Novel onium salts and mine-generating agents

Abstract

A chemically amplified photoresist composition is provided by combining a component that functions as a photogenerator, and furthermore, the photogenerator is a resin whose solubility in alkali is increased by the action of an acid generated by irradiation with active energy lines such as light or electron beams. The present invention is an onium salt that can be represented by the general formula (1), and among the two isomers of an anionic structure, a facial body and a meridional body, the ratio of the facial body is 15.0 weight% or less. [(R2)n+1-E]+[(R1)3(F)3P]-(1)

Description

Technology Field

[0001] The present invention relates to a novel onium salt and a novel onium salt-type photogenerator. More specifically, it relates to a photogenerator preferred as a resin composition for a chemically amplified resist used for pattern formation in semiconductors. Background Technology

[0002] Conventionally, photocatalytic agents that generate acid by irradiation with active energy beams such as light or electron beams are known. In addition, these photocatalytic agents are widely known as photocatalytic agents for resists (Patent Documents 1, 2).

[0003] In addition, the anions listed in these specifications include sulfonate and BF4 - , PF6 - , AsF6 - , SbF6 - It contains. In terms of the toxicity of As and Sb, in the field of resist materials, particularly semiconductor resists, AsF6 - , SbF6 - is reluctant, and BF4 - , PF6 - The acid strength was weak, making it very inconvenient to use. Additionally, special phosphorus-based materials were described, but they could not be said to exhibit sufficient sensitivity (Patent Document 3). Although a method for manufacturing these special phosphorus-based materials was described, it was not possible to identify a useful photocatalytic agent from this (Patent Document 4). Prior art literature

[0004] Japanese Published Patent Application No. Hei 2002-193925, Japanese Published Patent Application No. Hei 2001-354669, WO2005 / 116038, Japanese Published Patent Application No. 2004-533473 The problem to be solved

[0005] Therefore, the present invention was completed by discovering that, by having a specific anionic structure and controlling the stereoisomers of the anionic structure within a certain range, it exhibits particularly high sensitivity when used as a resist material. means of solving the problem

[0006] The inventors have synthesized an onium salt that can be represented by general formula (1), in which the ratio of the facial body among two isomers of an anionic structure, a facial body and a meridional body, is 15.0 weight% or less, and have found that it is desirable for the above purpose.

[0007] [(R 2 ) n+1 -E] + [(R 1 )3(F)3P] - (1)

[0008] In Equation (1), R 1 ...is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, or an aryl group having 6 to 18 carbon atoms (excluding the number of carbon atoms of the following substituents). Some of the hydrogen atoms in the aryl group may be substituted with an alkyl group having 1 to 18 carbon atoms, a halogen atom, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms;

[0009] E represents an element with valence n in groups 15 through 17 (IUPAC notation), n is an integer from 1 to 3, and R 2 is an organic group bonded to E, and R 2 The number of is n + 1, and there are (n + 1) R 2 Each may be identical or different from each other, and two or more R 2 They may form a ring structure containing element E either directly or through -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene groups, or phenylene groups. Effects of the invention

[0010] The onium salt of the present invention functions as a photogenerator, and a chemically amplified photoresist composition is produced by combining this photogenerator with a component such as a resin whose solubility in alkali is increased by the action of an acid generated by irradiation with active energy rays such as light or electron beams. The onium salt of the present invention exhibits a specific effect when used for the intended application.

[0011] In summary, the chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition using an acid generating agent containing an onium salt of the present invention make it possible to obtain a high-sensitivity resist (which enables pattern formation with a low exposure amount compared to conventional ones). In addition, the chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition of the present invention have good resist pattern shape. Specific details for implementing the invention

[0012] Hereinafter, embodiments of the present invention will be described in detail.

[0013] The onium salt of the present invention is represented by the following general formula (1).

[0014] An onium salt that can be represented by the general formula (1), wherein among the two isomers of an anionic structure, a facial body and a meridional body, the proportion of the facial body is 15.0 weight% or less.

[0015] [(R 2 ) n+1 -E] + [(R 1 )3(F)3P] - (1)

[0016] In Equation (1), R 1...is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, or an aryl group having 6 to 18 carbon atoms (excluding the number of carbon atoms of the following substituents). Some of the hydrogen atoms in the aryl group may be substituted with an alkyl group having 1 to 18 carbon atoms, a halogen atom, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms;

[0017] E represents an element with valence n in groups 15 through 17 (IUPAC notation), n is an integer from 1 to 3, and R 2 is an organic group bonded to E, and R 2 The number of is n + 1, and there are (n + 1) R 2 Each may be identical or different from each other, and two or more R 2 They may form a ring structure containing element E either directly or through -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene groups, or phenylene groups.

[0018] In the anion (B) of the onium salt (A) of the present invention, P represents a phosphorus atom and F represents a fluorine atom. Also, R 1 The is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, or an aryl group having 6 to 18 carbon atoms (excluding the carbon atoms of the following substituents). Some of the hydrogen atoms in the aryl group may be substituted with an alkyl group having 1 to 18 carbon atoms, a halogen atom, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms.

[0019] This anion (B) has P as the central element, and F, and R 1These structures are formed by coordinating three of each, for a total of six. In this case, there are two types of isomers: a facial body in which the same type of ligands are cis-type, and a meridional body in which the same ligands are on the same plane.

[0020] When the onium salt (A) functions as an acid generator, the proton added to this anion (B) functions as an acid, so controlling the ratio of the two types of isomers is a very important factor. Among the two types of isomers, the facial body and the meridional body, by setting the ratio of the facial body to 15.0 weight% or less, a resist with dramatically high sensitivity (which enables pattern formation with a lower exposure amount compared to conventional ones) can be manufactured. Among the two types of isomers, the more preferred range for the ratio of the facial body is 0.1 to 15.0 weight%, and most preferably 0.5 to 10.0 weight%.

[0021] R 1 ...is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, or an aryl group having 6 to 18 carbon atoms (excluding the carbon atoms of the following substituents). Some of the hydrogen atoms in the aryl group may be substituted with an alkyl group having 1 to 18 carbon atoms, a halogen atom, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms. Examples of these substituents are R described below. 2 It is identical to the example. In addition, among these, a perfluoroalkyl group and a phenyl group substituted with a fluorine atom are preferred, and specifically, a pentafluoroethyl group, a heptafluoro-n-propyl group, a nonafluoro-n-butyl group, a heptafluoro-i-propyl group, a trifluoromethyl group, etc. are more preferred.

[0022] To control the ratio of the two isomers, the facial and meridional forms, for example, the precursor phosphoran ((R 1When reacting )3(F)2P) with a fluorination agent, isomers suitable for the purpose can be synthesized by optimizing the polarity of the solvent, the amount of solvent and substrate (in other words, concentration), and the reaction temperature. In addition, examples of fluorination agents include hydrogen fluoride, fluoride metals (sodium fluoride, potassium fluoride), etc.

[0023] The cation (C) of the onium salt (A) is the cation site of general formula (1), E represents an element of valence n from groups 15 to 17 (IUPAC notation), n is an integer from 1 to 3, and R 2 is an organic group bonded to E, and R 2 The number of is n + 1, and there are (n + 1) R 2 Each may be identical or different from each other, and two or more R 2 They may form a ring structure containing element E either directly or through -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene groups, or phenylene groups.

[0024] Specific examples of E include N, O, F, P, S, Cl, As, Se, Br, Sb, Te, I, etc. Among these, preferred elements are S, I, N, and P. Corresponding cations (C) are sulfonium, iodonium, ammonium, and phosphonium. More preferred elements are S and I. Corresponding cations (C) are sulfonium and iodonium.

[0025] R 2 represents an organic group bonded to E, and may be the same or different. R 2 Examples of groups include C1 to C18 alkyl groups, C2 to C18 alkenyl groups, and C6 to C18 aryl groups, wherein the aryl group additionally includes C1 to C18 alkyl groups, C2 to C18 alkenyl groups, C6 to C18 aryl groups, nitro groups, hydroxyl groups, cyano groups, -OR5 an alkoxy group or aryloxy group represented by -SR 6 An alkylthio group or arylthio group represented by, R 7 Acyl group represented by CO-, R 8 Acyloxy group represented by COO-, -NR 9 R 10 It may be substituted with an amino group represented by, or a halogen atom.

[0026] The above R 2 Examples of alkyl groups having 1 to 18 carbon atoms include straight-chain alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, etc.), cross-linked cyclic alkyl groups (norbornyl, adamantyl and pinanyl, etc.) and arylalkyl groups (benzyl, naphthylmethyl, phenethyl, benzhydryl and phenacyl, etc.).

[0027] The above R 2 Examples of alkenyl groups having 2 to 18 carbon atoms include straight-chain or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl and 3-cyclohexenyl, etc.) and arylalkenyl groups (styryl and cinnamyl, etc.).

[0028] The above R 2The aryl groups having 6 to 18 carbon atoms (excluding the carbon atoms of the following substituents) include monocyclic aryl groups (phenyl, etc.), condensed polycyclic aryl groups (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl, etc.) and aromatic heterocyclic hydrocarbon groups (tienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, etc. monocyclic heterocyclic groups); and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantrenyl, phenoxazinyl, phenoxatininyl, Examples include condensed polycyclic complex rings such as chromanyl, isochromanyl, coumarinyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0029] As for the aryl group, in addition to the above, some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 18 carbon atoms, nitro groups, hydroxyl groups, cyano groups, -OR 5 an alkoxy group or aryloxy group represented by -SR 6 An alkylthio group or arylthio group represented by, R 7 Acyl group represented by CO-, R 8 Acyloxy group represented by COO-, -NR 9 R 10 It may be substituted with an amino group represented by, or a halogen atom.

[0030] In the above substituent, -OR 5 an alkoxy group represented by, -SR 6 The alkylthio group represented by, R 7 Acyl group represented by CO-, R 8 Acyloxy group represented by COO-, -NR 9 R 10 R of the amino group represented as 5 ~ R 10Examples include alkyl groups having 1 to 8 carbon atoms, and specifically, among the above alkyl groups, alkyl groups having 1 to 8 carbon atoms.

[0031] In the above substituent, -OR 5 An aryloxy group represented by -SR 6 The arylthio group represented as, R 7 Acyl group represented by CO-, R 8 Acyloxy group represented by COO-, -NR 9 R 10 R of the amino group represented as 5 ~ R 10 Examples include aryl groups having 6 to 18 carbon atoms, and specifically, the above-mentioned aryl groups having 6 to 18 carbon atoms.

[0032] -OR 5 Examples of alkoxy groups represented by include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy, and 2-methylbutoxy.

[0033] -OR 5 Examples of aryloxy groups represented by phenoxy, naphthoxy, etc.

[0034] -SR 6 Examples of alkyl thio groups represented by include methylthio, ethylthio, butylthio, hexylthio, and cyclohexylthio.

[0035] -SR 6 Examples of arylthio groups represented by phenylthio, naphthylthio, biphenylthio, 2-thioxanthonylthio, etc.

[0036] R 7 Acyl groups represented by CO- include acetyl, propanoyl, butanoyl, pivaloyl, and benzoyl.

[0037] R 8 Acyloxy groups represented by COO- include acetoxy, butanoyloxy, and benzoyloxy.

[0038] -NR 9 R 10 Amino groups represented by sylamino, ethylamino, propylamino, dimethylamino, diethylamino, methylethylamino, dipropylamino, dipropylamino, and piperidino, etc.

[0039] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0040] The above R 2 Among these, preferably are an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms and a nitro group, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, -OR 5 an alkoxy group represented by, -SR 6 The arylthio group represented as, R 7 Acyl group represented by CO-, R 8 It is an acyloxy group represented by COO- or an aryl group having 6 to 18 carbon atoms substituted with a chlorine atom.

[0041] More preferably, an alkyl group having 1 to 18 carbon atoms, a phenyl group and a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, -OR 5 an alkoxy group represented by, -SR 6 It is a phenyl group substituted with an arylthio group, acetyl group, benzoyl group, or acetoxy group.

[0042] Also, two or more R 2 They may form a ring structure containing element E either directly or through -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene groups, or phenylene groups.

[0043] Specific examples of cations (C) are given below.

[0044] Specific examples of ammonium ions include tetraalkylammoniums such as tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium; pyrrolidiniums such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N,N-diethylpyrrolidinium; imidazoliniums such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidiniums such as N,N'-dimethyltetrahydropyrimidinium; morpholiums such as N,N'-dimethylmorpholium; and piperidiniums such as N,N'-diethylpiperidinium. Examples include pyridiniums such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridinium; imidazoliums such as N,N'-dimethylimidazolium; quinoliums such as N-methylquinolium, N-benzylquinolium, and N-phenacylquinolium; isoquinoliums such as N-methylisoquinolium; thiazoniums such as benzylbenzothiazonium and phenacylbenzothiazonium; and acridiums such as benzylacridium and phenacylacridium.

[0045] Specific examples of phosphonium ions include tetraarylphosphonium such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, tetrakis(4-methoxyphenyl)phosphonium; triarylphosphonium such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium; and tetraalkylphosphonium such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, tributylphenacylphosphonium.

[0046] Specific examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thi-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thi-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthon, 2-[(diphenyl)sulfonio]thioxanthon, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, 5-tolyltianthrenium, 5-(4-ethoxyphenyl)thianthrenium,Triarylsulfonium such as 5-(2,4,6-trimethylphenyl)thiantrenium; diarylsulfonium such as diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, and diphenylmethylsulfonium; Phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetoxyphenylmethylbenzylsulfonium, 4-acetoxyphenyldimethylsulfonium, 4-hydroxyphenyl(1-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 4-hydroxyphenyl(4-nitrobenzyl)methylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetoxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium, etc. Monoarylsulfonium; examples include trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

[0047] Specific examples of iodium ions include diphenyliodonium, di-p-tolyliodonium, di(4-tert-butylphenyl)iodonium, di(4-dodecylphenyl)iodonium, di(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, di(4-decyloxyphenyl)iodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, phenyl(2,4,6-trimethoxyphenyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0048] The onium salt represented by Formula (1) of the present invention can be prepared by a double decomposition method. The double decomposition method is, for example, [referenced in] New Experimental Chemistry Lecture Vol. 14-I (1978, Maruzen) p-448; Advance in Polymer Science, 62, 1-48 (1984); New Experimental Chemistry Lecture Vol. 14-III (1978, Maruzen) pp1838-1846; Organic Sulfur Chemistry (Synthetic Reactions, 1982, Kagaku Tojin), Chapter 8, pp237-280; Journal of Japanese Chemistry, 87, (5), 74 (1966); Although described in Japanese Patent Publication No. Sho 64-45357, Japanese Patent Publication No. Sho 61-212554, Japanese Patent Publication No. Sho 61-100557, Japanese Patent Publication No. Hei 5-4996, Japanese Patent Publication No. Hei 7-82244, Japanese Patent Publication No. Hei 7-82245, Japanese Patent Publication No. Sho 58-210904, Japanese Patent Publication No. Hei 6-184170, etc., first, F of onium cation - , Cl - , Br - , I - Halogen ion salts of the like ; OH - Salt ; ClO4 - Salt ; FSO3 - , ClSO3 - , CH3SO3 - , C6H5SO3 - , CF3SO3 - Salts with sulfonate ions of the like; HSO4 - , SO4 2- Salts with sulfate ions such as ; HCO3 - , CO3 2- Salts with carbonate ions such as ; H2PO4 - , HPO4 2- , PO4 3-Salts such as those with phosphate ions are prepared, and these are added to an alkali metal salt, alkaline earth metal salt, or quaternary ammonium salt of an anion constituting the onium salt represented by formula (1) in a solvent and aqueous solution to undergo double decomposition. Water or organic solvents may be used as the solvent. Organic solvents include hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahydrofuran and dioxane, etc.), chlorine-based solvents (chloroform and dichloromethane, etc.), alcohols (methanol, ethanol and isopropyl alcohol, etc.), ketones (acetone, methyl ethyl ketone and methyl isobutyl ketone, etc.), nitriles (acetonitrile, etc.), and polar organic solvents (dimethyl sulfoxide, dimethylformamide and N-methylpyrrolidone, etc.). These solvents may be used alone or in combination of two or more types.

[0049] The target onium salt produced by this process is separated into a crystalline or oil phase. In the case of an oil phase, it is obtained by separating the precipitated oil phase from the organic solvent solution and further removing the organic solvent contained in the oil phase by distillation. In the case of a crystal, it is obtained by separating the precipitated solid from the organic solvent solution and further removing the organic solvent contained in the solid by distillation. The target onium salt obtained in this way can be purified as needed by methods such as recrystallization or washing with water or a solvent.

[0050] Purification by recrystallization can be carried out by dissolving the target onium salt in a small amount of organic solvent, and separating it from the organic solvent by adding a solvent-free agent directly (or after concentration) to the organic solvent solution containing the target onium salt to precipitate the target onium salt. The solvent-free agents used here include chain-type ethers (diethyl ether and dipropyl ether, etc.), esters (ethyl acetate and butyl acetate, etc.), aliphatic hydrocarbons (hexane and cyclohexane, etc.), and aromatic hydrocarbons (toluene and xylene, etc.). Additionally, purification can be carried out by utilizing the difference in solubility due to temperature. Purification can be achieved by recrystallization (a method utilizing the difference in solubility due to cooling, a method of precipitating by adding a solvent-free agent, or a combination thereof). Furthermore, if the target product is an oily substance (in which it does not crystallize), purification can be achieved by washing the oily substance with water or a solvent-free agent.

[0051] When using the onium salt of Formula (1), in order to facilitate dissolution into the chemically amplified resist composition, it may be dissolved in a solvent that does not inhibit polymerization, crosslinking, or deprotection reactions in advance.

[0052] As solvents, carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, and their derivatives; cyclic ethers such as dioxane; Examples include esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 2-methyl hydroxypropionate, 2-ethyl hydroxypropionate, 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutanoic acid, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc.; aromatic hydrocarbons such as toluene and xylene.

[0053] When using a solvent, the ratio of the solvent used is preferably 15 to 1000 parts by weight and more preferably 30 to 500 parts by weight per 100 parts by weight of the onium salt represented by Formula (1) of the present invention. The solvent used may be used alone or two or more types may be used in combination.

[0054] By using the onium salt of the present invention as a photocatalytic agent and further mixing it in various ways, this composition, which becomes an energy-ray curable composition, can be cured by irradiating it with an energy ray to obtain a cured body.

[0055] As for the energy line, any energy line having the energy to cause the decomposition of the photogenerative agent of the present invention may be used, but an energy line in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from low-pressure, medium-pressure, high-pressure, or ultra-high-pressure mercury lamps, metal halide lamps, LED lamps, xenon lamps, carbon arc lamps, fluorescent lamps, semiconductor solid-state lasers, argon lasers, He-Cd lasers, KrF excimer lasers, ArF excimer lasers, or F2 lasers is preferred. In addition, high-energy radiation such as electron beams or X-rays may be used as the energy line.

[0056] The irradiation time of the energy beam is affected by the intensity of the energy beam or the permeability of the energy beam to the energy-curable composition, but 0.1 to 10 seconds at room temperature (about 20 to 30°C) is sufficient. However, in cases where the permeability of the energy beam is low or the film thickness of the energy-curable composition is thick, it may be desirable to spend more time. Most energy-curable compositions are cured by cation polymerization 0.1 seconds to minutes after irradiation of the energy beam, but if necessary, it is also possible to after-cure by heating at room temperature (about 20 to 30°C) to 200°C for a few seconds to several hours after irradiation of the energy beam.

[0057] Specific applications of this energy-beam curable composition include positive-type resists (such as forming connection terminals or wiring patterns in the manufacture of electronic components such as circuit boards, CSPs, and MEMS devices), and negative-type resists (such as permanent film materials for surface protection films, interlayer insulating films, and planarization films for semiconductor devices).

[0058] Chemical amplification type resist materials include: (1) a two-component chemical amplification type positive resist having a resin that is soluble in an alkaline developer by the action of an acid and a photogenerator as essential components; (2) a three-component chemical amplification type positive resist having a resin that is soluble in an alkaline developer, a dissolution inhibitor that is soluble in an alkaline developer by the action of an acid, and a photogenerator as essential components; and (3) a chemical amplification type negative resist having a resin that is soluble in an alkaline developer, a crosslinking agent that crosslinks the resin and makes it insoluble in an alkaline developer by heat treatment in the presence of an acid, and a photogenerator as essential components.

[0059] The chemical amplification type positive type photoresist compositions of (1) and (2) above contain a resin component (F) in which the onium salt (A) of the present invention, which is a compound that generates acid by light or radiation irradiation, functions as an acid-generating agent, and the solubility for alkali is increased by the action of the acid.

[0060] It is preferable that the content of onium salt (A) be 0.05 to 5 weight% of the solid content of the chemically amplified positive type photoresist composition.

[0061] <Resin component (F) whose solubility in alkali is increased by the action of acid>

[0062] The “resin component (F) whose solubility in alkali is increased by the action of acid” (hereinafter referred to as “component (F)”) used in the chemically amplified positive type photoresist composition of the present invention is at least one resin selected from the group consisting of novolak resin (F1), polyhydroxystyrene resin (F2), and acrylic resin (F3), or a mixed resin or copolymer thereof.

[0063] [Novolak Resin (F1)]

[0064] As the novolak resin (F1), a resin represented by the following general formula (b1) can be used.

[0065] [Chemical Formula 1]

[0066]

[0067] Among the above general formula (b1), R 1b represents an acid dissociative dissolution inhibitor, and R 2b , R 3b Each represents independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents the number of repeating units of the structure in parentheses.

[0068] In addition, the above R 1b As for the acid dissociation dissolution inhibitor represented by, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group having 3 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group is preferred.

[0069] Here, the above R 1b Specific examples of acid dissociation dissolution inhibitors represented by include methoxyethyl groups, ethoxyethyl groups, n-propoxyethyl groups, isopropoxyethyl groups, n-butoxyethyl groups, isobutoxyethyl groups, tert-butoxyethyl groups, cyclohexyloxyethyl groups, methoxypropyl groups, ethoxypropyl groups, 1-methoxy-1-methylethyl groups, 1-ethoxy-1-methylethyl groups, tert-butoxycarbonyl groups, tert-butoxycarbonylmethyl groups, trimethylsilyl groups, and tri-tert-butyldimethylsilyl groups.

[0070] [Polyhydroxystyrene resin (F2)]

[0071] As the polyhydroxystyrene resin (F2), a resin represented by the following general formula (b4) can be used.

[0072] [Chemical Formula 2]

[0073]

[0074] Among the above general formula (b4), R8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 9b represents an acid dissociative dissolution inhibitor, and n represents the number of repeating units of the structure inside the parentheses.

[0075] The above alkyl group having 1 to 6 carbon atoms is a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, and examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc., and examples of cyclic alkyl groups include a cyclopentyl group, a cyclohexyl group, etc.

[0076] The above R 9b As an acid dissociative dissolution inhibitor represented by, the above R 1b The same acid dissociation inhibitor as exemplified in can be used.

[0077] In addition, the polyhydroxystyrene resin (F2) may include other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds or anionic polymerizable compounds. For instance, monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having carboxyl groups and ester bonds such as 2-methacryloyloxyethylsuccinic acid; alkyl esters of (meth)acrylate such as methyl (meth)acrylate; hydroxyalkyl esters of (meth)acrylate such as 2-hydroxyethyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate; vinyl group-containing aromatic compounds such as styrene and vinyltoluene; vinyl group-containing aliphatic compounds such as vinyl acetate; Examples include conjugated diolefins such as butadiene and isoprene; polymerizable compounds containing nitrile groups such as acrylonitrile; polymerizable compounds containing chlorine such as vinyl chloride; and polymerizable compounds containing amide bonds such as acrylamide.

[0078] [Acrylic Resin (F3)]

[0079] As the acrylic resin (F3), resins represented by the following general formulas (b5) to (b10) can be used.

[0080] [Chemical Formula 3]

[0081]

[0082] [Chemical Formula 4]

[0083]

[0084] Among the above general formulas (b5) to (b7), R 10b ~ R 17bEach represents independently a hydrogen atom, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group having 3 to 6 carbon atoms, a fluorine atom, or a straight-chain fluorinated alkyl group having 1 to 6 carbon atoms or a branched-chain fluorinated alkyl group having 3 to 6 carbon atoms, and X b It forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded, and Y b represents an aliphatic cyclic group or an alkyl group that may have a substituent, n represents the number of repeating units of the structure in parentheses, p is an integer from 0 to 4, and q is 0 or 1.

[0085] In general formulas (b8), (b9) and (b10), R 18b , R 20b and R 21b represents, independently of each other, a hydrogen atom or a methyl group, and in general formula (b8), each R 19b is, independently of each other, a hydrogen atom, a hydroxyl group, a cyano group, or COOR 23b (Dan, R 23b represents a hydrogen atom, a straight-chain alkyl group having 1 to 4 carbon atoms, a branched-chain alkyl group having 3 to 4 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, and in general formula (b10), each R 22b ...independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, a straight-chain alkyl group having 1 to 4 carbon atoms or a branched-chain alkyl group having 3 to 4 carbon atoms, and also R 22b At least one of is the alicyclic hydrocarbon group or its derivative, or any two R 22b A bonds to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, together with the common carbon atom to which each is bonded, and the remaining R 22b...represents a straight-chain alkyl group having 1 to 4 carbon atoms, a branched-chain alkyl group having 3 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof.

[0086] Among the above components (F), it is preferable to use acrylic resin (F3).

[0087] In addition, the weight average molecular weight of the polystyrene equivalent of component (F) is preferably 10,000 to 600,000, more preferably 50,000 to 600,000, and even more preferably 230,000 to 550,000. By having such a weight average molecular weight, the resin properties of the resist are excellent.

[0088] In addition, it is preferable that component (F) be a resin with a dispersion degree of 1.05 or higher. Here, "dispersion degree" refers to the value obtained by dividing the weight-average molecular weight by the number-average molecular weight. By having such a dispersion degree, the plating resistance and resin properties of the resist are excellent.

[0089] It is preferable that the content of the above component (F) be 5 to 60 weight% of the solid content of the chemically amplified positive type photoresist composition.

[0090] <Alkali-soluble resin (G)>

[0091] In the chemically amplified positive type photoresist composition of the present invention, it is preferable to additionally include an alkali-soluble resin (referred to as "component (G)" in this specification) to improve the resin properties of the resist. As for component (G), it is preferable that at least one is selected from the group consisting of novolak resin, polyhydroxystyrene resin, acrylic resin, and polyvinyl resin.

[0092] The content of the above component (G) is preferably 5 to 95 parts by weight with respect to 100 parts by weight of the above component (F), and more preferably 10 to 90 parts by weight. By making it 5 parts by weight or more, the resin properties of the resist can be improved, and by making it 95 parts by weight or less, film reduction during development can be prevented.

[0093] <Acid Diffusion Control Agent (H)>

[0094] In order to improve the resist pattern shape, post-exposure stability, etc., the chemically amplified positive type photoresist composition of the present invention preferably contains an acid diffusion control agent (H) (referred to as “Component (H)” in this specification). As for Component (H), a nitrogen-containing compound is preferred, and additionally, an organic carboxylic acid or a phosphoric oxo acid or a derivative thereof may be contained as needed.

[0095] In addition, the chemically amplified positive type photoresist composition of the present invention may further contain an adhesion aid to improve adhesion to a substrate. A functional silane coupling agent is preferred as the adhesion aid used.

[0096] In addition, the chemically amplified positive type photoresist composition of the present invention may further contain a surfactant to improve coating properties, anti-foaming properties, leveling properties, etc.

[0097] In addition, the chemically amplified positive type photoresist composition of the present invention may additionally contain an acid, an acid anhydride, or a high-boiling point solvent to finely adjust solubility with respect to an alkaline developer.

[0098] In addition, the chemically amplified positive type photoresist composition of the present invention basically does not require a sensitizer, but may contain a sensitizer as needed to supplement sensitivity. As such a sensitizer, conventionally known ones may be used, and specifically, the above-mentioned ones may be cited.

[0099] The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the total weight of the onium salt represented by the above formula (1).

[0100] In addition, an organic solvent may be appropriately incorporated into the chemically amplified positive type photoresist composition of the present invention to adjust viscosity. Specific examples of organic solvents include those mentioned above.

[0101] The amount of these organic solvents used is preferably in a range where the solid content concentration is 30 weight% or more, so that the film thickness of the photoresist layer obtained using the chemically amplified positive type photoresist composition (e.g., spin coat method) is 5 μm or more.

[0102] The preparation of the chemically amplified positive type photoresist composition for thick films may be done by, for example, simply mixing and stirring each of the above components in a conventional manner, or, if necessary, using a disperser such as a dissolver, homogenizer, or three-roll mill to disperse and mix the components. Additionally, after mixing, the components may be further filtered using a mesh, membrane filter, etc.

[0103] The chemically amplified positive type photoresist composition of the present invention is suitable for forming a photoresist layer on a support with a film thickness of typically 5 to 150 μm, more preferably 10 to 120 μm, and even more preferably 10 to 100 μm. The photoresist laminate is a photoresist layer made of the chemically amplified positive type photoresist composition of the present invention laminated on a support.

[0104] As for the support, there are no particular limitations, and conventionally known materials may be used. Examples include substrates for electronic components or substrates having a predetermined wiring pattern formed thereon. Examples of such substrates include metal substrates made of silicon, silicon nitride, titanium, tantalum, palladium, tungsten titanium, copper, chromium, iron, aluminum, etc., or glass substrates. In particular, the chemically amplified positive photoresist composition of the present invention can effectively form a resist pattern on a copper substrate. For example, copper, solder, chromium, aluminum, nickel, gold, etc. are used as the material for the wiring pattern.

[0105] The above photoresist laminate can be manufactured, for example, as follows. That is, a solution of the chemically amplified positive type photoresist composition prepared as described above is applied onto a support, and a desired film is formed by removing the solvent by heating. As a method of application onto the support, methods such as spin coating, slit coating, roll coating, screen printing, and applicator methods may be employed. The pre-baking conditions of the film of the composition of the present invention vary depending on the type of each component in the composition, the mixing ratio, the thickness of the coating film, etc., but typically, it should be done at 70 to 150°C, preferably 80 to 140°C, for about 2 to 60 minutes.

[0106] The thickness of the photoresist layer can be typically in the range of 5 to 150 μm, preferably 10 to 120 μm, and more preferably 10 to 100 μm.

[0107] To form a resist pattern using the photoresist laminate obtained in this way, a mask of a predetermined pattern is interposed on the obtained photoresist layer, and localized irradiation (exposure) of light or radiation, for example, ultraviolet or visible light with a wavelength of 300 to 500 nm, is performed.

[0108] Here, "light" refers to any light that activates a photo-generating agent to generate acid, and includes ultraviolet, visible, and far-ultraviolet rays, and "radiation" refers to X-rays, electron beams, ion rays, etc. As a source of light or radiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, LED lamps, etc., may be used. In addition, the radiation dose varies depending on the type and amount of each component in the composition, the thickness of the coating film, etc., but, for example, when using an ultra-high-pressure mercury lamp, it is 50 to 10,000 mJ / ㎠.

[0109] Then, after exposure, the diffusion of acid is promoted by heating using a known method, thereby changing the alkali solubility of the photoresist layer in the exposed area. Subsequently, for example, a predetermined alkaline aqueous solution is used as a developer to dissolve and remove the unnecessary parts, thereby obtaining a predetermined resist pattern.

[0110] The development time varies depending on the type of each component of the composition, the mixing ratio, and the thickness of the dry film of the composition, but is typically 1 to 30 minutes, and the development method may be any of the liquid mounting method, dipping method, paddle method, spray development method, etc. After development, rinse with water for 30 to 90 seconds, and dry using an air gun or an oven, etc.

[0111] In the non-resist portion (the portion removed by the alkaline developer) of the resist pattern obtained in this way, a conductor such as a metal can be embedded, for example by plating, to form connection terminals such as metal posts or bumps. In addition, the plating method is not particularly limited, and various conventionally known methods can be employed. As for the plating solution, solder plating, copper plating, gold plating, and nickel plating solutions are preferably used. The remaining resist pattern is removed using a stripping solution, etc., according to the method determined at the end.

[0112] The chemically amplified positive type photoresist composition of the present invention can also be used as a dry film. This dry film is formed by having protective films formed on both sides of a layer composed of the chemically amplified positive type photoresist composition of the present invention. The film thickness of the layer composed of the chemically amplified positive type photoresist composition can typically be in the range of 10 to 150 μm, preferably 20 to 120 μm, and more preferably 20 to 80 μm. In addition, the protective film is not particularly limited and can use a resin film that is conventionally used in dry films. As an example, one can be a polyethylene terephthalate film and the other can be one selected from the group consisting of polyethylene terephthalate film, polypropylene film, and polyethylene film.

[0113] A chemically amplified positive type dry film as described above can be manufactured, for example, as follows. That is, a solution of the chemically amplified positive type photoresist composition prepared as described above is applied onto a protective film, and a desired film is formed by removing the solvent by heating. The drying conditions vary depending on the type of each component in the composition, the mixing ratio, the thickness of the coating film, etc., but typically, it is sufficient to dry at 60 to 100°C for about 5 to 20 minutes.

[0114] To form a resist pattern using the chemically amplified dry film obtained in this manner, one protective film of the chemically amplified positive dry film is peeled off, and a photoresist layer is obtained by laminating it onto a support with the exposed side facing the support side described above. Afterward, the resist is dried by performing a pre-bake, and then the other protective film is peeled off.

[0115] In this way, a resist pattern can be formed on the photoresist layer obtained on the support in the same manner as described above with respect to the photoresist layer formed by direct application on the support.

[0116] Next, the chemically amplified negative type photoresist composition of (3) contains an onium salt (A) of the present invention, which is a compound that generates acid by light or radiation irradiation, as an acid-generating agent, an alkali-soluble resin (I) having a phenolic hydroxyl group by the action of the acid, and a crosslinking agent (J).

[0117] Alkali-soluble resin having phenolic hydroxyl groups (I)

[0118] In the present invention, the "alkali-soluble resin having a phenolic hydroxyl group" (hereinafter referred to as "phenol resin (I)") is used, for example, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, a copolymer of hydroxystyrene and styrene, a copolymer of hydroxystyrene, styrene and (meth)acrylic acid derivative, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, etc. Among these, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, a copolymer of hydroxystyrene and styrene, a copolymer of hydroxystyrene, styrene and (meth)acrylic acid derivative, and phenol-xylylene glycol condensation resin are preferred. In addition, these phenol resins (I) may be used as a single type or as a mixture of two or more types.

[0119] In addition, the above phenol resin (I) may contain a phenolic low-molecular-weight compound as part of its components.

[0120] Examples of the above-mentioned phenolic low molecular weight compounds include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, etc.

[0121] Crosslinking agent (J)

[0122] The “crosslinking agent” (hereinafter also referred to as “crosslinking agent (J)”) in the present invention is not particularly limited as long as it acts as a crosslinking component (curing component) that reacts with the phenol resin (I). Examples of the crosslinking agent (J) include, for instance, a compound having at least two alkyl etherified amino groups in its molecule, a compound having at least two alkyl etherified benzene backbones in its molecule, an oxirane ring-containing compound, a tyran ring-containing compound, an oxetanyl group-containing compound, an isocyanate group-containing compound (including those that are blocked), etc.

[0123] Among these crosslinking agents (J), compounds having at least two alkyl etherified amino groups in the molecule and oxiran ring-containing compounds are preferred. Furthermore, it is more preferable to use a combination of compounds having at least two alkyl etherified amino groups in the molecule and oxiran ring-containing compounds.

[0124] In the present invention, the amount of crosslinking agent (J) is preferably 1 to 100 parts by weight per 100 parts by weight of the phenol resin (I), and more preferably 5 to 50 parts by weight. When the amount of crosslinking agent (J) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the resulting cured product has a good pattern shape with high resolution and excellent heat resistance and electrical insulation properties, which is preferred.

[0125] In addition, when a compound having an alkyl etherified amino group and an oxiran ring-containing compound are used in combination, the content ratio of the oxiran ring-containing compound is preferably 50% by weight or less when the total of the compound having an alkyl etherified amino group and the oxiran ring-containing compound is 100% by weight, more preferably 5% to 40% by weight, and particularly preferably 5% to 30% by weight.

[0126] In this case, the resulting hardened film is desirable because it does not impair high resolution and has excellent chemical resistance.

[0127] Cross-linked microparticles (K)

[0128] The chemically amplified negative type photoresist composition of the present invention may additionally contain cross-linked microparticles (hereinafter also referred to as “cross-linked microparticles (K)”) to improve the durability or thermal shock resistance of the resulting cured product.

[0129] The average particle size of the cross-linked microparticles (K) is typically 30 to 500 nm, preferably 40 to 200 nm, and more preferably 50 to 120 nm.

[0130] The method for controlling the particle size of this cross-linked microparticle (K) is not particularly limited, but for example, when cross-linked microparticles are synthesized by emulsion polymerization, the particle size can be controlled by controlling the number of micelles in the emulsion polymerization according to the amount of emulsifier used.

[0131] In addition, the average particle size of the cross-linked microparticles (K) is a value measured by diluting the dispersion of cross-linked microparticles according to a conventional method using a light scattering flow distribution measuring device, etc.

[0132] The amount of crosslinked microparticles (K) is preferably 0.5 to 50 parts by weight per 100 parts by weight of the phenol resin (I), and more preferably 1 to 30 parts by weight. When the amount of crosslinked microparticles (K) is 0.5 to 50 parts by weight, compatibility or dispersibility with other components is excellent, and the thermal shock resistance and heat resistance of the resulting cured film can be improved.

[0133] Closeness aid

[0134] In addition, the chemically amplified negative type photoresist composition of the present invention may contain an adhesion aid to improve adhesion to a substrate.

[0135] Examples of the above-mentioned coupling aids include functional silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups.

[0136] The amount of the adhesion aid is preferably 0.2 to 10 parts by weight per 100 parts by weight of the phenol resin (I), and more preferably 0.5 to 8 parts by weight. When the amount of the adhesion aid is 0.2 to 10 parts by weight, it is preferred because it provides excellent storage stability and good adhesion.

[0137] solvent

[0138] In addition, the chemically amplified negative type photoresist composition of the present invention may contain a solvent to improve the handling properties of the resin composition or to control viscosity or storage stability.

[0139] The above solvent is not particularly limited, but specific examples may include the above.

[0140] In addition, the chemically amplified negative type photoresist composition of the present invention may contain a sensitizer as needed. As such a sensitizer, conventionally known ones may be used, and specifically, the above-mentioned ones may be cited.

[0141] The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total weight of the sulfonium salt represented by the above formula (1).

[0142] Other additives

[0143] In addition, the chemically amplified negative type photoresist composition of the present invention may contain other additives as needed to an extent that does not impair the characteristics of the present invention. Examples of such other additives include inorganic fillers, quenchers, leveling agents, surfactants, etc.

[0144] The method for preparing the chemically amplified negative type photoresist composition of the present invention is not particularly limited and can be prepared by known methods. In addition, it can also be prepared by stirring a sample bottle containing each component and completely closing it with a stopper on a wave rotor.

[0145] The cured product in the present invention is characterized by being formed by curing the chemically amplified negative type photoresist composition.

[0146] The chemically amplified negative type photoresist composition related to the present invention described above has a high residual film rate and excellent resolution, and since the cured product has excellent electrical insulation and thermal shock resistance, the cured product can be preferably used as a surface protective film, planarization film, interlayer insulating film material, etc., for electronic components such as semiconductor devices and semiconductor packages.

[0147] To form a cured product of the present invention, first, the chemically amplified negative type photoresist composition related to the present invention described above is coated onto a support (such as a copper foil with resin attached, a copper-clad laminate, or a silicon wafer or alumina substrate with a metal sputtered film attached), and dried to volatilize a solvent, etc., thereby forming a coating film. Then, exposure is performed through a desired mask pattern, and a heat treatment (hereinafter referred to as "PEB") is carried out to promote the reaction between the phenol resin (I) and the crosslinking agent (J). Subsequently, the desired pattern can be obtained by developing with an alkaline developer to dissolve and remove the unexposed portion. In addition, a cured film can be obtained by performing a heat treatment to express insulating film characteristics.

[0148] As a method for coating a resin composition onto a support, coating methods such as dipping, spraying, bar coating, roll coating, or spin coating can be used. In addition, the thickness of the coating film can be appropriately controlled by adjusting the coating means, the concentration of solids in the composition solution, or the viscosity.

[0149] Radiation used for exposure includes, for example, ultraviolet rays from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, g-hi-line steppers, electron beams, laser beams, etc. In addition, the exposure amount is appropriately selected depending on the light source used and the thickness of the resin film, but for example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, it is about 100 to 50,000 J / m² for a resin film thickness of 1 to 50 μm.

[0150] After exposure, the above PEB treatment is performed to promote the curing reaction between the phenol resin (I) and the crosslinking agent (J) by the generated acid. The PEB conditions vary depending on the amount of resin composition or the thickness of the film used, but are typically 70 to 150°C, preferably 80 to 120°C, for about 1 to 60 minutes. Afterwards, the desired pattern is formed by developing with an alkaline developer to dissolve and remove unexposed areas. Examples of development methods in this case include shower development, spray development, immersion development, and paddle development. The development conditions are typically 20 to 40°C for about 1 to 10 minutes.

[0151] In addition, to fully exhibit properties as an insulating film after development, sufficient curing can be achieved by performing a heat treatment. Although such curing conditions are not particularly limited, depending on the application of the cured material, the composition can be cured by heating at a temperature of 50 to 250°C for about 30 minutes to 10 hours. Furthermore, to ensure sufficient curing or to prevent deformation of the obtained pattern shape, heating may be performed in two stages; for example, in the first stage, the composition may be heated at a temperature of 50 to 120°C for about 5 minutes to 2 hours, and then heated again at a temperature of 80 to 250°C for about 10 minutes to 10 hours to achieve curing. Under such curing conditions, a general oven or an infrared oven can be used as the heating equipment.

[0152] Examples

[0153] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. Additionally, parts in each example represent parts by weight.

[0154] Preparation example of anion (B1) ~ (B6), (B'1)

[0155] Preparation example of anion (B1)

[0156] While cooling, 4.44 g of potassium fluoride (KF) was slowly added to 50.0 g of dimethoxyethane, and then 32.5 g of tris(pentafluoroethyl)difluorophosphorane was added while stirring. The mixture was slowly added and reacted while cooling so that the temperature was 30 ℃ or lower, and the potassium salt of tris(heptafluoroethyl)trifluorophosphonate (K + [(C2F5)3(F)3P] - A solution of ) was obtained. As a result of F-NMR, the proportion of the facial isomer among the two isomers was 0.0 wt%.

[0157] Preparation example of anion (B2)

[0158] While cooling, 4.44 g of potassium fluoride (KF) was slowly added to 50.0 g of dimethoxyethane, and then 43.9 g of tris(heptafluoropropyl)difluorophosphorane was added while stirring. The mixture was slowly added and reacted while cooling so that the temperature was 30 ℃ or lower, and the potassium salt of tris(heptafluoropropyl)trifluorophosphonate (K + [(C3F7)3(F)3P] - A solution of ) was obtained. As a result of F-NMR, the proportion of the facial isomer among the two isomers was 0.0 wt%.

[0159] Preparation example of anion (B3)

[0160] 7.04 g of a 40% aqueous hydrofluoric acid solution was diluted with 19.0 g of deion-exchanged water and cooled to below 5°C beforehand. Then, 60.0 g of tris(pentafluoroethyl)difluorophosphorane was slowly added while stirring. The reaction was carried out by slowly adding the solution while cooling to keep the temperature below 10°C. Subsequently, 7.90 g of potassium hydroxide, which had been dissolved in 30 g of deion-exchanged water beforehand, was added to form the potassium salt of tris(heptafluoropropyl)trifluorophosphonate (K + [(C2F5)3(F)3P] - A solution of ) was obtained. As a result of F-NMR, the proportion of the facial isomer among the two isomers was 0.1 wt%.

[0161] Preparation example of anion (B4)

[0162] 5.65 g of a 40% aqueous hydrofluoric acid solution was diluted with 6.73 g of deion-exchanged water and cooled to below 5 ℃ beforehand. Then, 47.8 g of tris(pentafluoroethyl)difluorophosphorane was slowly added while stirring. The reaction was carried out by slowly adding the solution while cooling to keep the temperature below 10 ℃. Subsequently, 6.29 g of potassium hydroxide, which had been dissolved in 30 g of deion-exchanged water beforehand, was added to form the potassium salt of tris(heptafluoropropyl)trifluorophosphonate (K +[(C2F5)3(F)3P] - A solution of ) was obtained. As a result of F-NMR, the proportion of the facial isomer among the two isomers was 5.0 wt%.

[0163] Preparation example of Anion (B5)

[0164] While cooling, 1.66 g of hydrogen fluoride (HF) was slowly added to 11.0 g of diethyl ether, and then 33.6 g of tris(pentafluoroethyl)difluorophosphorane was slowly added while stirring. The reaction was carried out by slowly adding the ingredients while cooling so that the temperature remained below 5 ℃. Subsequently, 4.42 g of potassium hydroxide was added to the potassium salt of tris(heptafluoropropyl)trifluorophosphonate (K + [(C2F5)3(F)3P] - A solution of ) was obtained. As a result of F-NMR, the proportion of the facial isomer among the two isomers was 14.6 wt%.

[0165] Preparation example of Anion (B6)

[0166] 7.51 g of a 40% aqueous hydrofluoric acid solution was diluted with 10.0 g of deion-exchanged water and cooled to below 5°C beforehand. Then, 63.6 g of tris(pentafluorophenyl)difluorophosphorane was slowly added while stirring. The reaction was carried out by slowly adding the solution while cooling to keep the temperature below 10°C. Subsequently, 8.36 g of potassium hydroxide, which had been dissolved in 30 g of deion-exchanged water beforehand, was added to form the potassium salt of tris(pentafluorophenyl)trifluorophosphonate (K + [(C6F5)3(F)3P] - A solution of ) was obtained. As a result of F-NMR, the proportion of the facial isomer among the two isomers was 5.0 wt%.

[0167] Preparation example of anion (B'1)

[0168] While cooling, 1.64 g of hydrogen fluoride (HF) was slowly added to 6.00 g of methanol, and then 32.5 g of tris(pentafluoroethyl)difluorophosphorane was slowly added while stirring. The reaction was carried out by slowly adding the ingredients while cooling so that the temperature remained below 5 ℃. Subsequently, 4.28 g of potassium hydroxide was added to form the potassium salt of tris(heptafluoropropyl)trifluorophosphonate (K + [(C2F5)3(F)3P] - A solution of ) was obtained. As a result of F-NMR, the proportion of the facial isomer among the two isomers was 18.4 wt%.

[0169] Example of onium salt (A1-1)

[0170] Preparation of 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0171] 12.12 g of diphenylsulfoxide, 9.3 g of diphenylsulfide, and 43.0 g of methanesulfonic acid were uniformly mixed, and then 7.9 g of acetic anhydride was added dropwise. After reacting at 50°C for 5 hours, the mixture was cooled to room temperature. To this reaction solution, 124.5 g of an anion (B1) adjusted to a 20% aqueous solution or solvent-exchanged was added dropwise, and the mixture was stirred for 2 hours. The precipitated oil phase was extracted with 120 g of ethyl acetate, and after separating the water bath, the organic layer was washed three more times. The solvent was removed from the organic layer, and 50 g of toluene was added to dissolve it. Then, 270 g of hexane was added and mixed, and the mixture was left for 1 hour to separate into two layers. The upper layer was removed, and 150 g of hexane was added to the remaining lower layer. When the mixture was stirred well, crystals precipitated. By filtering this crystal and drying under reduced pressure, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.0 wt%) (A1-1) was obtained. The chemical formula is as shown in (a1) below.

[0172] [Chemical Formula 5]

[0173]

[0174] Examples of onium salts (A1-2) to (A1-6), and comparative example (A'1-1)

[0175] In place of the anion (B1) of the preparation example of (A1-1), anions (B2) to (B6) and anion (B'1) were used, respectively, to obtain onium salts (A1-2) to (A1-6) and (A'1-1). Additionally, the amount of a 20% aqueous solution of anion (B2) was 167 g. The names of the synthesized compounds are as follows.

[0176] (A1-2) : 4-(phenylthio)phenyldiphenylsulfonium·tris(heptafluoropropyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0177] (A1-3) : 4-(phenylthio)phenyldiphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.1 wt%)

[0178] (A1-4) : 4-(phenylthio)phenyldiphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0179] (A1-5) : 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 14.6 wt%)

[0180] (A1-6) : 4-(phenylthio)phenyldiphenylsulfonium·tris(pentafluorophenyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0181] (A'1-1) : 4-(phenylthio)phenyldiphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 18.4 wt%)

[0182] The chemical formulas are as follows: (A1-2) is (a2), (A1-3) to (A1-5), and (A'1-1) is (a1), and (A1-6) is (a3).

[0183] [Chemical Formula 6]

[0184]

[0185] [Chemical Formula 7]

[0186]

[0187] Example of onium salt (A2-1)

[0188] Preparation of (4-isopropylphenyl)tolyliodonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0189] 20 g of 4-methyliodobenzene was added, and 50 g of acetic acid and 10 g of sulfuric acid were added and dissolved. While cooling in an ice bath, 10 g of potassium persulfate was added dropwise at 15 ℃ or lower. The reaction was carried out at 20 ℃ for 4 hours, and 24.4 g of cumene was added dropwise so as not to exceed 20 ℃. Afterward, the reaction was carried out at room temperature for 20 hours. The reaction mixture was added to 50 parts of an aqueous solution containing equimolar anion (B1) and stirred for an additional 3 hours. 500 parts of dichloromethane were added thereto. After standing, the aqueous layer was removed by separating the liquid, and the organic layer was washed 5 times with 100 parts of water. Dichloromethane was concentrated and recrystallized with cyclohexane to obtain (4-isopropylphenyl)tolyliodonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.0 wt%). The chemical formula is as follows in formula (a4).

[0190] [Chemical Formula 8]

[0191]

[0192] Examples of onium salts (A2-2) to (A2-6), and comparative example (A'2-1)

[0193] Instead of the anion (B1) of the preparation example of (A2-1), anions (B2) to (B6) and anion (B'1) were used, respectively, to obtain onium salts (A2-2) to (A2-6) and (A'2-1). In addition, the amount of a 20% aqueous solution of anion (B2) was 167 g. The names of the synthesized compounds are as follows.

[0194] (A2-2) : (4-isopropylphenyl)tolyliodonium·tris(heptafluoropropyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0195] (A2-3) : (4-isopropylphenyl)tolyliodonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.1 wt%)

[0196] (A2-4) : (4-isopropylphenyl)tolyliodonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0197] (A2-5) : (4-isopropylphenyl)tolyliodonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 14.6 wt%)

[0198] (A2-6) : (4-isopropylphenyl)tolyliodonium tris(pentafluorophenyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0199] (A'2-1) : (4-isopropylphenyl)tolyliodonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 18.4 wt%)

[0200] The chemical formulas are as follows: (A2-2) is (a5), (A2-3) to (A2-5), and (A'2-1) is (a4), and (A2-6) is (a6).

[0201] [Chemical Formula 9]

[0202]

[0203] [Chemical Formula 10]

[0204]

[0205] Example of Onium Salt (A3-1)

[0206] Preparation of [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0207] 11 g of 4-[(phenyl)sulfinyl]biphenyl, 12 g of 4-(phenylthio)biphenyl, 22 g of acetic anhydride, and 16 parts of methanesulfonic acid were homogeneously mixed and reacted at 65 °C for 3 hours. The reaction solution was cooled to room temperature, added to 100 mL of ion-exchanged water, extracted with 100 g of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator to remove the solvent by distillation, thereby obtaining a brown solid. This was washed with ethyl acetate / hexane, and the organic solvent was concentrated to obtain an intermediate.

[0208] 6.2 g of this intermediate was dissolved in 60 mL of dichloromethane, and 70 g of an aqueous solution containing anion (B1) was mixed at room temperature and stirred for 3 hours. After washing the dichloromethane layer with water 5 times by separatory operation, the mixture was transferred to a rotary evaporator to remove the solvent by distillation, thereby obtaining [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (facial body of anion: 5.0 wt%). The chemical formula is as shown in formula (a7) below.

[0209] [Chemical Formula 11]

[0210]

[0211] Examples of onium salts (A3-2) to (A3-6), and comparative example (A'3-1)

[0212] In place of the anion (B1) of the preparation example of (A3-1), anions (B2) to (B6) and anion (B'1), respectively, were used to obtain onium salts (A3-2) to (A3-6) and (A'3-1). Additionally, the amount of a 20% aqueous solution of anion (B2) was 167 g. The names of the synthesized compounds are as follows.

[0213] (A3-2) : [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium·tris(heptafluoropropyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0214] (A3-3) : [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.1 wt%)

[0215] (A3-4) : [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0216] (A3-5) : [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 14.6 wt%)

[0217] (A3-6) : [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium·tris(pentafluorophenyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0218] (A'3-1) : [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 18.4 wt%)

[0219] The chemical formulas are as follows: (A3-2) is (a8), (A3-3) to (A3-5), and (A'3-1) is (a7), and (A3-6) is (a9).

[0220] [Chemical Formula 12]

[0221]

[0222] [Chemical Formula 13]

[0223]

[0224] Example of Onium Salt (A4-1)

[0225] Preparation of [4-(4-acetylphenylthio)]phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0226] 89 parts of a dichloromethane solution containing 32 parts of (4-phenylthio)phenyldiphenylsulfonium trifluoromethanesulfonate were added dropwise to a suspension of 36 parts of aluminum chloride, 12 parts of acetyl chloride, and 200 parts of dichloromethane under conditions of stirring, cooling, and a temperature of 10°C or lower. After adding, the mixture was stirred at room temperature for 2 hours, and then 300 parts of cold water were added. The upper layer was removed, and the dichloromethane layer was washed with ion-exchanged water until the pH became neutral. Next, 70 g of an aqueous solution containing anion (B1) was mixed at room temperature and stirred for 3 hours. After washing the dichloromethane layer with water 5 times by separating it, the solution was transferred to a rotary evaporator to remove the solvent by distillation, thereby obtaining [4-(4-acetylphenylthio)]phenyldiphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (facial body of anion: 0.0 wt%). The chemical formula is as follows in formula (a10).

[0227] [Chemical Formula 14]

[0228]

[0229] Examples of onium salts (A4-2) to (A4-6), and comparative example (A'4-1)

[0230] In place of the anion (B1) of the preparation example of (A4-1), anions (B2) to (B6) and anion (B'1), respectively, were used to obtain onium salts (A4-2) to (A4-6) and (A'4-1). Additionally, the amount of a 20% aqueous solution of anion (B2) was 167 g. The names of the synthesized compounds are as follows.

[0231] (A4-2) : [4-(4-acetylphenylthio)]phenyldiphenylsulfonium·tris(heptafluoropropyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0232] (A4-3) : [4-(4-acetylphenylthio)]phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.1 wt%)

[0233] (A4-4) : [4-(4-acetylphenylthio)]phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0234] (A4-5) : [4-(4-acetylphenylthio)]phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 14.6 wt%)

[0235] (A4-6) : [4-(4-acetylphenylthio)]phenyldiphenylsulfonium tris(pentafluorophenyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0236] (A'4-1) : [4-(4-acetylphenylthio)]phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 18.4 wt%)

[0237] The chemical formulas are as follows: (A4-2) is (a11), (A4-3) to (A4-5), and (A'4-1) is (a10), and (A4-6) is (a12).

[0238] [Chemical Formula 15]

[0239]

[0240] [Chemical Formula 16]

[0241]

[0242] Example of Onium Salt (A5-1)

[0243] Preparation of Fluorene-Backed Sulfonium Tris(Pentafluoroethyl)Trifluorophosphonate (Anionic Facial: 0.0 wt%)

[0244] 1.0 parts of 2-[(phenyl)sulfinyl]-9,9-dimethylfluorene, 1.1 parts of 2-(phenylthio)-9,9-dimethylfluorene, 2.0 parts of acetic anhydride, and 1.6 parts of methanesulfonic acid were added and stirred at 65°C for 3 hours. The reaction solution was cooled to room temperature, added to 5.0 parts of ion-exchanged water, extracted with 5.0 parts of dichloromethane, and washed with ion-exchanged water until the pH of the aqueous layer became neutral. Next, 70 g of an aqueous solution containing anion (B1) was mixed into the dichloromethane layer under stirring at room temperature and stirred for 3 hours. After washing the dichloromethane layer with water 5 times by separating it, the solution was transferred to a rotary evaporator to remove the solvent by distillation, thereby obtaining [4-(4-acetylphenylthio)]phenyldiphenylsulfonium·tris(pentafluoroethyl)trifluorophosphonate (facial body of anion: 0.0 wt%). The chemical formula is as shown in formula (a13) below.

[0245] [Chemical Formula 17]

[0246]

[0247] Examples of onium salts (A5-2) to (A5-6), and comparative example (A'5-1)

[0248] In place of the anion (B1) of the preparation example of (A5-1), anions (B2) to (B6) and anion (B'1), respectively, were used to obtain onium salts (A5-2) to (A5-6) and (A'5-1). Additionally, the amount of a 20% aqueous solution of anion (B2) was 167 g. The synthesized compounds are as follows.

[0249] (A5-2) : Fluorene-skeletal sulfonium tris(heptafluoropropyl)trifluorophosphonate (anionic facial body: 0.0 wt%)

[0250] (A5-3) : Fluorene-skeleton sulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 0.1 wt%)

[0251] (A5-4) : Fluorene-skeletal sulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0252] (A5-5) : Fluorene-skeletal sulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 14.6 wt%)

[0253] (A5-6) : Fluorene-skeletal sulfonium tris(pentafluorophenyl)trifluorophosphonate (anionic facial body: 5.0 wt%)

[0254] (A'5-1) : Fluorene-skeletal sulfonium tris(pentafluoroethyl)trifluorophosphonate (anionic facial body: 18.4 wt%)

[0255] The chemical formulas are as follows: (A5-2) is (a14), (A5-3) to (A5-5), and (A'5-1) is (a13), and (A5-6) is (a15).

[0256] [Chemical Formula 18]

[0257]

[0258] [Chemical Formula 19]

[0259]

[0260] [Evaluation of Chemically Amplified Positive Type Photoresist Composition]

[0261] <Preparation of Samples for Evaluation>

[0262] As shown in Table 1, 1 part by weight of the onium salts (A1-1) to (A1-6), (A2-1) to (A2-6), (A3-1) to (A3-6), (A4-1) to (A4-6), and (A5-1) to (A5-6) of the present invention as a photogenerator, 40 parts by weight of a resin represented by the following chemical formula (Resin-1) as a resin component (F), and 60 parts by weight of a novolak resin obtained by addition condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst as a resin component (G) are uniformly dissolved in a solvent (propylene glycol monomethyl ether acetate), and filtered by passing through a membrane filter with a pore size of 1 μm to obtain a chemically amplified positive type photoresist composition (Examples P1 to P30) having a solid content concentration of 40 wt%. A chemical amplification type positive type photoresist composition (Comparative Examples P'1 to 5) was prepared. In addition, comparative examples were carried out in the same manner with the mixing amounts shown in Table 1 to prepare chemical amplification type positive type photoresist compositions.

[0263]

[0264] [Chemical Formula 20]

[0265]

[0266] <Sensitivity Evaluation>

[0267] A positive-type resist composition prepared in Examples P1 to P30 and Comparative Examples P'1 to P'5 was spin-coated onto a silicon wafer substrate and then dried to obtain a photoresist layer having a film thickness of approximately 20 μm. This resist layer was pre-baked at 130°C for 6 minutes using a hot plate. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon), followed by exposure and heating (PEB) at 75°C for 5 minutes using a hot plate. Subsequently, a development treatment was performed for 5 minutes by an immersion method using a 2.38 wt% aqueous tetramethylammonium hydroxide solution, followed by rinsing with running water and blowing with nitrogen to obtain a line and space (L&S) pattern of 10 μm. In addition, the minimum exposure amount at which the residue of this pattern is not detected below that level, that is, the minimum essential exposure amount required to form the resist pattern (corresponding to sensitivity), was measured.

[0268] <Pattern Shape Evaluation>

[0269] The dimensions La of the lower side and Lb of the upper side of the cross-sectional shape of the 10 μm L&S pattern formed on a silicon wafer substrate by the above operation were measured using a scanning electron microscope, and the pattern shape was determined according to the following criteria. The results are shown in Table 2.

[0270] ◎ : 0.90 ≤ Lb / La ≤ 1

[0271] ○ : 0.85 ≤ Lb / La < 0.90

[0272] × : Lb / La < 0.85

[0273]

[0274] As shown in Table 2, the chemically amplified positive photoresist compositions of Examples P1 to P30 require a lower minimum exposure amount than Comparative Examples P'1 to P'5, and in short, it can be seen that the photogenerator of the present invention has higher sensitivity and superior pattern shape compared to the photogenerators of comparison.

[0275] [Evaluation of Chemically Amplified Negative Type Photoresist Compositions]

[0276] <Preparation of Samples for Evaluation>

[0277] As shown in Table 3, 1 part by weight of the onium salts (A1-1) to (A1-6), (A2-1) to (A2-6), (A3-1) to (A3-6), (A4-1) to (A4-6), and (A5-1) to (A5-6) of the present invention as a photocatalytic agent; 100 parts by weight of a copolymer (Mw = 10,000) composed of p-hydroxystyrene / styrene = 80 / 20 (molar ratio) as component (I), which is a phenol resin; 20 parts by weight of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name "Nicalac MW-390") as component (J), which is a crosslinking agent; and as component (K), which is a crosslinking microparticle, A copolymer composed of butadiene / acrylonitrile / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 64 / 20 / 8 / 6 / 2 (weight%) (average particle size = 65 nm, Tg = -38 ℃) was uniformly dissolved in 10 parts by weight of the copolymer (average particle size = 65 nm, Tg = -38 ℃) and 5 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, trade name "S510") as an adhesion aid in 150 parts by weight of a solvent (ethyl lactate) to prepare the chemically amplified negative type photoresist compositions of the present invention (Examples N1 to N30). In addition, comparative examples were carried out in the same manner with the formulation amounts shown in Table 3 to prepare chemically amplified negative type photoresist compositions (Comparative Examples N'1 to N'5).

[0278]

[0279] <Sensitivity Evaluation>

[0280] After spin-coating each composition onto a silicon wafer substrate, a resin film having a thickness of approximately 20 μm was obtained by heating and drying at 110°C for 3 minutes using a hot plate. Subsequently, pattern exposure (i-line) was performed using a TME-150RSC (manufactured by Topcon), and heating (PEB) was performed after exposure at 110°C for 3 minutes using a hot plate. Subsequently, a development treatment of 2 minutes was performed by an immersion method using a 2.38 wt% aqueous tetramethylammonium hydroxide solution, followed by rinsing with running water and blowing with nitrogen to obtain a line and space pattern of 10 μm. In addition, the minimum required exposure amount (corresponding to sensitivity) required to form a pattern with a residual film rate of 95% or more, which indicates the ratio of the residual film before and after development, was measured.

[0281] <Pattern Shape Evaluation>

[0282] The dimensions La of the lower side and Lb of the upper side of the cross-sectional shape of the 20 μm L&S pattern formed on a silicon wafer substrate by the above operation were measured using a scanning electron microscope, and the pattern shape was determined according to the following criteria. The results are shown in Table 4.

[0283] ◎ : 0.90 ≤ La / Lb ≤ 1

[0284] ○ : 0.85 ≤ La / Lb < 0.90

[0285] × : La / Lb < 0.85

[0286]

[0287] As shown in Table 4, the chemically amplified positive type photoresist compositions of Examples N1 to N30 require a lower minimum exposure amount than Comparative Examples N'1 to N'5, and in short, the photogenerator of the present invention is more sensitive than the photogenerator for comparison and has an excellent pattern shape.

[0288] Industrial applicability

[0289] The chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition using an acid generating agent containing an onium salt of the present invention make it possible to obtain a high-sensitivity resist (which enables pattern formation with a low exposure amount compared to conventional ones). In addition, the chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition of the present invention are used to have a good resist pattern shape.

Claims

Claim 1 An onium salt that can be represented by general formula (1), wherein among the two isomers of an anionic structure, a facial body and a meridional body, the proportion of the facial body is 15.0 weight% or less. [(R 2 ) n+1 -E] + [(R 1 )3(F)3P] - (1)[Equation (1), R 1 is a perfluoroalkyl group or a phenyl group substituted with a fluorine atom; E is I or S; if E is I, n is 1, and if E is S, n is 2.; R 2 is an organic group bonded to E, and the organic group is a C6 to C18 aryl group that may have a substituent, and the substituent is a C1 to C18 alkyl group, a C6 to C18 aryl group, or an arylthio group. R 2 The number of is n + 1, and there are (n + 1) R 2 may each be identical or different, and 2 or more R 2 They may form a ring structure containing element E either directly or through -O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene groups, or phenylene groups. Claim 2 In claim 1, an onium salt having a facial body ratio of 0.1 to 15.0 weight%. Claim 3 A photogenerative agent containing an onium salt as described in claim 1 or 2. Claim 4 A chemically amplified resist composition using an onium salt as described in claim 1 or 2. Claim 5 delete Claim 6 delete

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