containing N, O and/or S 2 -C 20 A heterocyclic group of (a);
R 3 can be
，R 5 Selected from the following groups: hydrogen, C 1 -C 20 <xnotran> , -CH2- -O-, -S-, -CO-, -COO- -OCO- ; </xnotran> C 3 -C 20 Wherein the hydrogen atom may be substituted by a halogen atom or a hydroxyl group, C 1 -C 20 Linear or branched alkyl (wherein-CH 2-is-O-) -S-, -CO-),
-COO-or-OCO-, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Linear or branched alkynyl; c 2 -C 20 The linear or branched alkenyl group of (1); c 2 -C 20 The straight-chain or branched alkynyl group of (1); c 1 -C 20 Linear or branched hydroxy-substituted alkyl of (1), C 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of (A) by C 6 -C 10 Aryl of (2)Or aryloxy-substituted C 1 -C 20 Alkyl, C interrupted by more than 1-O-, -S-, -O-CO-or-CO-O-) 2 -C 20 The linear or branched alkyl or alkoxy group of (1); C6-C30 aryl, at least one hydrogen atom of the phenyl group of C6-C30 aryl being replaced by C 1 -C 20 A linear or branched alkyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms, a C1-C20 carbon atom-containing group 1 -C 20 Straight-chain or branched alkylthio of (A) or (B) 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with an oxyacyl group of (a); c 6 -C 20 Arylthio of (a), C containing N, O and/or S 2 -C 20 A heterocyclic group of (a);
R 3 can be that
，R 6 、R 7 And R 8 Selected from the following groups: hydrogen, C 6 -C 30 Aryl radical, by C 1 -C 20 Alkyl or alkoxy substituted C 6 -C 30 Aryl radical, C 1 -C 20 Straight or branched alkyl of (2), or C 1 -C 20 Of a linear or branched alkyl group of (A) — CH 2 -may be substituted with-O-, -S-, -CO-, -COO-or-OCO-to form a substituent; linked to each other to form a ring or to form a ring with an alkenyl carbon atom between them;
R 3 can be that
，L=O、S、N-R 9 '，R 9 （R 9 ' and R 9 May be the same or different) is selected from the following groups: c 1 -C 20 Straight or branched alkyl or haloalkyl or hydroxy-substituted alkyl of (1), C 3 -C 20 Cycloalkyl of (C) 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (2), C 1 -C 20 Straight or branched alkoxy or alkylthio of (2), C 2 -C 20 OfChain or branched hydroxyalkoxyl groups substituted with C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 An alkyl group, a carboxyl group, is substituted by 1 or more of-O-, -S-, -O-CO-or-CO-O-interrupted C 2 -C 20 The linear or branched alkyl group of (1); c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom in the phenyl radical of an aryl group being bound by C 1 -C 20 Straight or branched alkyl or alkoxy or alkylthio of (1), C 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy or C of 1 -C 20 Substituted with an oxyacyl group of (a); c containing N, O and/or S 2 -C 20 A heterocyclic group of (a).
As a preferable embodiment, in the structure represented by the above general formula (I), R 1 Is represented by C 1 -C 10 Straight or branched alkyl of (2), C 3 -C 10 Cycloalkyl of, C 1 -C 8 Straight or branched fluoroalkyl of (2), C 3 -C 10 Fluorocycloalkyl, fluorophenyl, substituted by C 1 -C 4 Alkyl or fluoroalkyl substituted phenyl, camphoryl, camphorquinone or azidonaphthalenone groups.
Further preferably, R 1 Is represented by C 1 -C 8 Straight or branched alkyl of (2), C 1 -C 8 Linear or branched perfluoroalkyl, perfluorophenyl, or C 1 -C 4 Alkyl or perfluoroalkyl substituted phenyl, camphoryl, camphorquinone or azidonaphthalenone groups.
As a preferable embodiment, in the structure represented by the above general formula (I), R 2 Can be the same or different and are each independently selected from the following groups: hydrogen, C 1 -C 12 Linear or branched alkyl of (2), C 3 -C 12 Cycloalkyl of, C 2 -C 12 Linear or branched alkenyl of (2), C 2 -C 12 Straight-chain or branched alkynyl of (2), C 1 -C 12 Linear or branched alkoxy of (2), C 1 -C 12 In a straight chain orA branched alkylthio group having a structure represented by the general formula, C interrupted by more than 1-O-, -S-, -O-CO-or-CO-O-) 2 -C 12 Is a straight-chain or branched alkyl or alkoxy group, unsubstituted or substituted by C 1 -C 4 Alkyl or alkoxy substituted C 6 -C 10 Aryl radical, C 6 -C 10 Arylthio radicals, C containing N, O and/or S 4 -C 10 A heterocyclic group of (i); or two R 2 Are linked to each other to form a five-membered ring or a six-membered ring.
Further preferably, R 2 Can be the same or different and are each independently selected from the following groups: hydrogen, C 1 -C 8 Linear or branched alkyl of (2), C 3 -C 8 Cycloalkyl of (C) 2 -C 8 Linear or branched alkenyl of (2), C 2 -C 8 Straight-chain or branched alkynyl of (2), C 1 -C 8 Linear or branched alkoxy of (2), C 1 -C 8 The straight-chain or branched alkylthio group of (3), C interrupted by more than 1-O-, -S-, -O-CO-or-CO-O-) 2 -C 7 Straight or branched alkyl or alkoxy of (2), phenyl, by C 1 -C 4 Alkyl or alkoxy substituted phenyl, thiophenyl, thienyl, N-pyrrolyl, pyridyl, indolyl; or two R 2 Are linked to each other to form a five-membered ring or a six-membered ring.
As a preferred embodiment, in the structure represented by the above general formula (I), R 3 Selected from the following groups:
hydrogen, nitro, cyano, or a salt thereof,
hydroxy, halogen, C 1 -C 20 The chain hydrogen atom of the linear or branched alkyl group (2) may be a halogen atom or a hydroxyl group, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl group of (2), C 1 -C 20 Is linear or branched alkyl substituted, or C 1 -C 20 wherein-CH 2-in the straight-chain or branched-chain alkyl group is replaced by-O-) -S-, -CO-),
-COO-or-OCO-substituted; c 3 -C 30 Wherein the hydrogen atom may be replaced by halogen, C 1 -C 20 Or a linear or branched alkyl group, is formed by more than 1-O-) -S-, C interrupted by-OCO-or-COO- 2 -C 20 Linear or branched alkyl groups; bridged cycloalkyl radicals in which the hydrogen atoms may be replaced by halogen, C 1 -C 20 Is a straight-chain or branched alkyl group, is formed by more than 1-O-) -S-) C interrupted by-OCO-or-COO- 2 -C 20 Linear or branched alkyl groups; c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom of the phenyl radical of the aryl group being replaced by C 1 -C 20 Linear or branched alkyl of (2), C 1 -C 20 Straight or branched alkoxy of (2), C 6 -C 20 Aryl-substituted C of 1 -C 20 Alkoxy radical, C 1 -C 20 Straight or branched alkylthio of (2), C 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with the formed substituent group; c containing N, O and/or S 2 -C 20 Wherein the hydrogen atom may be replaced by a halogen atom or a hydroxyl group, C 2 -C 20 Straight or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (1), C 1 -C 20 Linear or branched alkyl of (2), or C 1 -C 20 In the straight or branched alkyl group of (2) — CH 2 -by-O-, -S-, -CO-),
-COO-or-OCO-substituted;
R
，R 4 selected from the following groups: c 1 -C 20 Straight or branched alkyl or haloalkyl of (1)Or hydroxy-substituted alkyl, C 3 -C 20 Cycloalkyl of, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (2), C 1 -C 20 Linear or branched alkoxy or alkylthio of (A), C 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of (A) by C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 An alkyl group, a carboxyl group, by 1 or more of-O-, -S-) -O-CO-or-CO-O-interrupted C 2 -C 20 The linear or branched alkyl group of (1); c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom of the phenyl radical of the aryl group being replaced by C 1 -C 20 Straight-chain or branched alkyl, alkoxy or alkylthio of 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with an oxyacyl group of (a); c containing N, O and/or S 2 -C 20 A heterocyclic group of (a);
Exemplarily, the following steps are carried out: when R is 2 =R 2 When' is H or alkyl, the photoacid generator represented by the above general formula (I) of the present invention may be selected from the following structures:
in addition, when R is 2 =R 2 ' may be an alkenyl or heteroatom substituted alkane, cycloalkane, aryl, heterocycle, illustratively selected from the following structures:
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R 2 and R 2 ' Ring formation, which may be a cycloalkane, alkenyl or heteroatom-substituted cycloalkane, illustratively may be selected from the following structures:
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R 2 and R 2 ' differently, the following structures may illustratively be selected:
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according to another aspect of the present invention, there is provided a method for producing an oxime sulfonate photoacid generator represented by the general formula (I) above, comprising the steps of:
(1) 2-halofluorene with R under alkaline conditions 2 X（R 2 'X) reaction to give 9, 9' -R 2 R 2 ' fluorene compounds;
(2) Coupling reaction of the product 2-halogen of the step (1) and butyl acrylate to generate a 2-alkenyl ester compound;
(3) Hydrogenating and reducing the double bond at the 2-position of the product obtained in the step (2) under a catalytic condition to generate a 2-ester compound;
(4) Hydrolyzing the ester group at the 2-position of the product obtained in the step (3) under an alkaline condition to generate a 2-propionic fluorene compound;
(5) The product of step (4) with R 3 XH（R 3 Hn) reaction to form 7-R 3 A fluorene compound;
(6) Performing cyclization on the product obtained in the step (5) under the catalysis of polyphosphoric acid to form a cyclopentanone structure;
(7) Oximation reaction is carried out on the product obtained in the step (6) and nitrous acid or alkyl nitrite to generate an oxime compound;
(8) Step (7) Oxime Compound with acylating agent, i.e. R 1 -SO 2 X or (R) 1 SO 2 ) 2 And carrying out esterification reaction on the O in an inert solvent under the alkaline condition to generate the oxime sulfonate photo-acid generator.
The reaction scheme is as follows:
wherein X is halogen, R 1 、R 2 （R 2 ’）、R 3 Is as defined above.
The starting materials and reagents used in the above preparation processes are all known compounds in the art, and can be obtained commercially or conveniently by known processes.
In the step (7), the product of the step (6) is subjected to oximation reaction with nitrous acid or alkyl nitrite under alkaline or acidic conditions to generate a hydroxylamine compound. Wherein the alkyl nitrite can be selected from methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite. The temperature of the oximation reaction is controlled between-5 ℃ and 100 ℃, preferably between 20 ℃ and 80 ℃.
In step (8), the oxime compound is reacted with an acylating agent, R 1 SO 2 X or (R) 1 SO 2 ) 2 And carrying out esterification reaction on the O in an inert solvent under the alkaline condition to generate the oxime sulfonate compound. The esterification reaction temperature is controlled between-10 ℃ and 60 ℃, preferably between-5 ℃ and 5 ℃.
The compound of the general formula (I) belongs to a non-ionic photoacid generator, has a photosensitive group and an acid-generating group, is directly connected with an oxime structure, and can generate N-O bond fracture under the irradiation of active energy rays to generate sulfonic acid with stronger acidity. The photo-acid generator has high sensitivity and strong absorption to active energy rays with the wavelength of 300-450nm, particularly 365nm (i line), and can generate acid quickly under lower exposure. At the same time, it has good solubility, thermal stability and chemical stability.
In view of this, according to a third aspect of the present invention, there is provided an acid generating method of irradiating the above-mentioned photoacid generator, i.e., the compound of the general formula (I), with active energy rays. The active energy ray may be, without limitation, an electromagnetic wave having a wavelength in a visible light region (visible light ray), an electromagnetic wave having a wavelength in an ultraviolet light region (ultraviolet ray), an electromagnetic wave having a wavelength in an infrared light region (infrared ray), an electromagnetic wave having a wavelength in a non-visible light region such as an X-ray, or the like. However, the active energy ray is preferably an active energy ray having a wavelength of 300 to 450nm in the near ultraviolet region and the visible light region, and particularly preferably an active energy ray having a wavelength of 365nm (i-line).
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 micro-stereolithography, and the like. Among them, as a photoacid generator in a resist composition, a resist can be prepared together with a resin having an acid-dissociable group and applied to semiconductor lithography.
According to a fourth aspect of the present invention, there is provided a resist composition comprising an oxime sulfonate photoacid generator represented by general formula (I). For convenience of reference to the composition components, the oxime sulfonate photoacid generator represented by general formula (I) is hereinafter understood to be component (a) of the composition; the photoacid generator (a) also means the same unless otherwise specified.
The oxime sulfonate photoacid generator of the present invention is applied to a resist composition, and is first soluble in a solvent. The common solvent is an organic solvent, which can be selected from: esters such as gamma-butyrolactone (GBL), ethyl acetate, butyl acetate, ethyl lactate, methyl pyruvate, and the like; ketones such as acetone, butanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and the like; ethers such as methyl ether, ethyl ether, propyl ether, butyl ether, anisole, ethylbenzyl ether, cresolmethyl ether, diphenyl ether, dibenzyl ether, butylphenyl ether and the like; polyhydric alcohols and derivatives such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monopropionate, diethylene glycol monopropionate, propylene glycol monopropionate, dipropylene glycol monopropionate, propylene glycol monomethyl ether, and Propylene Glycol Methyl Ether Acetate (PGMEA), etc.; aromatic organic solvents such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, cymene and mesitylene; nitrogen-containing polar solvents such as N, N' -tetramethylurea, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone, 2-trimethylpropionamide, and the like. These organic solvents may be used alone or as a mixed solvent of two or more.
The solvent dissolves the respective components in the resist composition to form a uniform solution for adjusting viscosity and coatability. The solvent is preferably one or a mixture of two or more of Propylene Glycol Methyl Ether Acetate (PGMEA), cyclohexanone, and γ -butyrolactone (GBL). In general, it is preferable to select the solvent amount so that the solid content concentration of the composition is 5 to 30% (w/w).
The resist composition of the present invention can be classified into a positive type composition and a negative type composition according to the application. The positive type composition generally contains a resin component (B1) whose solubility in an alkali developer is increased by the action of an acid. In the composition pattern formation process, upon selective exposure, the acid labile group protected by a protecting group in the positive type resin in the exposed region is deprotected by an acid generated from a photoacid generator to be soluble in an alkali developer. Therefore, when the alkali development operation is performed, the unexposed region of the pattern remains, and a positive pattern is formed. Unlike the positive type composition, the negative type composition uses a resin-crosslinking agent component (B2) which is crosslinked by the action of an acid and is insoluble in an alkali developing solution. The exposed area is catalyzed by acid generated by a photoacid generator, the resin reacts with a crosslinking agent to form a polymer insoluble in an alkali developing solution and remains, and the unexposed area is dissolved and removed by the alkali developing solution to finally form a negative pattern.
In the positive/negative resist composition, the oxime sulfonate photoacid generator can generate N-O bond fracture to generate sulfonic acid under the irradiation of active energy rays, and the difference of the solubility of an exposed area and an unexposed area to a developing solution is realized through a PEB process. The oxime sulfonate photoacid generator product can be used singly or in a mixture of more than two. The content of the oxime sulfonate photoacid generator is 0.01 to 5%, preferably 0.1 to 3% (w/w) with respect to the mass of the solid content of the composition. When the amount is within this range, the properties of the insoluble portion in an alkaline developer can be satisfactorily exhibited while the sensitivity to active energy rays is satisfactorily exhibited, and the developing effect can be improved.
In the positive resist composition of the present invention, the resin component (B1) may be obtained by vinyl polymerization of a vinyl monomer containing an alkali-soluble acidic group, in which a part or all of hydrogen atoms of the alkali-soluble acidic group are substituted with an acid-dissociable group as a protecting group, and optionally a hydrophobic group-containing vinyl monomer. The alkali-soluble acidic group may be a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group, and the acid-dissociable group may be dissociated in the presence of a strong acid generated from the photoacid generator (I).
For convenience 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 acid-based resin and the unit structure formed by polymerization of the vinyl monomer containing a hydrophobic group constitute the resin component (B1). The acid-based resin itself is alkali-insoluble or poorly alkali-soluble.
The alkali-soluble acidic group in the resin component (B1) may be a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group.
The phenolic hydroxyl group-containing resin (B1-1) may be selected from the group consisting of novolak resins, polyhydroxystyrene-hydroxystyrene copolymers, hydroxystyrene-styrene- (meth) acrylic acid derivative copolymers, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, polyimides containing phenolic hydroxyl groups, polyamic acids containing phenolic hydroxyl groups, phenol-dicyclopentadiene condensation resins, and the like, and novolak resins, polyhydroxystyrene-hydroxystyrene copolymers, hydroxystyrene-styrene- (meth) acrylic acid derivative copolymers, phenol-xylylene glycol condensation resins, and cresol-xylylene glycol condensation resins are preferred. The phenolic hydroxyl group-containing resin may be used alone or in combination of two or more.
The novolak resin is obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") with an aldehyde under an acid catalyst. The phenols are mainly alkyl phenols and aromatic phenols, and may be selected from phenol, o-cresol, m-cresol, p-cresol, o-ethyl phenol, m-ethyl phenol, p-ethyl phenol, o-butyl phenol, m-butyl phenol, p-butyl phenol, 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 monomethyl ether, catechol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, alpha-naphthol, beta-naphthol, etc. The aldehydes may be selected from formaldehyde, trioxymethylene, acetaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and the like. Specific examples of the novolak resin include phenol-formaldehyde condensation novolak resins, cresol-formaldehyde condensation novolak resins, phenol-naphthol-formaldehyde condensation novolak resins, and the like.
The molecular weight of the resin containing phenolic hydroxyl is preferably about 1000-50000. As described above, a crosslinking group such as a carboxyl group bonded to an aromatic group, an alcoholic hydroxyl group and a cyclic ether group can be introduced into the phenolic hydroxyl group-containing resin as necessary.
The carboxyl groups may be derived from: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and the like; unsaturated polycarboxylic acids such as maleic acid, itaconic acid, fumaric acid, citraconic acid, and the like; unsaturated polycarboxylic acid alkyl (C) 1 -C 10 ) Esters such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, citraconic acid monoalkyl esters, and the like; and salts thereof such as alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), amine salts, ammonium salts, etc. The carboxyl groups are preferably derived from (meth) acrylic acid.
As a preferred example of the carboxyl group-containing resin, the acrylic resin is a resin obtained by copolymerizing (meth) acrylic acid with another monomer having an unsaturated bond. The monomer copolymerized with (meth) acrylic acid may be selected from unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, and the like. The (meth) acrylate may be selected from methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, t-octyl (meth) acrylate, and the like. Among the (meth) acrylates having no epoxy group, a (meth) acrylate having an alicyclic skeleton is preferable; in the (meth) acrylate having an alicyclic skeleton, the alicyclic group may be monocyclic or polycyclic, the monocyclic alicyclic group may be selected from cyclopentyl and cyclohexyl, and the polycyclic alicyclic group may be selected from norbornyl, isobornyl, tricyclononyl, and the like.
The sulfonic acid group may be derived from: vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, α -methylstyrene sulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, and salts thereof such as alkali metal salts (sodium, potassium, and the like), alkaline earth metal salts (calcium, magnesium, and the like), 1-3-stage amine salts, ammonium salts, quaternary ammonium salts, and the like.
The hydrophilic-lipophilic balance (HLB) value of the resin containing an alkali-soluble acidic group varies depending on the resin skeleton of the alkali-soluble resin, and is generally 4 to 19, preferably 6 to 17. The HLB value is more than or equal to 4, the developing property is better when the developing is carried out; if the HLB value is less than or equal to 19, the water resistance of the cured product is better.
The content of the acid-based resin in the resin component (B1) is 1 to 100% (w/w), preferably 10 to 70% (w/w). When within this range, better developability of the resist composition can be obtained.
The hydrophobic group-containing vinyl monomer may be selected from (meth) acrylate, aromatic olefin monomers, and the like.
The (meth) acrylate may be selected from: (meth) acrylic acid C 1 -C 20 Alkyl esters, e.g. methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylateEsters, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like; examples of the alicyclic group-containing (meth) acrylate include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and the like.
The aromatic olefin monomer may be selected from alkanes and aromatics having a styrene skeleton, such as styrene, alpha-methylstyrene, vinyltoluene, 2, 4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, vinylnaphthalene, and the like.
The content of the unit structure formed by polymerization of the hydrophobic group-containing vinyl monomer in the resin component (B1) is preferably 30 to 90% (w/w). When within this range, better developability of the resist composition can be obtained.
The acid-dissociable group as a protecting group may be selected from: substituted methyl, 1-substituted ethyl, 1-branched alkyl, silyl, alkoxycarbonyl, acyl, and cyclic acid-dissociable groups. The acid-dissociable group may be used alone or in combination of two or more.
The substituted methyl group may be selected from: methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzylthiomethyl, phenacyl, bromobenzoylmethyl, methoxybenzoylmethyl, methylthiophenacyl, α -methylbenzoylmethyl, cyclopropylmethyl, benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl, piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, t-butoxycarbonylmethyl and the like.
Said 1-substituted ethyl group may be selected from: 1-methoxyethyl group, 1-methylthioethyl group, 1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1-diethoxyethyl group, 1-ethoxypropyl group, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group and the like.
The 1-branched alkyl group may be selected from: isopropyl, isobutyl, tert-butyl, 1-dimethylpropyl, 1-methylbutyl, 1-dimethylbutyl, and the like.
The silane group, may be selected from: trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, methyl di-tert-butylsilyl, tri-tert-butylsilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl and the like.
Said alkoxycarbonyl group may be selected from: methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, tert-butoxycarbonyl and the like.
The acyl group may be selected from: acetyl, propionyl, butyryl, heptanoyl, hexanoyl, pentanoyl, pivaloyl, isovaleryl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl, adipyl, pimeloyl, suberoyl, azelaioyl, sebacoyl, acryloyl, propioloyl, methacryloyl, crotonyl, oleoyl, maleoyl, fumaroyl, mesoconyl, kacanoyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, atropic-oyl, cinnamoyl, furoyl, thenoyl, nicotinoyl, isonicotinoyl, p-toluenesulfonyl, methanesulfonyl, and the like.
The cyclic acid-dissociable group may be selected from: cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothienyl, 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl and the like.
In addition to the above groups, the acid-dissociable group as the protecting group may be selected from at least one of the following groups:
wherein, the first and the second end of the pipe are connected with each other,
R 15 、R 16 、R 17 each independently represents C 1 -C 6 Linear or branched alkyl of (2), C 1 -C 10 Linear or branched fluoroalkyl of (2), and R 15 、R 16 、R 17 Any two of which are adapted to bond to each other to form a ring;
R 11 、R 12 and R 13 Each independently represents C 1 -C 20 And R is a hydrocarbon group of 11 、R 12 、R 13 Any two of which are adapted to bond to each other to form a ring;
R 14 is represented by C 1 -C 6 Straight or branched alkyl of (2), C 3 -C 6 And n is 0 or 1.
Specifically, in the formula (a), when R is 8 、R 9 And R 10 When alkyl, exemplary groups 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, and the like; when R is 8 、R 9 And R 10 When any two groups in (1) are bonded to each other to form a ring, it preferably has C 5 -C 20 Monocyclic or polycyclic aliphatic hydrocarbons of, for exampleThe sex can be selected from cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, tricyclodecane, tetracyclodecane and the like; by binding to R 15 、R 16 And R 17 The ring formed by any two groups in (b) may have a substituent such as a hydroxyl group, a cyano group and an oxygen atom (= O), and have C 1 -C 4 Linear or branched alkyl. Preferably, formula (a) may be selected from the following formulae (formula a) 1 -formula a 6 ) A group of (a);
formula a 1 ：
In the formula a 2 ：
In the formula a 3 ：
In the formula a 4 ：
In the formula a 5 ：
In the formula a 6 ：
。
Specifically, in the formula (b), R 11 、R 12 And R 13 To have C 1 -C 20 Aliphatic or/and aromatic hydrocarbon groups. When R is 11 、R 12 And R 13 When the hydrocarbon group is an aliphatic hydrocarbon group, it may have a linear structure 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, n-undecyl, etc.; the cyclic structure is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclononylA group, cyclodecyl, cycloundecyl, cyclododecyl, and polycyclic groups of the formula (formula b) 1 -formula b 8 ）；
Formula b 1 ：
Formula b 2 ：
A formula b 3 ：
Formula b 4 ：
，
Formula b 5 ：
Formula b 6 ：
，
Formula b 7 ：
Formula b 8 ：
。
And, in formula (b), when R 11 、R 12 And R 13 When it is an aromatic hydrocarbon group, it may be selected from phenyl, naphthyl, anthryl, biphenyl, phenanthryl and fluorenyl groups. When R is 11 、R 12 And R 13 When both aliphatic and aromatic groups are contained, they may be selected from benzyl, phenethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, α -naphthylmethyl, β -naphthylmethyl, 2- (. Alpha. -naphthyl) ethyl, 2- (. Beta. -naphthyl) ethyl and the like. The aromatic ring may be substituted or partially substituted, the substituent being selected from the group consisting of a halogen atom, a hydroxyl group, a C 1 -C 10 Alkyl orAlkoxy radical, C 2 -C 10 Alkanoyl and alkanoyloxy of (1). In the 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 is 12 And R 13 When they are bonded to each other to form a ring, C containing O, S or N atom is preferable 4 -C 6 A heterocycle; when R is 11 And R 12 When they are bonded to each other to form a ring, C is preferred 3 -C 12 A saturated aliphatic hydrocarbon ring.
Preferably, formula (b) is also selected from the following formulae (formula b) 9 -formula b 14 ) The group of (a):
formula b 9 ：
A formula b 10 ：
，
Formula b 11 ：
A formula b 12 ：
，
Formula b 13 ：
Formula b 14 ：
。
Specifically, the formula (c) can be selected from tert-butoxycarbonyl and tert-butoxycarbonylmethyl.
As the acid dissociable group of the protecting group, preferred are a tert-butyl group, a benzyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a trimethylsilyl group, a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiofuranyl group, and the like.
The developing effect of the resist composition can be adjusted by adjusting the content of the acid-dissociable group, and in order to further improve the developing effect, the introduction rate of the acid-dissociable group (the ratio of the number of acid-dissociable groups to the total of the unprotected acid groups and the acid-dissociable groups) in the acid-based resin is preferably 15 to 100%.
The acid-based resin has an average molecular weight of 1,000-150,000. The average molecular weight of the acid-based resin includes, but is not limited to, the above range, and limiting it to the above range is advantageous in improving its water resistance, thereby improving its developing effect of the developed pattern. More preferably, the acid-based resin has an average molecular weight of 3,000 to 100,000.
In the negative resist composition of the present invention, the resin-crosslinking agent component (B2) is mainly a phenolic hydroxyl group-containing resin (B2-1) and a crosslinking agent (B2-2).
The phenolic hydroxyl group-containing resin (B2-1) may be the same as B1-1 described above. The B2-1 accounts for 30-90% (w/w), preferably 40-80% (w/w) of the solid components of the composition.
The crosslinking agent (B2-2) is a compound for crosslinking and polymerizing the resin (B2-1) containing a phenolic hydroxyl group under the catalysis of an acid generated by the photoacid generator (a), and may be selected from bisphenol a-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac-based epoxy compounds, phenol-novolac-based epoxy compounds, poly (hydroxystyrene) -based epoxy compounds, oxetane compounds, methylol-containing melamine compounds, methylol-containing benzoguanamine compounds, methylol-containing urea compounds, methylol-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. Among these crosslinking agents, methoxymethyl group-containing melamine compounds (e.g., hexamethoxymethylmelamine, etc.), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like are preferable. Illustratively, methoxymethyl-containing melamine compounds are commercially available under trade names of CYMEL300, CYMEL301, CYMEL303, CYMEL305 and the like, methoxymethyl-containing glycoluril compounds are commercially available under trade names of CYMEL1174 and the like, and methoxymethyl-containing urea compounds are commercially available under trade names of MX290 and the like.
In view of the reduction in the residual film ratio and the problem of resolution, the content of the crosslinking agent (B2-2) is usually 10 to 50mol%, preferably 15 to 40mol%, relative to all the acidic functional groups in the phenolic hydroxyl group-containing resin (B2-1).
As an optional component, the above positive-or negative-type resist composition may further contain an aromatic carboxylic acid compound (C), i.e., at least one carboxylic acid group is bonded to an aromatic group. In a positive resist composition, for example, an aromatic carboxylic acid compound can promote deprotection reaction of a resin component in the composition after exposure.
The aromatic carboxylic acid compound (C) may be at least one selected from a low-molecular-weight aromatic carboxylic acid compound and a high-molecular-weight aromatic carboxylic acid compound.
In the aromatic carboxylic acid compound, in addition to the carboxylic acid group, 1 or more substituents may be present, and the substituents may be selected from: halogen, hydroxyl, mercapto, sulfide groups, silyl, silanol groups, nitro, nitroso, sulfonate, phosphono, and phosphonate groups; alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, and arylalkyl groups; and a bond containing a hetero atom such as O, si, N, etc., such as an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, etc. The above substituents may be linear, branched or cyclic. As the substituent on the aromatic carboxylic acid compound, C is preferred 1 -C 12 Alkyl, aryl, alkoxy and halogen.
The low molecular weight aromatic carboxylic acid compound may be a monocarboxylic acid compound or a polyvalent carboxylic acid compound. Illustratively, the low molecular weight aromatic carboxylic acid compound may be selected from: benzoic acid; hydroxybenzoic acids such as salicylic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid, etc.; alkylbenzoic acids such as o-methylbenzoic acid, m-methylbenzoic acid and p-methylbenzoic acid; halogenated benzoic acids such as o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid and p-bromobenzoic acid; alkoxybenzoic acids such as o-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, o-ethoxybenzoic acid, m-ethoxybenzoic acid and p-ethoxybenzoic acid; aminobenzoic acids such as anthranilic acid, meta-aminobenzoic acid and para-aminobenzoic acid; acyloxybenzoic acids such as o-acetoxybenzoic acid, m-acetoxybenzoic acid and p-acetoxybenzoic acid; naphthoic acids such as 1-naphthoic acid and 2-naphthoic acid; hydroxynaphthoic acids such as 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; aminonaphthoic acids such as 1-amino-2-naphthoic acid, 1-amino-3-naphthoic acid, 1-amino-4-naphthoic acid, 1-amino-5-naphthoic acid, 1-amino-6-naphthoic acid, 1-amino-7-naphthoic acid, 1-amino-8-naphthoic acid, 2-amino-1-naphthoic acid, 2-amino-3-naphthoic acid, 2-amino-4-naphthoic acid, 2-amino-5-naphthoic acid, 2-amino-6-naphthoic acid, 2-amino-7-naphthoic acid, and 2-amino-8-naphthoic acid; alkoxy naphthoic acids such as 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-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-6-naphthoic acid, 2-ethoxy-7-naphthoic acid, 2-ethoxy-8-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2-ethoxy-3-naphthoic acid, 2-ethoxy-4-naphthoic acid, 2-ethoxy-8-naphthoic acid, and 8-naphthoic acid; phthalic acids such as phthalic acid, terephthalic acid and isophthalic acid; naphthalenedicarboxylic acids, such as 1, 2-naphthalenedicarboxylic acid, 1, 3-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 1, 7-naphthalenedicarboxylic acid, 1, 8-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid and 2, 7-naphthalenedicarboxylic acid; biphenyl carboxylic acids such as 1,1' -biphenyl-4-carboxylic acid, 1' -biphenyl-3-carboxylic acid and 1,1' -biphenyl-2-carboxylic acid; biphenyldicarboxylic acids such as 1,1 '-biphenyl-4, 4' -dicarboxylic acid, 1 '-biphenyl-3, 3' -dicarboxylic acid, 1 '-biphenyl-2, 2' -dicarboxylic acid, 1 '-biphenyl-3, 4' -dicarboxylic acid, 1 '-biphenyl-2, 4' -dicarboxylic acid and 1,1 '-biphenyl-2, 3' -dicarboxylic acid; trivalent or higher aromatic polycarboxylic acids such as pyromellitic acid and trimellitic acid; hydroxybenzenedicarboxylic acids, such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid and 2-hydroxyisophthalic acid; dihydroxybenzodicarboxylic acids such as 2, 5-dihydroxyterephthalic acid, 2, 6-dihydroxyisophthalic acid, 4, 6-dihydroxyisophthalic acid, 2, 3-dihydroxyphthalic acid, 2, 4-dihydroxyphthalic acid, 3, 4-dihydroxyphthalic acid, and the like; pyridine carboxylic acids such as pyridine-2-carboxylic acid, pyridine-3-carboxylic acid and pyridine-4-carboxylic acid, etc.; dipicolinic acids such as pyridine-2, 5-dicarboxylic acid, pyridine-3, 5-dicarboxylic acid, pyridine-2, 6-dicarboxylic acid, pyridine-2, 4-dicarboxylic acid, and the like; pyrimidine carboxylic acids such as pyrimidine-2-carboxylic acid, pyrimidine-4-carboxylic acid, pyrimidine-5-carboxylic acid and pyrimidine-6-carboxylic acid; and pyrimidinedicarboxylic acids such as 2, 6-pyrimidinedicarboxylic acid and 2, 5-pyrimidinedicarboxylic acid. These low molecular weight aromatic carboxylic acid compounds may be used alone or in combination of two or more.
The high molecular weight aromatic carboxylic acid compound may be an aromatic high molecular weight compound having an aromatic group to which a carboxylic acid group is bonded. Suitably, the monomer has a carboxylic acid group bound to an aromatic group and an unsaturated double bond, and does not include an acid labile group protected by a protecting group. The polymer compound may be a homopolymer or a copolymer. As preferable comonomers used together with the above monomers, the above monomers for producing the acrylic resin, such as (meth) acrylic acid, unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrene, can be used.
Further, the resist composition of the present application may further include the following auxiliary raw materials, as required for the function: a bridging group compound, a dissolution control agent, a dissolution inhibitor, an alkaline compound, a surfactant, a storage stabilizer, and a defoaming agent.
In order to improve the combination property of the resist composition, the resist composition may further include other additives, and the type of the additives may be selected from materials commonly used in resist compositions, which are not described herein again.
When the resist composition of the present invention is applied, a resin solution obtained by dissolving or dispersing the resin solution in an organic solvent is first applied onto a substrate by a spin coating method, the solvent is then volatilized by heating to form a resist film on the substrate, and then light irradiation (i.e., exposure) is performed in a wiring pattern shape, followed by heat treatment (PEB) after the exposure, and then alkali development is performed to form a wiring pattern.
The drying conditions of the resin solution after coating vary depending on the solvent used, and are preferably carried out at 50 ℃ to 150 ℃ for 1 to 30 minutes, and are appropriately determined depending on the amount (wt%) of the residual solvent after drying.
After a resist film is formed on a substrate, a wiring pattern shape is irradiated with light. The light irradiation may use a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electron beam irradiation apparatus, an X-ray irradiation apparatus, a laser (such as an argon laser, a dye laser, a nitrogen laser, an LED, a helium cadmium laser), or the like, preferably a high-pressure mercury lamp and an LED lamp.
The temperature of the post-exposure heat treatment (PEB) is usually 40 ℃ to 200 ℃, preferably 60 ℃ to 150 ℃. If the temperature is less than 40 ℃, the release reaction or the crosslinking reaction cannot be sufficiently performed, and thus the difference in solubility between the exposed portions and the unexposed portions is insufficient and a pattern cannot be formed; if the temperature is higher than 200 ℃, the productivity is lowered. The heating time is usually 0.5 to 30 minutes.
The development is carried out with an alkali developer, and the alkali developing method includes using an alkali developer. The alkaline developer may be selected from 0.1-10% (w/w) aqueous solution of tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, and water-soluble organic solvent such as methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, etc. The developing method may be selected from a dipping method, a spraying method and a spraying method, and preferably the spraying method. The temperature of the developer is preferably used at 25 to 40 c, and the developing time is appropriately determined according to the thickness of the resist film, finally to obtain a pattern corresponding to the mask.
According to a fifth aspect of the present invention, there is provided the use of the above resist composition, including the use of the resist composition in the preparation of protective films, interlayer insulating materials, and pattern transfer materials for electronic components.
The resist composition has high sensitivity and strong absorption to active energy rays with the wavelength of 300-450nm (particularly 365 nm), can generate acid quickly under lower exposure, and has better solubility, thermal stability and chemical stability. Therefore, when the resist composition is used for forming a protective film, an interlayer insulating material or a pattern transfer material by a pattern development method, the corresponding electronic component can have better comprehensive performance.
Specifically, the above applications may include the use of the resist composition for forming interlayer insulating films, TFTs for liquid crystal display devices, panels; can also be used as a protective film for color filters and spacing columns; can also be used as PS photoresist and BCS photoresist for pattern transfer.
The 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.
According to a sixth aspect of the present invention, there is provided an electronic component comprising a protective film, an interlayer insulating material or a pattern transfer material prepared from the resist composition of the present invention.
Based on excellent photosensitivity, thermal stability, solubility and chemical stability, the oxime sulfonate photoacid generator can also be applied to other photosensitive fields.
Detailed Description
The present invention is described in detail below with reference to examples, but it should not be construed as limiting the scope of the present invention.
Preparation examples
Example 1
Adding 245.12g of 2-bromo-9H-fluorene, 32.24g of tetrabutylammonium bromide and 1000.00g of DMSO into a four-neck flask, starting stirring, cooling to-5-0 ℃, then slowly adding 1066.67g of liquid alkali (30 percent w/w) and stirring for 0.5H, dropwise adding 287.76g of 1-bromobutane into the system, after the dropwise addition is finished, heating to room temperature and keeping the temperature for 6H; 600.00 portions of pure water and 1000.00 portions of methylene chloride (DCM) were poured in and stirred for 0.5h. The organic phase was separated and the aqueous phase was extracted 3 times with 200.00g of DCM; the organic phases are combined and washed once with 200.00g of water. Adding 12.27g of activated carbon, stirring for 0.5h, and filtering; the filtrate was collected, DCM was distilled off, and 800.00g of n-hexane was added thereto for crystallization at-5-0 ℃ to obtain 343.48g of 2-bromo-9, 9-dibutylfluorene.
Under the protection of nitrogen, 321.62g 2-bromo-9, 9-dibutylfluorene is dissolved in 1500g DMF, stirring is started, 286.17g sodium carbonate, 8.04g palladium acetate, 15.54g tri-tert-butylphosphine and 461.44g butyl acrylate are added, the temperature is raised to 110 ℃, the reaction is carried out until the raw material is less than 0.1%, the temperature is reduced to 50 ℃, and the mixture passes through a silica gel column; adding 300.00g of water into the filtrate, stirring, cooling to 0 ℃, crystallizing and filtering; the filter cake was slurried with 1000.00g of methanol 2 times, respectively, and concentrated to give 185.77g of a solid.
Weighing 182.06g of the solid, dissolving in 1500g of THF, evacuating with nitrogen, introducing hydrogen, adding 36.43g of palladium-carbon (10%), and stirring at room temperature (25 ℃) for reaction for 6 hours; filtration through celite and concentration gave 181.16g of intermediate product.
Dissolving 162.65g of the intermediate in 1000.00g of ethanol, adding 44.90g of potassium hydroxide (2 eq) and 1000.00g of water, heating to reflux, reacting for 1h, distilling to remove ethanol, cooling the obtained aqueous solution to 0-5 ℃, and adjusting the pH value to 2-3 by using concentrated hydrochloric acid; white solid is separated out, and the mixture is continuously stirred and crystallized for 1 hour; filtration and rinsing with a small amount of pure water gave 112.19g of the powdered product.
105.15g of the product is added, and 500.00g of DCM is added for dissolution; 56.72g fuming HNO3 is dissolved in glacial acetic acid to form nitric acid solution; putting 91.89g of acetic anhydride into a four-neck flask, stirring and cooling to-5-0 ℃, simultaneously dropwise adding a DCM solution and a nitric acid solution, and after the HPLC neutral control raw material disappears; 400.00g of ice water and 400.00g of DCM were added to separate the organic phase of DCM, and then washed with 60.00g of pure water for 4 times, respectively, and DCM was distilled to give 90.18g of off-white powder.
Putting 79.16g of the white powder into a flask, adding 500.00g of polyphosphoric acid, and reacting for 24 hours at 90 ℃; 500.00g of pure water was added to precipitate a solid, which was then subjected to suction filtration, and the filter cake was then slurried with 150.00g of methanol to obtain 64.05g of an off-white solid.
Into a 1000ml four-necked flask, 60.00g of the above solid and 300.00g of THF were charged, and while stirring, 31.76g of concentrated hydrochloric acid was slowly added, 20.46g of isoprene nitrite was added dropwise, and the mixture was kept warm for 2 hours after the addition. Adding 500.50g of DCM, separating the liquid, and washing the lower layer with 60.00g of pure water for 3 times respectively; adding activated carbon 1.20g, stirring for 30min, and filtering; most of DCM was distilled off, 200.00g of n-hexane was added, and crystallization was carried out by cooling to obtain 48.46g of an off-white solid.
Taking 40.67g of the obtained off-white solid, adding 250.06g of DCM for dissolution, then adding 11.16g of DMAP, stirring and cooling to 0-5 ℃, dropwise adding 42.33g of trifluoromethanesulfonic anhydride, heating to 20-25 ℃, preserving heat for 1h, and counting plates to show that the raw materials are completely reacted; filtering, washing the filtrate with 40.00g of water for 3 times, and then crystallizing with n-hexane to obtain 29.16g of off-white solid powder with the purity of 99.65%, which is the compound shown in the structural formula (6).
The product structure was characterized by 1H NMR and the results were as follows: 1 H-NMR（CDCl 3 ，400MHz）：δ8.36 (dd,J=8.4,2.2Hz,1H),8.26(d,J=2.2Hz,1H),8.10(s,1H),7.95(d, J=8.4Hz,1H),6.78(s,1H),3.38 (s,2H),2.03–1.93 (dt,J =12.8,6.3 Hz, 4H),1.53–1.28(m,8H),0.88(t,J=7.5Hz,6H)。
examples 2 to 9
Other photoacid generator compounds as shown in table 1 below were synthesized by changing the respective raw materials according to the method of example 1.
TABLE 1
Comparative example Compound
Comparative example 1
Nonionic photoacid generator (A1)
Comparative example 2
Non-ionic photoacid (A2)
Comparative example 3
Nonionic photoacid (A3)
Evaluation of Performance
The performance of the photoacid generator compounds synthesized in examples and the compounds of comparative examples were evaluated, respectively, and evaluation indices included molar absorption coefficients, solubilities, and chemical stabilities at 365nm, 385nm, 405nm, and 436 nm.
(1) Molar absorptivity
The compound was diluted to 0.25mmol/L with acetonitrile, and the absorbance was measured at a cell length of 1cm using an ultraviolet-visible spectrophotometer (UPG-752) in the range of 200 to 600 nm. The molar absorption coefficient ε was calculated by the following equation at each wavelength.
ε（L•mol -1 •cm -1 ）=A/(0.00025mol/L*1cm)
In the formula, A represents the absorbance at each wavelength.
(2) Solubility in water
The high solubility not only facilitates the purification of the photoacid generator compound, but also allows the photoacid generator compound to be used in an extended concentration range in photoresists and different solvent systems. 1.0000g of the photoacid generator compound product is taken, and the solvent is gradually added at 25 ℃ until all solids in each test tube are dissolved, the mass of the solvent used is recorded, and the solubility is represented by the following formula.
(3) Chemical stability
In the formulated composition containing the photoacid generator, various auxiliaries are contained to achieve storage stability of the composition and to satisfy conditions for subsequent processes. This requires that the photoacid generator not only does not affect the adjuvant in the composition, but also is itself stable in its presence and does not undergo any chemical reaction. Triethylamine was used as a test aid, 10% of the amount of the photoacid generator (w/w) added was dissolved in PGMEA together with the photoacid generator, sealed and stored at room temperature for 168 hours, and the storage stability of the photoacid generator was tested by HPLC. The results were ranked as follows:
high Performance Liquid Chromatography (HPLC) content is more than or equal to 95.00 percent;
O-HPLC content 85.00-95.00%;
x-HPLC content < 85.00%.
The evaluation results are shown in table 2.
TABLE 2
The test results in table 2 show that the photoacid of the present invention has a higher molar absorptivity at 365nm, a strong light absorption capacity, can make full use of light energy, can ensure a higher utilization rate in resist applications, does not absorb outside 400nm, has significantly better performance than the existing products of comparative examples 1,2 and 3, and also has certain advantages in terms of solubility and chemical stability.
Industrial applicability
The following describes industrial applicability with reference to composition examples and comparative examples.
Examples of resist compositions
Each raw material was uniformly dissolved in 100% PGMEA (propylene glycol methyl ether acetate) to obtain a resist composition having a solid content concentration of 20% (w/w). Wherein, the component types and the contents of the oxime sulfonate photoacid generator (a), the resin component (B), and the aromatic carboxylic acid compound (C) are shown in table 3.
Example 10
Wherein the resin component (B) is B 1 A resin of the type represented by the formula B 11 And formula B 12 And formula B 13 The numerical value below the right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B 1 The weight average molecular weight of the resin was about 10000.
Formula B 11 ：
(ii) a Formula B 12 ：
(ii) a Formula B 13 ：
。
The oxime sulfonate photoacid generator (a) was the photoacid generator of example 1 (No. 6).
The aromatic carboxylic acid compound (C) is prepared by mixing an aromatic carboxylic acid compound (C) and an aromatic carboxylic acid compound (C) in a molar ratio of 1:1 and 2,3', 4' -biphenyl tetracarboxylic dianhydride.
Examples 11 to 18
The differences from example 10 are: as the oxime sulfonate photoacid generators (A), those numbered 11, 23, 51, 77, 99, 121, 276 and 277 in examples 2 to 9 were used, respectively.
The remaining component types and contents are shown in table 3.
Example 19
The differences from composition example 1 are: the resin component (B) is B 2 A resin of the type represented by the formula B 21 And formula B 22 And formula B 23 The numerical value below the right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B is 2 The weight average molecular weight of the resin was about 10000.
Formula B 21 ： 
(ii) a Formula B 22 ：
(ii) a Formula B 23 ：
。
The remaining component types and contents are shown in table 3.
Example 20
The differences from composition example 1 are: the resin component (B) is B 3 A resin of the type represented by the formula B 31 And formula B 32 The repeating unit shown is constituted, and the numerical value below the right of each repeating unit represents the content (mass%) of the repeating unit in the resin. B is 3 The weight average molecular weight of the resin was about 10000.
Formula B 31 ：
(ii) a Formula B 32 ：
。
The remaining component types and contents are shown in table 3.
Examples 21 to 22
The difference from composition example 1 is that: the content of the photoacid generator was varied.
The remaining component types and contents are shown in table 3.
Comparative examples 4 to 6
The difference from example 2 is that: comparative photoacid generators a 1, a 2, a 3 were used.
Component types and contents are shown in table 3.
The resist compositions prepared in examples 10 to 22 and comparative examples 4 to 6 were evaluated for sensitivity and resolution by the following methods, and the results are reported in table 3.
(1) Method for evaluating sensitivity
On each silicon wafer, the resist compositions of examples and comparative examples were coated to a film thickness of 3 μm, which enables pattern formation, to form a coating film. The formed coating film was prebaked at 90 ℃ for 100 seconds. After the prebaking, the coating film was exposed through a mask for hole pattern formation having a diameter of 10 μm while gradually changing the exposure amount, and then developed with a 2.0% aqueous tetramethylammonium hydroxide solution at 25 ℃ for 30 seconds. The minimum exposure required to form a 10 μm diameter hole pattern was determined by the method described above. From the obtained minimum exposure values, the sensitivity was evaluated according to the following criteria: o-50 mJ/cm 2 X-300mJ/cm 2 As described above.
(2) Evaluation of resolution
A mask for forming a hole pattern having a diameter of 5 μm was used except at 100mJ/cm 2 The formation of a coating film, exposure of the coating film and development were carried out in the same manner as in the sensitivity evaluation except that the exposure amount of (2) was changed. The coating film after development was observed, and the resolution was evaluated according to the following criteria: o-can form a pattern with a diameter of 5 μm, and X-cannot form a pattern with a diameter of 5 μm.
TABLE 3
As is clear from table 3, the resist composition formed by mixing the photoacid a, 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 aryl group of the present invention can form a pattern excellent in sensitivity and resolution.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The high-acid-yield oxime sulfonate photoacid generator has a structure shown in the following general formula (I):
wherein, the first and the second end of the pipe are connected with each other,
R 1 is represented by C 1 -C 20 Linear or branched alkyl and fluoroalkyl groups of (1); c 3 -C 20 Cycloalkyl, fluorocycloalkyl of (a); c 6 -C 18 Substituted or unsubstituted aryl, camphoryl, camphorquinone or azidonaphthalenone groups of (a);
R 2 and R 2 ' may be the same or different and are each independently selected from the group consisting of: hydrogen, halogen, C 1 -C 20 Linear or branched alkyl of (2), C 3 -C 20 Cycloalkyl of, C 2 -C 20 Linear or branched alkenyl and cycloalkenyl of (A), C 2 -C 20 Straight-chain or branched alkynyl of (2), C 1 -C 20 Linear or branched alkoxy of (2), C 1 -C 20 Linear or branched alkylthio of (A), C 1 -C 20 Linear or branched haloalkyl of (A), C 1 -C 20 Linear or branched hydroxy-substituted alkyl of (A), C 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of (A) by C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 Alkyl, C interrupted by more than 1-O-, -S-, -O-CO-or-CO-O-) 2 -C 20 Linear or branched alkyl or alkoxy, substituted or unsubstituted C 6 -C 10 Aryl radical, C 6 -C 20 Arylthio of (a), C containing N, O and/or S 2 -C 20 A heterocyclic group of (a); or two R 2 Are linked to each other to form a ring;
R 3 selected from the following groups: hydrogen, nitro, cyano, nitro,
hydroxy, halogen, C 1 -C 20 The alkyl group being a linear or branched alkyl group, the hydrogen atom in the chain being optionally substituted by a halogen atom or a hydroxyl group, C 2 -C 20 Straight or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (1), C 1 -C 20 Is linear or branched alkyl substituted, or C 1 -C 20 In the straight or branched alkyl group of (2) — CH 2 -by-O-, -S-, -CO-),
-COO-or-OCO-substituted; c 3 -C 30 Cycloalkyl in which the hydrogen atom may be replaced by halogen, C 1 -C 20 Or a linear or branched alkyl group, is formed by more than 1-O-) -S-, C interrupted by-OCO-or-COO- 2 -C 20 Substituted with a linear or branched alkyl group; bridged cycloalkyl radicals in which the hydrogen atoms may be replaced by halogen, C 1 -C 20 Or a linear or branched alkyl group, is formed by more than 1-O-) -S-, C interrupted by-OCO-or-COO- 2 -C 20 Linear or branched alkyl groups; c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom of the phenyl radical of the aryl group being replaced by C 1 -C 20 Straight or branched alkyl of (2), C 1 -C 20 Linear or branched alkoxy of (2), C 6 -C 20 Aryl-substituted C of 1 -C 20 Alkoxy radical, C 1 -C 20 Straight-chain or branched alkylthio of (A) or (B) 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with the formed substituent group; c containing N, O and/or S 2 -C 20 Wherein the hydrogen atom may be substituted by a halogen atom or a hydroxyl group, C 2 -C 20 Straight or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl group of (2), C 1 -C 20 Linear or branched alkyl of (2), or C 1 -C 20 In the straight-chain or branched alkyl group, -CH 2 -is substituted by-O-, -S-, -CO-),
-COO-or-OCO-substituted;
R 3 can be
，R 4 Selected from the following groups: c 1 -C 20 Linear or branched alkyl, haloalkyl or hydroxy-substituted alkyl of (A), C 3 -C 20 Cycloalkyl of, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (2), C 1 -C 20 Linear or branched alkoxy or alkylthio of (A), C 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of (A) by C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 An alkyl group, which is a radical of an alkyl group, is substituted by 1 or more of-O-, -S-, -O-CO-or-CO-O-interrupted C 2 -C 20 The linear or branched alkyl group of (1); c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom in the phenyl radical of an aryl group being bound by C 1 -C 20 Straight-chain or branched alkyl, alkoxy or alkylthio of 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 By substitution with an oxyacyl groupA group; c containing N, O and/or S 2 -C 20 A heterocyclic group of (i);
R 3 can be
，R 5 Selected from the following groups: hydrogen, C 1 -C 20 In the straight-chain or branched-chain alkyl or haloalkyl group of (1) (-CH) 2 -may be substituted with-O-, -S-, -CO-, -COO-or-OCO-to form a substituent; c 3 -C 20 The cycloalkyl group of (1), wherein the hydrogen atom may be substituted by a halogen atom or a hydroxyl group, C1-C20 straight-chain or branched alkyl (wherein-CH 2-in the chain is-O-) -S-, -CO-),
-COO-or-OCO-, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Linear or branched alkynyl; c 2 -C 20 The straight-chain or branched alkenyl group of (4); c 2 -C 20 The straight-chain or branched alkynyl group of (1); c 1 -C 20 Straight or branched hydroxy-substituted alkyl of (1) 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of (A) by C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 Alkyl, C interrupted by more than 1-O-, -S-, -O-CO-or-CO-O-) 2 -C 20 The linear or branched alkyl or alkoxy group of (1); c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom in the phenyl radical of an aryl group being bound by C 1 -C 20 Linear or branched alkyl of (2), C 1 -C 20 Straight or branched alkoxy of (2), C 1 -C 20 Straight or branched alkylthio of (2), C 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with an oxyacyl group of (a); c 6 -C 20 Arylthio of (a), C containing N, O and/or S 2 -C 20 A heterocyclic group of (a);
R 3 can be that
，R 6 、R 7 And R 8 Selected from the following groups: hydrogen, C 6 -C 30 Aryl radical, quilt C 1 -C 20 Alkyl or alkoxy substituted C 6 -C 30 Aryl radical, C 1 -C 20 Straight or branched alkyl of (2), or C 1 -C 20 Of a linear or branched alkyl group of (2) — CH 2 -may be substituted with-O-, -S-, -CO-, -COO-or-OCO-to form a substituent; linked to each other to form a ring or to form a ring with an alkenyl carbon atom between them;
R 3 can be
，L=O、S、N-R 9 ' ，R 9 （R 9 ', and R 9 May be the same or different) is selected from the following groups: c 1 -C 20 Linear or branched alkyl, haloalkyl or hydroxy-substituted alkyl of (A), C 3 -C 20 Cycloalkyl of, C 2 -C 20 Linear or branched alkenyl of (2), C 2 -C 20 Straight-chain or branched alkynyl of (2), C 1 -C 20 Straight or branched alkoxy or alkylthio of (2), C 2 -C 20 With a straight-chain or branched hydroxyalkoxy group of C 6 -C 10 Aryl or aryloxy substituted C of 1 -C 20 An alkyl group, a carboxyl group, is substituted by 1 or more of-O-, -S-, -O-CO-or-CO-O-interrupted C 2 -C 20 The linear or branched alkyl group of (1); c 6 -C 30 Aryl radical, C 6 -C 30 At least one hydrogen atom in the phenyl radical of an aryl group being bound by C 1 -C 20 Straight or branched alkyl or alkoxy or alkylthio of (1), C 1 -C 20 Acyl group of (1), C 1 -C 20 Acyloxy group or C of 1 -C 20 Substituted with the formed substituent group; c containing N, O and/or S 2 -C 20 A heterocyclic group of (a).
2. The method for preparing the high acid production oxime sulfonate photoacid generator set forth in claim 1, comprising the steps of:
(1) 2-halofluorene with R under alkaline conditions 2 X（R 2 'X) reaction to give 9, 9' -R 2 R 2 ' A fluorene compound;
(2) Coupling reaction of the product 2-halogen in the step (1) and butyl acrylate to generate a 2-alkenyl ester compound;
(3) Hydrogenating and reducing the double bond at the 2-position of the product in the step (2) under a catalytic condition to generate a 2-ester compound;
(4) Hydrolyzing the ester group at the 2-position of the product obtained in the step (3) under an alkaline condition to generate a 2-propionic fluorene compound;
(5) The product of step (4) with R 3 XH（R 3 Hn) reaction to form 7-R 3 A fluorene compound;
(6) Performing cyclization on the product obtained in the step (5) under the catalysis of polyphosphoric acid to form a cyclopentanone structure;
(7) Oximation reaction is carried out on the product obtained in the step (6) and nitrous acid or alkyl nitrite to generate an oxime compound;
(8) Step (7) Oxime Compound with acylating agent, i.e. R 1 -SO 2 X or (R) 1 SO 2 ) 2 Carrying out esterification reaction on O in an inert solvent under an alkaline condition to generate an oxime sulfonate photo-acid generator;
the reaction scheme is as follows:
wherein X is halogen, R 1 、R 2 （R 2 ’） 、R 3 Is defined as in claim 1.
3. The method for preparing the high-acid-yield oxime sulfonate photoacid generator according to claim 2, wherein: in the step (5), the alkyl nitrite is selected from methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite.
4. A method of acid production, comprising: the high acid production oxime sulfonate photoacid generator according to claim 1 is irradiated with active energy rays having a wavelength of 300 to 450nm in a near ultraviolet region and a visible light region.
5. Use of the oxime sulfonate photoacid generator with a high acid yield as claimed in claim 1 for a material for a resist film, a liquid resist, a negative resist, a positive resist, a resist for MEMS, stereolithography and micro stereolithography.
6. A resist composition comprising the high acid production oxime sulfonate photoacid generator of claim 1 in an amount of 0.1 to 3% (w/w) of the resin component of the composition.
7. The resist composition according to claim 6, characterized in that: the composition is a positive resist composition, and further contains a resin component (B1) which increases the solubility in an alkali developing solution by the action of an acid.
8. The resist composition according to claim 7, characterized in that: the resin component (B1) is obtained by vinyl polymerization of a vinyl monomer containing an alkali-soluble acidic group, in which a part or all of hydrogen atoms of the alkali-soluble acidic group is substituted with an acid-dissociable group as a protecting group, and optionally a hydrophobic-group-containing vinyl monomer;
the content of the unit structure formed by the polymerization of the vinyl monomer containing the alkali-soluble acidic group in the resin component (B1) is 10-70% (w/w), and the content of the unit structure formed by the polymerization of the vinyl monomer containing the hydrophobic group in the resin component (B1) is 30-90% (w/w);
the alkali-soluble acidic group is phenolic hydroxyl, carboxyl or sulfonic group;
the hydrophobic group-containing vinyl monomer is selected from (meth) acrylate and aromatic olefin monomers.
9. The resist composition according to claim 8, characterized in that: the acid-dissociable group as a protecting group is selected from: substituted methyl, 1-substituted ethyl, 1-branched alkyl, silane, alkoxycarbonyl, acyl and cyclic acid dissociable groups;
or at least one selected from the following groups:
wherein the content of the first and second substances,
R 15 、R 16 、R 17 each independently represents C 1 -C 6 Linear or branched alkyl of (2), C 1 -C 10 Linear or branched fluoroalkyl of (2), and R 15 、R 16 、R 17 Any two of which are adapted to bond to each other to form a ring;
R 11 、R 12 and R 13 Each independently represents C 1 -C 20 And R is a hydrocarbon group of 11 、R 12 、R 13 Any two of which are adapted to bond to each other to form a ring;
R 14 is represented by C 1 -C 6 Linear or branched alkyl of (2), C 3 -C 6 And n is 0 or 1.
10. The resist composition according to claim 6, characterized in that: the composition is a negative resist composition, and further contains a resin-crosslinking agent component (B2) which is crosslinked by the action of an acid and is insoluble in an organic developer, wherein the resin-crosslinking agent component (B2) comprises a phenolic hydroxyl group-containing resin (B2-1) and a crosslinking agent (B2-2);
the phenolic hydroxyl group-containing resin (B2-1) may be selected from the group consisting of novolak resins, polyhydroxystyrene-hydroxystyrene copolymers, hydroxystyrene-styrene- (meth) acrylic acid derivative copolymers, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, polyimides containing phenolic hydroxyl groups, polyamic acids containing phenolic hydroxyl groups, phenol-dicyclopentadiene condensation resins, and the like, preferably novolak resins, polyhydroxystyrene-hydroxystyrene copolymers, hydroxystyrene-styrene- (meth) acrylic acid derivative copolymers, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins;
the crosslinking agent (B2-2) is selected from a bisphenol a-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolac-based epoxy compound, a phenol resin-based epoxy compound, a poly (hydroxystyrene) -based epoxy compound, an oxetane compound, a methylol-containing melamine compound, a methylol-containing benzoguanamine compound, a methylol-containing urea compound, a methylol-containing phenol compound, an alkoxyalkyl-containing melamine compound, an alkoxyalkyl-containing benzoguanamine compound, an alkoxyalkyl-containing urea compound, an alkoxyalkyl-containing phenol compound, a carboxymethyl-containing melamine resin, a carboxymethyl-containing benzoguanamine resin, a carboxymethyl-containing urea resin, a carboxymethyl-containing phenol resin, a carboxymethyl-containing melamine compound, a carboxymethyl-containing benzoguanamine compound, a carboxymethyl-containing urea compound, and a carboxymethyl-containing phenol compound;
the phenolic hydroxyl group-containing resin (B2-1) accounts for 40-80% (w/w) of the solid content of the composition, and the content of the crosslinking agent (B2-2) is 15-40mol%.
11. Resist composition according to any one of claims 6 to 10, characterized in that: the composition further comprises an aromatic carboxylic acid compound (C), i.e. at least one carboxylic acid group is bonded to an aromatic group.
12. Use of the resist composition as claimed in claim 6 for the preparation of protective films for electronic components, interlayer insulating materials, pattern transfer materials.
13. An electronic part comprising a protective film, an interlayer insulating material or a pattern transfer material prepared from the resist composition as claimed in claim 6.
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