Resist material and method for producing same

Abstract

The purpose of the present invention is to provide a novel resist material and a method for producing the resist material, the resist material having a film-forming property and comprising: a polyacid salt or a solvate thereof; a first solvent; and a second solvent.

Description

Resist material and manufacturing method thereof

[0001] The present invention relates to a resist material and a method for producing the same.

[0002] Polyacids are those having the general formula [M ｘ O ｙ ] ｎ－ (wherein x, y, and n are all natural numbers). The metal atom M constituting the polyacid is called a polyatom, and examples thereof include Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), and Ta (pentavalent). The polyacid is an isopolyacid composed of the polyatom M and an oxygen acid, or a polyacid containing a different type of heteroatom X (for example, P as the heteroatom X) in addition to the polyatom M and oxygen. ５＋ , Si ４＋ , Ge ４＋ , B ３＋ , S ６＋ Heteropolyacids containing [X ｗ M ｘ O ｙ ] ｎ－ (wherein w, x, y, and n are all natural numbers)

[0003] Isopolyacid salts and heteropolyacid salts have attracted attention as materials for optoelectronics, catalysts, etc. If it were possible to disperse or dissolve polyacid salts at high concentrations in water or organic solvents and improve the coatability, film-forming properties, etc. of such dispersions or solutions, it is expected that they would be effectively used in a variety of industrial applications, such as by coating the surfaces of various components and forming films.

[0004] Patent Document 1 discloses a metal-containing film-forming composition for extreme ultraviolet or electron beam lithography that can form a metal-containing film that is excellent in suppressing changes in coating film thickness and resist sensitivity. The metal-containing film-forming composition contains a compound having a metal-oxygen covalent bond and a solvent, and the solvent contains a first solvent component having a standard boiling point of less than 160°C and a second solvent component having a standard boiling point of 160°C or higher and lower than 400°C, and the solvent contains an alcohol-based solvent, and the content of the alcohol-based solvent is 30 mass%.

[0005] US Patent Publication No. 2020 / 159121

[0006] An object of the present invention is to provide a novel resist material that contains a polyacid salt or a solvate thereof and a solvent and has film-forming properties, and a method for producing the same. Means for solving the invention

[0007] As a result of extensive investigations into solving the above-mentioned problems, the present inventors have found that in a resist material comprising a polyacid salt or a solvate thereof, a first solvent, and a second solvent, the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ The present inventors have found that a resist material having film-forming properties can be obtained by using a solvent having a surface tension of 20 to 35 dyne / cm and a boiling point of 165°C or less, wherein the second solvent is a solvent different from the first solvent, and the second solvent is a ketone-based or alcohol-based solvent having a surface tension of 20 to 35 dyne / cm and a boiling point of 165°C or less, and have completed the present invention.

[0008] That is, the present invention relates to the following inventions: <1> A resist material comprising (A) a polyacid salt or a solvate thereof, (B) a first solvent, and (C) a second solvent, wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ A resist material, wherein the second solvent is a ketone-based or alcohol-based solvent different from the first solvent, has a surface tension of 20 to 35 dyne / cm, and a boiling point of 165°C or lower. <2> The resist material according to <1>, wherein the anion moiety of the polyacid salt is an isopolyoxomolybdate anion, an isopolyoxotungstate anion, an isopolyoxoniobate anion, an isopolyoxotantalate anion, a heteropolyoxomolybdate anion, a heteropolyoxotungstate anion, a heteropolyoxovanadate anion, a heteropolyoxoniobate anion, or a heteropolyoxotantalate anion. <3> The resist material according to <1>, wherein the boiling point difference between the first solvent and the second solvent is 50°C or lower. <4> The resist material according to <1>, wherein the boiling point difference between the first solvent and the second solvent is 30°C or lower. <5> The resist material according to <1>, wherein the cation moiety of the polyacid salt is an onium cation. <6> The resist material according to <5>, wherein the onium cation is an organic sulfonium cation, an organic iodonium cation, an organic quaternary ammonium cation, or an organic phosphonium cation. <7> A method for producing a resist material, comprising: a step of dissolving a polyacid salt in one or more first solvents that are good solvents for the polyacid salt to obtain a good solvent solution; and a step of adding a second solvent to the good solvent solution, wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２<8> A method for producing a resist material, comprising: a step of dissolving a polyacid salt in a first solvent to obtain a solvate of the polyacid salt with the first solvent; and a step of dissolving the solvate of the polyacid salt in the first solvent and the second solvent sequentially or simultaneously; wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ the second solvent is a ketone-based or alcohol-based solvent different from the first solvent, and has a surface tension of 20 to 35 dyne / cm and a boiling point of 165°C or lower. <9> A method for producing a resist material, comprising the steps of: dissolving a polyacid salt in a first solvent that is a good solvent for the polyacid salt to obtain a good solvent solution; adding a solvent that is a poor solvent for the polyacid salt to the good solvent solution to precipitate a solvate of the polyacid salt; and dissolving the solvate of the polyacid salt in the first solvent and the second solvent sequentially or simultaneously, wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ the antisolvent is a solvent having a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or the value of the hydrogen bond term (ΔH) in the Hansen solubility parameter is less than 17 MPa １／２<10> The method for producing a resist material according to <9>, wherein the poor solvent is a ketone-based solvent, an ether-based solvent, an ester-based solvent, an alcohol-based solvent, a hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a heterocyclic solvent, a halogen-based solvent, or water.

[0009] According to the present invention, a novel resist material having film-forming properties, which contains a polyacid salt or a solvate thereof and a solvent, and a method for producing the same can be provided. When the cation portion of the polyacid salt is an onium cation, it is particularly difficult to dissolve the polyacid salt in a solvent to an extent that allows film formation, and the range of solvents that can be used is limited. Furthermore, even when a polyacid salt is dissolved in a solvent with high solubility, it is difficult to obtain a resist material having film-forming properties that allow the formation of a film with few defects, including in terms of coatability. In contrast, according to the present invention, it is possible to provide a resist material having film-forming properties after successfully dissolving a polyacid salt or a solvate thereof in a solvent.

[0010] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0011] As used herein, the term "solvate" refers to a polyacid salt in which solvent molecules are bound to the salt by relatively weak forces such as electrostatic interactions, hydrogen bonds, charge transfer bonds, and coordinate bonds. The number of bound solvent molecules does not need to be constant, and multiple solvent molecules may be involved in the solvation. The solvate includes chemically acceptable solvates, including both stoichiometric and non-stoichiometric solvates. The solvate also includes both solution-phase and isolatable solvates.

[0012] In this specification, the term "boiling point" means the standard boiling point under the condition of 1 atmospheric pressure (760 mmHg).

[0013] As used herein, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0014] In this specification, for example, "C １－６ " and other terms refer to the number of carbon atoms in the core group.

[0015] As used herein, "C １－１８ The term "hydrocarbylene group" refers to a divalent hydrocarbon group generated by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear or branched, or may be partially or entirely cyclic. The hydrocarbylene group includes alkylene groups, arylene groups, etc. Also, "C １－１８ The divalent carbon atom at any position of the "hydrocarbylene group" may be -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). １－１８ The "hydrocarbylene group" is not particularly limited, and examples thereof include "C" such as methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadiyl group, cyclohexanediyl group, oxyethane-1,1-diyl group, oxyethane-1,2-diyl group, oxypropane-1,3-diyl group, oxypropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, and oxyethyleneoxyethane-1,1-diyl group. １－１８ alkylene group"; 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 4,4'-biphenylene group, anthracenediyl group, phenanthrenediyl group, naphthacenediyl group, pyrenediyl group, perylenediyl group, chrysenediyl group, etc. ６－１８ arylene group" and the like.

[0016] As used herein, "C １－１８ The term "alkyl group" means a linear or branched alkyl group having 1 to 18 carbon atoms. １－１８The divalent carbon atom at any position excluding the terminal contained in the "alkyl group" is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ However, adjacent divalent carbon atoms may not be replaced at the same time. １－１８ The "alkyl group" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an i-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1 , 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, and the like. １－１８ The alkyl group may have a divalent carbon atom at any position excluding the terminal, and the divalent carbon atom may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ The group substituted with - is not particularly limited, and examples thereof include a 2-methoxyethoxymethyl group, an ethoxycarbonylmethyl group, and the like.

[0017] As used herein, "C １－１８ The term "haloalkyl group" refers to "C １－１８ "C" means a group in which one or more hydrogen atoms of an "alkyl group" are substituted with halogen atoms. １－１８The "haloalkyl group" is not particularly limited, and examples thereof include a dichloromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 3,3,3-trifluoropropyl group.

[0018] As used herein, "C ２－１８ The term "alkenyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkenyl group having one or more double bonds, and includes alkadienyl groups, alkatrienyl groups, etc. ２－１８ The "alkenyl group" is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a 1-propenyl group, an isopropenyl group (1-methylvinyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group.

[0019] As used herein, "C ２－１８ The term "alkynyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkynyl group having one or more triple bonds in the "alkyl group." ２－１８ The "alkynyl group" is not particularly limited, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group.

[0020] As used herein, "C ３－１８ The term "alicyclic group" refers to a hydrocarbon group having, in whole or in part, a monocyclic or polycyclic structure having 3 to 18 carbon atoms. Alicyclic groups also include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc. ３－１８ A divalent carbon atom at any position excluding the terminals contained in the "alicyclic group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO ２- may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). ３－１８ The "cycloalkyl group" is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-i-propylcyclopentan-1-yl group, a cyclohexyl group, a t-butylcyclohexyl group, a tricyclodecanyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a 2-methyladamantan-2-yl group, a 2-i-propyladamantan-2-yl group, a bornyl group, a norbornyl group, a fenchyl group, a pinanyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a bornylmethyl group, a norbornylmethyl group, an adamantylmethyl group, a 1-methylcyclopentyloxycarbonylmethyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

[0021] As used herein, the term "3- to 18-membered non-aromatic heterocyclic group" refers to a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and may be a monocyclic, polycyclic, or fused ring, and may be saturated or partially unsaturated. The "3- to 18-membered non-aromatic heterocyclic group" is not particularly limited, and examples thereof include an aziridinyl group, an azetidyl group, a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a thiomorpholinyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an oxetanyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an imidazolinyl group, an oxazolinyl group, a 2,5-diazabicyclo[2.2.1]heptyl group, a 2,5-diazabicyclo[2.2.2]octyl group, a 3,8-diazabicyclo[3.2.1]octyl group, a 1,4-diazabicyclo[4.3.0]nonyl group, a 1-azaadamantyl group, and a 2-azaadamantyl group.

[0022] As used herein, "C ２－１８The term "aryl group" means an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 2 to 10 carbon atoms. In the case of an aromatic heterocyclic group, a ring is formed by a carbon atom having 2 to 10 carbon atoms and one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and each may be a monocyclic ring, a polycyclic ring, or a fused ring. ２－１８ The "aryl group" is not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an azulenyl group, a pentalenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a phenanthrenyl group, an anthracenyl group, and the like.

[0023] As used herein, "C ７－１８ The term "aralkyl group" refers to "C １－１２ The substitutable portion of the "C alkyl group" is ２－１２ "C" means a group substituted with an "aryl group." ７－１８ The "aralkyl group" is not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0024] As used herein, "C １－１８ The term "hydrocarbyl group" refers to a monovalent group formed by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, aralkyl groups, and the like. １－１８ A divalent carbon atom at any position excluding the terminal contained in the "hydrocarbyl group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (however, adjacent divalent carbon atoms cannot be replaced at the same time). １－１８ The term "C" used in the definition of "hydrocarbyloxy group" and the like is used in the definition of "C" １－１８ The same applies to "hydrocarbyl group" and the like. １－１８ The "hydrocarbyl group" is not particularly limited, and examples thereof include "C １－１８alkyl group," "C ２－１８ alkenyl group," "C ２－１８ alkynyl group," "C ３－１８ “Alicyclic group”, “C ２－１８ aryl group," "C ７－１８ aralkyl groups, etc.

[0025] As used herein, "C １－１８ The term "hydrocarbyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group." １－１８ The "hydrocarbyloxy group" is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentoxy group, an i-pentoxy group, a sec-pentoxy group, an n-hexoxy group, an i-hexoxy group, a 1,1-dimethylpropyloxy group, a 1,2-dimethylpropyloxy group, a 2,2-dimethylpropyloxy group, a 1-methyl- "C" groups such as 2-ethylpropyloxy group, 1-ethyl-2-methylpropyloxy group, 1,1,2-trimethylpropyloxy group, 1,2,2-trimethylpropyloxy group, 1,1-dimethylbutyloxy group, 1,2-dimethylbutyloxy group, 2,2-dimethylbutyloxy group, 2,3-dimethylbutyloxy group, 1,3-dimethylbutyloxy group, 2-ethylbutyloxy group, 2-methylpentyloxy group, and 3-methylpentyloxy group １－１８ alkoxy group"; cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-methylcyclopentyloxycarbonylmethoxy group, 1-ethylcyclohexyloxycarbonylmethoxy group, 1-methyladamantyloxycarbonylmethoxy group, etc. ３－１８ alicyclic oxy group"; phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, azulenyloxy group, pentalenyloxy group, heptalenyloxy group, indacenyloxy group, acenaphthyloxy group, phenanthrenyloxy group, anthracenyloxy group, etc. ６－１８ aryloxy group."１－１８ The "hydrocarbyloxy group" includes "C １－１８ It is preferred that a divalent carbon atom at any position except the terminal contained in the "hydrocarbyl group" is replaced with -O-, -C(=O)-, and / or -C(=O)O-. １－１８ A "hydrocarbyloxycarbonylalkyloxy group" is more preferred, and from the viewpoint of solubility, it is even more preferred that the carbon bonded to the oxygen atom of the hydrocarbyloxy is a tertiary carbon. Specific examples of the hydrocarbyloxy include optionally substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, etc.

[0026] As used herein, "C １－１８ The term "hydrocarbyl carbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyl group.” １－１８ The "hydrocarbyl carbonyl group" is not particularly limited, and examples thereof include "C" such as an acetyl group, a propionyl group, an isopropionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pentanoyl group, a 3-methylbutanoyl group, a pivaloyl group, a hexanoyl group, and a heptanoyl group. １－１８ alkylcarbonyl group"; cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, 2-methylcyclopentylcarbonyl group, 3-methylcyclopentylcarbonyl group, cyclohexylcarbonyl group, 2-methylcyclohexylcarbonyl group, 3-methylcyclohexylcarbonyl group, 4-methylcyclohexylcarbonyl group, adamantylcarbonyl group, etc. ３－１８ alicyclic carbonyl group"; "C" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. ６－１８ arylcarbonyl group" and the like.

[0027] As used herein, "C １－１８ The term "hydrocarbylcarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group." １－１８The "hydrocarbylcarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, an isopentylcarbonyloxy group, and a hexylcarbonyloxy group. １－１８ alkylcarbonyloxy group"; cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, etc. ３－１８ alicyclic carbonyloxy group"; "C" such as a phenylcarbonyloxy group, a naphthylcarbonyloxy group, an acenaphthylcarbonyloxy group, a phenanthrenylcarbonyloxy group, an anthracenylcarbonyloxy group, etc. ６－１８ arylcarbonyloxy group" and the like.

[0028] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyloxy group.” １－１８ The "hydrocarbyloxycarbonyl group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, an n-pentoxycarbonyl group, and a neopentyloxycarbonyl group. １－１８ alkoxycarbonyl group"; "C" such as a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2-methylcyclopentyloxycarbonyl group, a 3-methylcyclopentyloxycarbonyl group, a 2-methylcyclohexyloxycarbonyl group, a 3-methylcyclohexyloxycarbonyl group, and a 4-methylcyclohexyloxycarbonyl group; ３－１８alicyclic oxycarbonyl group"; "C" such as a phenoxycarbonyl group, a naphthoxycarbonyl group, an acenaphthyloxycarbonyl group, a phenanthrenyloxycarbonyl group, an anthracenyloxycarbonyl group, etc. ６－１８ aryloxycarbonyl group" and the like.

[0029] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group." １－１８ The "hydrocarbyloxycarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, an i-propyloxycarbonyloxy group, an n-butoxycarbonyloxy group, an i-butoxycarbonyloxy group, a sec-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, an i-pentyloxycarbonyloxy group, and an n-hexyloxycarbonyloxy group. １－１８ alkoxycarbonyloxy group"; "C" such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. ３－１８ alicyclic oxycarbonyloxy group"; "C" such as a phenoxycarbonyloxy group, a naphthoxycarbonyloxy group, an acenaphthyloxycarbonyloxy group, a phenanthrenyloxycarbonyloxy group, an anthracenyloxycarbonyloxy group, etc. ６－１８ aryloxycarbonyloxy group" and the like.

[0030] As used herein, "C １－１８ The term "hydrocarbylamino group" refers to a group consisting of one "C １－１８ "C" means a group bonded to an amino group. １－１８The "hydrocarbylamino group" is not particularly limited, and examples thereof include a "C hydrocarbylamino group" such as a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, an i-butylamino group, a sec-butylamino group, a t-butylamino group, an n-pentylamino group, an i-pentylamino group, a neopentylamino group, and an n-hexylamino group. １－１８ alkylamino group"; cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, 2-methylcyclopentylamino group, 3-methylcyclopentylamino group, cyclohexylamino group, 2-methylcyclohexylamino group, 3-methylcyclohexylamino group, 4-methylcyclohexylamino group, etc. ３－１８ alicyclic amino group"; phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. ６－１８ arylamino group" and the like.

[0031] As used herein, "diC １－１８ The term "hydrocarbylamino group" refers to two identical or different "C １－１８ "DiC" means a group in which a "hydrocarbyl group" is bonded to an amino group. １－１８ The "hydrocarbylamino group" is not particularly limited, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, an N-ethyl-N-methylamino group, an N-methyl-N-n-propylamino group, an N-isopropyl-N-methylamino group, an N-n-butyl-N-methylamino group, an N N-isobutyl-N-methylamino group, N-t-butyl-N-methylamino group, N-methyl-N-n-pentylamino group, N-n-hexyl-N-methylamino group, N-ethyl-N-n-propylamino group, N-ethyl-N-isopropylamino group, N-n-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, N-t-butyl-N-ethylamino group, N-ethyl-N-n-pentylamino group, N-ethyl-N-n-hexylamino group, and other "di-C １－１８alkylamino group"; "di-C" such as dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. ３－１８ alicyclic amino group"; "di-C" such as diphenylamino group, phenylnaphthylamino group, etc. ６－１８ "N-C arylamino group" such as N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. １－１８ Alkyl-N—C ３－１８ cycloalkylamino group"; "N-C cycloalkylamino group" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. １－１８ Alkyl-N—C ６－１８ arylamino group" and the like.

[0032] As used herein, "C １－１８ The term "hydrocarbylaminocarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbylamino group.” １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, a sec-butylaminocarbonyl group, a t-butylaminocarbonyl group, an n-pentylaminocarbonyl group, a 2-pentylaminocarbonyl group, a neopentylaminocarbonyl group, a 4-methyl-2-pentylaminocarbonyl group, an n-hexylaminocarbonyl group, and a 3-methyl-n-pentylaminocarbonyl group. １－１８ alkylaminocarbonyl group"; cyclopropylaminocarbonyl group, cyclobutylaminocarbonyl group, cyclopentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-methylcyclopentylaminocarbonyl group, 3-methylcyclopentylaminocarbonyl group, 2-methylcyclohexylaminocarbonyl group, 3-methylcyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc.６－１８ arylaminocarbonyl group.

[0033] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonyl group" refers to a "diC １－１８ "DiC" means a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group." １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a diisopropylaminocarbonyl group, a di-n-butylaminocarbonyl group, a diisobutylaminocarbonyl group, a di-t-butylaminocarbonyl group, a di-n-pentylaminocarbonyl group, a di-n-hexylaminocarbonyl group, an N-ethyl-N-methylaminocarbonyl group, an N-methyl-N-n-propylaminocarbonyl group, an N-isopropyl-N-methylaminocarbonyl group, an N-n-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an N-t-butyl-N-methylaminocarbonyl group, an N-methyl-N-n-pentylaminocarbonyl group, an N-n-hexyl-N-methylaminocarbonyl group, "diC" groups such as an N-ethyl-N-n-propylaminocarbonyl group, an N-ethyl-N-isopropylaminocarbonyl group, an N-n-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-isobutylaminocarbonyl group, an N-t-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-n-pentylaminocarbonyl group, and an N-ethyl-N-n-hexylaminocarbonyl group １－１８ alkylamino group"; "di-C" such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; "di-C" such as diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group, etc. ６－１８ arylaminocarbonyl group" and the like.

[0034] As used herein, "C １－１８ The term "hydrocarbylcarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which an amino group is bonded to a "hydrocarbyl carbonyl group." １－１８ The "hydrocarbylcarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, and n-hexylcarbonylamino group. １－１８ alkylcarbonylamino group; cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. ３－１８ alicyclic carbonylamino group"; "C" such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenanthrenylcarbonylamino group, anthracenylcarbonylamino group, etc. ６－１８ arylcarbonylamino group" and the like.

[0035] As used herein, "C １－１８ The term "hydrocarbylaminocarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyloxy group, an ethylaminocarbonyloxy group, and an n-propylaminocarbonyloxy group. １－１８ alkylaminocarbonyloxy group"; cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. ３－１８ alicyclic aminocarbonyloxy group"; phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc. ６－１８ arylaminocarbonyloxy group" and the like.

[0036] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonyloxy group" refers to a "diC １－１８"DiC" means a group in which an oxygen atom (—O—) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, and di-n-propylaminocarbonyloxy group. １－１８ alkylaminocarbonyloxy group, etc.

[0037] As used herein, "C １－１８ The term "hydrocarbylaminocarbonylamino group" refers to a group consisting of "C １－１８ "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylaminocarbonylamino group, ethylaminocarbonyloxy group, and n-propylaminocarbonylamino group. １－１８ alkylaminocarbonylamino group"; cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. ３－１８ alicyclic aminocarbonylamino group"; phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. ６－１８ arylaminocarbonylamino group" and the like.

[0038] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonylamino group" refers to a "diC １－１８ "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and di-n-propylaminocarbonylamino group. １－１８ alkylaminocarbonylamino group, etc.

[0039] As used herein, "C １－１８ The term "hydrocarbyloxycarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an i-propoxycarbonylamino group, an n-butoxycarbonylamino group, and a t-butoxycarbonylamino group. １－１８ alkoxycarbonylamino group"; cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. ３－１８ alicyclic oxycarbonylamino group"; phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. ６－１８ aryloxycarbonylamino group" and the like.

[0040] As used herein, "C １－１８ The term "hydrocarbylthio group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group." １－１８ The "hydrocarbylthio group" is not particularly limited, and examples thereof include a "C methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, a t-butylthio group, an n-pentylthio group, an n-hexylthio group, etc. １－１８ alkylthio group"; cyclopropylthio group, cyclobutylthio group, cyclopentylthio group, cyclohexylthio group, 2-methylcyclopentylthio group, 3-methylcyclopentylthio group, 2-methylcyclohexylthio group, 3-methylcyclohexylthio group, 4-methylcyclohexylthio group, etc. ３－１８ alicyclic thio group"; "C" such as a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, an acenaphthylthio group, a phenanthrenylthio group, an anthracenylthio group, etc. ６－１８ arylthio group" and the like.

[0041] As used herein, "C １－１８ The term "hydrocarbylsulfinyl group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfinyl group (-S(=O)-) is bonded to a "hydrocarbyl group."１－１８ The "hydrocarbylsulfinyl group" is not particularly limited, and examples thereof include "C" such as methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, and hexylsulfinyl group. １－１８ alkylsulfinyl group"; cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-methylcyclohexylsulfinyl group, 3-methylcyclohexylsulfinyl group, 4-methylcyclohexylsulfinyl group, etc. ３－１８ alicyclic sulfinyl group"; "C" such as a phenylsulfinyl group, a naphthylsulfinyl group, an acenaphthylsulfinyl group, a phenanthrenylsulfinyl group, an anthracenylsulfinyl group, etc. ６－１８ arylsulfinyl group" and the like.

[0042] As used herein, "C １－１８ The term "hydrocarbylsulfonyl group" refers to a group consisting of "C １－１８ The hydrocarbyl group may be a sulfonyl group (-SO ２ -) is bonded to the group. １－１８ The "hydrocarbylsulfonyl group" is not particularly limited, and examples thereof include "C" such as a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, an n-butylsulfonyl group, a t-butylsulfonyl group, and a pentylsulfonyl group. １－１８ alkylsulfonyl group"; "C" such as cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, and 4-methylcyclohexyl group; ３－１８ alicyclic sulfonyl group"; "C" such as a phenylsulfonyl group, a naphthylsulfonyl group, an acenaphthylsulfonyl group, a phenanthrenylsulfonyl group, an anthracenylsulfonyl group, etc. ６－１８arylsulfonyl group" and the like.

[0043] As used herein, the term "acid-dissociable group" refers to a group that substitutes a hydrogen atom of a carboxy group or a hydroxy group (including a phenolic hydroxyl group), and that dissociates under the action of an acid. The "acid-dissociable group" is not particularly limited, and examples thereof include a t-butyl group, a t-amyl group, a 1,1-dimethylpropyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, a 1-methyl-1-cyclohexyl group, a 1-ethyl-1-cyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0044] In this specification, the term "optionally having a substituent" is not particularly limited as long as it is chemically permissible and has the effect of the present invention. Examples of the "substituent" include (1) a halogen atom, (2) a hydroxy group, (3) a thiol group, (4) a nitro group, (5) a cyano group, (6) a carboxy group, (7) an amino group, (8) a sulfo group, (9) a group in which a hydrogen atom of a carboxy group or a hydroxy group is substituted with an acid-dissociable group, or (10) a C group in which at least a part of the hydrogen atoms may be substituted with the above (1) to (9). １－８ Hydrocarbyl group, C １－８ Hydrocarbyloxy group, C １－８ Hydrocarbyl carbonyl group, C １－８ Hydrocarbylcarbonyloxy group, C １－８ Hydrocarbyloxycarbonyl group, C １－８ Hydrocarbyloxycarbonyloxy group, C １－８ Hydrocarbylamino group, diC １－８ Hydrocarbylamino group, C １－８ Hydrocarbylaminocarbonyl group, diC １－８ Hydrocarbylaminocarbonyl group, C １－８ Hydrocarbylcarbonylamino group, C １－８ Hydrocarbylaminocarbonyloxy group, diC １－８ Hydrocarbylaminocarbonyloxy group, C１－８ Hydrocarbylaminocarbonylamino group, diC １－８ Hydrocarbylaminocarbonylamino group, C １－８ Hydrocarbyloxycarbonylamino group, C １－８ Hydrocarbylthio group, C １－８ Hydrocarbylsulfinyl group, C １－８ A hydrocarbylsulfonyl group, in which a divalent carbon atom at any position except the terminal of the substituent is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time), etc.

[0045] [1. Resist Material] The resist material according to this embodiment includes a polyacid salt or a solvate thereof, a first solvent, and a second solvent. The first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ The second solvent is a solvent different from the first solvent, and is a ketone or alcohol solvent having a surface tension of 20 to 35 dyne / cm and a boiling point of 165°C or lower. The "polyacid salt" and the "first solvent and second solvent" will be described in more detail below.

[0046] [1-1. Polyacid Salt] The polyacid salt used in this embodiment is not particularly limited, and known and commonly used salts can be used. As the polyacid salt, a solvate of a polyacid salt may be used from the viewpoint of improving solubility in a solvent. The polyacid salt is composed of an anion moiety of an isopolyacid anion or a heteropolyacid anion and a cation moiety that is a counter cation. The following describes the "anion moiety of a polyacid salt," the "cation moiety of a polyacid salt," the "solvate of a polyacid salt," and the like.

[0047] [1-1-1. Anion Moiety of Polyacid Salt] The anion moiety of the polyacid salt is composed of an isopolyacid anion or a heteropolyacid anion.

[0048] Examples of the isopolyacid anion include isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, and isopolyoxotantalate anion. Examples of the isopolyoxomolybdate anion include [MoO ４ ] ２－ , [Mo ７ O ２４ ] ６－ , [Mo ８ O ２６ ] ４－ Examples of the isopolyoxotungstate anion include [W ４ O １３ ] ２－ , [W ５ O １６ ] ２－ , [W ６ O １９ ] ２－ , [W ７ O ２２ ] ２－ , [W ７ O ２４ ] ６－ , [H ｚ W １２ O ４０ ] －（８－ｚ） (wherein z represents an integer of 1 to 4), [W １０ O ３２ ] ４－ , [H ４ W １１ O ３８ ] ６－ , [H ７ W １１ O ４０ ] ７－ , [HW ５ O １９ ] ７－ , [H ３ W １１ O ２２ ] ５－ Examples of the isopolyoxovanadate anion include [V ４O １２ ] ４－ , [V １０ O ２８ ] ６－ Examples of the isopolyoxoniobate anion include [Nb ６ O １９ ] ８－ , [Nb １０ O ２８ ] ６－ Examples of the isopolyoxotantalate anion include [Ta ６ O １９ ] ８－ , [Ta ８ O ２１ ] ２－ The isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, and isopolyoxotantalate anion include various isomers.

[0049] Examples of heteropoly acid anions include heteropolyoxomolybdate anions, heteropolyoxotungstate anions, heteropolyoxovanadate anions, heteropolyoxoniobate anions, and heteropolyoxotantalate anions. Examples of the heteropolyoxomolybdate anions include phosphomolybdate anions, silicomolybdate anions, boromolybdate anions, phosphotungstomolybdate anions, cobaltmolybdate anions, arsenic molybdate anions, and germanomolybdate anions. Examples of the heteropolyoxotungstate anions include phosphotungstate anions, silicotungstate anions, borotungstate anions, cobalttungstate anions, arsenic tungstate anions, and germanotungstate anions. Examples of the heteropolyoxovanadate anion include phosphomolybdovanadate anion, phosphomolybdotungstomolybdate anion, boromolybdovanadate anion, boromolybdotungstovanadate anion, etc. The heteropolyoxomolybdate anion, heteropolyoxotungstate anion, heteropolyoxovanadate anion, etc. include Keggin type, Dawson type, Anderson type, and deficiency species and isomers thereof.

[0050] [1-1-2. Cation Moiety of Polyacid Salt] The type of salt of a polyacid salt (isopolyoxometalate or heteropolyoxometalate) is not particularly limited, and may be a salt with a proton, an onium cation (e.g., organic onium cation, organic sulfonium cation, organic iodonium cation, organic quaternary ammonium cation, organic phosphonium cation, etc.), an alkali metal ion, or the like. From the viewpoint of improving actinic ray sensitivity or radiation sensitivity, the salt of a polyacid salt is preferably a salt with an onium cation. Furthermore, the onium cation is preferably an onium cation having at least one unsaturated bond which may have a substituent. Examples of the unsaturated bond include a carbon-carbon double bond or a carbon-carbon triple bond. Of these, a carbon-carbon double bond is more preferable, and a benzene ring is even more preferable. Examples of the onium cation include an organic sulfonium cation, an organic iodonium cation, an organic quaternary ammonium cation, and an organic phosphonium cation.

[0051] [1-1-2-1. Organic sulfonium cation] The organic sulfonium cation is not particularly limited, and known and commonly used ones can be used. Examples of the organic sulfonium cation include organic sulfonium cations represented by formula (I):

[0052]

[0053] In formula (I), R １Ａ , R １Ｂ and R １Ｃ are each independently C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ , R １Ｂ and R １Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ , R １Ｂ and R １Ｃ The hydrogen atoms contained in the group may be, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, or (j) a C group in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (i). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８ It may be substituted with a hydrocarbylthio group, and the divalent carbon atom at any position of these substituents except for the terminals may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ , R １Ｂ and R １Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the sulfur atom in formula (I).

[0054] R in formula (I) １Ａ , R １Ｂ and R １Ｃ Each of the C groups independently has a substituent. ６－１８ It is preferably an aryl group. ６－１８The substituent of the aryl group may be a halogen atom, a haloalkyl group, a hydroxy group, a nitro group, a cyano group, a C １－１２ Hydrocarbyl group, C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C １－１２ Hydrocarbyloxycarbonyl group, C １－１２ a hydrocarbyloxycarbonyloxy group, or C １－１２ A hydrocarbylthio group is preferred, a halogen atom, C １－４ Haloalkyl group, nitro group, C １－８ It is more preferably a hydrocarbyloxy group.

[0055] Specific examples of the organic sulfonium cation include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalen-1-yl)hexahydrothiopyrylium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrylium cation, (ethane-1,2-diylbisoxy)bis(4,1-phenylene)bis(diphenylsulfonium) dication, (thiodi-4,1-phenylene)bis(diphenylsulfonium) dication, di(naphthalen-1-yl)(fluorophenyl)sulfonium cation, and di(naphthalen-1-yl)(fluorophenyl)sulfonium cation. phenyl)sulfonium cation, phenylbis(2-(trifluoromethyl)phenyl)sulfonium cation, mesitylbis(2-(trifluoromethyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(phenyl)sulfonium cation, tris(3,5-difluorophenyl)sulfonium cation, (4-(dodecanoyloxy-3,5-dimethylphenyl))diphenylsulfonium cation, diphenyl(3-(trifluoromethoxy)phenyl)sulfonium cation, (4-(1-adamantylcarbonyloxy)phenyl)diphenylsulfonium cation, (4-phenylthiophenyl)diphenylsulfonium cation, 5-phenyl-5H-thianthren-5-ium cation, 5-(2,5-dimethylphenyl)thianthren-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophen-5-ium cation 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,Examples of the thiophene-5-ium cation include 1-(4-(t-butyl)phenyl)-1H-benzo[b]thiophen-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, dimesityl(trifluoromethyl)sulfonium cation, and tri-p-tolyl sulfonium cation.

[0056] [1-1-2-2. Organic iodonium cation] The organic iodonium cation is not particularly limited, and known and commonly used ones can be used. Examples of the organic iodonium cation include the organic iodonium cation represented by formula (II):

[0057]

[0058] In formula (II), R ２Ａ and R ２Ｂ are each independently C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ２Ａ and R ２Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ and R ２ＢThe hydrogen atoms contained in the group may be, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, or (j) a C group in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (i). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ a hydrocarbyloxycarbonyl group, or C １－１８ It may be substituted with a hydrocarbyloxycarbonyloxy group, and the divalent carbon atom at any position of these substituents except for the terminals may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ and R ２Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (II).

[0059] R in formula (II) ２Ａ and R ２Ｂ Each of the C groups independently has a substituent. ６－１８ It is preferably an aryl group. ６－１８ The substituent of the aryl group may be a halogen atom, a haloalkyl group, a hydroxy group, a nitro group, a cyano group, a C １－１２ Hydrocarbyl group, C １－１２ Hydrocarbyloxy group, C １－１２ Hydrocarbyl carbonyl group, C １－１２ Hydrocarbylcarbonyloxy group, C １－１２ a hydrocarbyloxycarbonyl group, or C １－１２A hydrocarbyloxycarbonyloxy group is preferred, and a halogen atom, C １－４ Haloalkyl group, nitro group, C １－８ Hydrocarbyl group, C １－８ It is preferably a hydrocarbyloxy group.

[0060] Specific examples of the organic iodonium cation include ethynyl(phenyl)iodonium cation, bis(pyridine)iodonium cation, bis(2,4,6-trimethylpyridine)iodonium cation, diphenyliodonium cation, bis(4-(t-butyl)phenyl)iodonium cation, (2-carboxyphenyl)(phenyl)iodonium cation, (4-nitrophenyl)(phenyl)iodonium cation, (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, Examples of iodonium cation include (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4-trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, and phenyl(2,4,6-trimethoxyphenyl)iodonium cation.

[0061] [1-1-2-3. Organic quaternary ammonium cation] The organic quaternary ammonium cation is not particularly limited, and any known or commonly used organic quaternary ammonium cation can be used. Examples of the organic quaternary ammonium cation include the organic quaternary ammonium cation represented by formula (III).

[0062]

[0063] In formula (III), R ３Ａ , R ３Ｂ , R ３Ｃ and R ３Ｄ are each independently C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ３Ａ , R ３Ｂ , R ３Ｃ and R ３Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ３Ａ , R ３Ｂ , R ３Ｃ and R ３Ｄ The hydrogen atoms contained in the group may be, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, or (j) a C group in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (i). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８It may be substituted with a hydrocarbylthio group, and the divalent carbon atom at any position of these substituents except for the terminals may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ３Ａ , R ３Ｂ , R ３Ｃ and R ３Ｄ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the nitrogen atom in formula (III).

[0064] R in formula (III) ３Ａ , R ３Ｂ , R ３Ｃ and R ３Ｄ Each of the C groups independently has a substituent. 1－１８ Preferably it is a hydrocarbyl group, C １－１２ Alkyl group, C １－１２ Alkenyl group, C １－１２ Alkynyl group, C １－１２ An alicyclic group is more preferred.

[0065] Specific examples of the organic quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, tetraheptylammonium cation, tetrahexylammonium cation, trimethylethylammonium cation, dimethyldiethylammonium cation, dimethylethylpropylammonium cation, methylethylpropylbutylammonium cation, trimethylphenylammonium cation, triethylhexylammonium cation, triethylcyclohexylammonium cation, and dodecyltrimethylammonium cation.

[0066] [1-1-2-4. Organic phosphonium cation] The organic phosphonium cation is not particularly limited, and known and commonly used organic phosphonium cations can be used. Examples of the organic phosphonium cation include organic phosphonium cations represented by formula (IV).

[0067]

[0068] In formula (IV), R ４Ａ , R ４Ｂ , R ４Ｃ and R ４Ｄ are each independently C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ４Ａ , R ４Ｂ , R ４Ｃ and R ４Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ , R ４Ｂ , R ４Ｃ and R ４Ｄ The hydrogen atoms contained in the group may be, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, or (j) a C group in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (i). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８It may be substituted with a hydrocarbylthio group, and the divalent carbon atom at any position of these substituents except for the terminals may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ , R ４Ｂ , R ４Ｃ and R ４Ｄ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the phosphorus atom in formula (IV).

[0069] R in formula (IV) ４Ａ , R ４Ｂ , R ４Ｃ and R ４Ｄ Each of the C groups independently has a substituent. 1－１８ Preferably it is a hydrocarbyl group, C １－１２ Alkyl group, C １－１２ Alkenyl group, C １－１２ Alkynyl group, C １－１２ An alicyclic group is more preferred.

[0070] Specific examples of the organic phosphonium cation include a (methoxymethyl)triphenylphosphonium cation, a tetrabutylphosphonium cation, a tetraethylphosphonium cation, an amyltriphenylphosphonium cation, an acetonyltriphenylphosphonium cation, a benzyltriphenylphosphonium cation, an ethyltriphenylphosphonium cation, a butyltriphenylphosphonium cation, a hexyltriphenylphosphonium cation, a (1-naphthylmethyl)triphenylphosphonium cation, a (4-nitrobenzyl)triphenylphosphonium cation, a (2-hydroxybenzyl)triphenylphosphonium cation, a tetraphenylphosphonium cation, a triphenyltetradecylphosphonium cation, a cyclopropylphenylphosphonium cation, an ethoxycarbonylmethyl(triphenyl)phosphonium cation, and a phenacyltriphenylphosphonium cation.

[0071] [1-1-3. Solvate of Polyacid Salt] As the polyacid salt used in this embodiment, it is preferable to use a solvate of polyacid salt from the viewpoint of improving solubility in a solvent. As a solvent that solvates the polyacid salt, a first solvent that is a good solvent for the polyacid salt, i.e., a solvent having a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ The inclusion of a solvent having a van der Waals volume (Å) or less can improve the solubility of the solvate of the polyacid salt in the solvent. The solvent that solvates the polyacid salt may further include a solvent that is a poor solvent for the polyacid salt. The poor solvent has a van der Waals volume (Å) or less. ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or the value of the hydrogen bond term (ΔH) in the Hansen solubility parameter is less than 17 MPa １／２ Larger solvents can be used.

[0072] <Dipole moment per van der Waals volume> Here, van der Waals volume refers to the volume of a solvent molecule when the atoms constituting the solvent molecule are approximated by a sphere having a van der Waals radius. In this specification, values ​​from alvaDesc 2.0.12 were used as the van der Waals volume values ​​of various solvent molecules. In addition, SCIGRESS FQ 3.4.4 manufactured by Fujitsu Limited was used to calculate the dipole moment of various solvent molecules.

[0073] Van der Waals dipole moment per volume is 0.055 D / Å ３ The above means that the solvent molecule has a fixed structure and is highly planar, or that the size of the solvent molecule is relatively small and the solvent molecule is polarized within the solvent molecule, and the solvent molecule can be said to be easily solvated with the polyacid salt.

[0074] <Hydrogen Bond Term Value (ΔH) in Hansen Solubility Parameters> The Hansen solubility parameter is a three-dimensional representation of the solubility of a substance, divided into three components: a dispersion term ΔD, a polar term ΔP, and a hydrogen bond term ΔH. Here, the dispersion term ΔD represents the effect of dispersion forces, the polar term ΔP represents the effect of dipole-dipole forces, and the hydrogen bond term ΔH represents the effect of hydrogen bonds. The Hansen solubility parameter can be calculated using known and commonly used methods and software. In this specification, the estimated ΔH value calculated using Hansen Solubility Parameters in Practice (HSPiP) 5th Edition 5.4.02 is used.

[0075] Here, the hydrogen bond term ΔH of the Hansen solubility parameter is 17 MPa. １／２ If the concentration exceeds this value, the energy required for the solvent molecules to break the hydrogen bonds formed between the solvent molecules and solvate with the polyacid salt becomes large, making the solvent less likely to be a good solvent for the polyacid salt.

[0076] Examples of the first solvent to be solvated into the polyacid salt include the various solvents shown in Table 1 below. Table 1 also lists the van der Waals volumes (Å) of these various solvents. ３), dipole moment (D), van der Waals dipole moment per volume (D / Å ３ The values ​​of the hydrogen bond term in the Hansen solubility parameters (ΔH) and the boiling point (°C @ 760 mmHg) are shown in Table 2. Examples of poor solvents that can solvate the polyacid salts include the various solvents shown in Table 2 below. Table 2 also lists the van der Waals volumes (Å) of these various solvents. ３ ), dipole moment (D), van der Waals dipole moment per volume (D / Å ３ ), and the value of the hydrogen bond term in the Hansen solubility parameters (ΔH), respectively.

[0077]

[0078]

[0079] The poor solvent used in this embodiment has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or the value of the hydrogen bond term (ΔH) in the Hansen solubility parameter is less than 17 MPa １／２ As larger solvents, for example, ketone solvents, ether solvents, ester solvents, alcohol solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, heterocyclic solvents, halogenated solvents, water, etc. that satisfy the above requirements can be used.

[0080] Examples of ketone solvents that can be used as poor solvents include methyl ethyl ketone, 4-methyl-2-pentanone (methyl isobutyl ketone), di-n-butyl ketone, acetophenone, and methyl pyruvate. Examples of ether solvents that can be used as poor solvents include chain ethers such as 1-methoxy-2-propanol, ethyl ether, isopropyl ether, t-butyl methyl ether, and anisole; and cyclic ethers such as 1,4-dioxane, tetrahydrofuran, and 1,3-dioxolane. Examples of ester solvents that can be used as poor solvents include ethanol, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, propylene glycol-1-monobutyl ether-2-acetate, ethylene glycol diacetate, diethyl oxalate, and methyl 3-methoxypropionate. Examples of alcohol solvents that can be used as poor solvents include isopropyl alcohol, t-butyl alcohol, 4-methylpentanol, benzyl alcohol, ethylene glycol, propylene glycol, ethyl lactate, butyl lactate, and 2-(hydroxymethyl)furan.

[0081] Examples of hydrocarbon solvents that can be used as poor solvents include chain hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, and n-octane; and cyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, butylcyclohexane, cycloheptane, and cyclooctane. Examples of aromatic hydrocarbon solvents that can be used as poor solvents include benzene, toluene, xylene, ethylbenzene, and mesitylene. Examples of heterocyclic solvents that can be used as poor solvents include pyridine, picoline, 2,6-dimethylpyridine, quinoline, 1-methylpyrrole, and 3-methylpyrrole. Examples of halogenated solvents that can be used as poor solvents include dichloromethane, chloroform, 1,2-dichloroethane, and chlorobenzene.

[0082] <Method for Producing Solvate of Polyacid Salt> The method for producing a solvate of a polyacid salt is not particularly limited, and any known or commonly used method for producing a solvate can be used. The process for producing a solvate of a polyacid salt may include (1) a step of dissolving or dispersing a polyacid salt in one or more first solvents that are good solvents for the polyacid salt to obtain a good solvent solution, (2) a step of distilling off the solvent from the good solvent solution under normal pressure or reduced pressure, (2') a step of cooling the good solvent solution from the temperature at which the polyacid salt was dissolved, (2'') a step of adding a solvent that is a poor solvent for the polyacid salt to the good solvent solution, and (2''') a step of adding the poor solvent to the good solvent solution and then cooling. If a precipitate or sediment is formed, the process may also include (3) a step of filtering out the solid, and (4) a step of drying the filtered solid.

[0083] An example of a method for producing a solvate of a polyacid salt according to this embodiment is a method for producing a solvate of a polyacid salt, the method comprising the step of dissolving a polyacid salt in one or more first solvents that are good solvents for the polyacid salt to obtain a good solvent solution.

[0084] Another embodiment of the method for producing a solvate of a polyacid salt includes, for example, a step of dissolving a polyacid salt in one or more first solvents that are good solvents for the polyacid salt to obtain a good solvent solution, and a step of adding a solvent that is a poor solvent for the polyacid salt to the good solvent solution to precipitate a solvate of the polyacid salt.

[0085] The solvates of polyacid salts are not limited to solids (including powders, etc.) or oils that have precipitated or sedimented through the above-mentioned production steps, or crude products, but also include the above-mentioned good solvent solutions themselves, concentrated solutions thereof, and saturated solutions thereof, and these may be used as they are.

[0086] [1-1-4. Content of Polyacid Salt] The content of polyacid salt in the resist material is not particularly limited and can be set appropriately depending on the method for applying the resist material to a substrate, etc., the thickness of the applied film, etc. The content of polyacid salt in the resist material is preferably 0.01 to 20 mass %, and more preferably 0.1 to 15 mass %.

[0087] [1-2. First Solvent and Second Solvent] The first solvent according to this embodiment has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ The solvent is:

[0088] The second solvent according to this embodiment is a solvent different from the first solvent, and is a ketone or alcohol solvent having a surface tension of 20 to 35 dyne / cm and a boiling point of 165° C. or lower. Here, in this specification, "different from the first solvent" means selecting a second solvent of a different type from the predetermined solvent selected as the first solvent.

[0089] [1-2-1. First Solvent] As the first solvent, the same solvent as the first solvent described in [1-1-3.] that can be used as a solvent to solvate the polyacid salt can be used. That is, as the first solvent, a solvent having a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa １／２ By satisfying the physical property below, the resist material acts as a good solvent for the polyacid salt, improving the solubility of the polyacid salt in the resist material, thereby enabling the resist material to be formed into a film.

[0090] Specific examples of the first solvent include various solvents listed in Table 1. Examples of the first solvent include N,N-dimethylformamide, 2-cyclopenten-1-one, 4-hydroxy-2-butanone, 3-methyl-2-cyclopentenone, acetylacetone, acetonylacetone, 2-cyclohexen-1-one, 1-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, cyclopentanone, diacetone alcohol, hydroxyacetone, 3-methoxypropionitrile, dimethylcyanamide, lactonitrile, ethylene sulfide, 3-hydroxy-3-methyl-2-butan ...acetylacetone, acetonylacetone, 2-cyclohexen-1-one, 1-methyl-2-pyrrolidone, γ-butyrolactone, acetylacetone, acetonylacetone, 2-cyclohexen-1-one, 1-methyl-2-pyrrolidone N,N-dimethylformamide, 2-cyclopenten-1-one, 4-hydroxy-2-butanone, 3-methyl-2-cyclopentenone, acetylacetone, acetonylacetone, 2-cyclohexen-1-one, 1-methyl-2-pyrrolidone, and γ-butyrolactone are more preferred, and N,N-dimethylformamide, 2-cyclopenten-1-one, 4-hydroxy-2-butanone, 3-methyl-2-cyclopentenone, and γ-butyrolactone are even more preferred.

[0091] [1-2-2. Second Solvent] The second solvent is a solvent different from the first solvent, and may be a ketone or alcohol solvent having a surface tension of 20 to 35 dyne / cm and a boiling point of 165° C. or less. By using a solvent having the above physical properties as the second solvent, a resist material having film-forming properties can be obtained.

[0092] In this specification, the surface tension values ​​of various solvents can be those registered in the database of The Good Scents Company Information System (http: / / www.thegoodscentscompany.com). The surface tension value of the second solvent is preferably 20 to 35 dyne / cm, and more preferably 22 to 34 dyne / cm. If the surface tension value significantly exceeds 35 dyne / cm, the contact angle during application increases due to the high surface tension, and there is a tendency for the resist material to aggregate as droplets, cause coating defects such as repellency and dents, and exhibit poor leveling properties. Furthermore, if the surface tension of the second solvent is significantly below 20 dyne / cm, it becomes difficult to uniformly adjust the film thickness during the application process of the resist material, which is undesirable.

[0093] The boiling point of the second solvent is preferably 165° C. or lower, and more preferably 160° C. or lower. By using a ketone or alcohol solvent with a boiling point of 165° C. or lower as the second solvent, the second solvent can be easily volatilized, which suppresses the occurrence of repellency and allows a resist material with few film defects to be obtained after drying.

[0094] As specific examples of the second solvent, Table 3 below shows the names of various solvents, their surface tension (dyne / cm), boiling points, and whether they are ketone-based or alcohol-based.

[0095]

[0096] The second solvent is preferably ethyl lactate, diacetone alcohol, 1-methoxy-2-propanol, cyclopentanone, cyclohexanone, methyl pyruvate, 4-methyl-2-pentanol, or 2,6-dimethylpyridine, more preferably ethyl lactate, diacetone alcohol, 1-methoxy-2-propanol, cyclopentanone, cyclohexanone, or 2,6-dimethylpyridine, and even more preferably ethyl lactate, diacetone alcohol, 1-methoxy-2-propanol, cyclopentanone, or cyclohexanone.

[0097] [1-2-3. Difference in Boiling Points Between First Solvent and Second Solvent] The difference in boiling points between the first solvent and the second solvent is not particularly limited, but is preferably 50° C. or less, more preferably 40° C. or less, and even more preferably 30° C. or less. When the difference in boiling points between the first solvent and the second solvent is 50° C. or less, it is possible to prevent one solvent from being preferentially removed during drying, and a film with fewer defects can be obtained.

[0098] Combinations of the first and second solvents such that the difference in boiling point is 50°C or less may be appropriately selected and combined from, for example, the first solvents listed in Table 1 and the second solvents listed in Table 3, but are not limited to these.

[0099] [1-2-4. Solvent Content and Content Ratio] The contents of the first solvent and second solvent in the resist material are not particularly limited and can be appropriately set depending on the type of polyacid salt or solvate thereof used, the method for applying the resist material to a substrate, the thickness of the applied film, etc. The content of the first solvent in the resist material is preferably 1 to 60 mass%, more preferably 3 to 50 mass%, and even more preferably 5 to 40 mass%. The content of the second solvent in the resist material is preferably 30 to 97 mass%, more preferably 40 to 95 mass%, and even more preferably 50 to 92 mass%.

[0100] The mass ratio of the first solvent to the second solvent in the resist material is not particularly limited and can be set appropriately depending on the type of polyacid salt or solvate thereof used, the method for applying the resist material to a substrate or the like, the thickness of the applied film, etc. The mass ratio of the first solvent to the second solvent is preferably 0.5-6:4-9.5, more preferably 1-5:5-9, and even more preferably 1-4:6-9.

[0101] [1-3. Others] The resist material according to this embodiment may further contain, as desired, miscible additives, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, etc. Preferably, the resist material according to this embodiment does not contain an epoxy resin. It is also preferable that the resist material does not contain hydrogen peroxide.

[0102] [2. Manufacturing Method of Resist Material] The manufacturing method of the resist material according to this embodiment is not particularly limited, and any known or commonly used method can be used. Examples of manufacturing methods for the resist material include a method in which a polyacid salt is dissolved in a mixed solvent of a first solvent and a second solvent to produce a resist material. Here, the polyacid salt is first dissolved in one or more first solvents that are good solvents for the polyacid salt, and the polyacid salt is solvated with the first solvent. Adding the second solvent to the first solvent allows the polyacid salt to be dissolved at a higher concentration than when the polyacid salt itself is directly dissolved in a mixed solvent of the first solvent and the second solvent.

[0103] Alternatively, a solvate of the polyacid salt can be precipitated through a step of dissolving the polyacid salt in one or more first solvents that are good solvents for the polyacid salt to obtain a good solvent solution, and the solvate of the polyacid salt obtained can be dissolved in the first solvent and the second solvent sequentially, or in a mixed solvent of the first solvent and the second solvent, thereby dissolving the polyacid salt at a higher concentration.

[0104] Furthermore, a solid (including powder, crystal, etc.) solvate of the polyacid salt precipitated through a step of dissolving the polyacid salt in one or more first solvents that are good solvents for the polyacid salt to obtain a good solvent solution, and a step of adding a solvent that is a poor solvent for the polyacid salt to the good solvent solution to precipitate a solvate of the polyacid salt may be dissolved in the first solvent and the second solvent sequentially or simultaneously.

[0105] 3. Film Forming Method The film forming method according to this embodiment includes a step of applying a resist material to a substrate. The "substrate" and "application method" will be described below.

[0106] <Substrate> The substrate used in this embodiment is not particularly limited, and known and commonly used substrates can be used. For example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed may be used. The material of the substrate is not particularly limited, and examples thereof include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and inorganic substrates such as glass, titanium oxide, and silicon dioxide. The size, shape, and the like of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or may be a flake-shaped substrate.

[0107] The surface of the substrate may be subjected to a surface treatment as necessary. In the case of a substrate having hydroxyl groups on its surface layer, the surface of the substrate is treated with a silane coupling agent capable of reacting with the hydroxyl groups, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane coupling agent include hexamethyldisilazane (HMDS).

[0108] <Coating Method> The method for applying the resist material onto the substrate is not particularly limited, and any known or commonly used method can be used. Examples of dry coating methods include CVD (chemical vapor deposition) methods such as thermal CVD, plasma CVD, and photo-CVD; and PVD (physical vapor deposition) methods such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Examples of wet coating methods include spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0109] As a method for applying the resist material according to this embodiment to a substrate, a wet method such as spin coating or screen printing is preferably used, and spin coating is more preferable, from the viewpoint of forming a uniform film thickness, etc. After forming the coating film, a backside rinse, an edge bead removal step, etc. may be performed to remove the edge bead.

[0110] The method for drying the resist film formed by applying a resist material to a substrate is not particularly limited, and can be performed using, for example, a heating device such as a hot plate (post-applied bake (PAB)), a pressure reducing device, or the like. The baking conditions are not particularly limited, and can be set appropriately depending on the type of resist film, application, etc. The baking temperature is preferably 80 to 300°C, more preferably 150 to 250°C, and even more preferably 170 to 230°C. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0111] The thickness of the resist film after drying is not particularly limited, but is preferably 0.5 to 100 nm, more preferably 1 to 75 nm, and even more preferably 1 to 60 nm.

[0112] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0113] [1. Synthesis of Polyacid Salts] Polyacid salts 1 to 7 were synthesized by the following methods.

[0114] <Polyacid salt 1: hexakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)metatungstate> 6.68 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride was dissolved in 99.36 g of pure water, and ammonium metatungstate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: ammonium metatungstate hydrate ((NH ４ ) ６ [H ２ W １２ O ４０ ]・xH ２ 6.88 g of HCl (O) was added, and the reaction solution was stirred at room temperature for 30 minutes. The reaction solution was filtered, and the resulting powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was dissolved in 100 g of dimethylformamide, and 335 g of methanol was added. Crystallization at room temperature yielded the target compound (Polyacid Salt 1). １H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.35-7.65 (m, 13H), 5.97 (s, 0.33H). １８３ W-NMR (20.84MHz, DMSO-D6): δ (ppm) = -100.13 (s, 12W). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 712.3 (median) ([H ４ W １２ O ４０ ] ４－ )

[0115] <Polyacid salt 2: metatungstate salt containing five phenylbis(2-(trifluoromethyl)phenyl)sulfonium groups (compound shown below)> Ammonium metatungstate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: ammonium metatungstate hydrate ((NH ４ ) ６ [H ２ W １２ O ４０ ]・xH ２ To 16.67 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride) was added 100 g of a 0.1 mol / L aqueous hydrochloric acid solution, and the mixture was stirred at room temperature for 60 minutes. Subsequently, an aqueous solution prepared by dissolving 13.47 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride in 200 g of pure water was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was filtered, and the resulting powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was dissolved in 100 g of dimethylformamide, and then 335 g of methanol was added. The mixture was crystallized at room temperature to obtain the target compound (polyacid salt 2). １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.35-7.65 (m, 13H), 6.77 (s, 0.60H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -87.59 (s, 12 W). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋) NEGATIVE m / z 712.3 (median) ([H ４ W １２ O ４０ ] ４－ )

[0116] <Polyacid Salt 3: Tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate> 37.26 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride was dissolved in 50 g of cyclohexanone, and silicotungstic acid (H ４ [SiW １２ O ４０ ]・26H ２ 41.06 g of methyl 2-hydroxybenzoate (C10-20) was added, and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered, and the resulting powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized at room temperature using dichloromethane and acetonitrile to obtain the target compound (polyacid salt 3). １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.34-7.63 (m, 52H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis S:W (molar ratio of S to W) = 4:12

[0117] <Polyacid Salt 4: Tris(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)phosphotungstate> In the synthesis method of polyacid salt 3, the raw material compound was changed from 37.26 g of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride to 27.95 g, and silicotungstic acid was replaced with phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ The target compound (polyacid salt 4) was obtained in the same manner as above, except that 41.97 g of methyl methyl acrylate (Methyl methyl acrylate) was used. １H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.36-7.63 (m, 39H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis S:W (molar ratio of S to W) = 3:12

[0118] <Polyacid Salt 5: Tris((2-hydroxyethyl)trimethylammonium)phosphotungstate> In the synthesis method of polyacid salt 3, the raw material compound was changed from phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride to 0.2 g of (2-hydroxyethyl)trimethylammonium chloride, and from silicotungstic acid to 0.2 g of phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ The target compound (polyacid salt 5) was obtained in the same manner as above, except that 1.0 g of methyl methyl ketone (C10) was used. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 5.28 (br, 3H), 3.84 (m, 6H), 3.40 (m, 6H), 3.11 (s, 27H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis N:W (molar ratio of N to W) = 3:12

[0119] <Polyacid salt 6: Tris(tetrahexylammonium)phosphotungstate> In the synthesis method of polyacid salt 3, the raw material compound was changed to 0.5 g of tetrahexylammonium iodide instead of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride, and phosphotungstic acid (H ３ [P.W. １２ O ４０]・30H ２ The target compound (polyacid salt 6) was obtained in the same manner as above, except that 1.0 g of methyl methyl ketone (C10) was used. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 3.16 (m, 24H), 1.57 (m, 24H), 1.30 (s, 72H), 0.88 (t, 36H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis N:W (molar ratio of N to W) = 3:12

[0120] <Polyacid salt 7: Tris(tetraphenylphosphonium)phosphotungstate> In the synthesis method of polyacid salt 3, the raw material compound was changed to 0.45 g of tetraphenylphosphonium chloride instead of phenylbis(2-(trifluoromethyl)phenyl)sulfonium chloride, and 0.45 g of phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ The target compound (polyacid salt 7) was obtained in the same manner as above, except that 1.0 g of methyl methyl ketone (C10) was used. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.05-7.65 (m, 60H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis P:W (molar ratio of P to W) = 4:12

[0121] 2. Synthesis of Solvates of Polyacid Salts As solvates of the above-mentioned polyacid salts 1 to 4, polyacid salt solvates 1 to 12 were synthesized by the methods shown below, respectively.

[0122] <Solvate of Polyacid Salt 1: Solvate of hexakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)metatungstate with 4-hydroxy-2-butanone and t-butyl methyl ether> 10 g of polyacid salt 1 (hexakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)metatungstate) was dissolved in 100 g of 4-hydroxy-2-butanone. 1,000 g of t-butyl methyl ether was added to this solution, and the mixture was stirred for 5 minutes. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 13H), 5.97 (s, 0.31H), 4.55 (br, 0.026H) , 3.63 (m, 0.051H), 3.08 (s, 0.014H), 2.53 (m, 0.051H), 2.09 (s, 0.077H), 1.11 (s, 0.042H).

[0123] <Solvate of Polyacid Salt 2: Solvate of hexakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)metatungstate with 2-cyclopenten-1-one, t-butyl methyl ether, and p-menthane> 2 g of polyacid salt 1 (hexakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)metatungstate) was dissolved in 8 g of 2-cyclopenten-1-one to prepare a 20 wt % solution. To this solution, 60 g of p-menthane and 100 g of t-butyl methyl ether were added in that order. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 80H), 6.0 (s, 2H), 3.08 ( s, 3H), 2.65 (m, 4H), 2.25 (m, 4.0H), 1.11 (s, 9.0H), 0.09-0.08 (m, 5.2H).

[0124] <Solvate 3 of polyacid salt: solvate in which polyacid salt 2 is solvated with 4-hydroxy-2-butanone and t-butyl methyl ether> 10 g of the polyacid salt 2 synthesized above was weighed out and dissolved in 90 g of 4-hydroxy-2-butanone. 1,000 g of t-butyl methyl ether was added to this and stirred for 5 minutes. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 65H), 6.71 (s, 3H), 4.55 (br, 3 H), 3.63 (t, 5.1H), 3.08 (s, 1.2H), 2.53 (m, 4.9H), 2.09 (s, 7.0H), 1.11 (s, 4H).

[0125] <Solvate of Polyacid Salt 4: Solvate of Polyacid Salt 2 with 2-cyclopenten-1-one, p-menthane, and t-butyl methyl ether> 2 g of the polyacid salt 2 synthesized above was weighed out and dissolved in 8 g of 2-cyclopenten-1-one. To this solution, 60 g of p-menthane and 600 g of t-butyl methyl ether were added in that order. The resulting precipitate was filtered under suction and dried for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 67H), 6.71 (s, 3H), 6.17 (s, 2H) , 3.08 (s, 2H), 2.65 (m, 4H), 2.25 (m, 4.0H), 1.11 (s, 6.0H), 0.08-0.09 (m, 4.7H).

[0126] <Solvate of Polyacid Salt 5: Solvate of tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate with 4-hydroxy-2-butanone> 2 g of polyacid salt 3 (tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate) was dissolved in 8 g of 4-hydroxy-2-butanone to prepare a 20 wt % solution. 1,000 g of t-butyl methyl ether was added to this solution. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 1H), 4.55 (br, 0.038H), 3.63 (m, 0.077H), 2.53 (m, 0.077H), 2.09 (s, 0.12H).

[0127] <Solvate of Polyacid Salt 6: Solvate in which 2-cyclopenten-1-one is solvated in tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)siliconstate> 2 g of polyacid salt 3 (tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)siliconstate) was dissolved in 8 g of 2-cyclopenten-1-one to prepare a 20 wt % solution. 1,000 g of t-butyl methyl ether was added to this solution. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 1H), 6.17 (s, 0.038H), 2.65 (m, 0.077H), 2.25 (m, 0.077H).

[0128] <Solvate of Polyacid Salt 7: Solvate of Tris(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)phosphotungstate with 4-hydroxy-2-butanone> 2 g of Polyacid Salt 4 (tris(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)phosphotungstate) was dissolved in 8 g of 4-hydroxy-2-butanone to prepare a 20 wt % solution. 1,000 g of t-butyl methyl ether was added to this solution. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 1H), 4.55 (br, 0.05H), 3.63 (t, 0.1H), 2.53 (m, 0.1H), 2.09 (s, 0.15H).

[0129] <Solvate of Polyacid Salt 8: Solvate of Tris(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)phosphotungstate with 2-cyclopenten-1-one> 2 g of Polyacid Salt 4 (tris(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)phosphotungstate) was dissolved in 18 g of 2-cyclopenten-1-one to prepare a 10 wt % solution. To this solution, 100 g of p-menthane and 100 g of t-butyl methyl ether were added in that order. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 1H), 6.17 (s, 0.05H), 2.65 (m, 1.0H), 2.25 (m, 1.0H).

[0130] <Solvate of Polyacid Salt 9: Solvate of Tris(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)phosphotungstate with Cyclohexanone and p-menthane> 2 g of Polyacid Salt 4 (tris(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)phosphotungstate) was dissolved in 18 g of cyclohexanone to prepare a 10 wt % solution. To this solution, 200 g of p-menthane and 200 g of t-butyl methyl ether were added in that order. The resulting precipitate was filtered by suction and dried under reduced pressure for 10 minutes. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 1H), 2.25 (m, 0.06H), 1. 77 (m, 0.06H), 1.66 (m, 0.03H), 1.50-1.2 (m, 0.04H), 1.0-0.8 (m, 0.08H).

[0131] <Solvate of Polyacid Salt 10: Solvate in which 2-cyclopenten-1-one is solvated in tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate> 2 g of Polyacid Salt 3 (tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate) was dissolved in 18 g of 2-cyclopenten-1-one to prepare a 10 wt % solution. The solution was distilled under reduced pressure until the content of Polyacid Salt 3 in the obtained 10 wt % solution reached 50 wt %, thereby preparing a 50 wt % solution.１ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 52H), 6.17 (s, 54H), 2.65 (m, 109H), 2.25 (m, 109H).

[0132] <Solvate of Polyacid Salt 11: Solvate of tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate with 4-hydroxy-2-butanone> 2 g of Polyacid Salt 3 (tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate) was dissolved in 18 g of 4-hydroxy-2-butanone to prepare a 10 wt % solution. The solution was distilled under reduced pressure until the content of Polyacid Salt 3 in the obtained 10 wt % solution reached 50 wt %, thereby preparing a 50 wt % solution. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 52H), 4.51 (s, 51H), 3.63 (m, 101H), 2.51 (m, 101H), 2.10 (m, 152H).

[0133] <Solvate of Polyacid Salt 12: Solvate of Tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate with γ-butyrolactone> 2 g of Polyacid Salt 3 (tetrakis(phenylbis(2-(trifluoromethyl)phenyl)sulfonium)silicate) was dissolved in 18 g of γ-butyrolactone to prepare a 10 wt % solution. The solution was distilled under reduced pressure until the content of Polyacid Salt 3 in the obtained 10 wt % solution became 50 wt %, thereby preparing a 50 wt % solution. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 8.40-7.60 (m, 52H), 4.26 (m, 104H), 2.4 (m, 104H), 2.12 (m, 104H).

[0134] [3. Solubility Test and Evaluation] The solubilities of the polyacid salt solvates 1 to 9 synthesized above in the various solvents listed in Table 4 were tested by the following method. First, 1 g of powder of each of the polyacid salt solvates 1 to 9 was weighed into a beaker. Next, a solvent listed in Table 4 was added, and the mass concentration (wt %) was calculated from the amount of solvent added at the point when dissolution was confirmed visually. The solubility was evaluated according to the following criteria. The results are shown in Table 4. A: Dissolved at 1 wt % or more B: Dissolved at 0.1 wt % or more but less than 1 wt % C: Not dissolved at less than 0.1 wt % As mentioned above, it was visually confirmed that polyacid salt 3 was soluble in 2-cyclopenten-1-one, 4-hydroxy-2-butanone, and γ-butyrolactone at 50 wt % or more, which corresponds to a grade A in the solubility evaluation criteria above.

[0135]

[0136] The solvents No. 1 to 23 listed in Table 4 have the same van der Waals volume (Å) as in Table 1. ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ These correspond to first solvents Nos. 1 to 23, which were exemplified as solvents having the above properties and a hydrogen bond term value (ΔH) in the Hansen solubility parameters of 17 or less. As can be seen from Table 4, polyacid salt solvates 1 to 9 all exhibited a certain degree of solubility in the first solvents having the above physical properties, and were evaluated as A or B for solubility. On the other hand, polyacid salt solvates 1 to 9 did not dissolve well in solvents Nos. 25 to 41, which are solvents other than the first solvent, and were evaluated as C for solubility. Furthermore, polyacid salt solvates 1 to 3 were well soluble in solvent No. 24, but polyacid salt solvates 4, 5, 7, and 9 were not well soluble in solvent No. 24, and were evaluated as C for solubility.

[0137] [4. Film-Forming Properties Test and Evaluation (Single Solvent)] Polyacid Salt Solvates 1 to 9 were dissolved in various solvents listed in Table 5 to prepare resist materials containing 1 wt % polyacid salt solvates. Each resist material was applied to an 8-inch silicon substrate using a spinner, prebaked (PAB) on a hot plate at 200°C for 60 seconds, and dried to form a film. The film-forming properties of each resist material were evaluated according to the following criteria: A: A film was formed without defects; B: A film was formed, although there were some defects; C: A film was not formed due to defects over the entire surface. Similarly, polyacid salt solvates 10 to 12 were prepared in various solvents listed in Table 5 to prepare resist materials containing 1 wt % polyacid salt solvates. The same test as above was then conducted to evaluate film-forming properties according to the above criteria, and all of the resist materials received a result of C (not shown in Table 5).

[0138]

[0139] In the resist materials using solvents No. 24 to 41 in Table 5, the solubility of the solvate of the polyacid salt was poor, and defects were observed throughout the film, resulting in a rating of C for film formability. In addition, in the resist materials using solvents No. 1 to 23 in Table 5, the solubility of the solvate of the polyacid salt was not poor, but the film formability was also rated C due to the solvent's excessively high surface tension, high boiling point, or low volatility.

[0140] [5. Solubility Test and Evaluation, and Film-Formability Test and Evaluation (Solvent Mixture) Part 1] To prepare a resist material with both solubility and film-formability, the first and second solvents shown in Table 6 below were mixed in the mass ratios shown in Table 6. The solubility of polyacid salt solvates 1 to 4 in the prepared mixed solvent was tested and evaluated using the same method as in "3. Solubility Test and Evaluation" above. Each resist material was also prepared by dissolving 1 wt % of polyacid salt solvates 1 to 4 in the prepared mixed solvent. Films were formed using each resist material, and their film-formability was evaluated according to the same evaluation criteria as in "4. Film-Formability Test and Evaluation (Single Solvent)" above. In Table 6, a rating of "Good" was given if both the solubility test and the film-formability test were evaluated as A or B. On the other hand, a rating of "Poor" was given if either the solubility test or the film-formability test was evaluated as C.

[0141]

[0142] In the resist materials using mixed solvents Nos. 3, 13, and 25 in Table 6, the ester solvent propylene glycol-1-monomethyl ether-2-acetate was used as the second solvent, and the film-forming properties were poor, resulting in an overall rating of x. Furthermore, as in the mixed solvents Nos. 1, 2, 4-12, 14-24, 26, and 27 in Table 6, when a ketone or alcohol solvent with a surface tension of 20-35 dyne / cm and a boiling point of 165°C or less was used as the second solvent in addition to the first solvent, good solubility and film-forming properties were obtained in all cases. Furthermore, Nos. 7-9 and 16-19 in Table 6 are three-solvent systems, and when two types of second solvents were used in addition to the first solvent, good solubility and film-forming properties were obtained. By using a three-solvent system, as in Nos. 7-9 and 16-19, it is possible to fine-tune the film-forming properties.

[0143] [6. Dissolution Test and Evaluation, and Film-Formability Test and Evaluation (Mixed Solvent) Part 2] Next, for solvates 10 to 12 of polyacid salts, resist materials were prepared using the mixed solvents shown in Table 7 below so that the polyacid salt was 1 wt %, and films were formed using these. The film-formability of each resist material was evaluated according to the same evaluation criteria as above. In Table 7, if the film-formability test result was A or B, it was evaluated as ○. On the other hand, if the film-formability test result was C, it was evaluated as ×.

[0144]

[0145] The results in Table 7 show that even when a resist material is prepared by dissolving a polyacid salt in a first solvent, concentrating the solution, and then adding a mixed solvent of the first solvent and the second solvent, as in the case of solvates 10 to 12 of a polyacid salt, a resist material with good solubility and film-forming properties can be obtained.

[0146] The above results demonstrate that the effect of improving the solubility of a polyacid salt in a mixed solvent of the first solvent and the second solvent can be achieved whether the solvate of the polyacid salt is dissolved or dispersed in the first solvent and then precipitated as a solid, or whether the solvate is stored as a concentrated solution. Furthermore, it is clear that a resist material with excellent film-forming properties can be provided by incorporating a solvate of a polyacid salt, the first solvent, and the second solvent into the resist material.

Claims

1. A resist material comprising: (A) a polyacid salt or a solvate thereof; (B) a first solvent; and (C) a second solvent, wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa or more. １／２ The resist material comprises the following solvent: wherein the second solvent is different from the first solvent, has a surface tension value of 20 to 35 dyne / cm, and is a ketone-based or alcohol-based solvent having a boiling point of 165° C. or lower.

2. The resist material according to claim 1, wherein the difference in boiling point between said first solvent and said second solvent is 50° C. or less.

3. The resist material according to claim 1, wherein the difference in boiling point between said first solvent and said second solvent is 30° C. or less.

4. The resist material according to claim 1, wherein the anion portion of the polyacid salt is an isopolyoxomolybdate anion, an isopolyoxotungstate anion, an isopolyoxoniobate anion, an isopolyoxotantalate anion, a heteropolyoxomolybdate anion, a heteropolyoxotungstate anion, a heteropolyoxovanadate anion, a heteropolyoxoniobate anion, or a heteropolyoxotantalate anion.

5. The resist material according to claim 1, wherein the cationic portion of the polyacid salt is an onium cation.

6. The resist material according to claim 5, wherein the onium cation is an organic sulfonium cation, an organic iodonium cation, an organic quaternary ammonium cation, or an organic phosphonium cation.

7. A method for producing a resist material, comprising: a step of dissolving a polyacid salt in one or more first solvents that are good solvents for the polyacid salt to obtain a good solvent solution; and a step of adding a second solvent to the good solvent solution, wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa or more. １／２ The second solvent is a solvent different from the first solvent, and is a ketone-based or alcohol-based solvent having a surface tension value of 20 to 35 dyne / cm and a boiling point of 165° C. or lower.

8. A method for producing a resist material, comprising: dissolving a polyacid salt in a first solvent to obtain a solvate of the polyacid salt in the first solvent; and dissolving the solvate of the polyacid salt in the first solvent and the second solvent, successively or simultaneously, wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa or more. １／２ The second solvent is a solvent different from the first solvent, and is a ketone-based or alcohol-based solvent having a surface tension value of 20 to 35 dyne / cm and a boiling point of 165° C. or lower.

9. A method for producing a resist material, comprising the steps of: dissolving a polyacid salt in a first solvent that is a good solvent for the polyacid salt to obtain a good solvent solution; adding a solvent that is a poor solvent for the polyacid salt to the good solvent solution to precipitate a solvate of the polyacid salt; and dissolving the solvate of the polyacid salt in the first solvent and the second solvent sequentially or simultaneously, wherein the first solvent has a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or more, and the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is 17 MPa or more. １／２ The antisolvent is a solvent having a van der Waals volume (Å ３ The dipole moment (D) value per unit area is 0.055 D / Å ３ or the value of the hydrogen bond term in the Hansen solubility parameter (ΔH) is less than 17 MPa. １／２ the second solvent is a solvent having a surface tension value of 20 to 35 dyne / cm and a boiling point of 165° C. or lower, the second solvent being a ketone-based or alcohol-based solvent different from the first solvent.

10. The method for producing a resist material according to claim 9, wherein the poor solvent is a ketone-based solvent, an ether-based solvent, an ester-based solvent, an alcohol-based solvent, a hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a heterocyclic solvent, a halogen-based solvent, or water.

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