Method for producing metatungstate compound, metatungstate compound for resist, and resist material

Abstract

To provide a method for selectively producing a metatungstate compound, in which a predetermined number of cation moieties are replaced with predetermined counter cations; and also to provide a metatungstate compound for novel resists, and a resist material containing the metatungstate compound for the novel resists.SOLUTION: Provided are a method for selectively producing a metatungstate compound which contains five onium cations or onium dications by performing a salt exchange reaction of a metatungstate in an acidic solution that has a pH of less than 3, a metatungstate compound for resists, the metatungstate compound being produced by the production method, and a resist material which contains the metatungstate compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a metatungstate compound, a metatungstate compound for a resist, and a resist material. [Background technology]

[0002] Ammonium metatungstate is widely used in the production of tungsten metal, steel alloys, flame retardant fabrics, and petrochemical catalysts.

[0003] In recent years, resist-related compositions containing metatungstate have been reported. For example, Patent Document 1 discloses a resist underlayer film-forming composition containing metatungstate (alkali metal salt, ammonium salt, etc.) and polysiloxane, etc. In addition, Patent Document 2 discloses a composition containing ammonium metatungstate and silane or polysiloxane, which is applied to a resist pattern and is used to reverse the pattern by utilizing the difference in etching rate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 9,725,618 [Patent Document 2] U.S. Pat. No. 1,055,8119 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide a method for selectively producing a metatungstate compound in which the cation moiety of metatungstate is replaced with a predetermined number of counter cations, and also provides a novel metatungstate compound for resist and a novel resist material containing the metatungstate compound for resist. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors discovered that a metatungstate compound containing five onium cations or five onium dications can be selectively produced by carrying out a salt exchange reaction of a metatungstate in an acidic solution having a pH of less than 3, thereby completing the present invention.

[0007] That is, the present invention relates to the following inventions: <1> A method for producing a metatungstate compound represented by general formula (I-1) or (I-2), comprising the steps of: The salt exchange step is performed in an acidic solution having a pH of less than 3. A method for producing a metatungstate compound. (A + )5·[H3W 12 O 40 ] 5- (I-1) (A' 2+ )5·([H3W 12 O 40 ] 5- )2(I-2) [In formulas (I-1) and (I-2), A + each independently represents an onium cation; A' 2+ each independently represents an onium dication. <2> The onium cation is at least one selected from the group consisting of an organic sulfonium cation, an organic iodonium cation, and an organic ammonium cation. <1> 2. A method for producing a metatungstate compound according to claim 1 . <3> The acidic solution having a pH of less than 3 contains an inorganic acid, an organic acid having a carboxyl group, or an organic acid having a sulfo group. <1> 2. A method for producing a metatungstate compound according to claim 1 . <4> The salt exchange is between a metatungstate represented by general formula (II) and an onium salt represented by general formula (III-1) or (III-2). <1> 2. A method for producing a metatungstate compound according to claim 1 . (B+ )6·[H2W 12 O 40 ] 6- (II) A + X - (III-1) A' 2+ ·(X - )2(III-2) [In formula (II), B + are each independently H + , a metal ion, or an ammonium ion; In formulas (III-1) and (III-2), A + represents an onium cation; A' 2+ represents an onium dication; X - represents a monovalent counter anion. <5> The monovalent counter anion is Br - , Cl - , I - , Br 3- , O.H. - , HSO4 - , CF3SO3 - , C2F5SO3 - , C3F7SO3 - , C4F9SO3 - , p-CH3(C6H4)SO3 - , ClSO3 - , ClO4 - , NO3 - , (C6F5)4B - , BF4 - , PF6 - , SbF6 - , AlCl4 - , BiF6 - , AsF6 - , (CF3SO2)2N - or (FSO2)2N - That is, <4> 2. A method for producing a metatungstate compound according to claim 1 . <6> A metatungstate compound for resist represented by general formula (I-1) or (I-2): (A+ )5·[H3W 12 O 40 ] 5- (I-1) (A' 2+ )5·([H3W 12 O 40 ] 5- )2(I-2) [In formulas (I-1) and (I-2), A + each independently represents an onium cation; A' 2+ each independently represents an onium dication. <7> <6> A resist material comprising the metatungstate for resist according to claim 1. <8> Further comprising a solvent, <7> The resist material according to claim 1. <9> Resist materials for electronics or EUV, <7> or <8> The resist material according to claim 1. <10> <7> or <8> A pattern structure formed using the resist material according to claim 1. Effect of the Invention

[0008] According to the present invention, a metatungstate compound containing five onium cations or onium dications can be selectively produced. In addition, the metatungstate compound has improved actinic ray sensitivity and / or radiation sensitivity, and can be suitably used as a metatungstate compound for resist. Furthermore, since the metatungstate compound selectively produced by the production method of the present invention has a certain degree of uniformity, when the metatungstate compound is contained in a resist material, a new resist material with little change in pattern dimension (CD: Critical Dimension) can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Preferred embodiments of the present invention will be described in detail below, however, the present invention is not limited to the following embodiments.

[0010] In this specification, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0011] In the present specification, for example, "C 1-6 " and other terms refer to the number of carbon atoms in the core group.

[0012] In this specification, "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, and the like. Also, "C 1-18 A divalent carbon atom at any position of the "hydrocarbylene group" may be replaced by -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time). "C 1-18 The "hydrocarbylene group" is not particularly limited, and examples thereof include a "C group" such as a methylene group, an ethylene group, an n-propylene group, an i-propylene group, a cyclopentadiyl group, a cyclohexanediyl group, an oxyethane-1,1-diyl group, an oxyethane-1,2-diyl group, an oxypropane-1,3-diyl group, an oxypropane-1,2-diyl group, a 2-methylpropane-1,3-diyl group, or an oxyethyleneoxyethane-1,1-diyl group. 1-18 Alkylene groups such as 1,4-phenylene groups, 1,3-phenylene groups, 1,2-phenylene groups, 1,4-naphthylene groups, 1,5-naphthylene groups, 1,8-naphthylene groups, 4,4'-biphenylene groups, anthracenediyl groups, phenanthrenediyl groups, naphthacenediyl groups, pyrenediyl groups, perylenediyl groups, and chrysenediyl groups. 6-18 An arylene group" is an example.

[0013] In this specification, "C 1-18The term "alkyl group" refers to a linear or branched alkyl group having 1 to 18 carbon atoms. Also, "C 1-18 Any divalent carbon atom at any position except the terminal end contained in the "alkyl group" may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2-. However, adjacent divalent carbon atoms may not be replaced at the same time. "C 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 Examples of the alkyl group include 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, and n-dodecyl group. "C 1-18 Examples of the "alkyl group" in which a divalent carbon atom at any position excluding the terminal is replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- include, but are not limited to, a 2-methoxyethoxymethyl group, an ethoxycarbonylmethyl group, and the like.

[0014] In this specification, "C 1-18 Haloalkyl group means "C 1-18 The term "alkyl group" refers to a group in which one or more hydrogen atoms of the "alkyl group" have been substituted with halogen atoms. "C1-18 The "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.

[0015] In this specification, "C 2-18 An alkenyl group is a group having two or more carbon atoms. 1-18 "Alkyl group" means an alkenyl group having one or more double bonds, and includes alkadienyl groups, alkatrienyl groups, etc. "C 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.

[0016] In this specification, "C 2-18 An alkynyl group is a group with two or more carbon atoms. 1-18 "Alkyl group" means an alkynyl group having one or more triple bonds. "C 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.

[0017] In this specification, "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, and the like. Also, "C 3-18A divalent carbon atom at any position except for the terminal position contained in the "alicyclic group" may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO2- (however, adjacent divalent carbon atoms are not replaced at the same time). "C 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.

[0018] 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 condensed 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.

[0019] In this specification, "C 2-18 The 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 an oxygen atom, and each of these may be a monocyclic ring, a polycyclic ring, or a condensed ring. "C 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, and an anthracenyl group.

[0020] In this specification, "C 7-18 Aralkyl groups are defined as groups consisting of C 1-12 The substitutable portion of the "alkyl group" is the above "C 2-12 The term "aryl group" refers to a group substituted with an "aryl group." "C 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.

[0021] In this specification, "C 1-18The term "hydrocarbyl group" refers to a monovalent group generated by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. Examples of hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, and aralkyl groups. Also, "C 1-18 Any divalent carbon atom at any position except the terminal contained in the "hydrocarbyl group" may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). This point is explained in the following section "C 1-18 "C" used in the explanation of the definition of "hydrocarbyloxy group" etc. 1-18 The same applies to "hydrocarbyl group" and the like. "C 1-18 The "hydrocarbyl group" is not particularly limited, and examples thereof include "C 1-18 Alkyl 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 group".

[0022] In this specification, "C 1-18 "Hydrocarbyloxy group" means "C 1-18 The term "hydrocarbyl group" refers to a group having an oxygen atom (-O-) bonded to a "hydrocarbyl group." "C 1-18The "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-2-ethylpropyloxy group, a 1-ethyl-2-methylpropyloxy group, a 1,1,2-trimethylpropyloxy group, a 1,2,2-trimethylpropyloxy group, a 1,1-dimethylbutyloxy group, a 1,2-dimethylbutyloxy group, a 2,2-dimethylbutyloxy group, a 2,3-dimethylbutyloxy group, a 1,3-dimethylbutyloxy group, a 2-ethylbutyloxy group, a 2-methylpentyloxy group, and a 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" and the like. "C 1-18 The hydrocarbyloxy group includes "C 1-18 It is preferable 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-. 1-18A "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, and the like.

[0023] In this specification, "C 1-18 The term "hydrocarbyl carbonyl group" means "C 1-18 The term "hydrocarbyl group" refers to a group having a carbonyl group (-C(=O)-) bonded to a "hydrocarbyl group." "C 1-18 The hydrocarbyl carbonyl group is not particularly limited, and examples thereof include acetyl, propionyl, isopropionyl, butyryl, isobutyryl, valeryl, isovaleryl, pentanoyl, 3-methylbutanoyl, pivaloyl, hexanoyl, and heptanoyl groups. 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, and other C 3-18 Alicyclic carbonyl group; Benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. 6-18 arylcarbonyl group" and the like.

[0024] In this specification, "C 1-18 The term "hydrocarbyl carbonyloxy group" means "C 1-18 The term "hydrocarbyl carbonyl group" refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group." "C 1-18The "hydrocarbylcarbonyloxy group" is not particularly limited, and examples thereof include a "C 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, a hexylcarbonyloxy group, and the like. 1-18 Alkylcarbonyloxy group; cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, etc. 3-18 Alicyclic carbonyloxy group; phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenanthrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc. 6-18 arylcarbonyloxy group" and the like.

[0025] In this specification, "C 1-18 The hydrocarbyloxycarbonyl group is defined as "C 1-18 The term "hydrocarbyloxy group" refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbyloxy group." "C 1-18 The "hydrocarbyloxycarbonyl group" is not particularly limited, and examples thereof include "C methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, neopentyloxycarbonyl group, etc. 1-18 alkoxycarbonyl group; cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 2-methylcyclopentyloxycarbonyl group, 3-methylcyclopentyloxycarbonyl group, 2-methylcyclohexyloxycarbonyl group, 3-methylcyclohexyloxycarbonyl group, 4-methylcyclohexyloxycarbonyl group, etc. 3-18Alicyclic oxycarbonyl group; phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenanthrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc. 6-18 aryloxycarbonyl group" and the like.

[0026] In this specification, "C 1-18 The term "hydrocarbyloxycarbonyloxy group" means "C 1-18 The term "hydrocarbyloxycarbonyl group" refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group." "C 1-18 The "hydrocarbyloxycarbonyloxy group" is not particularly limited, and examples thereof include a "C 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, an n-hexyloxycarbonyloxy group, and the like. 1-18 alkoxycarbonyloxy group; cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. 3-18 Alicyclic oxycarbonyloxy group; phenoxycarbonyloxy group, naphthoxycarbonyloxy group, acenaphthyloxycarbonyloxy group, phenanthrenyloxycarbonyloxy group, anthracenyloxycarbonyloxy group, etc. 6-18 aryloxycarbonyloxy group" and the like.

[0027] In this specification, "C 1-18 A "hydrocarbylamino group" is one "C 1-18 "Hydrocarbyl group" means a group attached to an amino group. "C 1-18The "hydrocarbylamino group" is not particularly limited, and examples thereof include 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, an n-hexylamino group, and the like. 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.

[0028] As used herein, "diC 1-18 A "hydrocarbylamino group" is a group consisting of two identical or different "C 1-18 "Hydrocarbyl group" means a group attached to an amino group. "JiC 1-18 The "alkylamino 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-Nn-propylamino group, an N-isopropyl-N-methylamino group, an Nn-butyl-N-methylamino group, "Di-C" groups such as N-isobutyl-N-methylamino group, Nt-butyl-N-methylamino group, N-methyl-Nn-pentylamino group, Nn-hexyl-N-methylamino group, N-ethyl-Nn-propylamino group, N-ethyl-N-isopropylamino group, Nn-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, Nt-butyl-N-ethylamino group, N-ethyl-Nn-pentylamino group, and N-ethyl-Nn-hexylamino group. 1-18Alkylamino group; dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. 3-18 Alicyclic amino group; diphenylamino group, phenylnaphthylamino group, etc. 6-18 Arylamino group; N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. 1-18 Alkyl-NC 3-18 Cycloalkylamino group; N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. 1-18 Alkyl-NC 6-18 arylamino group" and the like.

[0029] In this specification, "C 1-18 The term "hydrocarbylaminocarbonyl group" means "C 1-18 The term "hydrocarbylamino group" refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group." "C 1-18 The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include a "C aminocarbonyl group" 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. 3-18Alicyclic aminocarbonyl group; phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc. 6-18 arylaminocarbonyl group.

[0030] As used herein, "diC 1-18 The hydrocarbyl aminocarbonyl group is a di-C 1-18 The term "hydrocarbylamino group" refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group." "JiC 1-18 The "hydrocarbylamino 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-Nn-propylaminocarbonyl group, an N-isopropyl-N-methylaminocarbonyl group, an Nn-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an Nt-butyl-N-methylaminocarbonyl group, an N-methyl-Nn-pentylaminocarbonyl group, an Nn-hexyl-N-methylaminocarbonyl group, "Di-C" groups such as N-ethyl-Nn-propylaminocarbonyl group, N-ethyl-N-isopropylaminocarbonyl group, Nn-butyl-N-ethylaminocarbonyl group, N-ethyl-N-isobutylaminocarbonyl group, N-t-butyl-N-ethylaminocarbonyl group, N-ethyl-Nn-pentylaminocarbonyl group, and N-ethyl-Nn-hexylaminocarbonyl group. 1-18 Alkylamino group; dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. 3-18 Alicyclic aminocarbonyl group; diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group, etc. 6-18 arylaminocarbonyl group" and the like.

[0031] In this specification, "C 1-18 The term "hydrocarbyl carbonyl amino group" means "C 1-18 The term "hydrocarbyl carbonyl group" refers to a group in which an amino group is bonded to a "hydrocarbyl carbonyl group." "C 1-18 The "hydrocarbylcarbonylamino group" is not particularly limited, and examples thereof include a "C10 carbonylamino group" such as a methylcarbonylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, an i-propylcarbonylamino group, an n-butylcarbonylamino group, an i-butylcarbonylamino group, a sec-butylcarbonylamino group, a t-butylcarbonylamino group, an n-pentylcarbonylamino group, an i-pentylcarbonylamino group, or an n-hexylcarbonylamino group. 1-18 Alkylcarbonylamino group; cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. 3-18 Alicyclic carbonylamino group; phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenanthrenylcarbonylamino group, anthracenylcarbonylamino group, etc. 6-18 arylcarbonylamino group" and the like.

[0032] In this specification, "C 1-18 The term "hydrocarbylaminocarbonyloxy group" means "C 1-18 The term "hydrocarbylaminocarbonyl group" refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group." "C 1-18 The hydrocarbylaminocarbonyloxy group is not particularly limited, and examples thereof include a methylaminocarbonyloxy group, an ethylaminocarbonyloxy group, an n-propylaminocarbonyloxy group, and the like. 1-18 "C alkylaminocarbonyloxy group"; "C cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. 3-18Alicyclic aminocarbonyloxy group; phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc. 6-18 arylaminocarbonyloxy group" and the like.

[0033] As used herein, "diC 1-18 The hydrocarbylaminocarbonyloxy group is a di-C 1-18 The term "hydrocarbylaminocarbonyl group" refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group." "JiC 1-18 The hydrocarbylaminocarbonyloxy group is not particularly limited, and examples thereof include "di-C" such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, and di-n-propylaminocarbonyloxy group. 1-18 alkylaminocarbonyloxy group" and the like.

[0034] In this specification, "C 1-18 The term "hydrocarbylaminocarbonylamino group" means "C 1-18 "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. "C 1-18 The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "C methylaminocarbonylamino group, ethylaminocarbonyloxy group, n-propylaminocarbonylamino group, etc. 1-18 "C alkylaminocarbonylamino group"; "C cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. 3-18 Alicyclic aminocarbonylamino group; phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. 6-18 arylaminocarbonylamino group" and the like.

[0035] 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. "JiC 1-18The hydrocarbylaminocarbonylamino group is not particularly limited, and examples thereof include "di-C" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and di-n-propylaminocarbonylamino group. 1-18 alkylaminocarbonylamino group" and the like.

[0036] In this specification, "C 1-18 The term "hydrocarbyloxycarbonylamino group" means "C 1-18 "Hydrocarbyloxycarbonyl group" means a group bonded to an amino group. "C 1-18 The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc. 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.

[0037] In this specification, "C 1-18 The term "hydrocarbylthio group" means "C 1-18 The term "hydrocarbyl group" refers to a group having a sulfur atom (-S-) bonded to a "hydrocarbyl group." "C 1-18 The "hydrocarbylthio group" is not particularly limited, and examples thereof include a 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, and the like. 1-18Alkylthio 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; phenylthio group, 1-naphthylthio group, 2-naphthylthio group, acenaphthylthio group, phenanthrenylthio group, anthracenylthio group, etc. 6-18 arylthio group" and the like.

[0038] In this specification, "C 1-18 The term "hydrocarbylsulfinyl group" means "C 1-18 The term "hydrocarbyl group" refers to a group having a sulfinyl group (-S(=O)-) bonded to a "hydrocarbyl group." "C 1-18 The "hydrocarbylsulfinyl group" is not particularly limited, and examples thereof include a "C methylsulfinyl group, an ethylsulfinyl group, an n-propylsulfinyl group, an i-propylsulfinyl group, an n-butylsulfinyl group, a t-butylsulfinyl group, a pentylsulfinyl group, a hexylsulfinyl group, etc. 1-18 "C alkylsulfinyl group"; "C alkylsulfinyl group" such as cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-methylcyclohexylsulfinyl group, 3-methylcyclohexylsulfinyl group, and 4-methylcyclohexylsulfinyl group; 3-18 Alicyclic sulfinyl group; phenylsulfinyl group, naphthylsulfinyl group, acenaphthylsulfinyl group, phenanthrenylsulfinyl group, anthracenylsulfinyl group, etc. 6-18 arylsulfinyl group" and the like.

[0039] In this specification, "C 1-18 The term "hydrocarbylsulfonyl group" means "C 1-18 It means a group in which a sulfonyl group (-SO2-) is bonded to a "hydrocarbyl group." "C 1-18 The hydrocarbylsulfonyl group is not particularly limited, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, an n-butylsulfonyl group, a t-butylsulfonyl group, a pentylsulfonyl group, etc. 1-18 Alkylsulfonyl group; cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, 4-methylcyclohexyl group, etc. 3-18 Alicyclic sulfonyl group; phenylsulfonyl group, naphthylsulfonyl group, acenaphthylsulfonyl group, phenanthrenylsulfonyl group, anthracenylsulfonyl group, etc. 6-18 arylsulfonyl group" and the like.

[0040] In this specification, 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 due to the action of an acid. The "acid dissociable group" is not particularly limited, and examples thereof include t-butyl group, t-amyl group, 1,1-dimethylpropyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group, and the like.

[0041] 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, C 1-8 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 Examples of the hydrocarbylsulfonyl group include a divalent carbon atom at any position except for the terminal of the above-mentioned substituent, which may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0042] [1. Method for producing metatungstate compound] A method for producing a metatungstate compound according to one embodiment of the present invention is a method for producing a metatungstate compound represented by the following general formula (I-1) or (I-2) (hereinafter also referred to as "metatungstate compound (I-1)" or "metatungstate compound (I-2)"), and includes a step of salt exchange in an acidic solution having a pH of less than 3. (A + )5·[H3W 12 O 40 ] 5- (I-1) (A' 2+ )5·([H3W 12 O 40 ] 5- )2(I-2) [In formulas (I-1) and (I-2), A + each independently represents an onium cation; A' 2+ each independently represents an onium dication. In addition, [H3W 12 O 40 ] 5- This statement includes cases where protons are contained within the Keggin shell and cases where protons are contained outside the Keggin shell ((H + )·[H2W 12 O 40 ] 6- ) is also included in both cases.

[0043] [1-1. Salt exchange process] A metatungstate compound represented by general formula (I-1) or (I-2) can be selectively produced by salt exchange between a metatungstate represented by the following general formula (II) (hereinafter also referred to as "metatungstate (II)") and an onium salt represented by the following general formula (III-1) or (III-2) (hereinafter also referred to as "onium salt (III-1)" or "onium salt (III-2)") in an acidic solution of less than pH 3. (B + )6·[H2W 12 O 40 ] 6- (II) [In formula (II), B + are each independently H + , a metal ion, or an ammonium ion. A + X - (III-1) A' 2+ ·(X - )2(III-2) [In formulas (III-1) and (III-2), A + represents an onium cation; A' 2+ represents an onium dication; X - represents a monovalent counter anion.

[0044] [1-1-1. Metatungstate(II)] The metatungstate (II) used in this embodiment is not particularly limited, and any known or commonly used metatungstate can be used. (B + )6·[H2W 12 O 40 ] 6- (II) Metatungstic acid is a type of isopolyoxotungstic acid, an anionic metal oxide cluster, [H2W 12 O 40 ] 6- It is written as follows. In addition, in the general formula (II), B + are each independently H + , a metal ion, or an ammonium ion, and metatungstate (II) may contain one or more of these counter cations.

[0045] B + From the viewpoint of promoting the salt exchange reaction, + , Li + , Na + , K + , Rb + , Cs + , B.E. 2+ , Mg2+ , Ca 2+ , Sr 2+ , B.A. 2+ , Co 3+ , Bi 3+ , Zr 4+ , Hf 4+ , Bi 5+ , N.H. 4+ or a combination thereof, preferably H + , Na + , K + , Mg 2+ , Ca 2+ , N.H. 4+ or a combination thereof is more preferred, + , Na + , K + , N.H. 4+ Or a combination of these is more preferable.

[0046] Examples of commercially available metatungstate (II) include ammonium metatungstate hydrate manufactured by Merck & Co.; ammonium metatungstate manufactured by Nippon Inorganic Chemical Industry Co., Ltd.; and the like.

[0047] [1-1-2. Onium salt (III-1) or (III-2)] The onium salt (III-1) or (III-2) used in the present embodiment is not particularly limited, and any known or commonly used onium salt can be used. A, which is the cation moiety of the onium salt (III-1), + represents an onium cation, and X, which is the anion portion of the onium salt (III-1), - represents a monovalent counter anion. A', which is the cation portion of the onium salt (III-2), 2+ represents an onium dication, and X, which is the anion portion of the onium salt (III-2), - represents a monovalent counter anion. A + X - (III-1) A' 2+ ·(X - )2(III-2)

[0048] [1-1-2-1. Cation moiety of onium salt (III-1) or (III-2)] A + Or A' 2+ From the viewpoint of improving the actinic ray sensitivity and / or radiation sensitivity, the onium cation or onium dication is preferably an onium cation or onium dication having at least one unsaturated bond which may have a substituent, and the unsaturated bond may be, for example, a carbon-carbon double bond or a carbon-carbon triple bond, and more preferably a carbon-carbon double bond, and even more preferably a benzene ring. In addition, the onium cation may be, for example, an organic sulfonium cation, an organic iodonium cation, an organic quaternary ammonium cation, etc. Examples of the onium dication include, for example, an organic sulfonium dication, an organic iodonium dication, an organic ammonium dication, etc.

[0049] [1-1-2-1-1. Organic sulfonium cation or organic sulfonium dication] The organic sulfonium cation is not particularly limited, and any known and commonly used organic sulfonium cation can be used. For example, the organic sulfonium cation represented by the formula (IV) can be mentioned.

[0050] [ka]

[0051] In formula (IV), R 1A , R 1B and R 1C are each independently 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 1A , R 1B and R 1Ca divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Also, the above R 1A , R 1B and R 1C The hydrogen atoms contained in the above 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 Hydrocarbyloxycarbonyloxy group, or C 1-18 A hydrocarbylthio group in which a divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Further R 1A , R 1B and R 1C Any two of these are directly connected to each other via 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 (IV).

[0052] R in formula (IV) 1A , R 1B and R 1C Each of the C groups independently may have a substituent. 6-18It is preferably an aryl group. 6-18 The substituent of the aryl group is a halogen atom, a haloalkyl group, a hydroxyl group, a nitro group, a cyano group, a C 1-12 A hydrocarbylthio group is preferred, a halogen atom, C 1-4 A haloalkyl group or a nitro group is more preferred.

[0053] The organic sulfonium dication is not particularly limited, and any known and commonly used organic sulfonium dication can be used. For example, the organic sulfonium dication represented by the formula (V) can be mentioned.

[0054] [ka] In formula (V), R 2A , R 2B , R 2C and R 2D each independently represents a C which may have a substituent 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 2A , R 2B , R 2C and R 2D a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); K 2A , K 2B and L each independently represent C which may have a substituent. 1-18 represents a hydrocarbylene group, Above K 2A , K 2Band a divalent carbon atom at any position of L may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Also, the above R 2A , R 2B , R 2C , R 2D , K 2A , K 2B and the hydrogen atom contained in L is, for example, (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl 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 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 Hydrocarbyloxycarbonyloxy group, or C 1-18 A hydrocarbylthio group in which a divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); R 2A , R 2B and K 2A Any two of and / or R 2C , R 2D and K 2B Any two of the above 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 sulfur atom in formula (V).

[0055] Specific examples of the organic sulfonium cation or organic sulfonium dication include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalene-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(naphthalene- 1-yl)(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,d]thiophene-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b]thiophene-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, (2-bromoethyl)diphenylsulfonium cation, dimesityl(trifluoromethyl)sulfonium cation, tri-p-tolylsulfonium cation, etc. can be exemplified.

[0056] [1-1-2-1-2. Organic iodonium cation] The organic iodonium cation is not particularly limited, and any known and commonly used organic iodonium cation can be used. For example, the organic iodonium cation represented by the formula (VI) can be mentioned.

[0057] [ka]

[0058] In formula (VI), R 3A and R 3B are each independently 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 3A and R 3B a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Also, the above R 3A and R 3BThe hydrogen atoms contained in the above 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, or C 1-18 In the hydrocarbyloxycarbonyloxy group, a divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Further R 3A and R 3B 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 (VI).

[0059] R in formula (VI) 3A and R 3B Each of the C groups independently may have a substituent. 6-18 It is preferably an aryl group. 6-18 The substituent of the aryl group is a halogen atom, a haloalkyl group, a hydroxyl 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, or C 1-12Hydrocarbyloxycarbonyloxy group is preferred, 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 the 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] [1-1-2-1-3. Organic quaternary ammonium cations] The organic quaternary ammonium cation is not particularly limited, and any known and commonly used organic quaternary ammonium cation can be used. For example, the organic quaternary ammonium cation represented by formula (VII) can be mentioned.

[0062] [ka]

[0063] In formula (VII), R 4A , R 4B , R 4C and R 4D are each independently 1-18 Alkyl group, C 1-18 Alkynyl group, C 1-18 represents an alicyclic group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 4A , R 4B , R 4C and R 4D a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Also, the above R 4A , R 4B , R 4C and R 4D The hydrogen atoms contained in the above 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, C1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 In the hydrocarbylthio group, a divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Further R 4A , R 4B , R 4C and R 4D Any two of these are directly connected to each other via 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 (VII).

[0064] R in formula (VII) 4A , R 4B , R 4C and R 4D Each of the C groups independently may have a substituent. 1-18 is preferably a hydrocarbyl group, C 1-12 Alkyl 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, trimethylethylammonium cation, dimethyldiethylammonium cation, dimethylethylpropylammonium cation, methylethylpropylbutylammonium cation, trimethylphenylammonium cation, triethylhexylammonium cation, triethylcyclohexylammonium cation, and dodecyltrimethylammonium cation.

[0066] [1-1-2-2. Anion part of onium salt (III-1) or (III-2)] X, which is the anion portion of the onium salt (III-1) or (III-2) - represents a monovalent counter anion. A + X - (III-1) A' 2+ ·(X - )2(III-2)

[0067] X - The anion is not particularly limited, and examples thereof include inorganic anions and organic anions. Examples of inorganic or organic anions include F - , Cl - , Br - , I - Halide ions such as; hydroxide ions; HSO4 - , CF3SO3 - , C2F5SO3 - , C3F7SO3 - , C4F9SO3 - , p-CH3(C6H4)SO3 - , ClSO3 - Sulfonate ion such as; perchlorate ion; nitrate ion; (C6F5)4B - , BF4 - borate ions such as PF6 - , (PF5OH)- , ((CF3CF2)3PF3) - Fluorophosphate ion such as (CF3SO2)2N - , (FSO2)2N - Imide ions such as SbF6 - Antimonate ion such as AsF6 - Arsenate ions such as AlCl4 - ;BiF6 - The following can be given as examples:

[0068] X - From the viewpoint of promoting the salt exchange reaction, Br - , Cl - , I - , Br 3- , O.H. - , HSO4 - , CF3SO3 - , C2F5SO3 - , C3F7SO3 - , C4F9SO3 - , p-CH3(C6H4)SO3 - , ClSO3 - , ClO4 - , NO3 - , (C6F5)4B - , BF4 - , PF6 - , SbF6 - , AlCl4 - , BiF6 - , AsF6 - , (CF3SO2)2N - , (FSO2)2N - Preferably, Br - , Cl - , I - , O.H. - , CF3SO3 - , C4F9SO3 - , BF4 - , PF6 - , SbF6 - , (CF3SO2)2N - , (FSO2)2N - It is more preferable that - , Cl - , CF3SO3 -, BF4 - , PF6 - , SbF6 - , (CF3SO2)2N - , (FSO2)2N - It is even more preferable that:

[0069] [1-1-2-3. Specific examples of onium salt (III-1) or (III-2)] Commercially available onium salts (III-1) or (III-2) include, for example, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, diphenyl(4-methoxyphenyl)sulfonium trifluoromethanesulfonate, 4-methylphenyldiphenylsulfonium nonafluorobutanesulfonate, tris(4-methylphenyl)sulfonium nonafluorobutanesulfonate, tributylmethylammonium bis(trifluoromethanesulfonyl)imide, methyltrioctylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium bromide, tetrabutylammonium hexafluorophosphate, N-ethyl-N-(2-methoxyethyl)-N,N-dimethylammonium bis(trifluoromethanesulfonyl)imide, and benzyl(4-hydroxyphenyl)methylsulfonium hexafluorophosphate, manufactured by Tokyo Chemical Industry Co., Ltd. 1,2-Diphenylsulfonium tetrafluoroborate, trimethylsulfonium bromide, 4-hydroxyphenyldimethylsulfonium methylsulfate, (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium bromide, trimethylsulfonium hydroxide, triphenylsulfonium nonafluoro-1-butanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenyl(4-(phenylthio)phenyl)sulfonium hexafluoroantimonate, diphenyl(4-(phenylthio)phenyl)sulfonium hexafluorophosphate, (3-chloropropyl)diphenylsulfonium tetrafluoroborate, (2-carboxyethyl)dimethylsulfonium chloride, (2-carboxyethyl)dimethylsulfonium bromide, tri-p-tolylsulfonium trifluoromethanesulfonate, (difluoromethyl)bis(2,5-Dimethylphenyl)sulfonium tetrafluoroborate, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium hexafluoroantimonate, tributylsulfonium iodide, (thiodi-4,1-phenylene)bis(diphenylsulfonium)bis(hexafluorophosphate), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, bis(2,4,6-trimethylpyridine)iodonium hexafluorophosphate, bis(4-fluorophenyl)iodonium trifluoromethanesulfonate, ethynyl(phenyl)iodonium tetrafluoroborate, (4-(trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, (4-(trifluoromethyl)phenyl)(2,4,6-Trimethylphenyl)iodonium trifluoromethanesulfonate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, benzyltrimethylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldodecyldimethylammonium chloride, tetrabutylammonium chloride, tetraamylammonium chloride, benzoylcholine chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium bromide, tetraheptylammonium bromide, tetra-n-octylammonium bromide, 1-butyl-1-methylpiperidinium bromide, 1-methyl-1-propylpiperidinium bromide, benzoylcholine bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide, trimethylphenylammonium bromide, 3-(trifluoromethyl)phenyltrimethylammonium bromide, 4-ethyl-4- Examples of the methyl morpholinium bromide include 3-(trifluoromethyl)phenyl trimethylammonium iodide, acetylcholine iodide, acetylthiocholine iodide, benzoylcholine iodide, benzoylthiocholine iodide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, 3-(trifluoromethyl)phenyl trimethylammonium hydroxide, tetrabutylammonium tetrafluoroborate tetrabutylammonium hexafluorophosphate, amyltriethylammonium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, methyltri-n-octylammonium hydrogen sulfate, diethyl(methyl)propylammonium bis(fluorosulfonyl)imide, and 1-ethyl-1-methylpyrrolidinium tetrafluoroborate.

[0070] [1-1-3. Acid solution] By carrying out salt exchange between metatungstate (II) and onium salt (III-1) or (III-2) in an acidic solution, a metatungstate compound represented by general formula (I-1) or (I-2) can be selectively produced. The pH of the acidic solution is preferably less than 3, more preferably 2.7 or less, even more preferably 2.6 or less, particularly preferably 2.5 or less, and may be about 3 or less.

[0071] The type of acid contained in the acidic solution is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, and phosphoric acid; organic acids having a carboxy group such as tartaric acid, oxalic acid, formic acid, acetic acid, propionic acid, malic acid, lactic acid, citric acid, succinic acid, maleic acid, fumaric acid, glycolic acid, trifluoroacetic acid, and trichloroacetic acid; and organic acids having a sulfo group such as methanesulfonic acid, ethanesulfonic acid, sulfosuccinic acid, metatoluenesulfonic acid, and paratoluenesulfonic acid. The above acids may be used alone or in combination of two or more. The acid may vary depending on the solvent used, but is preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, oxalic acid, trichloroacetic acid, methanesulfonic acid, or meta- or para-toluenesulfonic acid, and more preferably hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or formic acid.

[0072] As a reaction pathway and mechanism by which the metatungstate compound (I-1) or (I-2) can be selectively produced by carrying out a salt exchange reaction in an acidic solution, it is speculated that metatungstate (II) reacts with [H3W 12 O 40 ] 5- It is thought that the ion beam exists in the form of a sigma-based ...

[0073] [1-2. Other processes] The method for producing a metatungstate compound according to the present embodiment may include other steps, which are common operations performed by a person skilled in the art to isolate and purify the target compound after the salt exchange reaction. The other steps are not particularly limited, and include, for example, steps of quenching the reaction, salting out by adding a poor solvent, filtration, separation by liquid-liquid extraction, purification by chromatography, recrystallization, etc.

[0074] [1-3. Number of onium cations or onium dications contained in metatungstate compound (I-1) or (I-2)] According to the method for producing a metatungstate compound according to this embodiment, it is possible to selectively produce the metatungstate compound (I-1) or (I-2) containing five onium cations or five onium dications. The number of onium cations contained in the metatungstate compound can be determined, for example, by XRF analysis or XPS analysis.

[0075] When the onium cation contained in the metatungstate compound is an organic sulfonium cation or an organic sulfonium dication, for example, the molar ratio of S and W in the metatungstate compound can be determined by XRF analysis, a calibration curve method, or SQX analysis using the fundamental parameter (FP) method. In addition, the molar ratio of S and W in the metatungstate compound can be determined by XPS analysis to determine the atomic % of each element based on the peak areas of S2p and W4f.

[0076] When the onium cation contained in the metatungstate compound is an organic iodonium cation, the molar ratio of I and W in the metatungstate compound can be determined, for example, by XRF analysis, a calibration curve method, or SQX analysis using the fundamental parameter (FP) method. The molar ratio of I and W in the metatungstate compound can be determined by XPS analysis to determine the atomic % of each element based on the peak areas of I3d and W4f.

[0077] Furthermore, when the onium cation contained in the metatungstate compound is an organic ammonium cation, the molar ratio of N and W in the metatungstate compound can be determined, for example, by XRF analysis, a calibration curve method, or SQX analysis using the fundamental parameter (FP) method. Also, the molar ratio of N and W in the metatungstate compound can be determined by determining the atomic% of each element based on the peak areas of N1s and W4f by XPS analysis.

[0078] [2. Metatungstate compounds for resists] The hexavalent anion metatungstate ([H2W 10 O 40 ] 6- ), it was difficult to selectively produce a metatungstate compound containing five onium cations or onium dications represented by general formula (I-1) or (I-2). That is, when produced by a conventional method, a mixture of metatungstate compounds containing 4 to 6 onium cations or onium dications was obtained, and it was not possible to selectively produce a metatungstate compound containing five onium cations or onium dications. In contrast, the method for producing a metatungstate compound according to the present embodiment makes it possible to selectively produce a metatungstate compound (I-1) or (I-2) containing five onium cations or onium dications. The metatungstate compound (I-1) or (I-2) has improved actinic ray and / or radiation sensitivity due to the onium cations or onium dications, and is also uniform, making it suitable as a metatungstate compound for resists.

[0079] [3. Resist materials] The resist material according to the present embodiment contains a metatungstate compound (I-1) or (I-2). The resist material may also contain an organic solvent.

[0080] [3-1. Organic solvents] The organic solvent used in the present embodiment is not particularly limited, and any known and commonly used organic solvent can be used. The organic solvent is preferably an organic solvent capable of uniformly dissolving or dispersing the metatungstate compound (I-1) or (I-2).

[0081] Examples of the organic solvent include polar solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, nitrile-based solvents, and aprotic polar solvents, and non-polar solvents such as hydrocarbon-based solvents. These organic solvents may be used alone or in combination of two or more.

[0082] Specific examples of polar solvents include, for example, Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); Ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; Ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); Nitrile solvents such as acetonitrile, propionitrile, benzonitrile, etc.: aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactams, δ-lactams, dimethylsulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea; Non-polar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene; etc. The organic solvents may be used alone or in combination of two or more kinds.

[0083] The organic solvent contained in the resist material according to the present embodiment is preferably a polar solvent in terms of coatability, and more preferably contains an amide-based solvent, an ester-based solvent, an alcohol-based solvent, or a ketone-based solvent in terms of solubility. The amide-based solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. In addition, the ester-based solvent or alcohol-based solvent is preferably one having an ester bond and / or a hydroxyl group in terms of solubility, and among the above, it is preferably at least one selected from the group consisting of propylene glycol monomethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, and propylene glycol monomethyl ether acetate.

[0084] When the organic solvent contains both an amide solvent and an ester solvent, the blending ratio (mass ratio) of the amide solvent to the ester solvent is preferably 1:99 to 40:60, and more preferably 5:95 to 20:80.

[0085] The content of the organic solvent in the resist material is not particularly limited and can be appropriately set depending on the method for applying the resist material to a substrate or the like, the thickness of the applied film, etc. The content of the organic solvent in the resist material is preferably such that the solids concentration of the resist material is 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably in the range of 0.2 to 10 mass%.

[0086] [3-2.Other] The resist material according to this embodiment may further contain, as desired, compatible additives such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like. The resist material according to the present embodiment preferably does not contain an epoxy resin, and more preferably does not contain hydrogen peroxide.

[0087] [4. Pattern formation method] The pattern forming method according to this embodiment includes the steps of applying a resist material to a substrate, exposing the resist film formed by the application step, and developing the exposed resist film.

[0088] [4-1. Coating process] The pattern formation method according to this embodiment includes a step of applying a resist material to a substrate.

[0089] <Substrate> The substrate used in this embodiment is not particularly limited, and any known and commonly used substrate may 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 substrates made of metals such as silicon wafers, copper, chromium, iron, and aluminum, and substrates made of inorganic substances such as glass, titanium oxide, and silicon dioxide. The size, shape, etc. of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or may be a thin plate-shaped substrate.

[0090] The surface of the substrate may be subjected to a surface treatment as necessary. In the case of a substrate having a hydroxyl group on the surface layer of the substrate, the surface of the substrate is treated with a silane coupling agent capable of reacting with the hydroxyl group, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic, and thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane coupling agent include hexamethyldisilazane (HMDS) and the like.

[0091] <Application method> The method of applying the resist material onto the substrate is not particularly limited, and any known and commonly used method can be used. As the application method, for example, a CVD method (chemical vapor deposition method) such as thermal CVD, plasma CVD, and photo CVD; a PVD method (physical vapor deposition method) such as vacuum deposition, plasma assisted deposition, sputtering, and ion plating can be used as a dry method. In addition, for example, a coating method such as spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing can be used as a wet method.

[0092] As a method for applying the resist material according to the present embodiment onto a substrate, a wet method such as spin coating or screen printing is preferably used, and spin coating is more preferably used, from the viewpoint of forming a uniform film thickness, etc. After forming the coating film, a backside rinse, an edge bead removal step, etc. can be performed to remove the edge bead.

[0093] The method for drying the resist film formed by applying the resist material onto the 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 appropriately set depending on the type of resist film, the 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.

[0094] The thickness of the resist film after drying is not particularly limited, but is preferably from 0.5 to 100 nm, more preferably from 1 to 75 nm, and even more preferably from 1 to 60 nm.

[0095] [4-2. Exposure process] The pattern forming method according to this embodiment includes a step of exposing the resist film formed in the above-mentioned coating step.

[0096] As an exposure device in the exposure step of the resist film, for example, an ArF exposure device, an electron beam lithography device, an EUV exposure device, etc. In the exposure step, exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by lithography using direct irradiation with an electron beam without using a mask pattern.

[0097] The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser (wavelength 193 nm), KrF excimer laser (248 nm), F2 excimer laser (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays may be used.

[0098] The exposure dose on the resist film is 1 to 200 mJ / cm in the case of an ArF excimer laser or a KrF excimer laser. 2 is preferably 20 to 60 mJ / cm 2 In the case of extreme ultraviolet rays, the exposure amount is, for example, 500 mJ / cm. 2 Less than 0.1 to 200 mJ / cm2 is preferably 3 to 100 mJ / cm 2 More preferably, the concentration is 5 to 50 mJ / cm 2 It is even more preferable that: For electron beams, 3μC / cm at 50kV 2 ~2mC / cm 2 It is preferable to expose with a dose of 10 μC / cm 2 ~1.5mC / cm 2 It is more preferable to expose to a dose of 1000 nm or less.

[0099] After the resist film is exposed to light, a bake (post-exposure bake (PEB)) treatment may or may not be performed. The bake conditions are not particularly limited and can be appropriately set depending on the type of resist film, the application, etc. The bake temperature is preferably 80 to 300°C, more preferably 150 to 250°C, and even more preferably 170 to 230°C, using a heating device such as a hot plate. The bake time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0100] [4-3. Development process] The pattern forming method according to the present embodiment includes a step of developing the exposed resist film. In the development step, the exposed resist film can be developed with a developer to form a pattern. A negative pattern forming process is performed when the exposed region remains as a pattern after development, and a positive pattern forming process is performed when the exposed region is removed after development. Whether a positive or negative pattern is formed can be appropriately selected depending on the resist material or the developer. After the development, the resist film may be washed with a rinse solution and then dried, and in some cases, a bake treatment may be further performed.

[0101] <Developer> The developer used in this embodiment may contain at least one organic solvent, such as a polar solvent, such as a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, a nitrile-based solvent, an amide-based solvent, or an ether-based solvent, or a hydrocarbon-based solvent.

[0102] Specific examples of the organic solvent include, for example, Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); Nitrile solvents such as acetonitrile, propionitrile, benzonitrile, etc.: Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; Ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; Hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene; These may be used alone or in combination of two or more.

[0103] Among these, the organic solvent used in the developer is preferably a polar solvent, and preferably contains an amide-based solvent, an alcohol-based solvent, or an ester-based solvent, and more preferably contains an amide-based solvent or an ester-based solvent and an alcohol-based solvent. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester-based solvent is preferably at least one selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate. The alcohol-based solvent is preferably at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol.

[0104] When the developer contains both an amide-based solvent or an ester-based solvent and an alcohol-based solvent, the blending ratio (weight ratio) of the amide-based solvent or the ester-based solvent to the alcohol-based solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0105] The method of developing the resist film exposed by using the developer is not particularly limited, and can use a known and commonly used method.The method of developing by using the developer can be, for example, the method of immersing the substrate having the resist film after exposure in the developer for a certain time (dip method), the method of spraying the developer on the surface of the resist film after exposure (spray method), the method of discharging the developer from a discharge nozzle at a certain speed toward the surface of the resist film after exposure on the substrate rotating at a certain speed (dynamic dispense method), etc.

[0106] <Rinse solution> After developing with the developer, a step of washing with a rinse liquid may be included. The rinse liquid is not particularly limited, and any known and commonly used liquid may be used. As the rinse liquid, an organic solvent that does not easily dissolve the resist pattern may be appropriately selected from the organic solvents contained in the developer.

[0107] The rinse liquid is not particularly limited, and may be, for example, at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. Among these, it is preferable to use at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent as the rinse liquid, it is more preferable to use at least one solvent selected from the group consisting of an alcohol solvent and an ester solvent, and it is even more preferable to use at least one alcohol solvent.

[0108] The alcohol-based solvent used in the rinse liquid is preferably a monohydric alcohol having 2 to 8 carbon atoms, and the monohydric alcohol may be any of linear, branched, and cyclic. Specific examples of the monohydric alcohol include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. These organic solvents may be used alone or in combination of two or more.

[0109] The rinse solution may contain, in addition to the organic solvents described above, an organic solvent other than the above or water. When the rinse solution contains water, the content of water is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on the total amount of the rinse solution.

[0110] The method of cleaning the resist pattern with the rinse liquid is not particularly limited, and any known and commonly used method can be used. Examples of the method of cleaning with the rinse liquid include a method of immersing the resist pattern in the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid on the surface of the resist pattern (spray method), and a method of discharging the rinse liquid from a discharge nozzle at a constant speed toward the surface of the resist pattern rotating at a constant speed (dynamic dispense method).

[0111] [5. Patterned Structure] The patterned structure according to this embodiment can be obtained by forming a pattern of the resist material on a substrate using the pattern formation method.

[0112] The average thickness of a part or the whole of the patterned structure according to this embodiment is not particularly limited and can be appropriately set depending on the intended use, etc. In the patterned structure, it is preferable that the part has an average thickness of 10 to 100 nm, more preferably 15 to 75 nm, and further preferably 20 to 60 nm.

[0113] Furthermore, the pitch of a part or the whole of the patterned structure according to this embodiment is not particularly limited and can be set appropriately depending on the intended use, etc. In the patterned structure, it is preferable that the patterned structure has a portion with a pitch of 100 nm or less, more preferable that the patterned structure has a portion with a pitch of 50 nm or less, and even more preferable that the patterned structure has a portion with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the above-described pattern formation method, it is possible to create portions with pitches of 50 nm, 20 nm, and 15 nm in part or all of the patterned structure.

[0114] [6. Electron beam or EUV resist materials] The resist material according to this embodiment has good sensitivity to electron beam and EUV light sources, and can therefore be suitably used as a resist material compatible with these exposure light sources. EXAMPLES

[0115] The present invention will be specifically described below by showing examples, but the present invention is not limited to these examples.

[0116] [1. Synthesis of metatungstate compounds] <Synthesis Example 1> Ammonium metatungstate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: ammonium metatungstate hydrate ((NH4)6[H2W 12 O 40 To 16.67 g of bis(2-trifluoromethylphenyl)phenylsulfonium chloride (10 g) were added 10 g of water and 1 mol / L hydrochloric acid solution, and the mixture was stirred at room temperature for 60 minutes. Then, an aqueous solution of 13.47 g of bis(2-trifluoromethylphenyl)phenylsulfonium chloride dissolved in 200 g of pure water was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was filtered, and the obtained 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 and the mixture was crystallized at room temperature to obtain the target compound shown below.

[0117] [ka] 1 H-NMR (400MHz, DMSO-D6): δ(ppm)=6.77(s, 0.60H), 7.65-8.35(m, 13H). 183W-NMR (20.84MHz, DMSO-D6): δ(ppm)=-87.59(s, 12W). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 712.3 (median) ([H4W 12 O 40 ] 4- )

[0118] <Synthesis Examples 2 to 8 and Comparative Synthesis Examples 1 to 2> In Synthesis Examples 2 to 8 and Comparative Synthesis Examples 1 and 2, metatungstate compounds were synthesized in a manner similar to that of Synthesis Example 1, except that the type, concentration, and amount of acid, the amount of water, the type and amount of onium salt, and the amount of pure water were changed as shown in Table 1 below. The following hexakis(bis(2-trifluoromethylphenyl)phenylsulfonium)metungstate obtained in Comparative Synthesis Example 1 is shown below. 1 H-NMR, 183 W-NMR and ESI-MS are shown, respectively.

[0119] [ka] 1 H-NMR (400MHz, DMSO-D6): δ(ppm)=5.97(s, 0.33H), 7.65-8.35(m, 13H). 183 W-NMR (20.84MHz, DMSO-D6): δ(ppm)=-100.13(s, 12W). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 712.3 (median) ([H4W 12 O 40 ] 4- )

[0120] The onium salts (1) and (2) shown in Table 1 are as follows. Onium salt (1): Bis(2-trifluoromethylphenyl)phenylsulfonium chloride Onium salt (2): Bis(4-tert-butylphenyl)iodonium sulfonate (MeOH solution)

[0121] In the above Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 and 2, the production ratio of the metatungstate compound containing five onium cations to the metatungstate compound containing six onium cations is as follows: 1 H-NMR peak at 6.77 ppm ([H 12 O 40 ] 5- The integral value of the peak near 5.97 ppm ([H2W 12 O 40 ] 6- The peak integrals of the two proton peaks were compared. The results are shown in the "Percentage" section of Table 1.

[0122] [Table 1]

[0123] From Table 1, it can be seen that in Synthesis Examples 1 to 8, which used an acidic solution with a pH of less than 3, a metatungstate compound containing five onium cations can be selectively obtained. Moreover, in Synthesis Examples 1 to 7, no metatungstate compound containing six onium cations was obtained.

[0124] In contrast, in Comparative Synthesis Example 1, in which no acidic solution was used, metatungstate compounds containing six onium cations were selectively obtained, and metatungstate compounds containing five onium cations were also obtained. In addition, even when an acidic solution was used, as in Comparative Synthesis Example 2, when the pH was greater than 3, a mixture was obtained in which metatungstate compounds containing five onium cations and metatungstate compounds containing six onium cations were mixed, and the metatungstate compounds containing six onium cations were more abundant.

[0125] [2. Preparation of resist material] As resist materials, the metatungstate compounds obtained in the above Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 and 2 were mixed with dimethylformamide and ethyl lactate as organic solvents in the amounts shown in Table 2 to prepare resist materials R-1 to R-10.

[0126] [Table 2]

[0127] [3. LS pattern formation] Resist materials R-1 to R-10 were applied onto a silicon wafer substrate using a spinner, and post-applied bake (PAB) treatment was performed on a hot plate at a temperature of 200° C. for 60 seconds, followed by drying to produce resist films M-1 to M-9 with a thickness of 50 nm. The thickness of the formed resist film was measured using a film thickness measuring device (JA Woollam's "M-2000D").

[0128] The resist films M-1 to M-10 were exposed through a mask using an EUV exposure machine while changing the exposure dose stepwise. After PEB treatment at 180°C for 60 seconds, development was performed at 23°C using a developer (DMF (10 parts by mass), IPA (90 parts by mass)) for 60 seconds, and rinsing was performed with IPA for 60 seconds to produce a negative 1:1 LS pattern with a line width of 50 nm. The optimal exposure dose Eop (mJ / cm) at which a LS pattern of the target size was formed was 2 ) was calculated, and the resist films M-1 to M-6 were 100 mJ / cm 2 and the resist film M-9 was 115 mJ / cm 2 and the resist film M-10 was 110 mJ / cm 2 For each of the resist films M-1 to M-10, a 1:1 LS pattern with a line width of 50 nm was fabricated in the same manner as above, using the optimum exposure dose determined above. Note that for the resist films M-7 and M-8, the optimum exposure dose was not confirmed, but it was 100 mJ / cm 2 was used as the optimum exposure.

[0129] <Temporal stability: CD change rate> The prepared LS pattern was observed from above with a scanning electron microscope (product name: S-9380) manufactured by Hitachi High-Technologies Corporation, and the line width (nm) was measured. The ratio of change in the pattern dimension (CD) of the line width of the produced LS pattern to that of the mask pattern (CD change rate) was calculated, and the stability of the resist bottle over time was evaluated according to the following criteria. The results are shown in Table 3. CD change rate = (|Line width of LS pattern - Mask pattern|) / (Mask pattern) x 100 ○: CD change rate is 5.0% or less △: CD change rate is greater than 5.0% and less than 7.5% ×: CD change rate is greater than 7.5%

[0130] [Table 3]

[0131] As shown in Table 3, the resist films M-9 and M-10 made using resist materials R-9 and R-10, which are mixtures of a metatungstate compound containing five onium cations and a metatungstate compound containing six onium cations, and which contain a higher amount of the metatungstate compound containing six onium cations, had large CD change rates of 12.0% and 8.0%, respectively.

[0132] In contrast, in the resist films R-1 to R-7 using resist materials R-1 to R7 containing a metatungstate compound containing five onium cations but not containing a metatungstate compound containing six onium cations, the CD change rate was smaller than 5.0%. In addition, in the resist film M-8 using resist material R-8, which is a mixture of a metatungstate compound containing five onium cations and a metatungstate compound containing six onium cations, and contains a larger amount of the metatungstate compound containing five onium cations, the CD change rate was 6.0%, which was a better result than the CD change rates of the resist films R-9 and R-10.

[0133] From the above, it can be seen that a resist material containing a metatungstate compound synthesized by a method of selectively synthesizing a metatungstate compound containing five onium cations, such as in Synthesis Examples 1 to 8, provides an excellent resist film.

Claims

1. A method for producing a metatungstate compound represented by general formula (I-1) or (I-2), carrying out salt exchange in an acidic solution having a pH of less than 3; A method for producing a metatungstate compound. (A ＋ ) ５ ・[H ３ W １２ O ４０ ] ５－ (--1) (A' ２＋ ) ５ ・([H ３ W １２ O ４０ ] ５－ ) ２ (--2) [In formulas (I-1) and (I-2), A ＋ each independently represents an onium cation; A' ２＋ each independently represents an onium dication.

2. 2. The method for producing a metatungstate compound according to claim 1, wherein the onium cation is at least one selected from the group consisting of an organic sulfonium cation, an organic iodonium cation, and an organic ammonium cation.

3. 2. The method for producing a metatungstate compound according to claim 1, wherein the acidic solution having a pH of less than 3 contains an inorganic acid, an organic acid having a carboxy group, or an organic acid having a sulfo group.

4. The method for producing a metatungstate compound according to claim 1, wherein the salt exchange is a salt exchange between a metatungstate represented by general formula (II) and an onium salt represented by general formula (III-1) or (III-2). (B ＋ ) ６ ・[H ２ W １２ O ４０ ] ６－ (II) _ ＋ ・︸ － (_.).) .' ２＋ ・(︸ － ) ２ (_). [In formula (II), B ＋ are each independently H ＋ , a metal ion, or an ammonium ion; In formulas (III-1) and (III-2), A ＋ represents an onium cation; A' ２＋ represents an onium dication; X － represents a monovalent counter anion.

5. A metatungstate compound for resist represented by general formula (I-1) or (I-2): (A ＋ ) ５ ・[H ３ W １２ O ４０ ] ５－ (--1) (A' ２＋ ) ５ ・([H ３ W １２ O ４０ ] ５－ ) ２ (--2) [In formulas (I-1) and (I-2), A ＋ each independently represents an onium cation; A' ２＋ each independently represents an onium dication.

6. A resist material comprising the metatungstate for resist according to claim 5 .

7. The resist material of claim 6 further comprising a solvent.

8. The resist material according to claim 6 or 7, which is a resist material for electron or EUV use.

9. A pattern structure formed by using the resist material according to claim 6 or 7.

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