Resist material, and pattern formation method

Abstract

The present invention provides a novel resist material which contains a heteropolyoxometalate having a modified lacunary site or a mixture thereof, the resist material being characterized in that the anion moiety of the heteropolyoxometalate having a modified lacunary site includes a plurality of polar groups having an acid-dissociable group. The present invention also provides a pattern formation method.

Description

Resist material and pattern forming method

[0001] The present invention relates to a resist material and a pattern forming method.

[0002] In recent years, advances in lithography techniques such as immersion lithography and EUV lithography have led to advances in circuit patterns. As lithography techniques advance, new resist materials are required to accommodate these advances.

[0003] In addition to conventional chemically amplified resists, new resist materials containing metal compounds, organometallic compounds, metal nanoparticles, metal clusters, etc. have been proposed.

[0004] For example, Patent Document 1 discloses a ZrO core. ２ , HfO ２ , TiO ２ Patent Document 2 discloses a nanoparticle polymer resist containing nanoparticles containing, for example, alkyl tin clusters (t-BuSn) １２ O １４ (OH) ６ (HCO ２ ) ２ A resist based on the above is disclosed.

[0005] U.S. Patent No. 9,696,624 WO2019 / 195522

[0006] An object of the present invention is to provide a novel resist material and a pattern formation method.

[0007] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that resist materials containing heteropolyacid salts or mixtures thereof, in which the deficiency sites of a heteropolyacid anion having deficiency sites are modified to introduce multiple polar groups having acid-dissociable groups, exhibit drastic changes in physical properties, such as solubility in a developer, between exposed areas to actinic rays and unexposed areas, and have completed the present invention.

[0008] That is, the present invention relates to the following inventions. <1> A resist material containing (A) a heteropolyacid salt having modified defect sites or a mixture thereof, wherein the anion moiety of the heteropolyacid salt having modified defect sites contains a plurality of polar groups having an acid-dissociable group. <2> The resist material according to <1>, which is a resist material that generates acid upon exposure and whose solubility in a developer is changed by the action of the acid. <3> The resist material according to <1>, wherein the acid-dissociable group is a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group. <4> The resist material according to <1>, wherein the anion moiety of the (A) heteropolyacid salt having modified defect sites or a mixture thereof is a heteropolyacid anion having defect sites and wherein the defect sites have been modified. <5> The resist material according to <4>, wherein the modification is achieved by bonding a group having one or more heteroatoms P, Si, Ge, or Sn, to which one or more organic groups are bonded, to the heteropolyacid anion having the vacant site via some or all of the heteroatoms, and the organic group has two or more polar groups having an acid-dissociable group. <6> The resist material according to <4>, wherein the organic group is a C group optionally having a substituent. １－１８ C is a hydrocarbyl group, which may have the above-mentioned substituent. １－１８ Any divalent carbon atom excluding the terminal carbon atom of the hydrocarbyl group may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １－１８ The resist material according to <5>, wherein two or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group. <7> The resist material according to <5>, wherein the organic group is represented by general formula (VII-2): [In general formula (VII-2), L ２Ｂ is an optionally substituted C １－１２In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ represents a group substituted with ２Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ｃ each independently represents a polar group having an acid-dissociable group; x represents an integer of 2 to 6; and * represents a bond between the organic group and a heteroatom such as P, Si, Ge, or Sn.

[0009] <8> The resist material according to <4>, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge. <9> The resist material according to <4>, wherein the heteropolyacid anion having a deficiency site is a defective Keggin-type heteropolyacid anion or a defective Dawson-type heteropolyacid anion. <10> The resist material according to <9>, wherein the defective Keggin-type heteropolyacid anion is represented by general formula (II-1), (II-2), or (II-3): [XM １１ O ３９ ] ｃ１１－ (II-1) [XM １０ O ３６ ] ｃ１２－ (II-2) [XM ９ O ３４ ] ｃ１３－ (II-3) (wherein X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.) <11> The resist material according to <9>, wherein the deficient Dawson-type heteropolyacid anion is represented by general formula (III-1), (III-2), or (III-3). [X ２ M １７ O ６１ ] ｃ２１－ (III-1) [X ２M １６ O ５８ ] ｃ２２－ (III-2) [X ２ M １５ O ５６ ] ｃ２３－ (III-3) (wherein X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.) <12> The resist material according to <1>, wherein the (A) heteropolyacid salt having modified deficiency sites or a mixture thereof is a heteropolyacid salt having modified deficiency sites represented by general formula (I) or a mixture thereof. (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In general formula (I), A ｍ＋ are each independently H ＋ , metal ions, NH ４ ＋ , an onium cation, or an onium dication; （ａｍ）－ represents a heteropolyacid anion in which the defective sites have been modified in a heteropolyacid anion having defective sites, and the heteropolyacid anion in which the defective sites have been modified in the heteropolyacid anion having defective sites contains a plurality of polar groups having an acid dissociable group, and m is an integer of 1 to 5, and a is a real number greater than 0.] <13> The resist material according to <1>, wherein the (A) defective site-modified heteropolyacid salt or mixture thereof is a defective site-modified heteropolyacid salt represented by general formula (I') or a mixture thereof. (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C'(a'm'+bn)-) (I') [In general formula (I'), A' ｍ’＋ are each independently H ＋ , metal ions, or NH ４ ＋ represents; B ｎ＋each independently represent an onium cation or an onium dication; C'(a'm'+bn)- represents a heteropolyacid anion obtained by modifying a heteropolyacid anion having defective sites, the defective sites of which are modified in the heteropolyacid anion having defective sites, the heteropolyacid anion having defective sites includes a plurality of polar groups having an acid-dissociable group, m' is an integer of 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0.] <14> The resist material according to <13>, wherein the onium cation is a sulfonium cation or an iodonium cation.

[0010] <15> The resist material according to <1>, further comprising (B) an acid diffusion controller. <16> The resist material according to <15>, wherein the (B) acid diffusion controller is (B1) a photodegradable base. <17> The resist material according to <1>, further comprising an organic solvent. <18> The resist material according to any one of <1> to <17>, which is a resist material that is sensitive to EUV, BEUV, or an electron beam. <19> A pattern formation method, comprising: forming a resist film using the resist material according to any one of <1> to <17>; exposing the resist film; and developing the exposed resist film using a developer.

[0011] According to the present invention, a novel resist material and a pattern formation method can be provided.

[0012] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0013] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0014] As used herein, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0015] In this specification, for example, "C １－６ " and other terms refer to the number of carbon atoms in the core group.

[0016] As used herein, "C １－１８ The term "hydrocarbylene group" refers to a divalent hydrocarbon group generated by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear or branched, or may be partially or entirely cyclic. The hydrocarbylene group includes alkylene groups, arylene groups, etc. Also, "C １－１８ The divalent carbon atom at any position of the "hydrocarbylene group" may be -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). １－１８ The "hydrocarbylene group" is not particularly limited, and examples thereof include "C" such as methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadiyl group, cyclohexanediyl group, oxyethane-1,1-diyl group, oxyethane-1,2-diyl group, oxypropane-1,3-diyl group, oxypropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, and oxyethyleneoxyethane-1,1-diyl group. １－１８ alkylene group"; 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 4,4'-biphenylene group, anthracenediyl group, phenanthrenediyl group, naphthacenediyl group, pyrenediyl group, perylenediyl group, chrysenediyl group, etc. ６－１８ arylene group" and the like.

[0017] As used herein, "C １－１８ The term "alkyl group" means a linear or branched alkyl group having 1 to 18 carbon atoms. １－１８ The divalent carbon atom at any position excluding the terminal contained in the "alkyl group" is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２However, adjacent divalent carbon atoms may not be replaced at the same time. １－１８ The "alkyl group" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an i-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1 , 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, and the like. １－１８ The alkyl group may have a divalent carbon atom at any position excluding the terminal, and the divalent carbon atom may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ The group substituted with - is not particularly limited, and examples thereof include a 2-methoxyethoxymethyl group, an ethoxycarbonylmethyl group, and the like.

[0018] As used herein, "C １－１８ The term "haloalkyl group" refers to "C １－１８ "C" means a group in which one or more hydrogen atoms of an "alkyl group" are substituted with halogen atoms. １－１８ 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.

[0019] As used herein, "C ２－１８The term "alkenyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkenyl group having one or more double bonds, and includes alkadienyl groups, alkatrienyl groups, etc. ２－１８ The "alkenyl group" is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a 1-propenyl group, an isopropenyl group (1-methylvinyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group.

[0020] As used herein, "C ２－１８ The term "alkynyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkynyl group having one or more triple bonds in the "alkyl group." ２－１８ The "alkynyl group" is not particularly limited, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group.

[0021] As used herein, "C ３－１８ The term "alicyclic group" refers to a hydrocarbon group having, in whole or in part, a monocyclic or polycyclic structure having 3 to 18 carbon atoms. Alicyclic groups also include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc. ３－１８ A divalent carbon atom at any position excluding the terminals contained in the "alicyclic group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). ３－１８The "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.

[0022] As used herein, the term "3- to 18-membered non-aromatic heterocyclic group" refers to a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and may be a monocyclic, polycyclic, or fused ring, and may be saturated or partially unsaturated. The "3- to 18-membered non-aromatic heterocyclic group" is not particularly limited, and examples thereof include an aziridinyl group, an azetidyl group, a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a thiomorpholinyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an oxetanyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an imidazolinyl group, an oxazolinyl group, a 2,5-diazabicyclo[2.2.1]heptyl group, a 2,5-diazabicyclo[2.2.2]octyl group, a 3,8-diazabicyclo[3.2.1]octyl group, a 1,4-diazabicyclo[4.3.0]nonyl group, a 1-azaadamantyl group, and a 2-azaadamantyl group.

[0023] As used herein, "C ２－１８The term "aryl group" means an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 2 to 10 carbon atoms. In the case of an aromatic heterocyclic group, a ring is formed by a carbon atom having 2 to 10 carbon atoms and one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and each may be a monocyclic ring, a polycyclic ring, or a fused ring. ２－１８ The "aryl group" is not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an azulenyl group, a pentalenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a phenanthrenyl group, an anthracenyl group, and the like.

[0024] As used herein, "C ７－１８ The term "aralkyl group" refers to "C １－１２ The substitutable portion of the "C alkyl group" is ２－１２ "C" means a group substituted with an "aryl group." ７－１８ The "aralkyl group" is not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0025] As used herein, "C １－１８ The term "hydrocarbyl group" refers to a monovalent group formed by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, aralkyl groups, and the like. １－１８ A divalent carbon atom at any position excluding the terminal contained in the "hydrocarbyl group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (however, adjacent divalent carbon atoms cannot be replaced at the same time). １－１８ The term "C" used in the definition of "hydrocarbyloxy group" and the like is used in the definition of "C" １－１８ The same applies to "hydrocarbyl group" and the like. １－１８ The "hydrocarbyl group" is not particularly limited, and examples thereof include "C １－１８alkyl group," "C ２－１８ alkenyl group," "C ２－１８ alkynyl group," "C ３－１８ “Alicyclic group”, “C ２－１８ aryl group," "C ７－１８ aralkyl groups, etc.

[0026] As used herein, "C １－１８ The term "hydrocarbyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group." １－１８ The "hydrocarbyloxy group" is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentoxy group, an i-pentoxy group, a sec-pentoxy group, an n-hexoxy group, an i-hexoxy group, a 1,1-dimethylpropyloxy group, a 1,2-dimethylpropyloxy group, a 2,2-dimethylpropyloxy group, a 1-methyl- "C" groups such as 2-ethylpropyloxy group, 1-ethyl-2-methylpropyloxy group, 1,1,2-trimethylpropyloxy group, 1,2,2-trimethylpropyloxy group, 1,1-dimethylbutyloxy group, 1,2-dimethylbutyloxy group, 2,2-dimethylbutyloxy group, 2,3-dimethylbutyloxy group, 1,3-dimethylbutyloxy group, 2-ethylbutyloxy group, 2-methylpentyloxy group, and 3-methylpentyloxy group １－１８ alkoxy group"; cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-methylcyclopentyloxycarbonylmethoxy group, 1-ethylcyclohexyloxycarbonylmethoxy group, 1-methyladamantyloxycarbonylmethoxy group, etc. ３－１８ alicyclic oxy group"; phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, azulenyloxy group, pentalenyloxy group, heptalenyloxy group, indacenyloxy group, acenaphthyloxy group, phenanthrenyloxy group, anthracenyloxy group, etc. ６－１８ aryloxy group."１－１８ The "hydrocarbyloxy group" includes "C １－１８ It is preferred that a divalent carbon atom at any position except the terminal contained in the "hydrocarbyl group" is replaced with -O-, -C(=O)-, and / or -C(=O)O-. １－１８ A "hydrocarbyloxycarbonylalkyloxy group" is more preferred, and from the viewpoint of solubility, it is even more preferred that the carbon bonded to the oxygen atom of the hydrocarbyloxy is a tertiary carbon. Specific examples of the hydrocarbyloxy include optionally substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, and the like.

[0027] As used herein, "C １－１８ The term "hydrocarbyl carbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyl group.” １－１８ The "hydrocarbyl carbonyl group" is not particularly limited, and examples thereof include "C" such as an acetyl group, a propionyl group, an isopropionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pentanoyl group, a 3-methylbutanoyl group, a pivaloyl group, a hexanoyl group, and a heptanoyl group. １－１８ alkylcarbonyl group"; cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, 2-methylcyclopentylcarbonyl group, 3-methylcyclopentylcarbonyl group, cyclohexylcarbonyl group, 2-methylcyclohexylcarbonyl group, 3-methylcyclohexylcarbonyl group, 4-methylcyclohexylcarbonyl group, adamantylcarbonyl group, etc. ３－１８ alicyclic carbonyl group"; "C" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. ６－１８ arylcarbonyl group" and the like.

[0028] As used herein, "C １－１８ The term "hydrocarbylcarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group." １－１８The "hydrocarbylcarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, an isopentylcarbonyloxy group, and a hexylcarbonyloxy group. １－１８ alkylcarbonyloxy group"; cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, etc. ３－１８ alicyclic carbonyloxy group"; "C" such as a phenylcarbonyloxy group, a naphthylcarbonyloxy group, an acenaphthylcarbonyloxy group, a phenanthrenylcarbonyloxy group, an anthracenylcarbonyloxy group, etc. ６－１８ arylcarbonyloxy group" and the like.

[0029] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyloxy group.” １－１８ The "hydrocarbyloxycarbonyl group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, an n-pentoxycarbonyl group, and a neopentyloxycarbonyl group. １－１８ alkoxycarbonyl group"; "C" such as a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2-methylcyclopentyloxycarbonyl group, a 3-methylcyclopentyloxycarbonyl group, a 2-methylcyclohexyloxycarbonyl group, a 3-methylcyclohexyloxycarbonyl group, and a 4-methylcyclohexyloxycarbonyl group; ３－１８alicyclic oxycarbonyl group"; "C" such as a phenoxycarbonyl group, a naphthoxycarbonyl group, an acenaphthyloxycarbonyl group, a phenanthrenyloxycarbonyl group, an anthracenyloxycarbonyl group, etc. ６－１８ aryloxycarbonyl group" and the like.

[0030] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group." １－１８ The "hydrocarbyloxycarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, an i-propyloxycarbonyloxy group, an n-butoxycarbonyloxy group, an i-butoxycarbonyloxy group, a sec-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, an i-pentyloxycarbonyloxy group, and an n-hexyloxycarbonyloxy group. １－１８ alkoxycarbonyloxy group"; "C" such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. ３－１８ alicyclic oxycarbonyloxy group"; "C" such as a phenoxycarbonyloxy group, a naphthoxycarbonyloxy group, an acenaphthyloxycarbonyloxy group, a phenanthrenyloxycarbonyloxy group, an anthracenyloxycarbonyloxy group, etc. ６－１８ aryloxycarbonyloxy group" and the like.

[0031] As used herein, "C １－１８ The term "hydrocarbylamino group" refers to a group consisting of one "C １－１８ "C" means a group bonded to an amino group. １－１８The "hydrocarbylamino group" is not particularly limited, and examples thereof include a "C hydrocarbylamino group" such as a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, an i-butylamino group, a sec-butylamino group, a t-butylamino group, an n-pentylamino group, an i-pentylamino group, a neopentylamino group, and an n-hexylamino group. １－１８ alkylamino group"; cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, 2-methylcyclopentylamino group, 3-methylcyclopentylamino group, cyclohexylamino group, 2-methylcyclohexylamino group, 3-methylcyclohexylamino group, 4-methylcyclohexylamino group, etc. ３－１８ alicyclic amino group"; phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. ６－１８ arylamino group" and the like.

[0032] As used herein, "diC １－１８ The term "hydrocarbylamino group" refers to two identical or different "C １－１８ "DiC" means a group in which a "hydrocarbyl group" is bonded to an amino group. １－１８ The "hydrocarbylamino group" is not particularly limited, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, an N-ethyl-N-methylamino group, an N-methyl-N-n-propylamino group, an N-isopropyl-N-methylamino group, an N-n-butyl-N-methylamino group, an N N-isobutyl-N-methylamino group, N-t-butyl-N-methylamino group, N-methyl-N-n-pentylamino group, N-n-hexyl-N-methylamino group, N-ethyl-N-n-propylamino group, N-ethyl-N-isopropylamino group, N-n-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, N-t-butyl-N-ethylamino group, N-ethyl-N-n-pentylamino group, N-ethyl-N-n-hexylamino group, and other "di-C １－１８alkylamino group"; "di-C" such as dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. ３－１８ alicyclic amino group"; "di-C" such as diphenylamino group, phenylnaphthylamino group, etc. ６－１８ "N-C arylamino group" such as N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. １－１８ Alkyl-N—C ３－１８ cycloalkylamino group"; "N-C cycloalkylamino group" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. １－１８ Alkyl-N—C ６－１８ arylamino group" and the like.

[0033] As used herein, "C １－１８ The term "hydrocarbylaminocarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbylamino group.” １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, a sec-butylaminocarbonyl group, a t-butylaminocarbonyl group, an n-pentylaminocarbonyl group, a 2-pentylaminocarbonyl group, a neopentylaminocarbonyl group, a 4-methyl-2-pentylaminocarbonyl group, an n-hexylaminocarbonyl group, and a 3-methyl-n-pentylaminocarbonyl group. １－１８ alkylaminocarbonyl group"; cyclopropylaminocarbonyl group, cyclobutylaminocarbonyl group, cyclopentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-methylcyclopentylaminocarbonyl group, 3-methylcyclopentylaminocarbonyl group, 2-methylcyclohexylaminocarbonyl group, 3-methylcyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc.６－１８ arylaminocarbonyl group.

[0034] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonyl group" refers to a "diC １－１８ "DiC" means a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group." １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a diisopropylaminocarbonyl group, a di-n-butylaminocarbonyl group, a diisobutylaminocarbonyl group, a di-t-butylaminocarbonyl group, a di-n-pentylaminocarbonyl group, a di-n-hexylaminocarbonyl group, an N-ethyl-N-methylaminocarbonyl group, an N-methyl-N-n-propylaminocarbonyl group, an N-isopropyl-N-methylaminocarbonyl group, an N-n-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an N-t-butyl-N-methylaminocarbonyl group, an N-methyl-N-n-pentylaminocarbonyl group, an N-n-hexyl-N-methylaminocarbonyl group, "diC" groups such as an N-ethyl-N-n-propylaminocarbonyl group, an N-ethyl-N-isopropylaminocarbonyl group, an N-n-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-isobutylaminocarbonyl group, an N-t-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-n-pentylaminocarbonyl group, and an N-ethyl-N-n-hexylaminocarbonyl group １－１８ alkylamino group"; "di-C" such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; "di-C" such as diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group, etc. ６－１８ arylaminocarbonyl group" and the like.

[0035] As used herein, "C １－１８ The term "hydrocarbylcarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which an amino group is bonded to a "hydrocarbyl carbonyl group." １－１８ The "hydrocarbylcarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, and n-hexylcarbonylamino group. １－１８ alkylcarbonylamino group"; cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. ３－１８ alicyclic carbonylamino group"; "C" such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenanthrenylcarbonylamino group, anthracenylcarbonylamino group, etc. ６－１８ arylcarbonylamino group" and the like.

[0036] As used herein, "C １－１８ The term "hydrocarbylaminocarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyloxy group, an ethylaminocarbonyloxy group, and an n-propylaminocarbonyloxy group. １－１８ alkylaminocarbonyloxy group"; cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. ３－１８ alicyclic aminocarbonyloxy group"; phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc. ６－１８ arylaminocarbonyloxy group" and the like.

[0037] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonyloxy group" refers to a "diC １－１８"DiC" means a group in which an oxygen atom (—O—) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, and di-n-propylaminocarbonyloxy group. １－１８ alkylaminocarbonyloxy group, etc.

[0038] As used herein, "C １－１８ The term "hydrocarbylaminocarbonylamino group" refers to a group consisting of "C １－１８ "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylaminocarbonylamino group, ethylaminocarbonyloxy group, and n-propylaminocarbonylamino group. １－１８ alkylaminocarbonylamino group"; cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. ３－１８ alicyclic aminocarbonylamino group"; phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. ６－１８ arylaminocarbonylamino group" and the like.

[0039] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonylamino group" refers to a "diC １－１８ "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and di-n-propylaminocarbonylamino group. １－１８ alkylaminocarbonylamino group, etc.

[0040] As used herein, "C １－１８ The term "hydrocarbyloxycarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an i-propoxycarbonylamino group, an n-butoxycarbonylamino group, and a t-butoxycarbonylamino group. １－１８ alkoxycarbonylamino group"; cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. ３－１８ alicyclic oxycarbonylamino group"; phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. ６－１８ aryloxycarbonylamino group" and the like.

[0041] As used herein, "C １－１８ The term "hydrocarbylthio group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group." １－１８ The "hydrocarbylthio group" is not particularly limited, and examples thereof include a "C methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, a t-butylthio group, an n-pentylthio group, an n-hexylthio group, etc. １－１８ alkylthio group"; cyclopropylthio group, cyclobutylthio group, cyclopentylthio group, cyclohexylthio group, 2-methylcyclopentylthio group, 3-methylcyclopentylthio group, 2-methylcyclohexylthio group, 3-methylcyclohexylthio group, 4-methylcyclohexylthio group, etc. ３－１８ alicyclic thio group"; "C" such as a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, an acenaphthylthio group, a phenanthrenylthio group, an anthracenylthio group, etc. ６－１８ arylthio group" and the like.

[0042] As used herein, "C １－１８ The term "hydrocarbylsulfinyl group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfinyl group (-S(=O)-) is bonded to a "hydrocarbyl group."１－１８ The "hydrocarbylsulfinyl group" is not particularly limited, and examples thereof include "C" such as methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, and hexylsulfinyl group. １－１８ alkylsulfinyl group"; cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-methylcyclohexylsulfinyl group, 3-methylcyclohexylsulfinyl group, 4-methylcyclohexylsulfinyl group, etc. ３－１８ alicyclic sulfinyl group"; "C" such as a phenylsulfinyl group, a naphthylsulfinyl group, an acenaphthylsulfinyl group, a phenanthrenylsulfinyl group, an anthracenylsulfinyl group, etc. ６－１８ arylsulfinyl group" and the like.

[0043] As used herein, "C １－１８ The term "hydrocarbylsulfonyl group" refers to a group consisting of "C １－１８ The hydrocarbyl group may be a sulfonyl group (-SO ２ -) is bonded to the group. １－１８ The "hydrocarbylsulfonyl group" is not particularly limited, and examples thereof include "C" such as a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, an n-butylsulfonyl group, a t-butylsulfonyl group, and a pentylsulfonyl group. １－１８ alkylsulfonyl group"; "C" such as cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, and 4-methylcyclohexyl group; ３－１８ alicyclic sulfonyl group"; "C" such as a phenylsulfonyl group, a naphthylsulfonyl group, an acenaphthylsulfonyl group, a phenanthrenylsulfonyl group, an anthracenylsulfonyl group, etc. ６－１８arylsulfonyl group" and the like.

[0044] As used herein, the term "acid-dissociable group" refers to a group that substitutes a hydrogen atom of a polar group, such as a hydroxy group (including a phenolic hydroxy group), a carboxy group, an amino group, or a sulfo group, and dissociates under the action of an acid. A compound having the acid-dissociable group can increase the polarity of the compound by dissociating the acid-dissociable group under the action of an acid, thereby generating the polar group. This can change the solubility of the compound in a developer. More specifically, when a highly polar developer, such as an alkaline aqueous solution, is used as the developer, the solubility of the compound in the developer relatively increases, while when a less polar organic developer is used as the developer, the solubility of the compound in the developer relatively decreases. Preferred polar groups include a hydroxy group (including a phenolic hydroxy group) and a carboxy group.

[0045] The acid-dissociable group is not particularly limited, and any known and commonly used acid-dissociable group that can be used in chemically amplified resists can be used. Examples of the acid-dissociable group include an acid-dissociable group G for a polar group having an acid-dissociable group represented by the following general formulas (G-1) to (G-4).

[0046] The acid-dissociable group G is not particularly limited as long as it dissociates under the action of an acid, and any known and commonly used group can be used. Examples of the acid-dissociable group G include "tertiary carbon-type acid-dissociable groups G" represented by the following general formula (g-1): Ａ ", "allyl or benzyl acid-dissociable group G represented by the following general formula (g-2) Ｂ ", "acetal-type acid-dissociable group G represented by the following general formula (g-3) Ｃ Each of these will be explained in turn below.

[0047] <Tertiary carbon type acid dissociable group G ＡThe acid-dissociable group G is a "tertiary carbon-type acid-dissociable group G" represented by the following general formula (g-1): Ａ ", a carbon atom directly bonded to a polar group, and R Ａ ｇ１ ~R Ａ ｇ３ An acid-labile group in which the carbon atom to which the group is bonded is a tertiary carbon atom can be used.

[0048] "R Ａ ｇ１ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0049] R Ａ ｇ１ As the C １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１２ an alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0050] Also, "R Ａ ｇ２ " and "R Ａ ｇ３" are each independently a C １－１２ A hydrocarbyl group in which a divalent carbon atom at any position except the terminal is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), or R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0051] R Ａ ｇ２ and R Ａ ｇ３ As for R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ３－１８The alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group contains a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and a divalent carbon atom at any position excluding the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is more preferable that the group may be substituted with - (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0052] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1): Ａ Examples of the aryl group include a t-butyl group, a t-amyl group, a 1,1-dimethylpropyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, a 1-methyl-1-cyclohexyl group, a 1-ethyl-1-cyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0053] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1): Ａ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0054]

[0055] <<Tertiary carbon type acid dissociable group G Ａ１ and G Ａ２ >> Also, the "tertiary carbon-type acid-dissociable group G" represented by general formula (g-1) Ａ " In R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８In the case where an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, for example, a tertiary carbon-type acid-dissociable group G represented by the following general formula (g-1-1) is included: Ａ１ and a tertiary carbon-type oxygen-dissociating group G represented by (g-1-2): Ａ２ etc.

[0056] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) Ａ１ >> A tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1): Ａ１ In this case, R Ａ ｇ１１ is a C which may have a substituent １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0057] Also Cy Ａ ｇ１ represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0058] Cy Ａ ｇ１The tertiary carbon atom may be, together with the tertiary carbon atom, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0059] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1): Ａ１ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0060]

[0061]

[0062]

[0063]

[0064] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) Ａ２ >> In the above general formula (g-1-2), R Ａ ｇ２１ ~R Ａ ｇ２３ are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), R Ａ ｇ２１ and R Ａｇ２２ , and / or R Ａ ｇ２２ and R Ａ ｇ２３ are directly connected to each other by a single bond or are divalently connected to each other by -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.

[0065] R Ａ ｇ２１ and R Ａ ｇ２２ , and / or R Ａ ｇ２２ and R Ａ ｇ２３ Examples of the case where each of these groups forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond include the case where each of these groups forms a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, or the like, which may have a substituent.

[0066] Also Cy Ａ ｇ２ represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0067] Cy Ａ ｇ２The tertiary carbon atom may be, together with the tertiary carbon atom, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0068] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2): Ａ２ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0069]

[0070]

[0071]

[0072] <Allyl or benzyl acid-dissociable group G Ｂ The acid-dissociable group G is an allyl or benzyl acid-dissociable group G represented by the following general formula (g-2): Ｂ An acid-labile group in which the carbon atom directly bonded to the polar group is at an allylic or benzyl position, such as:

[0073] "R Ｂ ｇ１ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0074] R Ｂ ｇ１ As the C １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１２ an alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0075] Also, "R Ｂ ｇ２ " ~ "R Ｂ ｇ４ " are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0076] R Ｂ ｇ１ and R Ｂ ｇ２ , R Ｂ ｇ２ and R Ｂ ｇ３ , and / or R Ｂ ｇ３ and R Ｂ ｇ４are directly connected to each other by a single bond or are divalently connected to each other by -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.

[0077] An allyl or benzyl acid-dissociable group G represented by general formula (g-2): Ｂ In this case, R Ｂ ｇ１ and R Ｂ ｇ２ , R Ｂ ｇ２ and R Ｂ ｇ３ , and / or R Ｂ ｇ３ and R Ｂ ｇ４ forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond, and examples thereof include a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, a benzyl group, or a 2,3-dihydro-1H-indanyl group, which may have a substituent.

[0078] An allyl or benzyl acid-dissociable group G represented by general formula (g-2): Ｂ Examples of such an acid-dissociable group include the following allyl or benzyl acid-dissociable groups:

[0079]

[0080] <Acetal-type acid-dissociable group G Ｃ The acid-dissociable group G is an acetal-type acid-dissociable group G represented by the following general formula (g-3): Ｃ An acid-dissociable group in which an oxygen atom is bonded to a carbon atom directly bonded to a polar group, such as

[0081] "R Ｃ ｇ１ " and "R Ｃ ｇ３ " are each independently a hydro group or an optionally substituted C １－１２In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0082] R Ｃ ｇ１ and R Ｃ ｇ３ is a hydro group or a C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0083] Also, "R Ｃ ｇ２ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0084] R Ｃ ｇ２ As the C １－１２ Alkyl group or C ３－１２In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0085] An acetal-type acid-dissociable group G represented by general formula (g-3): Ｃ Examples of the alkoxy group include a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, an n-butoxymethoxy group, a 2,2-dimethylpropoxymethoxy group, a 2,2-dimethylbutoxymethoxy group, a cyclohexyloxymethoxy group, a 1-ethoxyethoxy group, a 1-n-butoxyethoxy group, and a 1-cyclohexyloxyethoxy group.

[0086] As used herein, the term "hydroxy group or carboxy group having a protecting group" refers to a hydroxy group (including a phenolic hydroxy group) or a carboxy group that is protected with an ether-based protecting group, a silyl ether-based protecting group, an acyl-based protecting group, an aminocarbonyl-based protecting group, or the like.

[0087] The ether-based protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, and a di(p-methoxyphenyl)phenylmethyl group. The silyl ether-based protecting group is not particularly limited, and examples thereof include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), and a t-butyldiphenylsilyl group (TBDPS). The acyl-based protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, and a benzoyl group. The aminocarbonyl-based protecting group is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.

[0088] 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 haloalkyl group, (3) a hydroxy group, (4) a thiol group, (5) a nitro group, (6) a cyano group, (7) a carboxy group, (8) an amino group, (9) a sulfo group, (10) a vinyl group, (11) an allyl group, (12) a (meth)acryloyl group, (13) a (meth)acryloyloxy group, (14) a (meth)acrylamide group, (15) a styryl group, (16) an epoxy group, (17) a glycidyl group, (18) an amide group, (19) a hydroxy group or a carboxy group having a protecting group, (20) a polar group having an acid-dissociable group, or (21) a C group in which at least a part of the hydrogen atoms may be substituted with the above (1) to (20). 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, C １－１８ Hydrocarbylamino group, diC １－１８Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ Hydrocarbylsulfinyl group, C １－１８ A hydrocarbylsulfonyl group, in which a divalent carbon atom at any position except the terminal of the substituent is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time), etc.

[0089] [1. Resist Material] The resist material according to this embodiment is a resist material containing (A) a heteropolyacid salt or a mixture thereof in which deficiency sites have been modified, and is characterized in that a plurality of polar groups having an acid-dissociable group have been introduced into the anion moiety of the heteropolyacid salt or the mixture thereof in which deficiency sites have been modified. The resist material according to this embodiment may also contain (B) an acid diffusion controller, an organic solvent, or the like as optional components.

[0090] [1-1. (A) Heteropolyacid salt having modified deficiency sites or mixture thereof] When the (A) heteropolyacid salt having modified deficiency sites or mixture thereof contains an onium cation or an onium dication in the cation moiety, it may function as a photoacid generator that generates acid upon exposure to actinic rays (including visible light, ultraviolet light, DUV, XUV, EUV, BEUV, X-rays, electron beams, α-rays, β-rays, γ-rays, etc.). When the cation moiety does not contain an onium cation or an onium dication, a known or commonly used photoacid generator may be added to the resist material.

[0091] Furthermore, the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment contains a plurality of polar groups having an acid-dissociable group in its anion portion, i.e., at least two or more polar groups having an acid-dissociable group, and therefore its solubility in a developer can be drastically changed by the action of an acid. The number of polar groups having an acid-dissociable group contained in the anion portion is not particularly limited, and is preferably, for example, 2 to 12, more preferably 4 to 10, and even more preferably 4 to 8. From the viewpoint of ease of synthesis, the number of polar groups having an acid-dissociable group contained in the anion portion is preferably 2, 4, 6, 8, 10, or 12, more preferably 4, 6, 8, or 10, and even more preferably 4, 6, or 8. Furthermore, by adjusting the bulkiness, hydrophobicity, liposolubility, etc. of the acid-dissociable group, the range of change in physical properties, such as solubility in a developer, between the exposed portion and the unexposed portion to actinic radiation, etc., can be adjusted.

[0092] Therefore, the resist material according to this embodiment can be suitably used as a resist material that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid.

[0093] The resist material containing the heteropolyacid salt or a mixture thereof in which the defect sites have been modified according to this embodiment can drastically change the solubility in a developer between the exposed and unexposed portions to actinic radiation or the like, thereby providing an excellent resist material with good dimensional controllability and a good LWR (Line Width Roughness) evaluation, i.e., the ability to suppress the 3σ (σ: standard deviation) of line width variation. Furthermore, by adding an optional component (B) acid diffusion controller to the resist material according to this embodiment in addition to component (A), the dimensional controllability and LWR evaluation can be further improved.

[0094] The anion moiety and the cation moiety of the heteropolyacid salt or mixture having (A) defective sites according to this embodiment will be described below.

[0095] [1-1-1. Anion Moiety of Heteropolyacid Salt Having Modified Defect Sites or a Mixture Thereof] The anion moiety of the heteropolyacid salt having modified defect sites or a mixture thereof according to this embodiment can be obtained by reacting a terminal oxygen atom at the defect site of a heteropolyacid anion having defect sites with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups.

[0096] [1-1-1-1. Heteropolyacid anion having a defect site] The heteropolyacid anion having a defect site according to this embodiment is not particularly limited, and may be a defect species in which a part of the basic skeleton of the heteropolyacid anion is defective, and any of a one-defect species, a two-defect species, a three-defect species, etc. Examples of the heteropolyacid anion having a defect site include a defective Keggin-type heteropolyacid anion and a defective Dawson-type heteropolyacid anion.

[0097] [1-1-1-1-1. Deficient Keggin type heteropolyacid anion] Examples of the defective Keggin type heteropolyacid anion include a one-deficient Keggin type heteropolyacid anion represented by the following general formula (II-1), a two-deficient Keggin type heteropolyacid anion represented by the following general formula (II-2), and a three-deficient Keggin type heteropolyacid anion represented by the following general formula (II-3). [XM １１ O ３９ ] ｃ１１－ (II-1) [XM １０ O ３６ ] ｃ１２－ (II-2) [XM ９ O ３４ ] ｃ１３－ (II-3) (wherein, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.)

[0098] In the general formulas (II-1) to (II-3), the values ​​of c11 to c13 vary depending on the types of X and M. For example, in the general formula (II-1), when X is P and M is Mo or W, c11 is 7 ([PMo １１ O ３９ ] ７－ , [P.W. １１ O ３９ ] ７－ ) and when X is Si and M is Mo or W, c11 is 8 ([SiMo １１ O ３９ ] ８－ , [SiW １１ O ３９ ] ８－ ) and when X is S and M is Mo or W, c11 is 6 ([SMo １１ O ３９ ] ６－ , [SW １１ O ３９ ] ６－ ) and when X is B and M is Mo or W, c11 is 9 ([BMo １１ O ３９ ] ９－ , [B.W. １１ O ３９ ] ９－) and when X is Ge and M is Mo or W, c11 is 8 ([GeMo １１ O ３９ ] ８－ , [GeW １１ O ３９ ] ８－ In addition, in the general formula (II-2), when X is P and M is Mo or W, c12 is 7 ([PMo １０ O ３６ ] ７－ , [P.W. １０ O ３６ ] ７－ ) and when X is Si and M is Mo or W, c12 is 8 ([SiMo １０ O ３６ ] ８－ , [SiW １０ O ３６ ] ８－ ) and when X is B and M is Mo or W, c12 is 9 ([BMo １０ O ３６ ] ９－ , [B.W. １０ O ３６ ] ９－ ) and when X is Ge and M is Mo or W, c12 is 8 ([GeMo １０ O ３６ ] ８－ , [GeW １０ O ３６ ] ８－ Furthermore, in the general formula (II-3), for example, when X is P and M is Mo or W, c13 is 9 ([PMo ９ O ３４ ] ９－ , [P.W. ９ O ３４ ] ９－ ) and when X is Si and M is Mo or W, c13 is 10 ([SiMo ９ O ３４ ] １０－ , [SiW ９ O ３４ ] １０－ ) and when X is S and M is Mo or W, c13 is 8 ([SMo ９ O ３４ ] ８－ , [SW ９ O ３４ ] ８－) and when X is Ge and M is Mo or W, c13 is 10 ([GeMo ９ O ３４ ] １０－ , [GeW ９ O ３４ ] １０－ )

[0099] The defect Keggin type heteropoly acid anion preferably has an isomeric structure of α-, β-, or γ-form. The isomeric structure of the one defect Keggin type heteropoly acid anion represented by the general formula (II-1) is preferably [α-PW １１ O ３９ ] ７－ , [β-PW １１ O ３９ ] ７－ , [γ-PW １１ O ３９ ] ７－ , [α-PMo １１ O ３９ ] ７－ , [β-PMo １１ O ３９ ] ７－ , [γ-PW １１ O ３９ ] ７－ , [α-SiW １１ O ３９ ] ８－ , [β-SiW １１ O ３９ ] ８－ , [γ-SiW １１ O ３９ ] ８－ , [α-SiMo １１ O ３９ ] ８－ , [β-SiMo １１ O ３９ ] ８－ , [γ-SiW １１ O ３９ ] ８－ is preferred, and [α-PW １１ O ３９ ] ７－ , [α-PMo １１ O ３９ ] ７－ , [α-SiW １１ O ３９ ] ８－ , [α-SiMo １１ O ３９] ８－ The isomer structure of the two-deficient Keggin type heteropoly acid anion represented by the general formula (II-1) is preferably [α-PW １０ O ３６ ] ７－ , [β-PW １０ O ３６ ] ７－ , [γ-PW １０ O ３６ ] ７－ , [α-PMo １０ O ３６ ] ７－ , [β-PMo １０ O ３６ ] ７－ , [γ-PW １０ O ３６ ] ７－ , [α-SiW １０ O ３６ ] ８－ , [β-SiW １０ O ３６ ] ８－ , [γ-SiW １０ O ３６ ] ８－ , [α-SiMo １０ O ３６ ] ８－ , [β-SiMo １０ O ３６ ] ８－ , [γ-SiW １０ O ３６ ] ８－ is preferred, and [γ-PW １０ O ３６ ] ７－ , [γ-PMo １０ O ３６ ] ７－ , [γ-SiW １０ O ３６ ] ８－ , [γ-SiMo １０ O ３６ ] ８－ Further, the isomeric structure of the 3-deficient Keggin type heteropoly acid anion represented by the general formula (III-1) is preferably [α-PW ９ O ３４ ] ９－ , [β-PW ９ O ３４ ] ９－ , [γ-PW９ O ３４ ] ９－ , [α-PMo ９ O ３４ ] ９－ , [β-PMo ９ O ３４ ] ９－ , [γ-PW ９ O ３４ ] ９－ , [α-SiW ９ O ３４ ] １０－ , [β-SiW ９ O ３４ ] １０－ , [γ-SiW ９ O ３４ ] １０－ , [α-SiMo ９ O ３４ ] １０－ , [β-SiMo ９ O ３４ ] １０－ , [γ-SiW ９ O ３４ ] １０－ is preferred.

[0100] [1-1-1-1-2. Deficient Dawson type heteropolyacid anion] Examples of the deficient Dawson type heteropolyacid anion include a mono-deficient Dawson type heteropolyacid anion represented by the following general formula (III-1), a di-deficient Dawson type heteropolyacid anion represented by the following general formula (III-2), and a tri-deficient Dawson type heteropolyacid anion represented by the following general formula (III-3): [X ２ M １７ O ６１ ] ｃ２１－ (III-1) [X ２ M １６ O ５８ ] ｃ２２－ (III-2) [X ２ M １５ O ５６ ] ｃ２３－ (III-3) (wherein X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.)

[0101] In the general formulas (III-1) to (III-3), the values ​​of c21 to c23 vary depending on the types of X and M. For example, in the general formula (III-1), when X is P and M is Mo or W, c21 is 10 ([P ２ Mo １７ O ６１ ] １０－ , [P ２ W １７ O ６１ ] １０－ ), and if X is S and M is W, c21 is 8([S ２ W １７ O ６１ ] ８－ In addition, in the general formula (III-2), when X is Ge and M is Mo, c22 is 12 ([Ge ２ Mo １６ O ５８ ] １２－ Furthermore, in the general formula (III-3), when X is P and M is Mo or W, c23 is 12 ([P ２ Mo １５ O ５６ ] １２－ , [P ２ W １５ O ５６ ] １２－ )

[0102] The deficient Dawson type heteropoly acid anion preferably has an isomeric structure of α-, β-, or γ-form. The isomeric structures of the deficient Dawson type heteropoly acid anions represented by the general formulae (III-1) to (III-3) include [α-P ２ W １７ O ６１ ] １０－ , [α-P ２ W １５ O ５６ ] １２－ , [α-S ２ W １７ O ６１ ] ８－ etc. can be suitably used.

[0103] [1-1-1-2. Modification of Defect Sites] The modification of the defect sites of the heteropolyacid anion having defect sites according to this embodiment is achieved by reacting a terminal oxygen atom at the defect site of the heteropolyacid anion with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups to modify the defect site. Through this reaction, the terminal oxygen atom at the defect site of the heteropolyacid anion bonds to a group having a P, Si, Ge, or Sn heteroatom to which one or more organic groups are bonded, via some or all of the heteroatom, thereby modifying the defect site.

[0104] [1-1-1-2-1. Bonding Form of Defect Site and Its Notation] In the heteropolyacid anion modified at a defect site according to this embodiment, the terminal oxygen atom at the defect site of the heteropolyacid anion having a defect site is modified with a group having a heteroatom of P, Si, Ge, or Sn bonded to one or more organic groups.

[0105] The bonding form between the terminal oxygen atom at the vacant site of the heteropolyacid anion and the group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded is not particularly limited, and can be represented, for example, by the following general formulas (IV-1) to (IV-5). [In the general formulas (IV-1) to (IV-5), X′ represents Si or Ge; X″ represents a heteroatom of Si, Ge, or Sn; R １Ａ１ ~R １Ｅ１ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ１ ~R １Ｅ１ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced),１Ａ１ ~R １Ｅ１ a hydrogen atom contained in the R may be substituted with (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, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; １Ａ１ ~R １Ｅ１ Two or more hydrogen atoms contained in (t) are replaced by a polar group having an acid-dissociable group; * represents a bond with a terminal oxygen atom of a vacant site of the heteropolyacid anion.]

[0106] In this specification, for convenience, a heteropolyacid anion in which the vacant site is modified with a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-1) may be represented as in the following general formula (V-1): [X ｗ M ｘ O ｙ (R １Ａ１ X') (R １Ａ２ X')O] ｃ－ (V-1) (wherein w, x, y, and c are all natural numbers, and X, M, X′, and R １Ａ１ and R １Ａ２ is the same as above.) Also, R １Ａ１ and R １Ａ２ If they are the same, call this R １Ａ can be expressed as in the following general formula (V-1'): [X ｗ M ｘ O ｙ (R １Ａ X') ２ O] ｃ－ (V-1′)

[0107] The heteropolyacid anion having a modified defect site represented by general formula (V-1) or (V-1′) is not particularly limited, and may be, for example, a heteropolyacid anion having a defect site and (R１Ａ ) X'Y ３ (Y represents a leaving group, for example, a halogen atom, a hydroxy group, an alkoxy group (C １－４ An alkoxy group is preferred, and C １－２ An alkoxy group is more preferred.), an alkylcarbonyloxy group (C １－４ alkylcarbonyloxy group), hydrocarbylsulfonyloxy group (C １－６ Alkyl or C ７－１０ An aralkylsulfonyloxy group is preferred. Examples include a methanesulfonyloxy group and a p-toluenesulfonyloxy group.

[0108] Similarly, in this specification, a heteropolyacid anion in which the vacant site is modified with a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-2) may be represented, for convenience, as in the following general formula (V-2): [X ｗ M ｘ O ｙ (R １Ｂ１ R １Ｂ２ X') (R １Ｂ３ R １Ｂ４ X') ｃ－ (V-2) (wherein w, x, y, and c are all natural numbers, and X, M, X′, and R １Ｂ１ , R １Ｂ２ , R １Ｂ３ and R １Ｂ４ is the same as above.) Also, R １Ｂ１ R １Ｂ２ and R １Ｂ３ R １Ｂ４ are the same, it can be expressed as in the following general formula (V-2'): ｗ M ｘ O ｙ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ－ (V-2′)

[0109] The heteropolyacid anion having a modified defect site represented by general formula (V-2) or (V-2′) is not particularly limited, and may be, for example, a heteropolyacid anion having a defect site and (R １Ｂ１ ) (R １Ｂ２ ) X'Y ２ (wherein Y represents a leaving group as above) to obtain the compound.

[0110] In this specification, for convenience, a heteropolyacid anion in which the vacant site is modified with a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-3) may be represented as in the following general formula (V-3): [X ｗ M ｘ O ｙ (R １Ｃ１ X'O) (R １Ｃ２ X'O) (R １Ｃ３ X'O) (R １Ｃ４ X'O)] ｃ－ (V-3) (wherein w, x, y, and c are all natural numbers, and X, M, X′, and R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ is the same as above.) Also, R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ If they are the same, call this R １Ｃ can be expressed as in the following general formula (V-3'): [X ｗ M ｘ O ｙ (R １Ｃ X'O) ４ ] ｃ－ (V-3′)

[0111] The heteropoly acid anion having modified defect sites represented by general formula (V-3) or (V-3′) is not particularly limited, and may be, for example, a heteropoly acid anion of two defect Keggin type or Dawson type and R １Ｃ X'Y ３ (wherein Y represents a leaving group as above) to obtain the compound.

[0112] In this specification, for convenience, a heteropolyacid anion in which the vacant site is modified with a group having a heteroatom P bonded to one or more organic groups represented by general formula (IV-4) may be represented as in the following general formula (V-4): [X ｗ M ｘ O ｙ (R １Ｄ１ P=O)(R １Ｄ２ P=O)] ｃ－ (V-4) (wherein w, x, y, and c are all natural numbers, and X, M, and R １Ｄ１ and R １Ｄ２ is the same as above.) Also, R １Ｄ１ and R １Ｄ２ If they are the same, call this R １Ｄ can be expressed as in the following general formula (V-4'): [X ｗ M ｘ O ｙ (R １Ｄ P=O) ２ )] ｃ－ (V-4')

[0113] The heteropolyacid anion having a modified defect site represented by general formula (V-4) or (V-4′) is not particularly limited, and for example, a heteropolyacid anion having a defect site and R １Ｄ P(=O)Y ２ (wherein Y represents a leaving group as above) to obtain the compound.

[0114] In this specification, for convenience, a heteropolyacid anion in which the vacant site is modified with a group having a heteroatom Si, Ge, or Sn bonded to one or more organic groups represented by general formula (IV-5) may be represented as in the following general formula (V-5): [X ｗ M ｘ O ｙ (R １Ｅ１ X'') ｃ－ (V-5) (wherein w, x, y, and c are all natural numbers, and X, M, X″, and R １Ｅ１ The above (V-5) may be expressed as the following general formula (V-5') in some cases.１Ｅ is R １Ｅ１ The same definition is used as for [X ｗ M ｘ O ｙ (R １Ｅ X'') ｃ－ (V-5')

[0115] The heteropolyacid anion having a modified defect site represented by general formula (V-5) or (V-5′) is not particularly limited, and for example, a heteropolyacid anion having a defect site and R １Ｅ X''Y ３ (wherein Y represents a leaving group as above) to obtain the compound.

[0116] Among the heteropolyacid anions having modified defect sites represented by the general formulae (V-1) to (V-5) and (V-1') to (V-5'), heteropolyacid anions having modified defect sites represented by the following general formulae (VI-1) to (VI-12) are preferred, from the viewpoint of being relatively stable and capable of controlling the reactivity. [XM １１ O ３９ (R １Ａ X') ２ O] ｃ３１－ (VI-1) [XM １１ O ３９ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３１－ (VI-2) [XM １１ O ３９ (R １Ｄ P=O) ２ ] ｃ３１－ (VI-3) [XM １１ O ３９ (R １Ｅ X'') ｃ３１－ (VI-4) [XM １０ O ３６ (R １Ａ X') ２ O] ｃ３２－ (VI-5) [XM １０ O ３６ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３２－ (VI-6) [XM１０ O ３６ (R １Ｃ X'O) ４ ] ｃ３２－ (VI-7) [XM １０ O ３６ (R １Ｄ P=O) ２ ] ｃ３２－ (VI-8) [X ２ M １７ O ６１ (R １Ａ X') ２ O] ｃ３３－ (VI-9) [X ２ M １７ O ６１ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３３－ (VI-10) [X ２ M １７ O ６１ (R １Ｄ P=O) ２ ] ｃ３３－ (VI-11) [X ２ M １７ O ６１ (R １Ｅ X'') ｃ３３－ (VI-12) (wherein, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; X' represents a heteroatom of Si or Ge; X'' represents a heteroatom of Si, Ge, or Sn; R １Ａ ~R １Ｅ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １Ｅ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １Ａ ~R １Ｅa hydrogen atom contained in the R may be substituted with (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, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; １Ａ ~R １Ｅ two or more hydrogen atoms contained in (t) are replaced by a polar group having an acid-dissociable group; and c31, c32, and c33 are natural numbers.

[0117] In a heteropolyacid anion in which the vacant sites are modified, four terminal oxygen atoms of the vacant sites are modified. Therefore, the value of c31 is usually c11-4 (c11 represents the absolute value of the number of negative charges in the mono-vacant Keggin type heteropolyacid anion represented by general formula (II-1)), the value of c32 is c12-4 (c12 represents the absolute value of the number of negative charges in the di-vacant Keggin type heteropolyacid anion represented by general formula (II-2)), and the value of c33 is c21-4 (c21 represents the absolute value of the number of negative charges in the mono-vacant Dawson type heteropolyacid anion represented by general formula (III-1)). On the other hand, the values ​​of c31 to c33 will differ from the above values, for example, when the organic group contains an amino group which is protonated to form an ammonium cation, or when the organic group contains a carboxy group which is formed into a carboxy anion.

[0118] [1-1-1-2-2. Organic group] The above R １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and R １ＥThe organic group represented by the formula (I) is not particularly limited, and any known or commonly used organic group can be used. From the viewpoint of providing a functional building block having different physical properties, such as solubility in a developer or the like, between the exposed and unexposed portions of the actinic ray, the organic group is preferably an organic group having two or more polar groups having an acid-dissociable group. The number of polar groups having an acid-dissociable group contained in the organic group is not particularly limited, and is, for example, preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4.

[0119] an organic group R having two or more polar groups having the acid-dissociable group; １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ As for R １Ａ ~R １Ｅ C which may have a substituent １－１８ is a hydrocarbyl group; １Ａ ~R １Ｅ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ one or more hydrogen atoms contained in the R may be substituted with (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, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; １Ａ ~R １ＥAt least two hydrogen atoms of R are replaced by (t) a polar group having an acid-dissociable group, １Ａ ~R １Ｅ C which may have a substituent １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; １Ａ ~R １Ｅ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ a hydrogen atom contained in the above R may be substituted with (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, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; １Ａ ~R １Ｅ More preferably, at least two hydrogen atoms of R are replaced by (t) a polar group having an acid-dissociable group, １Ａ ~R １Ｅ C which may have a substituent １－１８ Alkyl group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; １Ａ ~R １Ｅ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ More preferably, at least two hydrogen atoms of (t) are replaced by a polar group having an acid-dissociable group.

[0120] The above R １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ is characterized by having two or more polar groups having an acid-dissociable group, for example, two or more polar groups such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group are introduced. In addition, as the acid-dissociable group, for example, a tertiary carbon-type acid-dissociable group G Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ Examples of the acid-dissociable group G include the following. １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ For example, the following can be exemplified:

[0121] [G represents an acid-dissociable group G, and * represents a bond between the organic group and a heteroatom P, Si, Ge, or Sn.]

[0122] [* means the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0123] <Organic Group Having Two or More Polar Groups Having an Acid-Dissociable Group> The organic group having two or more polar groups having an acid-dissociable group according to another embodiment is not particularly limited, and examples thereof include an organic group represented by general formula (VII-1). [In general formula (VII-1), L ２Ａ is an optionally substituted C １－１２In the hydrocarbyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ represents a group substituted with ２Ａ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ａ and R ２Ｂ each independently represents a polar group having an acid-dissociable group, and * represents a bond between the organic group and a heteroatom such as P, Si, Ge, or Sn.

[0124] L in the organic group represented by general formula (VII-1) ２ As for L ２Ａ C which may have a substituent ２－１０ In the hydrocarbyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ is a group substituted with the above L ２Ａ and the end of R ２Ａ or R ２Ｂ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ａ C which may have a substituent ２－１０ Alkyl group, C ３－１０ Alicyclic group, C ６－１０ an aryl group, or C ６－１０ In the aralkyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ is a group substituted with the above L ２ and the end of R ２Ａ or R ２Ｂis -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ａ C which may have a substituent ２－８ Alkyl group, C ３－８ Alicyclic group, C ６－８ an aryl group, or C ６－８ In the aralkyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ is a group substituted with the above L ２Ａ and the end of R ２Ａ or R ２Ｂ is more preferably a divalent carbon atom at any position except for the carbon atom to which it is bonded, which may be replaced by —O— or —S— (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0125] R in the organic group represented by general formula (VII-1) ２Ａ and R ２Ｂ As for R ２Ａ and R ２Ｂ are preferably each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group, ２Ａ and R ２Ｂ are each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group; Ａ , an allyl or benzyl acid-dissociable group G Ｂ or an acetal-type acid-dissociable group G Ｃ More preferably, R ２Ａ and R ２Ｂ are each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group; Ａ It is more preferable that:

[0126] The organic group having two or more polar groups having an acid-dissociable group according to yet another embodiment is not particularly limited, and examples thereof include an organic group represented by general formula (VII-2).

[0127] [In general formula (VII-2), L ２Ｂ is an optionally substituted C １－１２ In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ represents a group substituted with ２Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ｃ each independently represents a polar group having an acid-dissociable group; x represents an integer of 2 to 6; and * represents a bond between the organic group and a heteroatom such as P, Si, Ge, or Sn.

[0128] L in the organic group represented by general formula (VII-2) ２Ｂ As for L ２Ｂ C which may have a substituent ２－１０ In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ is a group substituted with the above L ２Ｂ and the end of R ２Ｃ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ｂ C which may have a substituent ２－１０ Alkyl group, C ３－１０ Alicyclic group, C ６－１０an aryl group, or C ６－１０ In the aralkyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminal, are R ２Ｃ is a group substituted with the above L ２Ｂ and the end of R ２Ｃ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ｂ C which may have a substituent ２－８ Alkyl group, C ３－８ Alicyclic group, C ６－８ an aryl group, or C ６－８ In the aralkyl group, two or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminals are each R ２Ｃ is a group substituted with the above L ２Ｂ and the end of R ２Ｃ is more preferably a divalent carbon atom at any position except for the carbon atom to which it is bonded, which may be replaced by —O— or —S— (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0129] R in the organic group represented by general formula (VII-2) ２Ｃ As for R ２Ｃ are each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group, and R ２Ｃ are each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group; and the acid-dissociable group is a tertiary carbon-type acid-dissociable group G Ａ , an allyl or benzyl acid-dissociable group G Ｂ or an acetal-type acid-dissociable group G Ｃ More preferably, R ２Ｃare each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group; and the acid-dissociable group is a tertiary carbon-type acid-dissociable group G Ａ It is more preferable that:

[0130] x in the general formula (VII-2) is preferably an integer of 2 to 6, and may be an integer of 2 to 4. The organic group represented by the general formula (VII-2) may include R ２Ｃ Contains two or more R ２Ｃ may all be polar groups having the same acid-dissociable group, or may each be a polar group having a different acid-dissociable group.

[0131] [1-1-2. Cation Moiety of Heteropolyacid Salt or Mixture Thereof Having Modified Defect Sites] As the cation moiety of the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment, H ＋ , metal ions, onium cations or onium dications can be used.

[0132] [1-1-2-1. Metal Ion] The metal ion that can be used as the cation moiety of the heteropolyacid salt or mixture thereof whose defect site is modified is not particularly limited, and examples thereof include Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ Metal ions include Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co３＋ is preferred, and Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Ca ２＋ , Al ３＋ , Co ３＋ These metal ions may be used alone or in combination of two or more.

[0133] [1-1-2-2. Onium Cation or Onium Dication] The onium cation or onium dication that can be used as the cation moiety of the heteropolyacid salt or mixture thereof whose defect sites have been modified is not particularly limited, and known and commonly used ones can be used. Examples of the onium cation or onium dication include ammonium cation, ammonium dication, phosphonium cation, phosphonium dication, sulfonium cation, sulfonium dication, and iodonium cation. These onium cations or onium dications may be used alone or in combination of two or more.

[0134] The onium cation or onium dication is preferably a sulfonium cation, a sulfonium dication, or an iodonium cation, from the viewpoint of providing a building block that generates an acid when exposed to DUV, XUV, EUV, BEUV, an electron beam, or the like.

[0135] [1-1-2-2-1. Ammonium cation] The ammonium cation is not particularly limited, and known and commonly used ammonium cations can be used. The ammonium cation is not particularly limited, and examples thereof include ammonium ion (NH ４ ＋ ), primary ammonium cation (NH ３ (R ３Ａ ) ＋ )), secondary ammonium cation (NH ２ (R ３Ａ ) (R ３Ｂ )) ＋ ), tertiary ammonium cation (NH(R ３Ａ ) (R ３Ｂ) (R ３Ｃ ) ＋ ), quaternary ammonium cation (N(R ３Ａ ) (R ３Ｂ ) (R ３Ｃ ) (R ３Ｄ ) ＋ ) can be mentioned. ３Ａ ~R ３Ｄ shall represent the same as defined below.

[0136] The ammonium cation is ammonium ion (NH ４ ＋ ), and quaternary ammonium cations are preferred, and in particular, ammonium ions (NH ４ ＋ ), and organic quaternary ammonium cations represented by the following general formula (VIII-1) are more preferred.

[0137] In general formula (VIII-1), R ３Ａ ~R ３Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ３Ａ ~R ３Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), ３Ａ ~R ３ＤThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). 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, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ３Ａ ~R ３ＤAny two of these 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 nitrogen atom in general formula (VIII-1).

[0138] 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, dodecyltrimethylammonium cation, diallyldimethylammonium cation, (3-acrylamidopropyl)trimethylammonium cation, trimethyl-2-methacryloyloxyethylammonium cation, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation, Examples thereof include ammonium cation, trimethylvinylammonium cation, N-4-vinylbenzyltriallylammonium cation, 3-hydroxypropyltriallylammonium cation, 2-trifluoromethylbenzyltriallylammonium cation, di-2-(N-methylacrylamide)ethyldimethylammonium cation, allyltrimethylammonium cation, butyl(2-methacryloyloxyethyl)dimethylammonium cation, ethoxycarbonylmethyltriethylammonium cation, 2-hydroxyethyltrimethylammonium cation, 2-acetylethyltrimethylammonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)trimethylammonium cation, (4-(methacryloyloxy)phenyl)trimethylammonium cation, trimethyl(4-(nonanoyloxy)phenyl)ammonium cation, and the like.

[0139] [1-1-2-2-2. Ammonium Dication] The ammonium dication is not particularly limited, and any known or commonly used ammonium dication can be used. Examples of the ammonium dication include organic quaternary ammonium dications represented by the following general formula (VIII-2):

[0140] In general formula (VIII-2), R ４Ａ ~R ４Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ４Ａ ~R ４Ｆ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ４ is an optionally substituted C １－１８ represents a hydrocarbylene group, ４ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４Ｆ and L ４The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). 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, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ４Ａ ~R ４ＦAny two of these 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 nitrogen atom in general formula (VIII-2).

[0141] The organic quaternary ammonium dication represented by general formula (VIII-2) is not particularly limited, and examples thereof include 1,4-diallyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1,4-di(2-(meth)acryloyloxyethyl)-1,4-diazabicyclo[2.2.2]octane-1.4-diium, and 1,4-bis(2-(meth)acrylamidoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium.

[0142] [1-1-2-2-3. Phosphonium Cation] The phosphonium cation is not particularly limited, and any known or commonly used phosphonium cation can be used. Examples of the phosphonium cation include organic quaternary phosphonium cations represented by the following general formula (VIII-3):

[0143] In general formula (VIII-3), R ５Ａ ~R ５Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ５Ａ ~R ５Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ５Ａ ~R ５ＤThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). 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, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ５Ａ ~R ５ＤAny two of these 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 phosphorus atom in general formula (VIII-3).

[0144] The organic quaternary phosphonium cation represented by the general formula (VIII-3) is not particularly limited, and examples thereof include tributylcyanomethylphosphonium cation, methyltriphenylphosphonium cation, ethyltriphenylphosphonium cation, cyanomethyltriphenylphosphonium cation, formylmethyltriphenylphosphonium cation, methoxymethyltriphenylphosphonium cation, chloromethyltriphenylphosphonium cation, acetonyltriphenylphosphonium cation, tributyl-1,3-dioxan-2-ylmethylphosphonium cation, triphenylpropargylphosphonium cation, allyltriphenylphosphonium cation, and the like. phenyl)phosphonium cation, cyclopropyltriphenylphosphonium cation, benzyltriphenylphosphonium cation, tetrakis(hydroxymethyl)phosphonium cation, 2-carboxyethyltriphenylphosphonium cation, methoxycarbonylmethyltriphenylphosphonium cation, t-butoxycarbonylmethyltriphenylphosphonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)triphenylphosphonium cation, (4-(methacryloyloxy)phenyl)triphenylphosphonium cation, triphenyl(4-(nonanoyloxy)phenyl)phosphonium cation, and the like.

[0145] [1-1-2-2-4. Phosphonium dication] The phosphonium dication is not particularly limited, and known and commonly used phosphonium dications can be used. Examples of the phosphonium dication include organic quaternary phosphonium dications represented by the following general formula (VIII-4):

[0146] In general formula (VIII-4), R ６Ａ ~R６Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ６Ａ ~R ６Ｆ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), L ６ is an optionally substituted C １－１８ represents a hydrocarbylene group, ６ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ ~R ６Ｆ and L ６ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). 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, C １－１８ Hydrocarbylamino group, diC１－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ６Ａ ~R ６Ｆ Any two of these 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 phosphorus atom in general formula (VIII-4).

[0147] The organic quaternary phosphonium dication represented by general formula (VIII-4) is not particularly limited, and examples thereof include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylenebis(triphenylphosphonium) dication, and pentamethylenebis(triphenylphosphonium) dication.

[0148] [1-1-2-2-5. Sulfonium cation] The sulfonium cation is not particularly limited, and any known or commonly used sulfonium cation can be used. Examples of the sulfonium cation include organic sulfonium cations represented by the following general formula (VIII-5):

[0149] In general formula (VIII-5), R ７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ７Ａ , R ７Ｂ and R ７Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ , R ７Ｂ and R ７Ｃ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). 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, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ , R ７Ｂ and R ７Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the sulfur atom in general formula (VIII-5).

[0150] In the organic sulfonium cation represented by general formula (VIII-5), the R ７Ａ , R ７Ｂ and R ７Ｃ As for R ７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C １－１８ is a hydrocarbyl group; ７Ａ , R ７Ｂ and R ７Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ７Ａ , R ７Ｂ and R ７Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C ６－１８ is an aryl group; ７Ａ , R ７Ｂ and R ７Ｃ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ It is more preferable that the group may be substituted with - (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0151] Also R ７Ａ , R ７Ｂ and R ７Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ Examples of the case where R is linked via an alkylene group to form a ring together with the sulfur atom in general formula (VIII-5) include those having a thian-1-ium skeleton, a thiophen-1-ium skeleton, a 1,4-oxathiane-4-ium skeleton, a 1,4-dithian-1-ium skeleton, a 1H-thiophen-1-ium skeleton, a benzo[b]thiophen-1-ium skeleton, a dibenzothiophenium skeleton, a 9,10-dihydrothioxanthylium skeleton, a 10H-phenoxathiane-10-ium skeleton, and a 5H-thianthren-5-ium skeleton, and the following can be exemplified. Note that * indicates that R is not involved in ring formation. ７Ａ , R ７Ｂ or R ７Ｃ It means the junction with.

[0152]

[0153] Examples of the organic sulfonium cation include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalen-1-yl)hexahydrothiopyrylium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrylium cation, di(naphthalen-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]thiophen-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b]thiophen-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, (2-bromoethyl)diphenylsulfonium cation, dimesityl(trifluoromethyl)sulfonium cation, tri-p-tolyl sulfonium cation, and the like.

[0154] [1-1-2-2-6. Sulfonium dication] The sulfonium dication is not particularly limited, and any known or commonly used sulfonium dication can be used. Examples of the sulfonium dication include organic sulfonium dications represented by the following general formula (VIII-6):

[0155] In general formula (VIII-6), R ８Ａ , R ８Ｂ , R ８Ｃ and R ８Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ８Ａ , R ８Ｂ , R ８Ｃ and R ８Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ８ is an optionally substituted C １－１８ represents a hydrocarbylene group, ８The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ , R ８Ｂ , R ８Ｃ , R ８Ｄ , and L ８ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). 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, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８A divalent carbon atom at any position excluding the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ８Ａ , R ８Ｂ and L ８ and / or R ８Ｃ , R ８Ｄ and L ８ Any two of these 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 general formula (VIII-6).

[0156] [1-1-2-2-7. Iodonium cation] The iodonium cation is not particularly limited, and any known or commonly used iodonium cation can be used. Examples of the iodonium cation include organic iodonium cations represented by the following general formula (VIII-7):

[0157] In general formula (VIII-7), R ９Ａ and R ９Ｂ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ９Ａ and R ９Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ９Ａ and R ９ＢThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). 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, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ９Ａ and R ９Ｂare 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 general formula (VIII-7).

[0158] In the organic iodonium cation represented by general formula (VIII-7), R ９Ａ and R ９Ｂ As for R ９Ａ and R ９Ｂ each independently represents a C １－１８ is a hydrocarbyl group; ９Ａ and R ９Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ９Ａ and R ９Ｂ each independently represents a C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ９Ａ and R ９Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ９Ａ and R ９Ｂ each independently represents a C ６－１８ is an aryl group; ９Ａ and R ９ＢThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ It is more preferable that the group may be substituted with - (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0159] 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, )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, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4 (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)(mesityl)iodonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)(phenyl)iodonium cation, (4-(methacryloyloxy)phenyl)(phenyl)iodonium cation, (4-(nonanoyloxy)phenyl)(phenyl)iodonium cation, and the like.

[0160] [1-1-3. Heteropolyacid salts having modified defect sites or mixtures thereof (general formulas (I) and (I'))] <Heteropolyacid salts having modified defect sites represented by general formula (I) or mixtures thereof> A heteropolyacid salt having modified defect sites or mixtures thereof according to another embodiment is represented by the following general formula (I): (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In general formula (I), A ｍ＋ are each independently H ＋ , metal ions, NH ４ ＋ , an onium cation, or an onium dication; （ａｍ）－ represents a heteropolyacid anion obtained by modifying a heteropolyacid anion having a defect site, the defect site being modified in the heteropolyacid anion having a defect site, the heteropolyacid anion having a defect site and modified in the heteropolyacid anion containing a plurality of polar groups having an acid-dissociable group, m is an integer of 1 to 5, and a is a real number greater than 0.]

[0161] In the heteropolyacid salt having modified defect sites represented by the above general formula (I) or a mixture thereof, the "metal ion," the "onium cation," the "onium dication," and the "heteropolyacid anion having defect sites and having the defect sites modified" may be any of those described above.

[0162] The mixture of heteropolyacid salts having modified defect sites represented by the general formula (I) contains a plurality of types of A ｍ＋ In the above case, multiple types of A may be included. ｍ＋ The content ratio can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0163] <Heteropolyacid salt having modified defect sites represented by general formula (I') or a mixture thereof> A heteropolyacid salt having modified defect sites according to yet another embodiment of the present invention or a mixture thereof is represented by the following general formula (I'): (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ(C'(a'm'+bn)-) (I') [In general formula (I'), A' ｍ’＋ are each independently H ＋ , metal ions, or NH ４ ＋ represents; B ｎ＋ each independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents a heteropolyacid anion obtained by modifying a heteropolyacid anion having a defect site, the heteropolyacid anion obtained by modifying the defect site in the heteropolyacid anion having a defect site contains a plurality of polar groups having an acid-dissociable group, m' is an integer of 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0.

[0164] In the heteropolyacid salt having modified defect sites represented by the above general formula (I') or a mixture thereof, the "metal ion," the "onium cation," the "onium dication," and the "heteropolyacid anion having defect sites and in which the defect sites have been modified" can be appropriately selected from those described above.

[0165] The heteropolyacid salt or mixture thereof in which the deficiency sites represented by the above general formula (I') have been modified has a sulfonium cation, a sulfonium dication, or an iodonium cation in the cation moiety, and therefore can be endowed with the function of generating an acid by exposure to DUV, XUV, EUV, BEUV, an electron beam, or the like.

[0166] The mixture of heteropolyacid salts having modified defect sites represented by general formula (I') contains A' ｍ’＋ and B ｎ＋ In this case, the values ​​of a′ and b can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0167] The ratio of a' to b is as follows: A' is a heteropoly acid anion whose defect site is modified; ｍ’＋ , B ｎ＋Although it depends on the types of compounds, a':b is preferably 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a'm'+bn is an integer of 2-8 and m' and n are 1, it is preferable that a' is a real number of 0-7 and b is a real number of 1-8, and it is more preferable that a' is a real number of 0-4 and b is a real number of 2-8.

[0168] [1-1-4. Content of Component (A)] There are no particular limitations on the content of component (A) in the resist material, and it can be set appropriately 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 component (A) in the resist material is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.2 to 10 mass%, based on the resist material being 100 mass%.

[0169] [1-2. (B) Acid Diffusion Controller] The resist material according to this embodiment may contain (B) an acid diffusion controller that traps acid generated by exposure.

[0170] The acid diffusion controller is not particularly limited, and any known or commonly used acid diffusion controller can be used. Examples of the acid diffusion controller include (B1) a photodecomposable base that decomposes upon exposure to light and loses its acid diffusion control ability, and (B2) a nitrogen-containing organic compound that does not fall under the category of component (B1). These may be used alone or in combination of two or more.

[0171] [1-2-1. (B1) Photodegradable base] The photodegradable base (B1) loses its ability to control acid diffusion by decomposing upon exposure, but acts as a quencher in unexposed areas, thereby controlling acid diffusion. Therefore, by incorporating the photodegradable base (B1) into a resist material, it is possible to improve properties such as increased sensitivity, reduced roughness, and suppression of coating defects.

[0172] The photodegradable base is not particularly limited, and known and commonly used ones can be used. Examples of the photodegradable base include "carboxylate compound B" represented by the following general formula (IX-1): Ａ", "sulfonate compound B" represented by the following general formula (IX-2) Ｂ ", "sulfonylamide salt compound B" represented by the following general formula (IX-3) Ｃ ", etc. In the following, carboxylate anions, sulfonate anions, sulfonylamide anions, onium cations or onium dications (D ｐ＋ ) will be explained in this order.

[0173] [1-2-1-1. Carboxylate compound B Ａ The photodegradable base (B1) is a carboxylate compound B represented by the following general formula (IX-1): Ａ ", a carboxylate anion and an onium cation or an onium dication (D ｐ＋ ) can be used as a salt.

[0174] "R Ａ ｂ１ " is an optionally substituted C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, in which any divalent carbon atom excluding the terminal carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0175] R Ａ ｂ１ As the C １－１８ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0176] <Carboxylate Compound B Ａ１ Carboxylate compound B represented by the above general formula (IX-1) Ａ is a carboxylate compound B represented by the following general formula (IX-1-1): Ａ１ may be.

[0177] "X Ａ " is an optionally substituted C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0178] X Ａ As the C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ３－１８ an alicyclic group, or C ６－１８ In an aryl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0179] "L Ａ " is X Ａ and-COO － and a group linking L Ａ -1) to (L Ａ A linking group represented by the formula (I)-7) can be used. [In the formula, L Ａ ｂ１ and L Ａ ｂ２ represents a single bond or an optionally substituted C １－８ represents a hydrocarbylene group, and *1 represents X Ａ The connecting part with *2 is -COO － represents the connection between

[0180] L Ａ ｂ１ and L Ａ ｂ２ is a single bond or C which may have a substituent. １－８ Alkylene group or C ６－８ An arylene group is preferred, and C １－８ An alkylene group is more preferred.

[0181] <Examples of carboxylate anions> Carboxylate compound B Ａ or B Ａ１The carboxylate anion is not particularly limited, and examples thereof include trifluoroacetate anion, pentafluoropropionate anion, 2-methoxyacetate anion, 2-methoxy-2-methylpropionate anion, 2-hydroxyacetate anion, 2-hydroxy-2-methylpropionate anion, 2-acetoxyacetate anion, adamantane-1-carboxylate anion, 9,10-dihydro-9,10-ethanoanthracene-11-carboxylate anion, 9,10-dihydro-9,10-[1,2]benzenoanthracene-9-carboxylate anion, benzoate anion, salicylate anion, 3-hydroxybenzoate anion, and 3-trifluoromethylbenzoate anion.

[0182]

[0183]

[0184]

[0185] [1-2-1-2. Sulfonate compound B Ｂ The photodegradable base (B1) may be a sulfonate compound B represented by the following general formula (IX-2): Ｂ ", a sulfonate anion and an onium cation or an onium dication (D ｐ＋ ) can be used as a salt.

[0186] "R Ｂ ｂ１ " is an optionally substituted C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, in which any divalent carbon atom excluding the terminal carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0187] R Ｂ ｂ１ As the C １－１８In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0188] Sulfonate Compound B Ｂ１ Sulfonate compound B represented by the above general formula (IX-2) Ｂ is a sulfonate compound B represented by the following general formula (IX-2-1): Ｂ１ may be.

[0189] "X Ｂ " is an optionally substituted C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0190] X Ｂ As the C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ３－１８ an alicyclic group, or C ６－１８ In an aryl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0191] "L Ｂ " is X Ｂ and -SO ２ -O － and a group linking L Ｂ -1) to (L Ｂ A linking group represented by the formula (I)-7) can be used. [In the formula, L Ｂ ｂ１ and L Ｂ ｂ２ represents a single bond or an optionally substituted C １－８ represents a hydrocarbylene group, and *1 represents X Ｂ The connection part with *2 is -SO ２ -O － represents the connection between

[0192] L Ｂ ｂ１ and L Ｂ ｂ２ is a single bond or C which may have a substituent. １－８ Alkylene group or C ６－８ An arylene group is preferred, and C １－８ An alkylene group is more preferred.

[0193] <Examples of sulfonate anions> Sulfonate compound B Ｂ or B Ｂ１ The sulfonate anion is not particularly limited, and examples thereof include camphorsulfonate anion, (adamantan-1-yl)methanesulfonate anion, (adamantane-1-carbonyloxy)ethane-1-sulfonate anion, cyclohexanesulfonate anion, 2-(cyclohexanecarbonyloxy)ethane-1-sulfonate anion, bicyclo[2.2.1]heptane-2-sulfonate anion, benzenesulfonate anion, and 4-methylbenzenesulfonate anion.

[0194]

[0195] [1-2-1-3. Sulfonylamide salt compound B Ｃ The photodegradable base (B1) may be a sulfonylamide salt compound B represented by the following general formula (IX-3): Ｃ ", a sulfonyl amide anion and an onium cation or an onium dication (D ｐ＋ ) can be used as a salt.

[0196] "R Ｃ ｂ１ " is an optionally substituted C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, in which any divalent carbon atom excluding the terminal carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ - may be substituted (however, adjacent divalent carbon atoms are not substituted at the same time). Ｃ ｂ２ " is an optionally substituted C １－１８ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0197] R Ｃ ｂ１ As the C １－１８ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0198] R Ｃ ｂ２ As the C １－１８ Alkyl group, C ３－１８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted), and １－１２ More preferably, it is a haloalkyl group, and C １－５ A fluorinated alkyl group is more preferred.

[0199] <Sulfonylamide salt compound B Ｃ１ Sulfonylamide salt compound B represented by the above general formula (IX-3) Ｃ is a sulfonylamide salt compound B represented by the following general formula (IX-3-1): Ｃ１may be.

[0200] "X Ｃ " is an optionally substituted C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0201] X Ｃ As the C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ３－１８ an alicyclic group, or C ６－１８ In an aryl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0202] "L Ｃ " is X Ｃ and -N － -SO ２ -R Ｃ ｂ２ and a group linking L Ｃ -1) to (L Ｃ A linking group represented by the formula (I)-7) can be used. [In the formula, L Ｃ ｂ１ and L Ｃ ｂ２ represents a single bond or an optionally substituted C １－１２ represents a hydrocarbylene group, and *1 represents X Ｃ The connection part with *2 is -N － -SO ２ -R Ｃ ｂ２ represents the connection between

[0203] L Ｃ ｂ１ and L Ｃ ｂ２ is a single bond or C which may have a substituent. １－１２ Alkylene group, C １－１２ Cycloalkylene group or C ６－１２ An arylene group is preferred, and C １－８ Alkylene group or C １－８ A cycloalkylene group is more preferred.

[0204] <Examples of sulfonylamide anions> The above sulfonylamide salt compound B Ｃ or B Ｃ１The sulfonylamide anion is not particularly limited, and examples thereof include methyl((trifluoromethyl)sulfonyl)amide anion, i-propyl((trifluoromethyl)sulfonyl)amide anion, methacryloyloxy((trifluoromethyl)sulfonyl)amide anion, 2-(methacryloyloxy)ethyl((trifluoromethyl)sulfonyl)amide anion, cyclohexyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclopentanecarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclohexanecarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1 ]heptan-2-ylmethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1]heptan-7-ylmethyl((trifluoromethyl)sulfonyl)amide anion, 2-((adamantane-1-carbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(adamantane-1-carboxamido)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(4-((adamantane-1-carbonyl)oxy)cyclohexyl)ethyl((trifluoromethyl)sulfonyl)amide anion, 4-((adamantane-1-carbonyl)oxy)phenyl((trifluoromethyl)sulfonyl)amide anion, and the like.

[0205]

[0206]

[0207]

[0208] [1-2-1-4. Onium cation or onium dication (D ｐ＋ The cation moiety of the photodegradable base (B1) is an onium cation or an onium dication (D ｐ＋ Here, "(D)" represented by general formulas (IX-1) to (IX-3) can be used. ｐ+ ) １／ｐ", D represents an onium cation or an onium dication, and p represents an integer of 1 or 2. The onium cation or onium dication is not particularly limited, and the above-mentioned "sulfonium cation," "sulfonium dication," "iodonium cation," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," etc. can be used.

[0209] [1-2-2. (B2) Nitrogen-Containing Organic Compound] As the other (B) acid diffusion controller, (B2) may be contained a nitrogen-containing organic compound that does not fall under (B1). The nitrogen-containing organic compound is not particularly limited, and examples thereof include aliphatic amines, aromatic amines, and heterocyclic amines.

[0210] Examples of nitrogen-containing organic compounds include aliphatic amines such as n-hexylamine, n-heptylamine, diethylamine, di-n-propylamine, di-n-butylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n-octylamine; aromatic amines such as aniline, N-methylaniline, N-ethylamine, N,N-dimethylaniline, 4-methylaniline, and pyrrole; and heterocyclic amines such as pyridine, imidazole, benzimidazole, piperidine, piperazine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane. These nitrogen-containing organic compounds may be used alone or in combination of two or more.

[0211] [1-2-3. Amount] There are no particular limitations on the amount of acid diffusion controller (B) contained in the resist material according to this embodiment, and this can be set appropriately depending on the amount and type of component (A). The amount of component (B) in the resist material is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass, and even more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A).

[0212] [1-3. Organic Solvent] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and any known or commonly used organic solvent can be used. The organic solvent is preferably an organic solvent that can uniformly dissolve or disperse (A) the heteropolyacid salt having modified defect sites or a mixture thereof when prepared.

[0213] Examples of the organic solvent include polar solvents such as alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, nitrile solvents, and aprotic polar solvents, and nonpolar solvents such as hydrocarbon solvents. These organic solvents may be used alone or in combination of two or more.

[0214] Specific examples of the polar solvent include: 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-based 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-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Amide-based solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ester-based 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-based solvents such as acetonitrile, propionitrile, and benzonitrile; aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea; and nonpolar solvents such as hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. The above organic solvents may be used alone or in combination of two or more.

[0215] The organic solvent contained in the resist material according to this embodiment is preferably a polar solvent in terms of coatability, and more preferably an amide solvent, an ester solvent, an alcohol solvent, or a ketone solvent in terms of solubility. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. Furthermore, the ester solvent or alcohol solvent preferably has an ester bond and / or a hydroxyl group in terms of solubility, and among the above, 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 is preferred.

[0216] The amount of organic solvent in the resist material is not particularly limited and can be set appropriately depending on the method for applying the resist material to a substrate, the thickness of the applied film, etc. The amount of 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 0.2 to 10 mass%.

[0217] [1-4. Others] The resist material according to this embodiment may further contain, as desired, miscible additives, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, etc. Preferably, the resist material according to this embodiment does not contain an epoxy resin. It is also preferable that the resist material does not contain hydrogen peroxide.

[0218] 2. Pattern Forming 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.

[0219] [2-1. Coating Step] The pattern forming method according to this embodiment includes a step of coating a substrate with a resist material.

[0220] <Substrate> The substrate used in this embodiment is not particularly limited, and known and commonly used substrates can be used. For example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed may be used. The material of the substrate is not particularly limited, and examples thereof include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and inorganic substrates such as glass, titanium oxide, and silicon dioxide. The size, shape, and the like of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or may be a flake-shaped substrate.

[0221] The surface of the substrate may be subjected to a surface treatment as necessary. In the case of a substrate having hydroxyl groups on its surface layer, the surface of the substrate is treated with a silane coupling agent capable of reacting with the hydroxyl groups, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane coupling agent include hexamethyldisilazane (HMDS).

[0222] <Coating Method> The method for applying the resist material onto the substrate is not particularly limited, and any known or commonly used method can be used. Examples of dry coating methods include CVD (chemical vapor deposition) methods such as thermal CVD, plasma CVD, and photo-CVD; and PVD (physical vapor deposition) methods such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Examples of wet coating methods include spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0223] As a method for applying the resist material according to this embodiment to a substrate, a wet method such as spin coating or screen printing is preferably used, and spin coating is more preferable, from the viewpoint of forming a uniform film thickness, etc. After forming the coating film, a backside rinse, an edge bead removal step, etc. may be performed to remove the edge bead.

[0224] The method for drying the resist film formed by applying a resist material to a substrate is not particularly limited, and can be performed using, for example, a heating device such as a hot plate (post-applied bake (PAB)), a pressure reducing device, or the like. The baking conditions are not particularly limited, and can be set appropriately depending on the type of resist film, application, etc. The baking temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0225] The thickness of the resist film after drying is not particularly limited, but is preferably 0.5 to 100 nm, more preferably 1 to 75 nm, and even more preferably 1 to 60 nm.

[0226] [2-2. Exposure Step] The pattern formation method according to this embodiment includes a step of exposing the resist film formed in the above-described coating step.

[0227] As an exposure apparatus in the exposure step of the resist film, for example, an ArF exposure apparatus, an electron beam lithography apparatus, an EUV exposure apparatus, a BEUV exposure apparatus, etc. Furthermore, 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.

[0228] The wavelength used for exposure is not particularly limited, and examples thereof include ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), F ２ Radiation such as excimer laser (wavelength 157 nm), EUV (extreme ultraviolet (wavelength 13.5 nm)), BEUV (Beyond EUV (wavelength 6.X nm)), VUV (vacuum ultraviolet), EB (electron beam), X-ray, or soft X-ray may be used.

[0229] 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. ２is preferably 20 to 60 mJ / cm ２ In the case of extreme ultraviolet rays, the exposure dose is, for example, 500 mJ / cm ２ or less, and 0.1 to 200 mJ / cm ２ is preferably 3 to 100 mJ / cm ２ More preferably, it is 5 to 50 mJ / cm ２ Furthermore, in the case of BEUV, the exposure dose is, for example, 1000 mJ / cm ２ or less, and 0.1 to 400 mJ / cm ２ is preferably 1 to 200 mJ / cm ２ More preferably, it is 5 to 150 mJ / cm ２ In the case of an electron beam, it is more preferable that the concentration is 3 μC / cm at 50 kV. 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 at a dose of 1000 ppm.

[0230] After the resist film is exposed to light, it may or may not be baked (post-exposure bake (PEB)). The baking conditions are not particularly limited and can be set appropriately depending on the type of resist film, its intended use, etc. The baking temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C, using a heating device such as a hot plate. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0231] [2-3. Development Step] The pattern formation method according to this embodiment includes a step of developing the exposed resist film. In the development step, a pattern can be formed by developing the exposed resist film with a developer. A negative pattern formation process is one in which the exposed region remains as a pattern after development, while a positive pattern formation process is one in which 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 baking treatment may be further performed.

[0232] The developer used in this embodiment may be an alkaline developer for an alkaline development process, or a developer containing an organic solvent (organic developer) for an organic solvent development process.

[0233] <Alkaline Development Process> With conventional metal oxide resist materials, it has been difficult to form a positive-tone pattern with good resolution using an alkaline development process. In contrast, the resist material of this embodiment makes it possible to form a pattern with good resolution using a developer containing water.

[0234] The alkaline developer used in the alkaline development process is not particularly limited, and any known or commonly used one can be used. Examples of the alkaline developer include aqueous solutions containing one or more of quaternary ammonium salts such as tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide, inorganic alkalis such as sodium hydroxide and potassium hydroxide, and alkanolamines such as dimethylethanolamine and triethanolamine.

[0235] The method for developing the exposed resist film using the alkaline developer is not particularly limited, and any known or commonly used method can be used. Examples of the method for developing using the developer include a method of immersing a substrate having an exposed resist film in the developer for a certain period of time (dip method), a method of spraying the developer onto the surface of the exposed resist film (spray method), and a method of discharging the developer at a constant speed from a discharge nozzle toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispense method).

[0236] Furthermore, pure water can be used as a rinse liquid in the alkaline development process.

[0237] <Organic Solvent Development Process> Examples of developers used in the organic solvent development process include developers containing one or more organic solvents such as polar solvents, such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, and hydrocarbon-based solvents.

[0238] Specific examples of organic solvents include: ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; ester-based 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); and nitrile-based solvents such as acetonitrile, propionitrile, and benzonitrile. Examples of the solvent include amide-based solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ether-based 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; and hydrocarbon-based solvents such as n-pentane, n-hexane, toluene, and xylene. These may be used alone or in combination of two or more.

[0239] Among these, the organic solvent used in the developer is preferably a polar solvent, and preferably contains an amide solvent, an alcohol solvent, or an ester solvent, and more preferably contains an amide solvent or an ester solvent and an alcohol 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 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 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.

[0240] When the developer contains both an amide solvent or an ester solvent and an alcohol solvent, the blending ratio (weight ratio) of the amide solvent or the ester solvent to the alcohol solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0241] The method for developing the exposed resist film using the developer is not particularly limited, and any known or commonly used method can be used. Examples of the method for developing using the developer include a method of immersing a substrate having an exposed resist film in the developer for a certain period of time (dip method), a method of spraying the developer onto the surface of the exposed resist film (spray method), and a method of discharging the developer at a constant speed from a discharge nozzle toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispense method).

[0242] After development with the developer, a step of washing with a rinse liquid may be included. The rinse liquid is not particularly limited, and any known or commonly used liquid may be used. As the rinse liquid, water or an organic solvent contained in the developer that does not easily dissolve the resist pattern may be appropriately selected and used.

[0243] The rinse liquid is not particularly limited, and may be, for example, at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Among these, it is preferable to use at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents as the rinse liquid, it is more preferable to use at least one solvent selected from the group consisting of alcohol solvents and ester solvents, and it is even more preferable to use at least one alcohol solvent.

[0244] The alcohol-based solvent used in the rinse solution is preferably a monohydric alcohol having 2 to 8 carbon atoms, and the monohydric alcohol may be linear, branched, or 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.

[0245] The method for cleaning the resist pattern with the rinse liquid is not particularly limited, and any known or commonly used method can be used. Examples of the cleaning method using 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 onto the surface of the resist pattern (spray method), and a method of discharging the rinse liquid at a constant speed from a discharge nozzle toward the surface of the resist pattern that is rotating at a constant speed (dynamic dispense method).

[0246] 3. 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 described above.

[0247] The average thickness of part or all of the patterned structure according to this embodiment is not particularly limited and can be set appropriately depending on the intended use, etc. The patterned structure preferably has portions with an average thickness of 1 to 100 nm, more preferably 5 to 75 nm, and even more preferably 10 to 60 nm.

[0248] The pitch of part or all of the patterned structure according to this embodiment is not particularly limited and can be set appropriately depending on the purpose of use, etc. In the patterned structure, it is preferable to have a part with a pitch of 100 nm or less, more preferably a part with a pitch of 50 nm or less, and even more preferably a part with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the above-mentioned pattern formation method, it is possible to create parts with pitches of 50 nm, 20 nm, or 15 nm in part or all of the patterned structure.

[0249] [4. Resist Material for EUV, BEUV, or Electron Beam Use] The resist material according to this embodiment contains a heteropolyacid salt or a mixture thereof in which vacancy sites have been modified. By introducing an onium cation or an onium dication into the cation moiety of the heteropolyacid salt or the mixture thereof in which vacancy sites have been modified, an acid generating function can be imparted upon exposure to EUV (extreme ultraviolet), BEUV (very extreme ultraviolet), an electron beam, or the like.

[0250] Furthermore, the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment has a plurality of polar groups having an acid-dissociable group introduced into the anion moiety, and therefore the resist material has the function of significantly changing its solubility in a developer by the action of an acid or the like.

[0251] That is, the resist material according to this embodiment contains a heteropolyacid salt or a mixture thereof in which the defect sites have been modified, and can significantly change the solubility in a developer between the exposed portion and the unexposed portion by EUV, BEUV, electron beam, or the like.

[0252] Additionally, in the heteropolyacid anion used in the anion portion of the heteropolyacid salt or mixture thereof whose defect sites are modified according to this embodiment, the polyatom is Mo, W, V, Nb, or Ta, thereby enabling efficient absorption of actinic rays such as EUV, BEUV, and electron beams. In particular, when the polyatom is W, W has a high absorption cross section in BEUV, and therefore can be particularly suitably used in microfabrication processes using BEUV exposure.

[0253] Therefore, the resist material according to this embodiment is a resist material that is sensitive to EUV, BEUV, or electron beams, and can be suitably used as a resist material for EUV, BEUV, or electron beams.

[0254] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0255] [1. Synthesis of Polyacid Salt] <Production Example 1: Potassium undecatungstosilicate (α-K ８ [SiW １１ O ３９ ]) > Production of tungstosilicic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ４ [SiW １２ O ４０ ]・xH ２ To 63 g of 1M acetic acid (C10), 380 g was added, and the reaction solution was heated to 45 ° C. Potassium bicarbonate (52 g) was added so that the pH was 6.0. The reaction solution was then cooled to room temperature and filtered off by suction, yielding 56 g of a crude product. 216 g of purified water was added to the resulting crude product, which was then redissolved by heating to 73 ° C. The solution was cooled at 4 ° C. for 16 hours to recrystallize, which was then filtered off by suction and dried in vacuo to yield 34 g of the target compound. ２９ Si-NMR (119.22MHz, D ２O): δ (ppm) = -84.6 (s, 1Si). １８３ W-NMR (20.84MHz, D ２ O): δ (ppm) = -101.85 (s, 2W), -116.26 (s, 2W), -119.29 (s, 1W), -125.62 (s, 2W), -140.85 (s, 2W), -174.53 (s, 2W).

[0256] <Production Example 2: Production of di(1-methylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound B)>

[0257] Production Example 2-1: Production of di(1-methylcyclopentyl) (2E)-but-2-enedioate (Compound A) 1-Methylcyclopentanol (14.1 g), dichloromethane (60 g), and triethylamine (21.3 g) were charged and ice-cooled with stirring. Fumaryl chloride (10.3 g) was added thereto and stirred for 1 hour. Thereafter, a 5% aqueous potassium carbonate solution (60 g) was charged and stirred. After stirring was stopped, the aqueous layer was removed and washed with ultrapure water (60 g). The organic layer was concentrated under reduced pressure, yielding 14.5 g of Compound A.

[0258] Production Example 2-2: Production of di(1-methylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound B) Compound A (7.7 g), 3-mercaptopropyltrimethoxysilane (9.8 g), methyl ethyl ketone (20 ml), and 1,1'-azobis(cyclohexane-1-carbonitrile) (0.3 g) were charged in this order and stirred. Thereafter, the temperature was raised from room temperature to 90°C and the mixture was stirred for 7 hours. The reaction liquid was evaporated and further dried in vacuo to obtain 16.6 g of Compound B. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 2H), 1.38-1.82 (m, 20H), 1.90-2.10 (m, 4H), 2.50-2.80 (m, 4H), 3.45-3.50 (m, 10H).

[0259] <Production Example 3: Production of di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound D)>

[0260] Production Example 3-1: Production of di(1-t-butylcyclopentyl)(2E)-but-2-enedioate (Compound C) Compound C was obtained in the same manner as in Production Example 2-1, except that 1-methylcyclopentanol was changed to 1-t-butylcyclopentanol. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (s, 18H), 1.78-1.98 (m, 8H), 2.12-2.21 (m, 4H), 2.47-2.53 (m, 4H), 6.80 (s, 2H).

[0261] Production Example 3-2: Production of di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound D) Compound D was obtained by changing Compound A to Compound C in Production Example 2-2. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 2H), 0.95 (s, 18H), 1.62-1.82 (m, 10H), 1.90-2.10 (m, 4H), 2.20-2.32 (m, 4H), 2.50-2.80 (m, 4H), 3.45-3.50 (m, 10H).

[0262] <Production Example 4: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound F)>

[0263] Production Example 4-1: Production of di(1-phenylcyclopentyl) (2E)-but-2-enedioate (Compound E) Compound E was obtained by changing 1-methylcyclopentanol to 1-phenylcyclopentanol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.78-1.98 (m, 8H), 2.02-2.21 (m, 4H), 2.37-2.53 (m, 4H), 6.80 (s, 2H), 7.20-7.49 (m, 10H).

[0264] Production Example 4-2: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound F) Compound F was obtained by changing Compound A in Production Example 2-2 to Compound E. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 2H), 1.62-1.82 (m, 10H), 1.90-2.10 ( m, 4H), 2.20-2.32 (m, 4H), 2.50-2.80 (m, 4H), 3.45-3.50 (m, 10H), 7.10-7.39 (m, 10H).

[0265] <Synthesis Example 1: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-1))>

[0266] 5.6 g of Compound B was added to a mixed solvent of 402 g of acetonitrile and 184 g of pure water, and the mono-defective Keggin-type potassium undecatungstosilicate (α-K ８ [SiW １１ O ３９ 10.9 g of bis(2-trifluoromethylphenylphenylsulfonium chloride) was added to the concentrate. The pH was adjusted to 1.8 with 1 M hydrochloric acid, and the mixture was stirred for 2 hours. The filtrate was then concentrated to approximately 200 g. To this concentrated solution, 9.9 g (18.2 mol) of bis(2-trifluoromethylphenylphenylsulfonium chloride) and 40 g of pure water were added to precipitate a powder. The precipitated powder was separated by filtration, washed three times with 180 mL of pure water, and separated by filtration. The mixture was then thoroughly dried under vacuum to obtain 15.8 g of polyacid salt (A-1). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.38-1.82 (m, 40H), 1 90-2.10 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.65-8.35 (m, 52H). ２９Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 864.1 (median) ([C ３８ H ６２ O ４８ S ２ Si ３ W １１ ] ４－ )

[0267] <Synthesis Example 2: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-t-butylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-2))>

[0268] In Synthesis Example 1, compound B was changed to compound D, thereby obtaining polyacid salt (A-2). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 0.95 (s, 36H), 1.62-1.82 (m, 20H), 1.9 0-2.10 (m, 8H), 2.20-2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 906.2 (median) ([C ５０ H ８６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0269] <Synthesis Example 3: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-3))>

[0270] In Synthesis Example 1, compound B was changed to compound F, and polyacid salt (A-3) was obtained. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2. 20-2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.10-7.39 (m, 20H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0271] <Synthesis Example 4: Synthesis of tetrakis((4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-bis(3-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-4))>

[0272] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide, thereby obtaining polyacid salt (A-4). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 0.77-0.81 (t, 12H), 1.38-1.82 (m, 64H), 1.90-2.10 (m, 2 4H), 2.20-2.32 (m, 24H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 4.55 (s, 8H), 7.59 (s, 8H), 7.76-7.82 (m, 40H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 461.2 ([C ２９ H ３３ O ３ S] ＋ ) NEGATIVE m / z 864.1 (median) ([C ３８ H ６２ O ４８ S ２ Si ３ W １１ ] ４－ )

[0273] <Synthesis Example 5: Synthesis of tetrakis(triphenylsulfonium)(1,3-bis(3-(1,2-di(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-5))>

[0274] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to triphenylsulfonium chloride to obtain polyacid salt (A-5). １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.38-1.82 (m, 40H), 1 90-2.10 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.78-7.87 (m, 60H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 864.1 (median) ([C ３８ H ６２ O ４８ S ２ Si ３ W １１ ] ４－ )

[0275] Synthesis Example 6: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)silicate (polyacid salt (A-6))

[0276] 37.26 g of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was dissolved in 50 g of cyclohexanone, and silicotungstic acid (H ４ [SiW １２ O ４０ ]・26H ２ 41.06 g of methyl 2-hydroxybenzoate (A-1) was added, and the reaction solution was stirred at room temperature for 2 hours. The reaction solution was filtered, and the obtained powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized at room temperature using dichloromethane and acetonitrile to obtain polyacid salt (A-6). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.63-8.34 (m, 52H). １８３ W-NMR (20.84 MHz, DMSO-d6): δ (ppm) = -92.7 (s12W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ )

[0277] <Production Example 5: Production of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane (Compound G)>

[0278] Compound G was obtained by changing Compound A in Production Example 2-2 to 1-methylcyclopentyl acrylate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 2H), 1.49 (s, 3H), 1.54-1.71 (m, 8H), 1.99-2.08 (m, 2H), 2.49 (t, 2H), 2.58 (t, 2H), 2.67 (t, 2H), 3.50 (s, 9H).

[0279] <Synthesis Example 7: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-7))>

[0280] In Synthesis Example 1, compound B was changed to 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane to obtain polyacid salt (A-7). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.49 (s, 6H), 1.54-1.71 (m, 16H) , 1.99-2.08 (m, 4H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１] ４－ )

[0281] <Synthesis Example 8: Synthesis of tetrakis(bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-8))> In Synthesis Example 1, Compound B was changed to Compound F and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium triflate to obtain polyacid salt (A-8). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2.20-2. 32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 6.75-6.81 (m, 24H), 7.10-7.39 (m, 28H), 7.77 (d, 8H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 460.9 ([C １８ H １０ F ４ IS] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0282] <Production Example 6: Production of bis(3,5-difluorophenyl)(3,4-diiodophenyl)sulfonium triflate> 5.8 g of bis(3,5-difluorophenyl) sulfoxide and 8.3 g of 1,2-diiodobenzene were dissolved in 30 g of chloroform, stirred at room temperature for 30 minutes, and then cooled to 5°C. 7.1 g of trifluoromethanesulfonic anhydride was added to the resulting mixed solution, and the mixture was stirred at room temperature for 1 hour. 10 g of pure water was added and the mixture was stirred at room temperature for 30 minutes, after which the organic layer was separated and isolated. This organic layer was washed three times with pure water in the same manner, and then concentrated using a rotary evaporator. 30 g of t-butyl methyl ether was added to the resulting crude product, and 4.3 g of the precipitated powder was obtained as the target compound. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 6.75-6.81 (m, 6H), 7.09 (d, 1H), 7.48 (s, 1H), 7.54 (d, 1H).

[0283] <Synthesis Example 9: Synthesis of tetrakis(bis(3,5-difluorophenyl)(3,4-diiodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-9))> In Synthesis Example 1, Compound B was changed to Compound F and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to bis(3,5-difluorophenyl)(3,4-diiodophenyl)sulfonium triflate to obtain polyacid salt (A-9). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2.20-2.32 (m, 8 H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 6.75-6.81 (m, 24H), 7.09-7.39 (m, 24H), 7.48 (s, 4H), 7.54 (d, 4H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 586.8 ([C １８ H ９ F ４I ２ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0284] <Synthesis Example 10: Synthesis of tetrakis(bis(4-fluorophenyl)(4-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-10))> In Synthesis Example 1, Compound B was changed to Compound F, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to bis(4-fluorophenyl)(4-iodophenyl)sulfonium chloride, to obtain polyacid salt (A-10). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H) , 2.20-2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.10-7.39 (m, 60H), 7.77 (d, 8H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 425.0 ([C １８ H １２ F ２ IS] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0285] <Synthesis Example 11: Synthesis of tetrakis((3,4-diiodophenyl)di(4-fluorophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-11))> In Synthesis Example 1, Compound B was changed to Compound F and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (3,4-diiodophenyl)di(4-fluorophenyl)sulfonium chloride to obtain polyacid salt (A-11). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2.20 -2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.09-7.39 (m, 56H), 7.48 (d, 4H), 7.54 (d, 4H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 550.9 ([C １８ H １１ F ２ I ２ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0286] <Synthesis Example 12: Synthesis of tetrakis((4-iodophenyl)di(4-(trifluoromethyl)phenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-12))> In Synthesis Example 1, Compound B was changed to Compound F and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (4-iodophenyl)di(4-(trifluoromethyl)phenyl)sulfonium chloride to obtain polyacid salt (A-12). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2.20- 2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.10-7.39 (m, 44H), 7.47 (d, 16H), 7.77 (d, 8H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 525.0 ([C ２０ H １２ F ６ IS] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0287] <Production Example 7: Production of (3,5-dimethyl-4-((3-methyl-2-cyclohexen-1-yloxycarbonyl)methyloxy)phenyl)di(phenyl)sulfonium bromide> 6.04 g (15.6 mmol) of (4-hydroxy-3,5-dimethylphenyl)diphenylsulfonium bromide and 10.15 g (31.1 mmol) of cesium carbonate were dissolved in 150 mL of dimethylformamide, and 3.99 g (17.1 mmol) of 3-methyl-2-cyclohexen-1-yl 2-bromoacetate was added dropwise at 0°C under a nitrogen atmosphere. The solution was gradually warmed to room temperature and stirred for 16 hours, after which 400 mL of water and 400 mL of dichloromethane were added. The organic layer was separated, and the aqueous layer was extracted with dichloromethane. The combined organic layers were extracted with water, dried over sodium sulfate, and then concentrated to a volume of 100 mL. 700 mL of methyl t-butyl ether was added to this solution, resulting in the deposition of a precipitate. The precipitate was filtered off, washed with methyl t-butyl ether, and thoroughly dried in vacuo to obtain 8.07 g of the target compound as a white solid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.60-2.01 (m, 9H), 2.15 (s, 6H), 4. 90 (s, 2H), 5.13 (q, 1H), 5.37 (d, 1H), 7.11 (s, 2H), 7.33-7.36 (m, 10H).

[0288] <Production Example 8: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound I)>

[0289] Production Example 8-1: Production of di(1-phenylcyclohexyl)(2E)-but-2-enedioate (Compound H) Compound H was obtained by changing 1-methylcyclopentanol to 1-phenylcyclohexanol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.43-1.53 ​​(12H), 1.86 (m, 4H), 2.12 (m, 4H), 6.31 (s, 2H), 7.17 (m, 2H), 7.30 (t, 4H), 7.54 (dd, 4H).

[0290] Production Example 8-2: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound I) Compound I was obtained by changing Compound A to Compound H and 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane in Production Example 2-2. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.43-1.53 ​​(m, 12H), 1.86 (m, 4H), 2.12 (m, 4H), 2.40 (t, 2H), 2.81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 7.17 (m, 2H), 7.30 (t, 4H), 7.54 (dd, 4H).

[0291] <Synthesis Example 13: Synthesis of tetrakis((3,5-dimethyl-4-((3-methyl-2-cyclohexen-1-yloxycarbonyl)methyloxy)phenyl)di(phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-13))> In Synthesis Example 1, Compound B was changed to Compound I, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (3,5-dimethyl-4-((3-methyl-2-cyclohexen-1-yloxycarbonyl)methyloxy)phenyl)di(phenyl)sulfonium bromide, thereby obtaining polyacid salt (A-13). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.79 (m, 4H), 1.43-2.15 (m, 100H), 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 4.90 (s, 8H), 5.13 (q, 4H), 5.37 (d, 4H), 7.11-7.17 (m, 12H), 7.30-7.36 (m, 48H), 7.54 (dd, 8H). ２９Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -57.02 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 459.2 ([C ２９ H ３１ O ３ S] ＋ ) NEGATIVE m / z 963.4 (median) ([C ６４ H ８２ O ４８ S ４ Si ３ W １１ ] ４－ )

[0292] <Production Example 9: Production of (4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide> The target compound was obtained in Production Example 7, except that 3-methyl-2-cyclohexen-1-yl 2-bromoacetate was replaced with 2-cyclopenten-1-yl 2-bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.02 (m, 1H), 2.15 (s, 6H), 2.23-2.33 (m, 3H) , 4.90 (s, 2H), 5.45 (m, 1H), 5.60-5.61 (m, 2H), 7.11 (s, 2H), 7.33-7.36 (m, 10H).

[0293] <Synthesis Example 14: Synthesis of tetrakis((4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-14))> Polyacid salt (A-14) was obtained in Synthesis Example 1 by changing Compound B to Compound I and by changing bis(2-trifluoromethylphenyl)phenylsulfonium chloride to (4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.79 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.02-2.40 (m, 52H), 2.81-2.85 (m, 10H), 3. 10 (m, 2H), 4.00 (t, 2H), 4.90 (s, 8H), 5.45 (m, 4H), 5.60-5.61 (m, 8H), 7.11-7.17 (m, 12H), 7.30-7.36 (m, 48H), 7.54 (dd, 8H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -57.02 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 431.2 ([C ２７ H ２７ O ３ S] ＋ ) NEGATIVE m / z 963.4 (median) ([C ６４ H ８２ O ４８ S ４ Si ３ W １１ ] ４－ )

[0294] <Production Example 10: Production of (4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide> The target compound was obtained in Production Example 7, except that 3-methyl-2-cyclohexen-1-yl 2-bromoacetate was replaced with 1-indanyl 2-bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.15 (m, 7H), 2.40 (m, 1H), 3.11-3.21 (m, 2H), 4. 90 (s, 2H), 6.08 (t, 1H), 7.06-7.13 (m, 4H), 7.22-7.26 (m, 2H), 7.33-7.36 (m, 10H).

[0295] <Synthesis Example 15: Synthesis of tetrakis((4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-15))> Polyacid salt (A-15) was obtained by changing Compound I instead of Compound B and changing bis(2-trifluoromethylphenyl)phenylsulfonium chloride to (4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide in Synthesis Example 1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.79 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12-2.40 (m, 44H), 2.81- 2.85 (m, 10H), 3.10-3.21 (m, 10H), 4.00 (t, 2H), 4.90 (s, 8H), 6.08 (t, 4H), 7.06-7.36 (m, 76H), 7.54 (dd, 8H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) δ (ppm) = -57.02 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 481.2 ([C ３１ H ２９ O ３ S] ＋ ) NEGATIVE m / z 963.4 (median) ([C ６４ H ８２ O ４８ S ４ Si ３ W １１ ] ４－ )

[0296] <Production Example 11: Production of di(2-cyclopenten-1-yl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound K)>

[0297] Production Example 11-1: Production of di(2-cyclopenten-1-yl)(2E)-but-2-enedioate (Compound J) Compound J was obtained by changing 1-methylcyclopentanol to 2-cyclopenten-1-ol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.02-2.33 (m, 8H), 5.45 (m, 2H), 5.60-5.61 (m, 4H), 6.31 (s, 2H).

[0298] Production Example 11-2: Production of di(2-cyclopenten-1-yl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound K) Compound K was obtained by changing Compound A in Production Example 2-2 to Compound J. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.62 (quint, 2H), 2.02-2.33 (m, 8H), 2.60 ( t, 2H), 2.85 (m, 1H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 5.45 (m, 2H), 5.60-5.61 (m, 4H).

[0299] <Synthesis Example 16: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(2-cyclopenten-1-yloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-16))> In Synthesis Example 1, compound B was changed to compound K to obtain polyacid salt (A-16). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62 (quint, 4H), 2.02-2.33 (m, 16H), 2.60 ( t, 4H), 2.85 (m, 2H), 3.10 (m, 2H), 4.00 (t, 2H), 5.45 (m, 4H), 5.60-5.61 (m, 8H), 7.65-8.35 (m, 52H). ２９Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 847.9 (median) ([C ３４ H ４６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0300] <Production Example 12: Production of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound M)>

[0301] Production Example 12-1: Production of di(1-indanyl) (2E)-but-2-enedioate (Compound L) Compound L was obtained by changing 1-methylcyclopentanol to 1-indanol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.15 (m, 2H), 2.40 (m, 2H), 3.11-3.21 (m, 4H), 6.08 (t, 2H), 6.31 (s, 2H), 7.06-7.26 (m, 8H).

[0302] Production Example 12-2: Production of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound M) Compound M was obtained by changing Compound A in Production Example 2-2 to Compound L. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.62 (quint, 2H), 2.15 (m, 2H), 2.40 (m, 2H), 2.60 ( t, 2H), 2.85 (m, 1H), 3.10-3.21 (m, 5H), 3.55 (s, 9H), 4.00 (t, 1H), 6.08 (t, 2H), 7.06-7.26 (m, 8H).

[0303] <Synthesis Example 17: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-indanyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-17))> In Synthesis Example 1, compound B was changed to compound M to obtain polyacid salt (A-17). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62 (quint, 4H), 2.15 (m, 4H), 2.40 (m, 4H), 2.60 (t , 4H), 2.85 (m, 2H), 3.10-3.21 (m, 10H), 4.00 (t, 2H), 6.08 (t, 4H), 7.06-7.26 (m, 16H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 898.4 (median) ([C ５０ H ５４ O ４８ S ２ Si ３ W １１ ] ４－ )

[0304] <Production Example 13: Potassium undecatungstophosphate (α-K ７ [P.W. １１ O ３９ ]) > Preparation of phosphotungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ３ [P.W. １２ O ４０ ]・xH ２To 63 g of acetic acid (C10), 380 g of 1 M acetic acid was added, and the reaction solution was heated to 45°C. Sodium bicarbonate (43 g) was added so that the pH was 4.8. The reaction solution was then cooled to room temperature. 41 g of potassium chloride was added to the resulting solution, and the solution was redissolved by heating to 73°C. The solution was cooled at 4°C for 16 hours to allow recrystallization, which was filtered off by suction filtration and dried in vacuo to obtain 38 g of the target compound. ３１ P-NMR (242.92MHz, D ２ O): δ (ppm) = 10.08 (s, 1P).

[0305] <Synthesis Example 18: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-18))> In Synthesis Example 1, Compound B was changed to Compound I, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-18). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ P.S.４ Si ２ W １１ ] ３－ )

[0306] <Production Example 14: Production of di(1-methylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound N)>

[0307] Compound N was obtained in Production Example 2-2, except that 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.39 (s, 6H), 1.56-1.81 (m, 1 6H), 2.40 (t, 2H), 2.81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H).

[0308] <Synthesis Example 19: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-19))> In Synthesis Example 1, Compound B was changed to Compound N, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-19). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.39 (s, 12H), 1.56-1.81 (m, 32H) , 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.02 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.75 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H１３ F ６ S] ＋ ) NEGATIVE m / z 1184.2 (median) ([C ４０ H ６６ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0309] <Production Example 15: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound P)>

[0310] Production Example 15-1: Production of di(1-ethylcyclopentyl) (2E)-but-2-enedioate (Compound O) Compound O was obtained by changing 1-methylcyclopentanol to 1-ethylcyclopentanol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90 (t, 6H), 1.49-1.81 (m, 20H), 6.31 (s, 2H).

[0311] Production Example 15-2: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound P) Compound P was obtained by changing Compound A to Compound O and 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane in Production Example 2-2. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90-0.95 (m, 8H), 1.49-1.81 (m, 20H) , 2.40 (t, 2H), 2.81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H).

[0312] <Synthesis Example 20: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-20))> In Synthesis Example 1, Compound B was changed to Compound P, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-20). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90-1.04 (m, 16H), 1.49-1.81 (m, 40H), 2. 40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.05 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.74 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1202.2 (median) ([C ４４ H ７４ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0313] <Production Example 16: Production of di(1-phenylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound Q)> Compound Q was obtained in Production Example 2-2, except that 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.63-1.92 (m, 12H), 2.17 (m, 4H), 2.40 (t, 2H), 2. 81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 7.17 (m, 2H), 7.30 (t, 4H), 7.54 (dd, 4H).

[0314] <Synthesis Example 21: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-21))> In Synthesis Example 1, Compound B was changed to Compound Q, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-21). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.63-1.92 (m, 24H), 2.17 (m, 8H), 2.40 (t, 4H), 2.81- 2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.03 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1266.2 (median) ([C ６０ H ７４ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0315] <Production Example 17: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound S)>

[0316] Production Example 17-1: Production of di(3-methyl-2-cyclohexen-1-yl)(2E)-but-2-enedioate (Compound R) Compound R was obtained by changing 1-methylcyclopentanol to 3-methyl-2-cyclohexen-1-ol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.60-2.01 (m, 18H), 5.13 (q, 2H), 5.37 (d, 2H), 6.31 (s, 2H).

[0317] Production Example 17-2: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound S) Compound S was obtained by changing 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane and compound A to compound R in Production Example 2-2. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.60-2.01 (m, 18H), 2.40 (t, 2H), 2 .81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 5.13 (q, 2H), 5.37 (t, 2H).

[0318] <Synthesis Example 22: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(3-methyl-2-cyclohexen-1-yloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-22))> In Synthesis Example 1, Compound B was changed to Compound S, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-22). １H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.60-2.01 (m, 36H), 2.40 (t, 4H), 2.81- 2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 5.13 (q, 4H), 5.37 (t, 4H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.72 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1200.2 (median) ([C ４４ H ６６ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0319] <Production Example 18: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound U)>

[0320] Production Example 18-1: Production of tri(1-methylcyclopentyl)(E)-1-propene-1,2,3-tricarboxylate (Compound T) 2.54 g (20.0 mmol) of trans-aconitic acid was dissolved in 20 g of DCM, and a solution of 5.58 g (44.0 mmol) of oxalyl chloride and 0.15 g (2.0 mmol) of DMF was added dropwise at 0°C. The reaction solution was stirred at room temperature for 12 hours, and the solvent was distilled off from the resulting reaction solution under vacuum to obtain a mixture containing trans-aconitic acid chloride. Thereafter, 4.46 g of Compound T was obtained by the same method as in Production Example 2-1, except that fumaryl chloride was changed to trans-aconitic acid chloride. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.39 (s, 9H), 1.63-1.81 (m, 24H), 3.58 (s, 2H), 6.79 (s, 1H).

[0321] Production Example 18-2: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound U) Compound U was obtained by changing Compound A in Production Example 2-2 to Compound T. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.39 (s, 9H), 1.56-1.81 ( m, 26H), 2.60-2.69 (m, 3H), 2.94 (m, 1H), 3.55 (s, 9H), 3.86-3.90 (m, 2H).

[0322] <Synthesis Example 23: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-23))> In Synthesis Example 1, compound B was changed to compound U to obtain polyacid salt (A-23). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.39 (s, 18H), 1.56-1.81 ( m, 52H), 2.60-2.69 (m, 6H), 2.94 (m, 2H), 3.86-3.90 (m, 4H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.02 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 934.7 (median) ([C ５４ H ８６ O ５２ S ２ Si ３ W１１ ] ４－ )

[0323] <Production Example 19: Production of tri(1-methylcyclopentyl) 1-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)-1,2,3-propanetricarboxylate (Compound V)> Compound V was obtained by changing Compound A to Compound T and 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane in Production Example 2-2. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.39 (s, 9H), 1.56-1.81 (m, 24H), 2 .40 (t, 2H), 2.69 (m, 1H), 2.81 (s, 4H), 2.94 (m, 1H), 3.55 (s, 9H), 3.86-3.90 (m, 2H).

[0324] <Synthesis Example 24: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-24))> In Synthesis Example 1, Compound B was changed to Compound V, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-24). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.39 (s, 18H), 1.56-1.81 (m, 48H), 2.40 (t, 4H), 2.69 (m, 2H), 2.81 (s, 8H), 2.94 (m, 2H), 3.86-3.90 (m, 4H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.02 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.74 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H１３ F ６ S] ＋ ) NEGATIVE m / z 1277.6 (median) ([C ５６ H ９０ O ５２ P.S. ４ Si ２ W １１ ] ３－ )

[0325] <Production Example 20: Production of di(1-phenylcyclohexyl) 2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)-1-(3-(trimethoxysilyl)propylthio)ethylcarbonyloxy)butanedioate (Compound Y)>

[0326] Production Example 20-1: Production of di(1,2-bis(methyloxycarbonyl)ethyl)(2E)-but-2-enedioate (Compound W) Compound W was obtained in the same manner as in Production Example 2-1, except that 1-methylcyclopentanol was changed to dimethyl DL-malate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.75 (m, 2H), 3.00 (m, 2H), 3.60 (s, 6H), 3.70 (s, 6H), 6.13 (t, 2H), 6.31 (s, 2H).

[0327] Production Example 20-2: Production of di(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyl)(2E)-but-2-enedioate (Compound X) 8.09 g (20.0 mmol) of Compound W was dissolved in pure water / 1,4-dioxane (480 mL / 320 mL), and 17.24 g (431.0 mmol) of sodium hydroxide was added. The reaction solution was stirred at room temperature for 20 hours and washed twice with 200 mL of t-butyl methyl ether. Thereafter, the pH of the aqueous layer was adjusted to 1 with 6 M hydrochloric acid, and the target product was extracted into the organic layer with 400 mL of t-butyl methyl ether. This operation was repeated five times, and the resulting organic layer was concentrated using a rotary evaporator and dried in vacuo to obtain a carboxylic acid. Thereafter, in Production Example 18-1, trans-aconitic acid was changed to the carboxylic acid obtained above, and this was converted into carboxylic acid chloride. Then, in Production Example 2-1, fumaryl chloride was changed to the carboxylic acid chloride and 1-methylcyclopentanol was changed to 1-phenylcyclohexanol, and 11.77 g of Compound X was obtained by the same method. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.75 ( m, 2H), 3.00 (m, 2H), 6.13 (t, 2H), 6.31 (s, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H).

[0328] Production Example 20-3: Production of di(1-phenylcyclohexyl) 2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)-1-(3-(trimethoxysilyl)propylthio)ethylcarbonyloxy)butanedioate (Compound Y) Compound Y was obtained by changing Compound A in Production Example 2-2 to Compound X. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.43-1.62 (m, 26H), 1.86 (m, 8H), 2.12 (m, 8H), 2.60 (t, 2H), 2.75 -2.85 (m, 3H), 3.00-3.10 (m, 3H), 3.55 (s, 9H), 4.00 (t, 1H), 6.13 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H).

[0329] <Synthesis Example 25: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-25))> In Synthesis Example 1, compound B was changed to compound Y to obtain polyacid salt (A-25). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.43-1.62 (m, 52H), 1.86 (m, 16H), 2.12 (m, 16H), 2.60 (t, 4H), 2.75- 2.85 (m, 6H), 3.00-3.10 (m, 6H), 4.00 (t, 2H), 6.13 (t, 4H), 7.17 (m, 8H), 7.30 (t, 16H), 7.54 (dd, 16H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.03 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1214.8 (median) ([C １２６ H １５０ O ６４ S ２ Si ３ W １１ ] ４－ )

[0330] <Production Example 21: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-(3-(trimethoxysilyl)propylthio)propylthio)butanedioate (Compound AA)>

[0331] Production Example 21-1: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-hydroxypropylthio)butanedioate (Compound Z) Compound Z was obtained by changing Compound A to Compound O and 3-mercaptopropyltrimethoxysilane to 2,3-mercapto-1-propanol in Production Example 2-2. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90 (t, 12H), 1.49-1.81 (m, 40H), 2.62 (m, 1H) ), 2.81-2.88 (m, 4H), 3.10 (m, 2H), 3.71 (m, 1H), 3.96-4.00 (m, 3H), 6.24 (s, 1H).

[0332] Production Example 21-2: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-(3-(trimethoxysilyl)propylthio)propylthio)butanedioate (Compound AA) To a DCM solution of Compound Z and pyridine, tosyl chloride was added dropwise at 0°C. The mixture was then stirred at room temperature for 18 hours, and the resulting crude product was purified by column chromatography. Thereafter, the resulting tosylate ester was reacted with 3-mercaptopropyltrimethoxysilane in a DCM solution in the presence of triethylamine to obtain Compound AA. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 0.90 (t, 12H), 1.49-1.81 (m, 42H), 2.60-2.62 (m, 4H), 2.85-2.88 (m, 4H), 3.08-3.10 (m, 3H), 3.55 (s, 9H), 4.00 (t, 2H).

[0333] <Synthesis Example 26: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(2,3-bis(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)propylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-26))> In Synthesis Example 1, Compound B was changed to Compound AA, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-26). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.93 (m, 28H), 1.49-1.81 (m, 84H), 2.60-2 .62 (m, 8H), 2.85-2.88 (m, 8H), 3.08-3.10 (m, 6H), 4.00 (t, 4H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -58.08 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([[C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1448.7 (median) ([C ８４ H １３８ O ５６ P.S. ６ Si ２ W １１ ] ３－ )

[0334] [2. Preparation of Test Resist Materials] Test resist materials (R-1) to (R-30) were prepared by blending the polyacid salts (A-1) to (A-26) synthesized above, an acid diffusion controller, and an organic solvent at the contents (unit: parts by mass) shown in Tables 1 to 3 below.

[0335] The acid diffusion controllers (B) shown in Table 1 were the following acid diffusion controllers (B-1) to (B-3): Acid diffusion controller (B-1): a salt of a triphenylsulfonium cation represented by the following formula (B-1) and a salicylic acid anion. Acid diffusion controller (B-2): an acid diffusion controller which is a salt of (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation represented by the following formula (B-2) and salicylic acid anion Acid diffusion controller (B-3): an acid diffusion controller which is a salt of a triphenylsulfonium cation represented by the following formula (B-3) and a heptafluorobutyrate anion

[0336]

[0337]

[0338]

[0339] [3. Formation of Test LS Pattern] Each test resist material (R-1) to (R-30) was applied using a spinner to an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS). A post-applied bake (PAB) treatment was performed on a hot plate at 120°C for 60 seconds, followed by drying to form a 50 nm thick resist film. The thickness of the formed resist film was measured using a film thickness measurement device (J.A. Woollam's "M-2000D"). The resist film was subjected to exposure (writing) using an electron beam lithography system F7000S-VD2 (Advantest Corporation) at an acceleration voltage of 50 kV to form a 1:1 line and space pattern (hereinafter also referred to as "LS pattern") with a target size of 50 nm line width. The resist film was then subjected to post-exposure baking (PEB) at 90°C for 60 seconds. Next, development was carried out for 60 seconds using a developer (NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) at 23°C, and rinsing was carried out for 60 seconds using pure water. As a result, a 1:1 LS pattern with a line width of 50 nm was formed, and test LS patterns (LS-1) to (LS-30) corresponding to each of the test resist materials (R-1) to (R-30) were obtained. Note that the test LS patterns (LS-1) to (LS-30) were all positive patterns.

[0340] [4. Evaluation of Test LS Pattern Shape] The shapes of the above test LS patterns (LS-1) to (LS-30) were observed using a length-measuring SEM (scanning electron microscope, accelerating voltage 10 kV, product name: SU-5000, manufactured by Hitachi High-Technologies Corporation), and the shapes were evaluated according to the following criteria.

[0341] <Evaluation of Dimension Controllability> The interface between the substrate and the resist pattern of the test LS pattern was observed with a scanning electron microscope, and cases where no footing was observed or where footing was observed but the foot length was less than 13 nm were evaluated as "A", cases where the foot length was 13 nm or more but less than 14 nm were evaluated as "B", cases where the foot length was 14 nm or more but less than 15 nm were evaluated as "C", and cases where the foot length was 15 nm or more were evaluated as "D". The evaluation results for each test LS pattern are shown in Tables 4 to 6.

[0342] <Evaluation of LWR (Line Width Roughness)> For each test LS pattern, 3σ, a measure of LWR, was determined. "3σ" indicates three times the standard deviation (σ) (unit: nm) obtained from the measurement results of 400 line positions measured in the longitudinal direction of the line using a scanning electron microscope. The smaller the 3σ value, the smaller the roughness of the line sidewall, meaning that an LS pattern with a more uniform width was obtained. The 3σ values ​​for each test LS pattern are shown in Tables 4 to 6.

[0343]

[0344]

[0345]

[0346] Comparing the results of LS-8 and LS-9 in Table 4, it can be seen that LS-8 prepared using test resist material R-8 containing polyacid salt (A-1), which is a heteropolyacid salt in which a plurality of polar groups having an acid-dissociable group have been introduced to modify defect sites, provides better results in both the dimension controllability and LWR evaluations than LS-9 prepared using test resist material R-9 containing polyacid salt (A-6), which is a heteropolyacid salt that does not have a polar group having an acid-dissociable group.

[0347] Furthermore, comparing the results of LS-8 and LS-11 in Table 4, it can be seen that LS-8 prepared using test resist material R-8 containing polyacid salt (A-1), which is a heteropolyacid salt in which defect sites have been modified and which has four polar groups each having an acid-dissociable group, gave better results in the LWR evaluation than LS-11 prepared using test resist material R-11 containing polyacid salt (A-7), which is a heteropolyacid salt in which defect sites have been modified and which has two polar groups each having an acid-dissociable group.

[0348] Comparing the results of LS-1 to LS-7 and LS-10 in Table 4, LS-1 to LS-7, which were prepared using test resist materials R-1 to R-7 containing any of polyacid salts (A-1) to (A-5), which are heteropolyacid salts modified at defect sites by the introduction of multiple polar groups having an acid-dissociable group, provided better results in the evaluation of dimensional controllability and also provided better results in the evaluation of LWR than LS-10, which was prepared using resist material R-10 containing polyacid salt (A-6), which is a heteropolyacid salt that does not have a polar group having an acid-dissociable group.

[0349] Furthermore, comparing the results of LS-1 to LS-7 and LS-8 in Table 4, it can be seen that LS-1 to LS-7, which were prepared using test resist materials R-1 to R-7 containing acid diffusion controllers (B-1) to (B-3) in the test resist material, provided better results in both the dimension controllability and LWR evaluations than LS-8, which was prepared using test resist material R-8 that did not contain an acid diffusion controller.

[0350] Table 5 shows that when resist materials R-12 to R-16, which contain polyacid salts (A-8) to (A-12) having sulfonium cations into which iodine atoms and / or fluorine atoms have been introduced, are used, as in the case of LS-12 to LS-16, good results are obtained in both the evaluation of LS pattern size controllability and LWR.

[0351] Table 5 also shows that, like LS-17 to LS-21, resist materials R-17 to R-21 containing polyacid salts (A-13) to (A-17) in which a polar group having an allyl or benzyl acid-dissociable group as the acid-dissociable group is introduced into the cation or anion moiety also provide good results in the evaluation of LS pattern size controllability and LWR. In particular, LS-20 and LS-21, which use resist materials R-20 or R-21 containing polyacid salts (A-16) or (A-17) in which multiple polar groups having an allyl or benzyl acid-dissociable group are introduced into the anion moiety, provide excellent results in the evaluation of LS pattern size controllability and LWR.

[0352] Table 6 shows that when resist materials R-22 to R-26, R-28, and R-30, which contain polyacid salts (A-18) to (A-22), (A-24), or (A-26) having, as the anion moiety, a heteropolyacid anion in which a defect site is modified with one defect Keggin-type undecatungstophosphate, as in LS-22 to LS-26, LS-28, and LS-30, are used, excellent results are obtained in both the evaluation of LS pattern size controllability and LWR. Furthermore, Table 6 shows that when resist materials R-27 and R-28, which contain polyacid salts (R-23) or (R-24) in which six polar groups having an acid-dissociable group have been introduced into the anion moiety, as in LS-27 and LS-28, are used, and when resist materials R-29 and R-30, which contain polyacid salts (R-25) or (R-26) in which eight polar groups having an acid-dissociable group have been introduced into the anion moiety, as in LS-29 and LS-30, are used, remarkably good results are obtained in the evaluation of LS pattern size controllability and LWR.

[0353] [5. Microfabrication by BEUV Exposure] <Preparation of Test Resist Materials> Test resist materials (R'-1) and (R'-2) shown in Table 7 below were prepared as test resist materials. Note that test resist material (R'-1) is a metal oxide resist, whereas test resist material (R'-2) is a polymer-type chemically amplified resist (CAR).

[0354] The following polymers (P-1), photoacid generators (PAG), acid diffusion controllers (B'-1) and (B'-2), and quenchers were used as shown in Table 7. In Table 7, CP represents cyclopentanone, PGMEA represents propylene glycol methyl ether acetate, and PGME represents propylene glycol monomethyl ether.

[0355] Polymer (P-1): A polymer obtained by copolymerizing 4-vinylphenol represented by the following formula (P-1) with 1-phenylcyclopentyl methacrylate (molar ratio: 40:60; weight average molecular weight (Mw) calculated in terms of standard polystyrene obtained by GPC measurement: 7,000)

[0356] Photoacid generator (PAG): a photoacid generator which is a salt of a bis(3,5-difluorophenyl)(phenyl)sulfonium cation represented by the following formula (PAG) and a specific sulfonate anion

[0357] Acid diffusion controller (B'-1): an acid diffusion controller which is a salt of a (phenyl)bis(2-(trifluoromethyl)phenyl)sulfonium cation represented by the following formula (B'-1) and a salicylic acid anion

[0358] Acid diffusion controller (B'-2): an acid diffusion controller which is a salt of bis(3,5-difluorophenyl)(phenyl)sulfonium cation represented by the following formula (B'-2) and salicylic acid anion

[0359] Quencher: A quencher that is salicylic acid represented by the following formula:

[0360]

[0361] <Formation of Test LS' Pattern> Each test resist material (R'-1) and (R'-2) was applied using a spinner onto a 4-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then prebaked (PAB) on a hot plate at 110°C for 60 seconds, followed by drying to form a 28 nm thick resist film. The thickness of the formed resist film was measured using a film thickness measurement device ("M-2000D" manufactured by J.A. Woolam). The resist film was subjected to two-beam interference exposure by irradiating it with light having a wavelength of 6.7 nm through a diffraction grating to form a 1:1 run-and-space pattern (hereinafter also referred to as "LS' pattern") with a pitch of 50 nm. The LS' pattern formed from the test resist material (R'-1) was then subjected to post-exposure bake (PEB) at 85°C for 60 seconds. Furthermore, the LS' pattern prepared from the test resist material (R'-2) was subjected to PEB treatment at 90°C for 60 seconds. Next, the above LS' pattern was subjected to alkaline development for 30 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, and then rinsed with pure water for 15 seconds. As a result, test LS' patterns (LS'-1) and (LS'-2) corresponding to each test resist material (R'-1) and (R'-2) were obtained.

[0362] <Evaluation of Test LS' Patterns> The shapes of the above LS' patterns (LS'-1) and (LS'-2) were observed using a scanning electron microscope (SU8200, manufactured by Hitachi High-Technologies Corporation). As a result, the resist film prepared from the test resist material (R'-1) formed a 50 nm pitch LS' pattern even at an exposure dose of 50% of that of the resist film prepared from the test resist material (R'-2), assuming an exposure dose of 100%, and provided a good LS' pattern without residue or breaks. Furthermore, under the above conditions, the LWR(3σ) of the LS' pattern prepared from the test resist material (R'-2) was 5.9 nm, while the LWR(3σ) of the LS' pattern prepared from the test resist material (R'-1) was 5.7 nm, showing good values ​​for LWR(3σ).

[0363] From the above results, it can be seen that by incorporating W element, which has a high absorption cross section beyond EUV, as in the test resist material (R'-1), good results are obtained in the microfabrication process using beyond EUV exposure.

Claims

(A) A resist material containing a heteropolyacid salt or a mixture thereof in which defect sites are modified, the anion moiety of the heteropolyacid salt whose defect sites have been modified contains a plurality of polar groups each having an acid-dissociable group; Resist material.

2. The resist material according to claim 1, wherein the resist material generates an acid upon exposure and changes its solubility in a developer by the action of the acid.

2. The resist material according to claim 1, wherein the acid-dissociable group is a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group.

2. The resist material according to claim 1, wherein the anion moiety of the heteropolyacid salt or mixture thereof (A) having modified deficiency sites is a heteropolyacid anion having deficiency sites and wherein the deficiency sites are modified. 　 the modification is achieved by bonding a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more organic groups are bonded to the heteropoly acid anion having the defective site via some or all of the heteroatoms; the organic group has two or more polar groups each having an acid-dissociable group; The resist material according to claim 4. 　 The organic group may be C １－１８ is a hydrocarbyl group, C which may have the above-mentioned substituent １－１８ Any divalent carbon atom excluding the terminal carbon atom of the hydrocarbyl group may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time), C which may have the above-mentioned substituent １－１８ two or more hydrogen atoms contained in the hydrocarbyl group are replaced by polar groups having an acid-dissociable group; The resist material according to claim 5 . 　 The resist material according to claim 5, wherein the organic group is represented by general formula (VII-2): [In general formula (VII-2), L ２Ｂ is an optionally substituted C １－１２ In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ represents a group substituted with Said L ２Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time); R ２Ｃ each independently represents a polar group having an acid-dissociable group; x represents an integer of 2 to 6; * represents a bond between the organic group and a heteroatom P, Si, Ge, or Sn.] 　 5. The resist material according to claim 4, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge.

5. The resist material according to claim 4, wherein the heteropoly acid anion having a defect site is a defective Keggin type heteropoly acid anion or a defective Dawson type heteropoly acid anion.

10. The resist material according to claim 9, wherein the defective Keggin-type heteropolyacid anion is represented by general formula (II-1), (II-2), or (II-3). [XM １１ O ３９ ] ｃ１１－ (II-1) [XM １０ O ３６ ] ｃ１２－ (II-2) [XM ９ O ３４ ] ｃ１３－ (II-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.

10. The resist material according to claim 9, wherein the deficient Dawson type heteropoly acid anion is represented by general formula (III-1), (III-2), or (III-3). [X ２ M １７ O ６１ ] ｃ２１－ (III-1) [X ２ M １６ O ５８ ] ｃ２２－ (III-2) [X ２ M １５ O ５６ ] ｃ２３－ (III-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.

2. The resist material according to claim 1, wherein the (A) heteropolyacid salt having modified defect sites or a mixture thereof is a heteropolyacid salt having modified defect sites represented by general formula (I) or a mixture thereof: (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In general formula (I), A ｍ＋ are each independently H ＋ , metal ions, NH ４ ＋ , an onium cation, or an onium dication; C （ａｍ）－ represents a heteropolyanion having a defect site, the defect site of which has been modified, the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m is an integer from 1 to 5, and a is a real number greater than 0.

2. The resist material according to claim 1, wherein the (A) heteropolyacid salt having modified defect sites or a mixture thereof is a heteropolyacid salt having modified defect sites represented by general formula (I') or a mixture thereof: (A’ ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C’(a’m’+bn)-) (I’) [In general formula (I'), A' ｍ’＋ are each independently H ＋ , metal ions, or NH ４ ＋ represents; B ｎ＋ each independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents a heteropolyanion having a defect site, the defect site of which has been modified; the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m' is an integer from 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0. 　 The resist material of claim 13 , wherein the onium cation is a sulfonium cation or an iodonium cation. 　 The resist material according to claim 1 , further comprising (B) an acid diffusion controller. 　 The resist material according to claim 15 , wherein the (B) acid diffusion controller is (B1) a photodegradable base. 　 The resist material according to claim 1 , further comprising an organic solvent. 　 The resist material according to any one of claims 1 to 17, which is a resist material that is sensitive to EUV, BEUV, or an electron beam. 　 A step of forming a resist film using the resist material according to any one of claims 1 to 17; exposing the resist film to light; developing the exposed resist film using a developer; A pattern forming method comprising:

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