Resist material and pattern forming method

Abstract

The purpose of the present invention is to provide a novel resist material and a pattern forming method. The resist material comprises (A) a polymer and (B) a metal compound, wherein the component (A) comprises a structural unit containing a fluorine atom, the structural unit having a monovalent or divalent aromatic hydrocarbon cyclic group in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms.

Description

Resist material and pattern formation method

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

[0002] In recent years, advancements in lithography techniques such as immersion lithography and EUV lithography have led to the miniaturization of circuit patterns. This progress in lithography technology necessitates the development of new resist materials to accommodate these advancements.

[0003] In addition to conventional chemically amplified resists, new resist materials have been proposed that include metal compounds, organometallic compounds, metal nanoparticles, metal clusters, and the like.

[0004] For example, Patent Document 1 discloses a radiation-sensitive composition used in extreme ultraviolet or electron exposure, comprising a first polymer and a solvent, wherein the first polymer has a first structural unit comprising one or more metal atoms and carbon atoms chemically bonded to the metal atoms that do not constitute an unsaturated bond, and at least one of the chemical bonds is a covalent bond. Patent Document 1 also discloses that the composition may further contain fluorine atom-containing polymers other than the first polymer, and that by including the fluorine atom-containing polymer, when a film is formed, the distribution of the fluorine atom-containing polymer in the film tends to be concentrated near the film surface due to its oleophobic properties, thereby suppressing the elution of radiation-sensitive acid generators, acid diffusion control agents, etc., into the immersion medium during immersion exposure, etc.

[0005] WO2018 / 123388

[0006] In response to this, regulations on perfluoroalkyl and polyfluoroalkyl compounds (PFAS), which are persistent, environmentally persistent, and bioaccumulative, have become stricter in recent years. For example, the U.S. Environmental Protection Agency (EPA) has announced that it will impose reporting regulations on certain PFAS under the Toxic Substances Control Act (TSCA). In Europe, a draft PFAS regulation based on the REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulation has been submitted to the European Chemicals Agency (ECHA) and has been published.

[0007] Therefore, there is a need for the development of resist materials that do not contain the specified PFAS compounds subject to the above regulations. However, with resist materials that do not contain the specified PFAS compounds, it has been difficult to obtain the sensitivity and resolution necessary for forming fine resist patterns.

[0008] The present invention has been made in view of the above circumstances, and aims to provide a resist material and a pattern forming method that have good sensitivity in resist pattern formation and reduce environmental impact, even when a predetermined PFAS is not used.

[0009] As a result of diligent research to solve the above problems, the present inventors have found that a resist material containing (A) a polymer and (B) a metal compound, wherein component (A) includes a structural unit having a fluorine atom, and the structural unit having a fluorine atom is a monovalent or divalent aromatic hydrocarbon cyclic group, wherein at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms, thereby providing good sensitivity in the formation of a resist pattern and reducing the environmental burden, thus completing the present invention.

[0010] In other words, the present invention relates to the following inventions: <1> A resist material comprising (A) a polymer and (B) a metal compound, wherein component (A) comprises a structural unit having a fluorine atom, and the structural unit having a fluorine atom is a monovalent or divalent aromatic hydrocarbon cyclic group, wherein at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms. <2> The resist material according to <1>, wherein the structural unit having a fluorine atom is a structural unit having a fluorine atom represented by the following general formula (I). [In formula (I), R α L represents a hydrogen atom, a halogen atom, or an alkyl group; A1 1 R represents a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2-; R A1 1This represents a monovalent organic group having a monovalent or divalent aromatic hydrocarbon cyclic group in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted by substituents. <3> The resist material according to <1> or <2>, wherein the monovalent or divalent aromatic hydrocarbon cyclic group is a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, a phenanthrenyl group, a phenanthrylene group, anthryl group, or anthrylene group.<4> The group in which at least two hydrogen atoms on the monovalent or divalent aromatic hydrocarbon cyclic group are substituted with fluorine atoms is a 2,3-difluorobenzene-1-yl group, a 2,4-difluorobenzene-1-yl group, a 2,5-difluorobenzene-1-yl group, a 2,6-difluorobenzene-1-yl group, a 3,4-difluorobenzene-1-yl group, a 3,5-difluorobenzene-1-yl group, a 3,5-difluoro-4-nitrobenzene-1-yl group, a 3,5-difluoro-4-cyanobenzene-1-yl group, or a 2,3,4-trifluorobenzene-1 -yl group, 2,3,5-trifluorobenzene-1-yl group, 2,3,6-trifluorobenzene-1-yl group, 2,4,5-trifluorobenzene-1-yl group, 2,4,6-trifluorobenzene-1-yl group, 3,4,5-trifluorobenzene-1-yl group, 2,3,4,5-tetrafluorobenzene-1-yl group, 2,3,4,6-tetrafluorobenzene-1-yl group, 2,3,5,6-tetrafluorobenzene-1-yl group, 2,2',3,3',4,4',5,5',6-nonafluoro-1,1'-biphenyl-6' -yl group, 2,3-difluorobenzene-1,4-diyl group, 2,5-difluorobenzene-1,4-diyl group, 2,6-difluorobenzene-1,4-diyl group, 2,3,5-trifluorobenzene-1,4-diyl group, 2,3,6-trifluorobenzene-1,4-diyl group, 2,3,5,6-tetrafluorobenzene-1,4-diyl group, 2,4-difluorobenzene-1,3-diyl group, 2,5-difluorobenzene-1,3-diyl group, 2,6-difluorobenzene-1,3-diyl group, 2,4,5-trifluorobenzene A resist material according to <1> or <2>, wherein the resist is a -1,3-diyl group, a 2,4,6-trifluorobenzene-1,3-diyl group, a 2,4,5,6-tetrafluorobenzene-1,3-diyl group, a 3,4-difluorobenzene-1,2-diyl group, a 3,5-difluorobenzene-1,2-diyl group, a 3,6-difluorobenzene-1,2-diyl group, a 3,4,5-trifluorobenzene-1,2-diyl group, a 3,4,6-trifluorobenzene-1,2-diyl group, or a 3,4,5,6-tetrafluorobenzene-1,2-diyl group.<5> The resist material according to <1> or <2>, wherein the component (A) contains a structural unit for adjusting the solubility in a developer. <6> The resist material according to <1> or <2>, wherein the component (A) does not contain a trifluoromethyl group excluding the trifluoromethyl group having a structure represented by the following general formula (F-1), or a trifluoromethylene group excluding the trifluoromethylene group having a structure represented by the following general formula (F-2) or (F-3). [In formula (F-1), X f1 represents -L f1 -O-, -L f1 -N(R f1 )- or -L f1 -N(L f2 )-; L f1 and L f2 each independently represents a methylene group, a divalent aromatic hydrocarbon cyclic group which may have a substituent, or a carbonyl group; R f1 represents a C 1-6 hydrocarbyl group which may have a substituent other than a hydrogen atom and a fluorine atom, or a monovalent aromatic hydrocarbon cyclic group which may have a substituent. ] [In formula (F-2), X f1 represents -L f1 -O-, -L f1 -N(R f1 )- or -L f1 -N(L f2 )-; L f1 and L f2 each independently represents a methylene group, a divalent aromatic hydrocarbon cyclic group which may have a substituent, or a carbonyl group; R f1 represents a C 1-6 hydrocarbyl group which may have a substituent other than a hydrogen atom and a fluorine atom, or a monovalent aromatic hydrocarbon cyclic group which may have a substituent, and X f2 represents a C 1-6 hydrocarbyl group which may have a substituent other than a fluorine atom, a monovalent aromatic hydrocarbon cyclic group which may have a substituent, -O-R f2 , -S-R f2 , -N(R f2 )(R f3) represents; R f2 and R f3 Each of these C atoms may independently have substituents other than hydrogen and fluorine atoms. 1-6 This represents a hydrocarbyl group, or a monovalent aromatic hydrocarbon cyclic group which may have substituents. [In formula (F-3), X f1 is, -L f1 -O-, -L f1 -N(R) f1 ) - or - L f1 -N(L) f2 -)- represents; L f1 and L f2 Each independently represents a methylene group, a optionally substituted divalent aromatic hydrocarbon cyclic group, or a carbonyl group; R f1 C may have substituents other than hydrogen atoms and fluorine atoms. 1-6 X represents a hydrocarbyl group or a monovalent aromatic hydrocarbon cyclic group which may have substituents. f3 This includes a methylene group, a divalent aromatic hydrocarbon group which may have substituents, a carbonyl group, and -O-L f3 -, -S-L f3 -, -N(R f4 )-L f3 -, -N(L f3 -) L f4 - represents; L f3 and L f4 Each independently represents a methylene group, a optionally substituted divalent aromatic hydrocarbon cyclic group, or a carbonyl group; R f4 C may have substituents other than hydrogen atoms and fluorine atoms. 1-6 This represents a hydrocarbyl group, or a monovalent aromatic hydrocarbon cyclic group which may have substituents.

[0011] <7> The resist material according to <1> or <2>, wherein the component (B) is an organometallic compound B1 represented by the following general formula (IV), or an organometallic compound B2 represented by the following general formula (V). M B1 (X B1 R B1 1 ) n (R B12 ) 4-n (IV) [In formula (IV), M B1 represents a metal atom or metal oxide; X B1 R represents -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2-; R B1 1 Each of these independently contains a hydrogen atom or a C which may have a substituent. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously); R B1 2 Each of these is independently a C which may have substituents. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously); n is an integer from 0 to 4. ] [(R B2 1 -Sn) 12 O 14 (OH) 6] 2+ (Y - )2 (V) [In formula (V), R B2 1 Each of these is independently a C which may have substituents. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously); Y -represents a monovalent anion independently. <8> The resist material according to <1> or <2>, wherein the component (B) is a polyacid salt represented by the following general formula (VII-1) or (VII-2) or a mixture thereof. (A m+ a )(C (am)- )(VII-1) [In the formula (VII-1), A m+ each independently represents H + , a metal ion, NH4 + , an onium cation, or an onium dication; C (am)- represents an isopolyacid anion or a heteropolyacid anion, m is an integer of 1 to 5, and a is a real number greater than 0.](A' m’+ a’ (B n+ b (C'(a'm'+bn)-) (VII-2) [In the formula (VII-2), A' m’+ each independently represents H + , a metal ion, or NH4 + ; B n+ each independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents an isopolyacid anion or a heteropolyacid anion, 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.]<9> The resist material according to <1> or <2>, further containing (C) an acid generator. <10> A pattern forming method including a step of forming a resist film using the resist material according to <1> or <2>, a step of exposing the resist film, and a step of developing the exposed resist film using a developer.

[0012] According to the present invention, even when a predetermined PFAS is not used, a resist material and a pattern forming method can be provided, which have good sensitivity in forming a resist pattern and can reduce the environmental load.

[0013] Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. ​​​

[0014] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0015] In this specification, the term "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0016] In this specification, for example, terms such as "C 1-6 " mean the number of carbon atoms in the parent nucleus group.

[0017] In this specification, "C 1-18 hydrocarbylene group" means a divalent hydrocarbon group formed by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear, branched, or partially or entirely cyclic. The hydrocarbylene group includes an alkylene group, an arylene group, and the like. Also, the divalent carbon atom at any position of the "C 1-18 hydrocarbylene group" may be replaced by -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO2- (however, it is assumed that two adjacent divalent carbon atoms are not replaced simultaneously). The "C 1-18 hydrocarbylene group" is not particularly limited, and examples include "C 1-18 alkylene groups" such as a methylene group, an ethylene group, an n-propylene group, an i-propylene group, a cyclopentadienyl group, a cyclohexanediyl group, an oxyethane-1,1-diyl group, an oxyethane-1,2-diyl group, an oxypropane-1,3-diyl group, an oxypropane-1,2-diyl group, a 2-methylpropane-1,3-diyl group, an oxyethyleneoxyethane-1,1-diyl group; "C 6-18 arylene groups" such as a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,8-naphthylene group, a 4,4'-biphenylene group, an anthracenediyl group, a phenanthrenediyl group, a naphthacenediyl group, a pyrenediyl group, a perylenediyl group, a chrysenediyl group, and the like.

[0018] In this specification, "C 1-18 "Alkyl alkyl group" refers to a linear or branched alkyl group having 1 to 18 carbon atoms. 1-18 Any divalent carbon atom in an alkyl group, excluding the terminals, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2-. However, adjacent divalent carbon atoms may not be replaced simultaneously. 1-18 The "alkyl group" is not particularly limited and includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, i-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1 Examples include 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. 1-18 The alkyl group in which a divalent carbon atom at any position other than the terminal is replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- is not particularly limited, and examples include the 2-methoxyethoxymethyl group and the ethoxycarbonylmethyl group.

[0019] In this specification, "C 1-18 "Haloalkyl group" refers to "C 1-18 "Alkyl group" refers to a group in which one or more hydrogen atoms are substituted with halogen atoms. 1-18The term "haloalkyl group" is not particularly limited and includes, for example, dichloromethyl group, trifluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, etc.

[0020] In this specification, "C 2-18 An "alkenyl group" is a group with two or more carbon atoms. 1-18 "Alkyl group" refers to an alkenyl group having one or more double bonds, and includes alkadinyl groups, alkatrienyl groups, etc. 2-18 The "alkenyl group" is not particularly limited and includes, for example, vinyl group (ethenyl group), allyl group (2-propenyl group), 1-propenyl group, isopropenyl group (1-methylvinyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc.

[0021] In this specification, "C 2-18 An "alkynyl group" is a group with two or more carbon atoms. 1-18 "Alkyl group" refers to an alkynyl group having one or more triple bonds. 2-18 The "alkynyl group" is not particularly limited and includes, for example, ethynyl group, 1-propynyl group, 2-propynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, desynyl group, undecynyl group, dodecynyl group, etc.

[0022] In this specification, "C 3-18 A "cycloalicyclic group" refers to a hydrocarbon group that has a monocyclic or polycyclic cyclic structure with 3 to 18 carbon atoms, either entirely or partially. Cyclocyclic groups include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc. 3-18Divalent carbon atoms at any position in an alicyclic group, excluding the terminals, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). 3-18 The term "cycloalkyl group" is not particularly limited and includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-i-propylcyclopentan-1-yl group, cyclohexyl group, t-butylcyclohexyl group, tricyclodecanyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, 2-methyladamantan-2-yl group, 2-i-propyladamantan-2-yl group, bornyl group, norbonyl group, fenquil group, pinanyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, bornylmethyl group, norbornylmethyl group, adamantylmethyl group, 1-methylcyclopentyloxycarbonylmethyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, and the like.

[0023] In this specification, "3- to 18-membered non-aromatic heterocyclic group" means a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and may be monocyclic, polycyclic, or fused, and may be saturated or partially unsaturated. The "3- to 18-membered ring non-aromatic heterocyclic group" is not particularly limited and includes, for example, aziridinyl group, azetidyl group, pyrrolidinyl group, pyrrolyl group, piperidinyl group, piperazinyl group, morpholinyl group, thiomorpholinyl group, tetrahydrofuryl group, tetrahydropyranyl group, oxetanyl group, tetrahydrofuryl group, tetrahydropyranyl group, imidazolinyl group, oxazolinyl group, 2,5-diazabicyclo[2.2.1]heptyl group, 2,5-diazabicyclo[2.2.2]octyl group, 3,8-diazabicyclo[3.2.1]octyl group, 1,4-diazabicyclo[4.3.0]nonyl group, 1-azadamantyl group, 2-azadamantyl group, etc.

[0024] In this specification, "C 2-18 An "aryl group" refers to 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 with 2 to 10 carbon atoms and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and each ring may be monocyclic, polycyclic, or fused. 2-18 The "aryl group" is not particularly limited and includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, azlenyl group, pentarenyl group, heptarenyl group, indacenyl group, acenaphthyl group, phenantrenyl group, anthracenyl group, etc.

[0025] In this specification, "C 7-18 "Aralkyl group" refers to "C 1-12 The substituted portion in the alkyl group is the above "C 2-12 This refers to a group that has been substituted with an aryl group. 7-18 The "aralkyl group" is not particularly limited and examples include benzyl group, phenethyl group, 3-phenylpropyl group, 4-phenylbutyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0026] In this specification, "C 1-18 A "hydrocarbyl group" refers to a monovalent group produced 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, and aralkyl groups. 1-18 Any divalent carbon atom in the hydrocarbyl group, excluding the terminals, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). This point is explained in the following "C 1-18 The term "C" is used in the explanation of the definition of "hydrocarbyl oxy group," etc. 1-18 The same applies to "hydrocarbyl group," etc. 1-18The term "hydrocarbyl group" is not particularly limited; for example, "C 1-18 "Alkyl alkyl group", "C 2-18 "Alkenyl group", "C 2-18 "Alkynyl group", "C 3-18 “Alicyclic group”, “C 2-18 "Aryl group", "C 7-18 Examples include the "aralkyl group."

[0027] In this specification, "C 1-18 "Hydrocarbyloxy group" refers to "C 1-18 This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group". 1-18 The term "hydrocarbyloxy group" is not particularly limited and includes, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, i-pentoxy group, sec-pentoxy group, n-hexoxy group, i-hexoxy group, 1,1-dimethylpropyloxy group, 1,2-dimethylpropyloxy group, 2,2-dimethylpropyloxy group, 1-methyl- C 1-18 "Alkoxy group"; such as 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, pentarenyloxy group, heptarenyloxy group, indacenyloxy group, acenaphthyloxy group, phenantrenyloxy group, anthracenyloxy group, etc.6-18 Examples include "aryloxy group". 1-18 As for the "hydrocarbyl oxy group", C 1-18 It is preferable that the divalent carbon atoms at any position other than the terminals in the "hydrocarbyl group" are 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 substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, etc.

[0028] In this specification, "C 1-18 The term "hydrocarbyl carbonyl group" refers to "C 1-18 This refers to 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 includes, for example, acetyl group, propionyl group, isopropionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pentanoyl group, 3-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanol group, etc. 1-18 "Alkyl carbonyl group"; cyclopropyl carbonyl group, cyclobutyl carbonyl group, cyclopentyl carbonyl group, 2-methylcyclopentyl carbonyl group, 3-methylcyclopentyl carbonyl group, cyclohexyl carbonyl group, 2-methylcyclohexyl carbonyl group, 3-methylcyclohexyl carbonyl group, 4-methylcyclohexyl carbonyl group, adamantyl carbonyl group, etc. 3-18 "Alicyclic carbonyl group"; "C" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. 6-18 Examples include "arylcarbonyl group," etc.

[0029] In this specification, "C 1-18 "Hydrocarbylcarbonyloxy group" refers to "C 1-18This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group". 1-18 The "hydrocarbylcarbonyloxy group" is not particularly limited and includes, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, hexylcarbonyloxy group, etc. 1-18 "Alkyl carbonyloxy group"; such as cyclopropyl carbonyloxy group, cyclobutyl carbonyloxy group, cyclopentyl carbonyloxy group, cyclohexyl carbonyloxy group, etc. 3-18 "Alicyclic carbonyloxy group"; such as phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenantrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc. 6-18 Examples include "arylcarbonyloxy group," etc.

[0030] In this specification, "C 1-18 The term "hydrocarbyloxycarbonyl group" refers to "C 1-18 This refers to 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 includes, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, neopentyloxycarbonyl group, etc. 1-18 "Alkoxycarbonyl group"; such as cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 2-methylcyclopentyloxycarbonyl group, 3-methylcyclopentyloxycarbonyl group, 2-methylcyclohexyloxycarbonyl group, 3-methylcyclohexyloxycarbonyl group, 4-methylcyclohexyloxycarbonyl group, etc.3-18 "Alicyclic oxycarbonyl group"; such as phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenantrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc. 6-18 Examples include "aryloxycarbonyl group," etc.

[0031] In this specification, "C 1-18 The term "hydrocarbyloxycarbonyloxy group" refers to "C 1-18 This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group". 1-18 The "hydrocarbyloxycarbonyloxy group" is not particularly limited and includes, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propyloxycarbonyloxy group, i-propyloxycarbonyloxy group, n-butoxycarbonyloxy group, i-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, t-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, i-pentyloxycarbonyloxy group, n-hexyloxycarbonyloxy group, etc. 1-18 "Alkoxycarbonyloxy group"; such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. 3-18 "Alicyclic oxycarbonyloxy group"; such as phenoxycarbonyloxy group, naphthoxycarbonyloxy group, acenaphthyloxycarbonyloxy group, phenantrenyloxycarbonyloxy group, anthracenyloxycarbonyloxy group, etc. 6-18 Examples include "aryloxycarbonyloxy group".

[0032] In this specification, "C 1-18 A "hydrocarbylamino group" is a single "C" 1-18 A "hydrocarbyl group" refers to a group in which an amino group is bonded. 1-18The "hydrocarbylamino group" is not particularly limited and includes, for example, methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, sec-butylamino group, t-butylamino group, n-pentylamino group, i-pentylamino group, neopentylamino group, n-hexylamino group, etc. 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"; such as phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. 6-18 Examples include "arylamino group," etc.

[0033] In this specification, "Di C 1-18 A "hydrocarbylamino group" is two identical or different "C" groups. 1-18 "Hydrocarbyl group" refers to a group in which a hydroxyl group is bonded to an amino group. 1-18 The term "hydrocarbylamino group" is not particularly limited and includes, for example, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-t-butylamino group, di-n-pentylamino group, di-n-hexylamino group, N-ethyl-N-methylamino group, N-methyl-N-n-propylamino group, N-isopropyl-N-methylamino group, N-n-butyl-N-methylamino group, N DiC groups such as -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, etc. 1-18"Alkylamino group"; dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. 3-18 "Alicyclic amino group"; such as diphenylamino group, phenylnaphthylamino group, etc. 6-18 "Arylamino group"; "N-C" such as N-methylcyclopentaneamino group and N-methylcyclohexylamino group. 1-18 Alkyl-N-C 3-18 "Cycloalkylamino group"; "N-C" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group 1-18 Alkyl-N-C 6-18 Examples include "arylamino group," etc.

[0034] In this specification, "C 1-18 "Hydrocarbylaminocarbonyl group" refers to "C 1-18 This refers to 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 includes, for example, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, t-butylaminocarbonyl group, n-pentylaminocarbonyl group, 2-pentylaminocarbonyl group, neopentylaminocarbonyl group, 4-methyl-2-pentylaminocarbonyl group, n-hexylaminocarbonyl group, 3-methyl-n-pentylaminocarbonyl group, etc. 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"; such as phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc.6-18 An example is the "arylaminocarbonyl group."

[0035] In this specification, "Di C 1-18 "Hydrocarbylaminocarbonyl group" refers to "diC 1-18 This refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group". 1-18 The term "hydrocarbylaminocarbonyl group" is not particularly limited and includes, for example, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, diisopropylaminocarbonyl group, di-n-butylaminocarbonyl group, diisobutylaminocarbonyl group, di-t-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, N-ethyl-N-methylaminocarbonyl group, N-methyl-N-n-propylaminocarbonyl group, N-isopropyl-N-methylaminocarbonyl group, N-n-butyl-N-methylaminocarbonyl group, N-isobutyl-N-methylaminocarbonyl group, N-t-butyl-N-methylaminocarbonyl group, N-methyl-N-n-pentylaminocarbonyl group, N-n-hexyl-N-methylaminocarbonyl group DiC groups such as N-ethyl-N-n-propylaminocarbonyl group, N-ethyl-N-isopropylaminocarbonyl group, N-n-butyl-N-ethylaminocarbonyl group, N-ethyl-N-isobutylaminocarbonyl group, N-t-butyl-N-ethylaminocarbonyl group, N-ethyl-N-n-pentylaminocarbonyl group, N-ethyl-N-n-hexylaminocarbonyl group, etc. 1-18 "Alkylamino group"; such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. 3-18 "Alicyclic aminocarbonyl group"; "DiC" such as diphenylaminocarbonyl group and phenylnaphthylaminocarbonyl group. 6-18 Examples include "arylaminocarbonyl group," etc.

[0036] In this specification, "C 1-18 "Hydrocarbylcarbonylamino group" refers to "C 1-18This refers to a group in which an amino group is bonded to a "hydrocarbyl carbonyl group". 1-18 The "hydrocarbonylamino group" is not particularly limited and includes, for example, 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, n-hexylcarbonylamino group, etc. 1-18 "Alkylcarbonylamino group"; such as cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. 3-18 "Alicyclic carbonylamino group"; such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenantrenylcarbonylamino group, anthracenylcarbonylamino group, etc. 6-18 Examples include "arylcarbonylamino group," etc.

[0037] In this specification, "C 1-18 "Hydrocarbylaminocarbonyloxy group" refers to "C 1-18 This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group". 1-18 The "hydrocarbylaminocarbonyloxy group" is not particularly limited and includes, for example, methylaminocarbonyloxy group, ethylaminocarbonyloxy group, n-propylaminocarbonyloxy group, etc. 1-18 "Alkylaminocarbonyloxy group"; "C" such as cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. 3-18 "Alicyclic aminocarbonyloxy group"; "C" such as phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group 6-18 Examples include "arylaminocarbonyloxy group".

[0038] In this specification, "Di C 1-18 "Hydrocarbylaminocarbonyloxy group" is a "diC 1-18This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group". 1-18 The "hydrocarbylaminocarbonyloxy group" is not particularly limited and includes, for example, dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, di-n-propylaminocarbonyloxy group, etc. 1-18 Examples include "alkylaminocarbonyloxy group," etc.

[0039] In this specification, "C 1-18 "Hydrocarbylaminocarbonylamino group" refers to "C 1-18 "Hydrocarbylaminocarbonyl group" refers to a group in which an amino group is bonded. 1-18 The "hydrocarbylaminocarbonylamino group" is not particularly limited and includes, for example, methylaminocarbonylamino group, ethylaminocarbonyloxy group, n-propylaminocarbonylamino group, etc. 1-18 "Alkylaminocarbonylamino group"; "C" such as cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. 3-18 "Alicyclic aminocarbonylamino group"; "C" such as phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. 6-18 Examples include "arylaminocarbonylamino group," etc.

[0040] In this specification, "Di C 1-18 "Hydrocarbylaminocarbonylamino group" refers to "diC 1-18 "DiC" refers to a group in which a "hydrocarbylaminocarbonyl group" is bonded to an amino group. 1-18 The "hydrocarbylaminocarbonylamino group" is not particularly limited and includes, for example, dimethylaminocarbonylamino group, diethylaminocarbonylamino group, di-n-propylaminocarbonylamino group, etc. 1-18 Examples include "alkylaminocarbonylamino group," etc.

[0041] In this specification, "C 1-18 "Hydrocarbyloxycarbonylamino group" is "C 1-18This refers to a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. 1-18 The "hydrocarbyloxycarbonylamino group" is not particularly limited and includes, for example, methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc. 1-18 "Alkoxycarbonylamino group"; "C" such as cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. 3-18 "Alicyclic oxycarbonylamino group"; "C" such as phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. 6-18 Examples include "aryloxycarbonylamino group," etc.

[0042] In this specification, "C 1-18 A "hydrocarbylthio group" is a "C 1-18 This refers to a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group". 1-18 The "hydrocarbylthio group" is not particularly limited and includes, for example, methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, t-butylthio group, n-pentylthio group, 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"; such as phenylthio group, 1-naphthylthio group, 2-naphthylthio group, acenaphthylthio group, phenantrenylthio group, anthracenylthio group, etc. 6-18 Examples include "arylthio group," etc.

[0043] In this specification, "C 1-18 The term "hydrocarbyl sulfinyl group" refers to "C 1-18 This refers to a group in which a sulfinyl group (-S (=O)-) is bonded to a hydrocarbyl group.1-18 The "hydrocarbyl sulfinyl group" is not particularly limited and includes, for example, methyl sulfinyl group, ethyl sulfinyl group, n-propyl sulfinyl group, i-propyl sulfinyl group, n-butyl sulfinyl group, t-butyl sulfinyl group, pentyl sulfinyl group, hexyl sulfinyl group, etc. 1-18 "Alkyl sulfinyl group"; cyclopropyl sulfinyl group, cyclobutyl sulfinyl group, cyclopentyl sulfinyl group, cyclohexyl sulfinyl group, 2-methylcyclopentyl sulfinyl group, 3-methylcyclopentyl sulfinyl group, 2-methylcyclohexyl sulfinyl group, 3-methylcyclohexyl sulfinyl group, 4-methylcyclohexyl sulfinyl group, etc. 3-18 "Alicyclic sulfinyl group"; such as phenylsulfinyl group, naphthylsulfinyl group, acenaphthylsulfinyl group, phenantrenylsulfinyl group, anthracenylsulfinyl group, etc. 6-18 Examples include "aryl sulfinyl group," etc.

[0044] In this specification, "C 1-18 The term "hydrocarbyl sulfonyl group" refers to "C 1-18 This refers to a group in which a sulfonyl group (-SO2-) is bonded to a hydrocarbyl group. 1-18 The "hydrocarbyl sulfonyl group" is not particularly limited and includes, for example, methyl sulfonyl group, ethyl sulfonyl group, n-propyl sulfonyl group, i-propyl sulfonyl group, n-butyl sulfonyl group, t-butyl sulfonyl group, pentyl sulfonyl group, etc. 1-18 "Alkyl sulfonyl group"; cyclopropyl sulfonyl group, cyclobutyl sulfonyl group, cyclopentyl sulfonyl group, cyclohexyl sulfonyl group, 2-methylcyclopentyl sulfonyl group, 3-methylcyclopentyl sulfonyl group, 2-methylcyclohexyl sulfonyl group, 3-methylcyclohexyl sulfonyl group, 4-methylcyclohexyl group, etc. 3-18 "Alicyclic sulfonyl group"; such as phenylsulfonyl group, naphthylsulfonyl group, acenaphthylsulfonyl group, phenantrenylsulfonyl group, anthracenylsulfonyl group, etc. 6-18Examples include "aryl sulfonyl group," etc.

[0045] In this specification, "acid-dissociable group" means a polar group that substitutes a hydrogen atom, such as a hydroxyl group (including phenolic hydroxyl groups, etc.), a carboxyl group, an amino group, or a sulfo group, which dissociates upon the action of an acid. Compounds having a polar group having the above-mentioned acid-dissociable group can increase their polarity by dissociating the acid-dissociable group upon the action of an acid, thereby generating the above-mentioned 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 increases relatively, while when a less polar organic developer is used as the developer, the solubility of the compound in the developer decreases relatively. Hydroxyl groups (including phenolic hydroxyl groups, etc.) and carboxyl groups are preferred as the above-mentioned polar groups.

[0046] The above-mentioned acid-dissociable group is not particularly limited, and any known and conventional acid-dissociable group usable in chemically amplified resists can be used. Examples of acid-dissociable groups include the acid-dissociable group G for polar groups having an acid-dissociable group represented by the following general formulas (G-1) to (G-4).

[0047] The above-mentioned acid-dissociable group G is not particularly limited as long as it dissociates upon the action of an acid, and known and commonly used groups can be used. For example, the acid-dissociable group G is the "tertiary carbon type acid-dissociable group G" represented by the following general formula (g-1). A ", and "allyl-type or benzyl-type acid-dissociating group G" represented by the following general formula (g-2) B " and "acetal-type acid-dissociating group G" represented by the following general formula (g-3) C These are some examples. Each of these will be explained in turn below.

[0048] <Tertiary carbon type acid dissociable group G A> The above acid-dissociating group G is the "tertiary carbon type acid-dissociating group G" represented by the following general formula (g-1) A As shown above, the carbon is directly bonded to a polar group, and R A g1 ~R A g3 An acid-dissociable group can be used in which the bonded carbon is a tertiary carbon atom.

[0049] "R A g1 " may have substituents C 1-12 In a hydrocarbyl group, any divalent carbon atom other than the terminal atoms may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0050] R A g1 C may have substituents. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously), and may have substituents. 1-12 Alkyl alkyl group, or C 3-12 A more preferable alicyclic group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0051] Also, "R A g2 " and "R A g3 Each of these C atoms may independently have substituents. 1-12A hydrocarbyl group in which any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously), or R A g2 and R A g3 These are combined and may have substituents. 3-18 The group forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0052] R A g2 and R A g3 For example, R A g2 and R A g3 These are combined and may have substituents. 3-18 It is preferable that the group forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and that any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously), and furthermore, the C may have the above substituents. 3-18It is more preferable that the alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group includes a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, and tricyclodecene skeleton, and that any divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0053] Tertiary carbon type acid-dissociable group G represented by general formula (g-1) A Examples include t-butyl group, t-amyl group, 1,1-dimethylpropyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0054] Tertiary carbon type acid-dissociable group G represented by general formula (g-1) A Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0055]

[0056] <<Tertiary carbon type acid dissociable group G A1 and G A2 >> Also, the "tertiary carbon type acid-dissociable group G" represented by the general formula (g-1) A In ", R A g2 and R A g3 These are combined and may have substituents. 3-18In cases 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) A1 , and the tertiary carbon-type oxygen dissociable group G represented by (g-1-2) A2 These are some examples.

[0057] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) A1 >> The tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1) A1 In R A g11 C may have substituents. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 In an aralkyl group, any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0058] Also CC A g1 This is a C atom that may have substituents, along with the tertiary carbon atom mentioned above. 3-18 It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0059] Cy A g1Preferably, together with the above-mentioned tertiary carbon atoms, a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton is formed, and any divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms will not be replaced at the same time).

[0060] The tertiary carbon type acid-dissociable group G, represented by the general formula (g-1-1). A1 Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0061]

[0062]

[0063]

[0064]

[0065] <<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 Each of these may independently have a hydro group or a substituent. 1-12 In a hydrocarbyl group, any divalent carbon atom except at the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). A g21 and R A g22 , and / or, RA g22 and R A g23 These are directly linked by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via alkylene groups to form a ring.

[0066] R A g21 and R A g22 , and / or, R A g22 and R A g23 Examples of cases where a ring is formed together with the carbon atom included in the ethylenically unsaturated double bond include the formation of a cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexyllideneethenyl group, etc., which may have substituents.

[0067] Also CC A g2 This is a C atom that may have substituents, along with the tertiary carbon atom mentioned above. 3-18 It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0068] Cy A g2Preferably, together with the above-mentioned tertiary carbon atoms, a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton is formed, and any divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms will not be replaced at the same time).

[0069] Tertiary carbon type acid-dissociable group G represented by general formula (g-1-2) A2 Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0070]

[0071]

[0072]

[0073] <Allyl or benzyl acid-dissociating group G> B > The above acid-dissociating group G is an "allyl-type or benzyl-type acid-dissociating group G" represented by the following general formula (g-2). B As shown above, an acid-dissociable group can be used in which the carbon directly bonded to the polar group is located at the allylic or benzyl position.

[0074] "R B g1 " may have substituents C 1-12 In a hydrocarbyl group, any divalent carbon atom other than the terminal atoms may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0075] R Bg1 C may have substituents. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously), and may have substituents. 1-12 Alkyl alkyl group, or C 3-12 A more preferable alicyclic group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0076] Also, "R B g2 "~"R B g4 Each of these may independently have a hydro group or a substituent. 1-12 In a hydrocarbyl group, any divalent carbon atom other than the terminal atoms may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0077] R B g1 and R B g2 , R B g2 and R B g3 , and / or, R B g3 and R B g4 These are directly linked by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3They may be linked via alkylene groups to form a ring.

[0078] Allyl or benzyl acid-dissociable group G represented by general formula (g-2) B In R B g1 and R B g2 , R B g2 and R B g3 , and / or, R B g3 and R B g4 Examples of cases where a ring is formed together with the carbon atom included in the ethylenically unsaturated double bond include cases where a cyclic cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexyllideneethenyl group, benzyl group, or 2,3-dihydro-1H-indanyl group, which may have substituents, are formed.

[0079] Allyl or benzyl acid-dissociable group G represented by general formula (g-2) B Examples include the following allyl or benzyl acid-dissociating groups.

[0080]

[0081] <Acetal-type acid-dissociating group G> C > The above acid-dissociating group G is the "acetal-type acid-dissociating group G" represented by the following general formula (g-3). C As shown above, an acid-dissociable group can be used in which an oxygen atom is bonded to a carbon atom that is directly bonded to the polar group.

[0082] "R C g1 " and "R C g3 Each of these may independently have a hydro group or a substituent. 1-12In a hydrocarbyl group, any divalent carbon atom other than the terminal atoms may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0083] R C g1 and R C g3 This may include a hydro group or a C which may have a substituent. 1-12 Alkyl or C 3-12 The alicyclic group is preferably one in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously), and may have a hydro group or substituent. 1-6 Alkyl or C 3-8 A more preferable alicyclic group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0084] Also, "R C g2 " may have substituents C 1-12 In a hydrocarbyl group, any divalent carbon atom other than the terminal atoms may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0085] R C g2 C may have substituents. 1-12 Alkyl alkyl group or C 3-12The alicyclic group is preferably one in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously), and may have substituents. 1-6 Alkyl alkyl group or C 3-8 A more preferable alicyclic group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0086] Acetal-type acid-dissociable group G represented by general formula (g-3) C Examples include methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, n-butoxymethoxy group, 2,2-dimethylpropoxymethoxy group, 2,2-dimethylbutoxymethoxy group, cyclohexyloxymethoxy group, 1-ethoxyethoxy group, 1-n-butoxyethoxy group, and 1-cyclohexyloxyethoxy group.

[0087] In this specification, "hydroxyl group or carboxyl group having a protecting group" means a hydroxyl group (including phenolic hydroxyl group) or carboxyl group that is protected by an ether protecting group, a silyl ether protecting group, an acyl protecting group, an aminocarbonyl protecting group, or the like.

[0088] Examples of ether protecting groups are not particularly limited and include methyl group, benzyl group, p-methoxybenzyl group, t-butyl group, triphenylmethyl group, p-methoxyphenyldiphenylmethyl group, and di(p-methoxyphenyl)phenylmethyl group. Examples of silyl ether protecting groups are not particularly limited and include t-butyldimethylsilyl group (TBS), triisopropylsilyl group (TIPS), trimethylsilyl group (TMS), triethylsilyl group (TES), and t-butyldiphenylsilyl group (TBDPS). Examples of acyl protecting groups are not particularly limited and include acetyl group, pivaloyl group, and benzoyl group. Examples of aminocarbonyl protecting groups are not particularly limited and include dimethylaminocarbonyl group, diethylaminocarbonyl group, diisopropylaminocarbonyl group, and N-phenyl-N-methylaminocarbonyl group.

[0089] In this specification, "may have substituents," "may be substituted with substituents," "may be replaced by substituents," etc., are not particularly limited as long as they are chemically acceptable and have the effects of the present invention. Examples of "substituents" are: (1) halogen atoms, (2) haloalkyl groups, (3) hydroxyl groups, (4) thiol groups, (5) nitro groups, (6) cyano groups, (7) carboxyl groups, (8) amino groups, (9) sulfo groups, (10) vinyl groups, (11) allyl groups, (12) (meth)acryloyl groups, (13) (meth)acryloyloxy groups, (14) (meth)acrylamide groups, (15) styryl groups, (16) epoxy groups, (17) glycidyl groups, (18) amide groups, (19) hydroxyl or carboxyl groups having a protecting group, (20) polar groups having an acid-dissociable group, or (21) C in which at least one part of the hydrogen atoms is substituted with (1) to (20) above. 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C1-18 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 Hydrocarbyloxycarbonylamino group, C 1-18 Hydrocarbylthio group, C 1-18 Hydrocarbyl sulfinyl group, C 1-18 A hydrocarbyl sulfonyl group in which a divalent carbon atom at any position other than the terminal of the substituent may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0090] [1. Resist Material] The resist material according to this embodiment contains (A) a polymer and (B) a metal compound, wherein component (A) includes a structural unit having a fluorine atom, and the structural unit having a fluorine atom is a monovalent or divalent aromatic hydrocarbon cyclic group, wherein at least two or more hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms.

[0091] By including a fluorine atom-containing structural unit in component (A) that is a monovalent or divalent aromatic hydrocarbon cyclic group in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms, the proportion of trifluoromethyl groups, trifluoromethylene groups, etc., that may be subject to PFAS regulations in component (A) can be reduced. Therefore, by including the above-mentioned fluorine atom-containing structural unit in component (A), it becomes possible to reduce the environmental burden while also providing the necessary sensitivity in the formation of resist patterns.

[0092] [1-1. Polymer (A)] Polymer (A) according to this embodiment includes structural units containing fluorine atoms. The structural units having fluorine atoms are monovalent or divalent aromatic hydrocarbon cyclic groups, characterized in that at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms. Other hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted with substituents. In addition to structural units having fluorine atoms, polymer (A) may also include structural units for adjusting solubility in developing solutions, structural units having phenolic hydroxyl groups, or other structural units.

[0093] From the viewpoint of reducing environmental impact, it is preferable that the polymer (A) described above does not contain trifluoromethyl groups other than those having the structure represented by the following general formula (F-1), or trifluoromethylene groups other than those having the structure represented by the following general formula (F-2) or (F-3). Note that * represents a bonding site.

[0094] In a trifluoromethyl group having a structure represented by general formula (F-1), "X f1 " is -L f1 -O-, -L f1 -N(R) f1 ) - or - L f1 -N(L) f2 -)- represents; "L f1 " and "L f2Each of these independently represents a methylene group, a divalent aromatic hydrocarbon cyclic group which may have substituents, or a carbonyl group; "R f1 " may have substituents other than hydrogen atoms and fluorine atoms. 1-6 This represents a hydrocarbyl group or a monovalent aromatic hydrocarbon cyclic group which may have substituents. Therefore, a trifluoromethyl group having the structure represented by general formula (F-1) can be represented by the following general formula.

[0095]

[0096] In a trifluoromethylene group having a structure represented by the general formula (F-2), "X f1 " represents the same thing as in general formula (F-1); "X f2 " may have substituents other than fluorine atoms C 1-6 Hydrocarbyl group, optionally substituted monovalent aromatic hydrocarbon cyclic group, -O-R f2 , -S-R f2 , -N(R f2 ) (Caution f3 ) represents; "R f2 " and "R f3 Each of these atoms may independently have substituents other than hydrogen and fluorine atoms. 1-6 This represents a hydrocarbyl group or a monovalent aromatic hydrocarbon cyclic group which may have substituents. Therefore, a trifluoromethyl group having the structure represented by general formula (F-2) can be represented by the following general formula.

[0097]

[0098] In a trifluoromethylene group having a structure represented by the general formula (F-3), "X f1 " represents the same thing as in general formula (F-1); "X f3 " is a methylene group, a divalent aromatic hydrocarbon group which may have substituents, a carbonyl group, -O-L f3 -, -S-L f3 -, -N(R f4 )-L f3 -, -N(Lf3 -) L f4 - represents; "L f3 " and "L f4 Each of these independently represents a methylene group, a divalent aromatic hydrocarbon cyclic group which may have substituents, or a carbonyl group; "R f4 " may have substituents other than hydrogen atoms and fluorine atoms. 1-6 This represents a hydrocarbyl group or a monovalent aromatic hydrocarbon cyclic group which may have substituents. Therefore, a trifluoromethyl group having the structure represented by general formula (F-3) can be represented by the following general formula.

[0099]

[0100] [1-1-1. Structural Units Having Fluorine Atoms] As structural units having fluorine atoms in this embodiment, any known and conventional type can be used, as long as it includes a monovalent or divalent aromatic hydrocarbon cyclic group in which at least two or more hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms. Note that any hydrogen atoms other than those mentioned above on the aromatic hydrocarbon cyclic group may be substituted with substituents.

[0101] Examples of structural units containing a fluorine atom include structural unit A1, which is represented by the following general formula (I).

[0102] In general formula (I), “R α " represents a hydrogen atom, a halogen atom, or an alkyl group. α Examples include hydrogen atoms, halogen atoms, or C 1-4 It is preferably an alkyl group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and even more preferably a hydrogen atom or a methyl group.

[0103] "L A1 1 The symbols " represent a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2-. A11 Preferably, the bond is a single bond, -C(=O)-, -C(=O)O-, -OCO-, or -CONH-, and more preferably a single bond, -C(=O)O-, or -OCO-.

[0104] "R A1 1 " represents a monovalent or divalent aromatic hydrocarbon cyclic group having a monovalent organic group in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be replaced by substituents. In the above monovalent or divalent aromatic hydrocarbon cyclic group, it is preferable that at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, more preferably at least three hydrogen atoms, and even more preferably at least four hydrogen atoms.

[0105] Examples of monovalent or divalent aromatic hydrocarbon cyclic groups include phenyl groups, phenylene groups (1,2-phenylene, 1,3-phenylene, 1,4-phenylene), naphthyl groups, naphthylene groups (1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene), 4,4'-biphenylene groups, phenanthrylene groups, phenanthrylene groups, anthryl groups, and anthreylene groups.

[0106] Furthermore, monovalent or divalent aromatic hydrocarbon cyclic groups in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms include, for example, 2,3-difluorobenzene-1-yl group, 2,4-difluorobenzene-1-yl group, 2,5-difluorobenzene-1-yl group, 2,6-difluorobenzene-1-yl group, 3,4-difluorobenzene-1-yl group, 3,5-difluorobenzene-1-yl group, 3,5-difluoro-4-nitrobenzene-1-yl group, and 3,5-difluoro-4-cyanobenzene- 1-yl group, 2,3,4-trifluorobenzene-1-yl group, 2,3,5-trifluorobenzene-1-yl group, 2,3,6-trifluorobenzene-1-yl group, 2,4,5-trifluorobenzene-1-yl group, 2,4,6-trifluorobenzene-1-yl group, 3,4,5-trifluorobenzene-1-yl group, 2,3,4,5-tetrafluorobenzene-1-yl group, 2,3,4,6-tetrafluorobenzene-1-yl group, 2,3,5,6-tetrafluorobenzene-1-yl group, 2,2',3,3',4,4',5,5', 6-nonafluoro-1,1'-biphenyl-6'-yl group, 2,3-difluorobenzene-1,4-diyl group, 2,5-difluorobenzene-1,4-diyl group, 2,6-difluorobenzene-1,4-diyl group, 2,3,5-trifluorobenzene-1,4-diyl group, 2,3,6-trifluorobenzene-1,4-diyl group, 2,3,5,6-tetrafluorobenzene-1,4-diyl group, 2,4-difluorobenzene-1,3-diyl group, 2,5-difluorobenzene-1,3-diyl group, 2,6-difluorobenzene-1,3-diyl group Examples include yl groups, 2,4,5-trifluorobenzene-1,3-diyl groups, 2,4,6-trifluorobenzene-1,3-diyl groups, 2,4,5,6-tetrafluorobenzene-1,3-diyl groups, 3,4-difluorobenzene-1,2-diyl groups, 3,5-difluorobenzene-1,2-diyl groups, 3,6-difluorobenzene-1,2-diyl groups, 3,4,5-trifluorobenzene-1,2-diyl groups, 3,4,6-trifluorobenzene-1,2-diyl groups, and 3,4,5,6-tetrafluorobenzene-1,2-diyl groups.The hydrogen atoms on these aromatic hydrocarbon cyclic groups may be further substituted by substituents.

[0107] <Structural unit A containing a fluorine atom> 1a and A 1b > Furthermore, a structural unit A1 having a fluorine atom represented by general formula (I) is, for example, a structural unit A having a fluorine atom represented by the following general formula (I-1) 1a Or structural unit A having a fluorine atom represented by the following general formula (I-2) 1b That's fine.

[0108]

[0109]

[0110] <<Structural unit A having a fluorine atom represented by general formula (I-1) 1a >>

[0111] Structural unit A having a fluorine atom, represented by the above general formula (I-1) 1a In R α and L A1 1 This represents the same thing as in the case of general formula (I).

[0112] "L A1 a1 " is a single bond or a C which may have a substituent 1-8 A hydrocarbylene group is represented where any divalent carbon atom, excluding the terminals other than the bond, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0113] L A1 a1 This may consist of a single bond or a C that may have a substituent. 1-8The alkanediyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-8 An alkanediyl group is more preferably one in which one or more divalent carbon atoms, excluding the terminals other than the bonding site, are replaced with -O-, -C(=O)-, -C(=O)-O-, or -O-C(=O)- (however, adjacent divalent carbon atoms are not replaced at the same time).

[0114] "Ar A1 a1 " represents a monovalent aromatic hydrocarbon cyclic group in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms of the aromatic hydrocarbon cyclic group may be substituted by substituents.

[0115] Ar A1 a1 Preferably, the group is a monovalent aromatic hydrocarbon cyclic group in which at least three or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted by substituents; more preferably, the group is a monovalent aromatic hydrocarbon cyclic group in which at least three or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted by substituents; and even more preferably, the group is a monovalent aromatic hydrocarbon cyclic group in which at least four or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms.

[0116] Examples of the above-mentioned monovalent aromatic hydrocarbon cyclic groups include phenyl groups, naphthyl groups, phenantrenyl groups, and anthyl groups.

[0117] Furthermore, examples of monovalent aromatic hydrocarbon cyclic groups in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms include 2,3-difluorobenzene-1-yl group, 2,4-difluorobenzene-1-yl group, 2,5-difluorobenzene-1-yl group, 2,6-difluorobenzene-1-yl group, 3,4-difluorobenzene-1-yl group, 3,5-difluorobenzene-1-yl group, 3,5-difluoro-4-nitrobenzene-1-yl group, 3,5-difluoro-4-cyanobenzene-1-yl group, and 2,3,4-trifluorobenzene Examples include the benzene-1-yl group, 2,3,5-trifluorobenzene-1-yl group, 2,3,6-trifluorobenzene-1-yl group, 2,4,5-trifluorobenzene-1-yl group, 2,4,6-trifluorobenzene-1-yl group, 3,4,5-trifluorobenzene-1-yl group, 2,3,4,5-tetrafluorobenzene-1-yl group, 2,3,4,6-tetrafluorobenzene-1-yl group, 2,3,5,6-tetrafluorobenzene-1-yl group, and 2,2',3,3',4,4',5,5',6-nonafluoro-1,1'-biphenyl-6'-yl group. Hydrogen atoms on these aromatic hydrocarbon cyclic groups may be further substituted by substituents.

[0118] Structural unit A having a fluorine atom, represented by the above general formula (I-1) 1a Examples include the following structural units. Note that "R" in the examples below refers to... α " represents a hydrogen atom, a halogen atom, or an alkyl group.

[0119]

[0120] <<Structural unit A having a fluorine atom represented by general formula (I-2) 1b >>

[0121] Structural unit A having a fluorine atom, represented by the above general formula (I-2) 1b In R α and L A1 1 This represents the same thing as in the case of general formula (I).

[0122] "LA1 b1 " is a single bond or a C which may have a substituent 1-8 A hydrocarbylene group is represented where any divalent carbon atom, excluding the terminals other than the bond, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0123] L A1 b1 This may consist of a single bond or a C that may have a substituent. 1-8 The alkanediyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-8 An alkanediyl group is more preferably one in which one or more divalent carbon atoms, excluding the terminals other than the bonding site, are replaced with -O-, -C(=O)-, -C(=O)-O-, or -O-C(=O)- (however, adjacent divalent carbon atoms are not replaced at the same time).

[0124] "Ar A1 b1 " represents a divalent aromatic hydrocarbon cyclic group in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted by substituents.

[0125] Ar A1 b1Preferably, the group is a divalent aromatic hydrocarbon cyclic group in which at least three or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms of the aromatic hydrocarbon cyclic group may be substituted by substituents; more preferably, the group is a divalent aromatic hydrocarbon cyclic group in which at least three or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms of the aromatic hydrocarbon cyclic group may be substituted by substituents; and even more preferably, the group is a divalent aromatic hydrocarbon cyclic group in which at least four or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms.

[0126] Examples of the above-mentioned divalent aromatic hydrocarbon cyclic groups include phenylene groups (1,2-phenylene, 1,3-phenylene, 1,4-phenylene), naphthylene groups (1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene), 4,4'-biphenylene, phenanthrylene, and anthrylene.

[0127] Furthermore, divalent aromatic hydrocarbon cyclic groups in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms include, for example, 2,3-difluorobenzene-1,4-diyl group, 2,5-difluorobenzene-1,4-diyl group, 2,6-difluorobenzene-1,4-diyl group, 2,3,5-trifluorobenzene-1,4-diyl group, 2,3,6-trifluorobenzene-1,4-diyl group, 2,3,5,6-tetrafluorobenzene-1,4-diyl group, 2,4-difluorobenzene-1,3-diyl group, and 2,5-difluorobenzene-1,3-diyl group. Examples include yl groups, 2,6-difluorobenzene-1,3-diyl groups, 2,4,5-trifluorobenzene-1,3-diyl groups, 2,4,6-trifluorobenzene-1,3-diyl groups, 2,4,5,6-tetrafluorobenzene-1,3-diyl groups, 3,4-difluorobenzene-1,2-diyl groups, 3,5-difluorobenzene-1,2-diyl groups, 3,6-difluorobenzene-1,2-diyl groups, 3,4,5-trifluorobenzene-1,2-diyl groups, 3,4,6-trifluorobenzene-1,2-diyl groups, and 3,4,5,6-tetrafluorobenzene-1,2-diyl groups.

[0128] "R A1 b1 " may have substituents C 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding the terminals other than the bond, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0129] R A1 b1 For example, C which may have substituents. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12The aralkyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10 An aralkyl group is more preferably one in which any divalent carbon atom other than the terminals other than the bonding site may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0130] Structural unit A having a fluorine atom, represented by the above general formula (I-2) 1b Examples include the following structural units. Note that "R" in the examples below refers to... α " represents a hydrogen atom, a halogen atom, or an alkyl group.

[0131]

[0132] [1-1-2. Structural Units for Adjusting Solubility in Developer] The structural units for adjusting solubility in developer according to this embodiment are not particularly limited, and known and commonly used ones can be used. Examples of structural units for adjusting solubility in developer include structural unit A2 having a polar group having an acid-dissociable group, a lactone skeleton, a sultone skeleton, a sulfolane skeleton, a lactam skeleton, or structural unit A3 having a sultam skeleton. By including structural unit A2 having a polar group having an acid-dissociable group in polymer (A), the acid-dissociable group is removed by the action of acid, generating a polar group, which can significantly change the solubility in developer between the exposed and unexposed parts. Furthermore, by including structural unit A3 having a lactone skeleton or the like in polymer (A), the solubility in developer can be finely adjusted.

[0133] <Structural unit A2 having an acid-dissociable polar group> The structural unit A2 having an acid-dissociable polar group is not particularly limited, and known and commonly used ones can be used. For example, structural unit A2 can be represented by the following formula (II-1) or (II-2). 2a Or A 2b These are some examples.

[0134] <<Structural unit A having a polar group with an acid-dissociable group represented by general formula (II-1) 2a >> Structural unit A having a polar group with an acid-dissociable group represented by the following general formula (II-1) 2a It has a structure in which the hydrogen atom of the polar carboxyl group is replaced by an acid-dissociable group G.

[0135] In general formula (II-1), “R α " represents a hydrogen atom, a halogen atom, or an alkyl group. α Examples include hydrogen atoms, halogen atoms, or C 1-4 It is preferably an alkyl group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and even more preferably a hydrogen atom or a methyl group.

[0136] "L A2 a1 " is a single bond or a C which may have a substituent 1-8 A hydrocarbylene group is represented where any divalent carbon atom, excluding the terminals other than the bond, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0137] L A2 a1 This may consist of a single bond or a C that may have a substituent. 1-8The alkanediyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-8 The alkanediyl group is more preferably one in which one or more divalent carbon atoms, excluding the terminals other than the bonding site, are replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, or -CONH- (provided that adjacent divalent carbon atoms are not replaced at the same time), and even more preferably -C(=O)-, -C(=O)-O-, or -CONH-.

[0138] "G" represents an acid-dissociable group G, and is not particularly limited as long as it dissociates under the action of an acid; known and commonly used groups can be used. Examples of acid-dissociable groups G include tertiary carbon type acid-dissociable groups G A Allyl or benzyl acid-dissociating group G B Acetal-type acid-dissociating group G C These can be suitably used.

[0139] Structural unit A having a polar group with an acid-dissociable group 2a There are no particular limitations, and examples include the structural units shown below. Note that "R" in the examples below refers to... α " represents a hydrogen atom, a halogen atom, or an alkyl group.

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147] <<Structural unit A having a polar group with an acid-dissociable group represented by general formula (II-2) 2b >> Structural unit A having a polar group with an acid-dissociable group represented by the following general formula (II-2) 2b It has a structure in which the hydrogen atom of the polar phenolic hydroxyl group is substituted with an acid-dissociable group G.

[0148] In general formula (II-2), “R α " represents a hydrogen atom, a halogen atom, or an alkyl group. α Examples include hydrogen atoms, halogen atoms, or C 1-4 It is preferably an alkyl group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and even more preferably a hydrogen atom or a methyl group.

[0149] "L A2 b1 " is a single bond or a C which may have a substituent 1-8 A hydrocarbylene group is represented where any divalent carbon atom, excluding the terminals other than the bond, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0150] L A2 b1 This may consist of a single bond or a C that may have a substituent. 1-8 The alkanediyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and it is more preferably a single bond, or -C(=O)-O-, -CONH-.

[0151] "Ar A2 b1 " may have substituents C6-18 This represents an arylene group.

[0152] "G" represents an acid-dissociable group G, and is not particularly limited as long as it dissociates under the action of an acid; known and commonly used groups can be used. Examples of acid-dissociable groups G include tertiary carbon type acid-dissociable groups G A Allyl or benzyl acid-dissociating group G B Acetal-type acid-dissociating group G C These can be suitably used.

[0153] Structural unit A having a polar group with an acid-dissociable group 2b There are no particular limitations, and examples include the structural units shown below. Note that "R" in the examples below refers to... α " represents a hydrogen atom, a halogen atom, or an alkyl group.

[0154]

[0155] <Structural Unit A3 Having a Lactone Skeleton, etc.> Structural unit A3 having a lactone skeleton, etc. is not particularly limited, and known and commonly used ones can be used. Structural unit A3 has a ring containing a lactone skeleton (containing a CO-O- group in part of the ring: for example, β-propyrolactone, γ-butyrolactone, δ-valerolactone, adamantane lactone, etc.), a sultone skeleton (containing an SO2-O- group in part of the ring), a sulfolane skeleton (containing an -SO2- group in part of the ring), a lactam skeleton (containing an -C(OH)=N- group in part of the ring), or a sultam skeleton (containing an -SO2-NR- group in part of the ring), and the ring may be monocyclic, polycyclic, or fused.

[0156] Examples of structural unit A3 include the structural unit represented by the following general formula (III).

[0157] In general formula (III), “R α " represents a hydrogen atom, a halogen atom, or an alkyl group. α Examples include hydrogen atoms, halogen atoms, or C 1-4It is preferably an alkyl group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and even more preferably a hydrogen atom or a methyl group.

[0158] "L A3 1 " is a single bond or a C which may have a substituent 1-4 A hydrocarbylene group is represented where any divalent carbon atom, excluding the terminals other than the bond, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0159] L A3 1 This may consist of a single bond or a C that may have a substituent. 1-4 The alkanediyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and it is more preferably a single bond, or -C(=O)-O- or -CONH-.

[0160] "L A3 2 " is a single bond or a C which may have a substituent 1-8 A hydrocarbylene group is represented where any divalent carbon atom, excluding the terminals other than the bond, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0161] L A3 2 This may consist of a single bond or a C that may have a substituent. 1-8The alkanediyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-8 An alkanediyl group is more preferably one in which one or more divalent carbon atoms, excluding the terminals other than the bonding site, are replaced with -O-, -C(=O)-, -C(=O)-O-, or -O-C(=O)- (however, adjacent divalent carbon atoms are not replaced at the same time).

[0162] "Cy A3 1 " represents a monocyclic, polycyclic, or fused ring containing a lactone skeleton, sultone skeleton, sulfolane skeleton, lactam skeleton, or sultam skeleton, which may have substituents.

[0163] Cy A3 1 Preferably, the ring is a monocyclic, polycyclic, or fused ring containing a lactone skeleton, sultone skeleton, or sulfolane skeleton, which may have substituents, and more preferably, it is a monocyclic, polycyclic, or fused ring containing a lactone skeleton, sultone skeleton, or which may have substituents.

[0164] Cy A3 1 For example, monocyclic, polycyclic, or fused rings having the following lactone, sultone, or sulfolane skeletons can be used, where * is L A3 2 This represents the bond between the two atoms. Furthermore, any hydrogen atoms in these rings may be substituted by substituents.

[0165]

[0166]

[0167] The structural unit A3 having a lactone skeleton, etc., is not particularly limited, and examples include the structural units shown below. Note that "R" in the examples below refers to... α" represents a hydrogen atom, a halogen atom, or an alkyl group.

[0168]

[0169] [1-1-3. Other Structural Units] (A) The polymer may contain any other structural units in addition to the above structural units A1 to A3. Other structural units are not particularly limited and include, for example, structural units having a phenolic hydroxyl group; structural units having (meth)acrylic acid or (meth)acrylic acid ester derivatives; structural units having styrene or styrene derivatives; structural units having an alicyclic group having a carbonate skeleton, a carbamate skeleton, etc.

[0170] [1-1-4. Content of Component (A), etc.] The polymer (A) according to this embodiment contains structural unit A1 having a fluorine atom. When component (A) is 100 parts by mass on a solid content basis, the content of structural unit A1 having a fluorine atom is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and preferably 30 to 70 parts by mass.

[0171] (A) If the polymer contains structural unit A1 having a fluorine atom, as well as structural unit A2 or A3 that adjusts solubility in the developer, the molar ratio of structural unit A1 to structural units A2 and A3 is preferably 2 to 8:2 to 8, more preferably 3 to 7:3 to 7, and even more preferably 4 to 6:4 to 6.

[0172] (A) The method for synthesizing the polymer is not particularly limited, and known and conventional synthesis methods can be used. (A) Examples of polymer synthesis methods include dissolving monomers that induce each structural unit in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate to carry out polymerization.

[0173] (A) The weight-average molecular weight (Mw) of the polymer (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but its lower limit is preferably 1000, more preferably 2000, and even more preferably 3000. The upper limit of Mw is preferably 50000, more preferably 40000, and even more preferably 30000. By having the Mw of component (A) above the lower limit, the EL margin and sensitivity can be improved, and by having it below the upper limit, the solubility of component (A) can be maintained.

[0174] (A) The degree of dispersion (Mw / Mn) of the polymer is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. Hereinafter, Mn refers to the number-average molecular weight. (A) By setting the degree of dispersion of component (A) within the above range and narrowing the molecular weight distribution, the reactivity of the resist composition can be made uniform.

[0175] (A) The content of the polymer in the total solid components of the resist composition is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and even more preferably 0.5 to 10% by mass. "Total solid components" refers to the components of the resist composition other than the organic solvent.

[0176] [1-2. (B) Metal Compounds] The metal compounds according to this embodiment are not particularly limited, and may include metal atoms or metal ions of metal elements in groups 3 to 16 of the long-period periodic table, metal oxides of said metal atoms or metal ions, or organometallic compounds, organometallic complexes, polyacids (e.g., isopolyacids, heteropolyacids, etc.) containing a bond that forms an ionic bond, coordination bond, or covalent bond with said metal atom, metal ion, or metal oxide.

[0177] [1-2-1. Metallic Elements] As metallic elements included in the metal compound according to this embodiment, metallic elements from Group 3 to Group 16 of the long-period periodic table can be used. Examples of metallic elements from Group 3 to Group 16 of the long-period periodic table include: Group 3 metallic elements such as scandium (Sc), yttrium (Y), lanthanum (La), and cerium (Ce); Group 4 metallic elements such as titanium (Ti), zirconium (Zr), and hafnium (Hf); Group 5 metallic elements such as vanadium (V), niobium (Nb), and tantalum (Ta); Group 6 metallic elements such as chromium (Cr), molybdenum (Mo), and tungsten (W); Group 7 metallic elements such as manganese (Mn) and rhenium (Re); Group 8 metallic elements such as iron (Fe), ruthenium (Ru), and osmium (Os); cobalt (Co), etc. Examples include Group 9 metallic elements such as zinc (Rh) and iridium (Ir); Group 10 metallic elements such as nickel (Ni), palladium (Pd), and platinum (Pt); Group 11 metallic elements such as copper (Cu), silver (Ag), and gold (Au); Group 12 metallic elements such as zinc (Zn), cadmium (Cd), and mercury (Hg); Group 13 metallic elements such as aluminum (Al), gallium (Ga), indium (In), and thallium (Tl); Group 14 metallic elements such as germanium (Ge), tin (Sn), and lead (Pb); Group 15 metallic elements such as antimony (Sb) and bismuth (Bi); and Group 16 metallic elements such as tellurium (Te). The metal compound may contain one of the above metallic elements alone, or two or more of them in combination.

[0178] [1-2-2. Metal Atoms or Metal Oxides] As the metal atoms in this embodiment, metal atoms consisting of the above-mentioned metal elements can be used. The above metal atoms may be used individually or in combination of two or more types.

[0179] Furthermore, the metal oxides used in this embodiment are not particularly limited, and known and commonly used ones can be used. Examples of such metal oxides include scandium oxide (Sc2O3), yttrium oxide (Y2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), hafnium oxide (HfO2), vanadium oxide (V2O5), niobium oxide (Nb2O5), tantalum oxide (Ta2O5), chromium oxide (CrO3), molybdenum oxide (MoO3), tungsten oxide (WO3), aluminum oxide (Al2O3), gallium oxide (Ga2O3), indium oxide (In2O3), germanium dioxide (GaO2), tin oxide (SnO), antimony trioxide (Sb2O3), and the like. The metal oxides may be used individually or in combination of two or more.

[0180] [1-2-3. Organometallic Compounds, etc.] The organometallic compound or organometallic complex according to this embodiment is not particularly limited, and known and commonly used ones can be used. The core portion of the organometallic compound or organometallic complex may be formed of the above-mentioned metal atoms or metal oxides.

[0181] The organometallic compound according to this embodiment comprises the above metal atom or metal oxide M B1 In that case, it may be an organometallic compound B1 represented by the following general formula (IV). B1 (X B1 R B1 1 ) n (R B1 2 ) 4-n (IV) [In formula (IV), M B1 represents a metal atom or metal oxide; X B1 R represents -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2-; R B1 1 Each of these independently contains a hydrogen atom or a C which may have a substituent. 1-12A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously); R B1 2 Each of these is independently a C which may have substituents. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously); n is an integer from 0 to 4.

[0182] In general formula (IV), “M B1 " represents a metal atom or metal oxide. B1 Preferably, the material is hafnium, zirconium, tin, palladium, antimony, titanium, or oxides thereof, and more preferably hafnium, zirconium, tin, or titanium.

[0183] "X B1 " represents -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2-. B1 Preferably, the elements are -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, or -S-, and more preferably -O-, -O-C(=O)-, or -S-.

[0184] "R B1 1 Each of these terms independently contains a hydrogen atom or a C atom which may have a substituent. 1-12A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously); "R B1 2 Each of these is independently a C which may have substituents. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0185] R B1 1 Each of these can independently be a hydrogen atom or a C atom which may have a substituent. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have a hydrogen atom or substituent. 1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10 The aralkyl group is more preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously), and may have a hydrogen atom or substituent. 1-8A more preferable alkyl group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0186] R B1 2 Each of these C atoms may independently have a substituent. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10 The aralkyl group is more preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously), and may have substituents. 1-8 Alkyl group, C6 aryl group, or C 7-10 An aralkyl group in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferable.

[0187] The organometallic compound represented by the above general formula (IV) is not particularly limited, and for example, organometallic compound B represented by the following general formulas (IV-1) to (IV-3) 1a ~B1c These are some examples.

[0188] <Organometallic compound B represented by general formula (IV-1) 1a > Organometallic compound B represented by the above general formula (IV-1) 1a In M B1 This represents the same thing as in the general formula (IV).

[0189] "X B1 a1 "X" B1 a2 "X" B1 a3 " and "X B1 a4 Each of these is independently a part of the general formula (IV) "X B1 This represents something similar to the above X. B1 a1 ~X B1 a4 Preferably, the elements are -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, or -S-, and more preferably -O-, -O-C(=O)-, or -S-.

[0190] "R B1 1a1 "R" B1 1a2 "R" B1 1a3 ", and "R B1 1a4 Each of these is independently a part of the general formula (IV) "R B1 1 This represents something similar to the above R. B1 1a1 ~R B1 1a4 Each of these can independently be a hydrogen atom or a C atom which may have a substituent. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12The aralkyl group is preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have a hydrogen atom or substituent. 1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10 The aralkyl group is more preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously), and may have a hydrogen atom or substituent. 1-8 A more preferable alkyl group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0191] Organometallic compound B represented by the above general formula (IV-1) 1a Examples of such compounds include the organometallic compounds shown below.

[0192]

[0193]

[0194]

[0195] <Organometallic compound B represented by general formula (IV-2) 1b > Organometallic compound B represented by the above general formula (IV-2) 1b In M B1 This represents the same thing as in the general formula (IV).

[0196] "X B1 b1"X" B1 b2 " and "X B1 b3 Each of these is independently a part of the general formula (IV) "X B1 This represents something similar to the above X. B1 b1 ~X B1 b3 Preferably, the elements are -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, or -S-, and more preferably -O-, -O-C(=O)-, or -S-.

[0197] "R B1 1b1 "R" B1 1b2 " and "R B1 1b3 Each of these is independently a part of the general formula (IV) "R B1 1 This represents something similar to the above R. B1 1b1 ~R B1 1b3 Each of these can independently be a hydrogen atom or a C atom which may have a substituent. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have a hydrogen atom or substituent. 1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10The aralkyl group is more preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously), and may have a hydrogen atom or substituent. 1-8 A more preferable alkyl group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0198] "R B1 2b1 " is the "R" in general formula (IV). B1 2 This represents something similar to the above R. B1 2b1 C may have substituents. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10 The aralkyl group is more preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously), and may have substituents. 1-8 Alkyl group, C6 aryl group, or C 7-10An aralkyl group in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferable.

[0199] Organometallic compound B represented by the above general formula (IV-2) 1b Examples of such compounds include the organometallic compounds shown below.

[0200]

[0201]

[0202] <Organometallic compound B represented by general formula (IV-3) 1c > Organometallic compound B represented by the above general formula (IV-3) 1c In M B1 This represents the same thing as in the general formula (IV).

[0203] "R B1 2c1 "R" B1 2c2 "R" B1 2c3 ", and "R B1 2c4 Each of these is independently a part of the general formula (IV) "R B1 2 This represents something similar to . B1 2c1 ~R B1 2c4 Each of these C atoms may independently have a substituent. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents.1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10 The aralkyl group is more preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously), and may have substituents. 1-8 Alkyl group, C6 aryl group, or C 7-10 An aralkyl group in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferable.

[0204] Organometallic compound B represented by the above general formula (IV-3) 1c Examples of such compounds include the organometallic compounds shown below.

[0205]

[0206] <Other organometallic compounds> Other organometallic compounds according to this embodiment may include organometallic compound B2 represented by the following general formula (V). [(R B2 1 -Sn) 12 O 14 (OH) 6] 2+ (Y - )2 (V) [In formula (V), R B2 1 Each of these is independently a C which may have substituents. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously); Y -Each of these independently represents a monovalent anion.

[0207] In organometallic compound B2 represented by general formula (V), "R B2 1 " may have substituents C 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0208] R B2 1 For example, C which may have substituents. 1-12 alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-10 alkyl group, C 3-10 Alicyclic group, C 6-10 Aryl group, or C 7-10 An aralkyl group is more preferably one in which any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0209] "Y - " represents a monovalent anion, for example, F - , Cl - , Br - , I - , OH - , HCOO - CH3COO - , ClO4 -PF6 - BF4 - AsF6 - SbF6 - CF3SO3 - NO3 - Examples include Y. - is F - , Cl - , Br - , I - , OH - , HCOO - CH3COO - , ClO4 - PF6 - BF4 - AsF6 - SbF6 - CF3SO3 - , and NO3 - It may be one or more monovalent anions selected from the group consisting of Y. - This can be a single monovalent anion, or a combination of two or more monovalent anions.

[0210] Y - F - , Cl - , Br - , I - , OH - , HCOO - CH3COO - It is preferable that F - , Cl - , Br - , I - , OH - , HCOO - It is preferable that it be so.

[0211] [1-2-4. Polyate or Mixture thereof] Polyate or mixture thereof can be suitably used as the metal compound in this embodiment. The polyate or mixture thereof is not particularly limited, and known and commonly used ones can be used. Polyate (also called polyoxometalate) allows for adjustment of the absorption of the metal compound to the exposure light source by combining the anionic and cationic parts of the polyate.

[0212] Polyacids are those whose general formula is [Mx O y ] n- It is an anionic metal oxide cluster represented by the formula (where x, y, and n are all natural numbers). The metal atoms M that make up the polyacid are called polyatoms, and examples include Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), Ta (pentavalent), etc. Polyacids are isopolyacids composed of the above polyatoms M and oxygen acids, and polyacids composed of the above polyatoms M and oxygen, as well as different types of atoms X (for example, as heteroatoms X, P 5+ Si 4+ , Ge 4+ , B 3+ Examples include heteropolyates containing [X w M x O y ] n- It can be broadly divided into two categories: (where w, x, y, and n are all natural numbers) and (where w, x, y, and n are all natural numbers).

[0213] The method for synthesizing polyates is not particularly limited, and known and conventional methods can be used. Examples of polyate synthesis methods include salt exchange and ion exchange.

[0214] Polyate salts consist of an anionic moiety of an isopolyacid or heteropolyacid and a cationic moiety that acts as a countercation to it. Below, the anionic and cationic moieties of polyate salts will be described separately.

[0215] [1-2-4-1. Anionic part of polysalts] The anionic part of polysalts is composed of isopolyate anions or heteropolyate anions.

[0216] Examples of isopolyate anions include isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, and isopolyoxotantalate anion. An example of the above isopolyoxomolybdate anion is [MoO4] 2- [Mo7O] 24 ] 6- [Mo8O 26 ] 4-Examples include [W4O 13 ] 2- [W5O 16 ] 2- [W6O] 19 ] 2- W7O 22 ] 2- W7O 24 ] 6- [H z W 12 O 40 ] -(8-z) (However, z represents an integer from 1 to 4.) [W 10 O 32 ] 4- [H4W 11 O 38 ] 6- [H7W 11 O 40 ] 7- [HW5O 19 ] 7- [H3W 11 O 22 ] 5- Examples include [V4O 12 ] 4- 'yV' 10 O 28 ] 6- Examples include [Nb6O 19 ] 8- [Nb 10 O 28 ] 6- Examples include, and the above isopolyoxotantalate anion is, for example, [Ta6O 19 ] 8- [Ta8O 21 ] 2- Examples include the above. The isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, and isopolyoxotantalate anion may include various isomers.

[0217] Examples of heteropoly acid anions include heteropolyoxomolybdate anions, heteropolyoxotungstate anions, heteropolyoxovanadate anions, heteropolyoxoniobate anions, and heteropolyoxotantalate anions. Examples of the above heteropolyoxomolybdate anions include phosphomolybdate anions, silicamolybdate anions, boromolybdate anions, phosphotungstomolybdate anions, cobaltmolybdate anions, arsenicmolybdate anions, and germaniummolybdate anions. Examples of the above heteropolyoxotungstate anions include phosphotungstate anions, silicatungstate anions, borotungstate anions, cobalttungstate anions, arsenictungstate anions, and germaniumtungstate anions. Examples of the heteropolyoxovanadate anions include phosphomolybdovanadate anions, phosphomolybdotungstomolybdate anions, fomolybdovanadate anions, and fomolybdotungstvanadate anions. The heteropolyoxomolybdate anions, heteropolyoxotungstate anions, and heteropolyoxovanadate anions include the Keggin type, Dawson type, Anderson type, and their deficient species and isomers.

[0218] [1-2-4-2. Cationic portion of polysalt] As the cation portion of the polysalt according to this embodiment, H + Metal ions, onium cations, or onium dications can be used.

[0219] [1-2-4-2-1. Metal Ions] The metal ions that can be used in the cation portion of the polyate are not particularly limited, for example, Li + Na + _K + , Rb + , Cs + Be 2+ Mg 2+ Ca 2+ , Sr 2+ Ba 2+ Al 3+ Co3+ , Bi 3+ , Zr 4+ , Hf 4+ , Bi 5+ and the like can be mentioned. As the metal ion, Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Al 3+ , Co 3+ are preferred, and Na + , K + , Rb + , Cs + , Ca 2+ , Al 3+ , Co 3+ are more preferred. These metal ions may be used alone or in combination of two or more.

[0220] [1-2-4-2-2. Onium Cation or Onium Dication] The onium cation or onium dication that can be used as the cation part of the polyacid salt 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, iodonium cation, and the like. These onium cations or onium dications may be used alone or in combination of two or more.

[0221] From the viewpoint of providing a building block that generates an acid when exposed to DUV, XUV, EUV, electron beam, etc., the onium cation or onium dication is preferably a sulfonium cation, sulfonium dication, or iodonium cation.

[0222] [1-2-4-2-2-1. Ammonium Cation] The ammonium cation is not particularly limited and any known and commonly used one may be used. The above ammonium cation is not particularly limited and for example, ammonium ion (NH4) + ), primary ammonium cation (NH3(R 1A ) + )), secondary ammonium cation (NH2(R 1A ) (Caution 1B )) + ), tertiary ammonium cation (NH(R 1A ) (Caution 1B ) (Caution 1C ) + ), quaternary ammonium cation (N(R 1A ) (Caution 1B ) (Caution 1C ) (Caution 1D ) + ) are listed above. 1A ~R 1D This shall represent something equivalent to what is defined below.

[0223] Ammonium cations include ammonium ions (NH4) + ), preferably a quaternary ammonium cation, and in particular an ammonium ion (NH4 + ), more preferably an organic quaternary ammonium cation represented by the following general formula (VI-1).

[0224] In general formula (VI-1), R 1A ~R 1D Each of these may independently have substituents. 1-18 R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. 1A ~R 1D Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). 1A ~R1D The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be replaced by a hydrocarbylthio group, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Furthermore R 1A ~R 1DAny two of these are linked to each other by a single bond directly, or 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 alkylene groups and form a ring together with the nitrogen atom in formula (VI-1).

[0225] Specific examples of the above organic quaternary ammonium cations 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-methacroyloxyethylammonium cation, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium Examples include ammonium cations, 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, etc.

[0226] [1-2-4-2-2-2. Ammonium Dication] The ammonium dication is not particularly limited, and known and commonly used ones can be used. Examples of the ammonium dication include organic quaternary ammonium dications represented by the following general formula (VI-2).

[0227] In general formula (VI-2), R 2A to R 2F each independently represents a C 1-18 hydrocarbyl group which may have a substituent, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. Any divalent carbon atom at a position other than the terminal of the above R 2A to R 2F may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); L 2 represents a C 1-18 hydrocarbylene group which may have a substituent. Any divalent carbon atom at a position of the above L 2 may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); The hydrogen atoms contained in the above R 2A to R 2F and L 2 are (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 carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C 1-18 hydrocarbyl group in which at least a part of the hydrogen atoms may be substituted with the above (a) to (t), C1-18 Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be replaced by a hydrocarbylthio group, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously); R 2A ~R 2F Any two of these are linked to each other by a single bond directly, or 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 alkylene groups to form a ring with the nitrogen atom in formula (VI-2).

[0228] The organic quaternary ammonium dication represented by the above general formula (VI-2) is not particularly limited, and examples 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)acrylamideethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium.

[0229] [1-2-4-2-2-3. Phosphonium Cations] Phosphonium cations are not particularly limited and known and commonly used ones can be used. Examples of phosphonium cations include organic quaternary phosphonium cations represented by the following general formula (VI-3).

[0230] In general formula (VI-3), R 3A ~R 3D Each of these may independently have substituents. 1-18 Represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; the above R 3A ~R 3D Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time); the above R 3A ~R 3DThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be replaced by a hydrocarbylthio group, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Furthermore R 3A ~R 3DAny two of these are linked to each other by a single bond directly, or 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 alkylene groups and form a ring together with the phosphorus atom in formula (VI-3).

[0231] The organic quaternary phosphonium cation represented by the above general formula (VI-3) is not particularly limited, and includes, for example, 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, and allyltriphenyl Examples include phosphonium cations, cyclopropyltriphenylphosphonium cations, benzyltriphenylphosphonium cations, tetrakis(hydroxymethyl)phosphonium cations, 2-carboxyethyltriphenylphosphonium cations, methoxycarbonylmethyltriphenylphosphonium cations, t-butoxycarbonylmethyltriphenylphosphonium cations, (4-((diisopropylcarbamoyl)oxy)phenyl)triphenylphosphonium cations, (4-(methacryloyloxy)phenyl)triphenylphosphonium cations, and triphenyl(4-(nonanoyloxy)phenyl)phosphonium cations.

[0232] [1-2-4-2-2-4. Phosphonium Dication] The phosphonium dication is not particularly limited, and known and commonly used ones can be used. Examples of phosphonium dications include the organic quaternary phosphonium dication represented by the following general formula (VI-4).

[0233] In general formula (VI-4), R 4A ~R 4FEach of these may independently have substituents. 1-18 R 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 Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). 4 C may have substituents. 1-18 Represents a hydrocarbylene group, and the above L 4 Any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time); the above R 4A ~R 4F and L 4 The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy 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 1-18Hydrocarbylaminocarbonyl 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, or C 1-18 It may be replaced by a hydrocarbylthio group, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously); R 4A ~R 4F Any two of these are linked to each other by a single bond directly, or 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 alkylene groups to form a ring together with the phosphorus atoms in formula (VI-4).

[0234] The organic quaternary phosphonium dication represented by the above general formula (VI-4) is not particularly limited, and examples include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylenebis(triphenylphosphonium) dication, pentamethylenebis(triphenylphosphonium) dication, and the like.

[0235] [1-2-4-2-2-5. Sulfonium Cations] The sulfonium cation is not particularly limited, and known and commonly used ones can be used. Examples of sulfonium cations include the organic sulfonium cation represented by the following general formula (VI-5).

[0236] In general formula (VI-5), R 5A , R 5Band R 5C Each of these may independently have substituents. 1-18 R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. 5A , R 5B and R 5C Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time); the above R 5A , R 5B and R 5C The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy 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, C1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be replaced by a hydrocarbylthio group, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Furthermore R 5A , R 5B and R 5C Any two of these are directly linked by a single bond, or 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 alkylene groups and form a ring together with the sulfur atoms in formula (VI-5).

[0237] In an organic sulfonium cation represented by the general formula (VI-5), the above R 5A , R 5B and R 5C For example, R 5A , R 5B and R 5C However, each C may independently have substituents. 1-18 It is a hydrocarbyl group; the above R 5A , R 5B and R 5C It is preferable that the divalent carbon atoms at any position other than the terminals are replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time). 5A , R 5B and R 5C However, each C may independently have substituents. 1-18 alkyl group, C 3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18It is an aralkyl group; the above R 5A , R 5B and R 5C It is more preferable that any divalent carbon atom at any position other than the terminals of R may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). 5A , R 5B and R 5C However, each C may independently have substituents. 6-18 It is an aryl group; the above R 5A , R 5B and R 5C The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is preferable that these substituents may be replaced by hydrocarbylthio groups, and that the divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0238] Also R 5A , R 5B and R 5C Any two of these are directly linked by a single bond, or by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 Examples of structures that are linked via alkylene groups and form a ring with the sulfur atom in formula (VI-5) include those having the thian-1-ium skeleton, thiophene-1-ium skeleton, 1,4-oxatian-4-ium skeleton, 1,4-dithiane-1-ium skeleton, 1H-thiophene-1-ium skeleton, benzo[b]thiophene-1-ium skeleton, dibenzothiophenium skeleton, 9,10-dihydrothioxanthilium skeleton, 10H-phenoxathiyne-10-ium skeleton, 5H-thiantrene-5-ium skeleton, and the following are examples. Note that * indicates that R is not involved in ring formation. 5A , R 5B or R 5C It means the connection point.

[0239]

[0240] Examples of the above organic sulfonium cations include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalene-1-yl)hexahydrothiopyrillium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrillium cation, di(naphthalene-1-yl)(phenyl)sulfonium cation, and phenylbis(2-(trifluoromethyl)phenyl)sulfonium Mu 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-thianthrene-5-ium cation, 5-(2,5-dimethylphenyl)thianthrene-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophene-5-ium cation, 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,Examples include [d] thiophene-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b] thiophene-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, (2-bromoethyl)diphenylsulfonium cation, dimethyl(trifluoromethyl)sulfonium cation, tri-p-tolylsulfonium cation, etc.

[0241] [1-2-4-2-2-6. Sulfonium Dications] Sulfonium dications are not particularly limited, and known and commonly used ones can be used. Examples of sulfonium dications include the organic sulfonium dication represented by the following general formula (VI-6).

[0242] In general formula (VI-6), R 6A , R 6B , R 6C and R 6D Each of these may independently have substituents. 1-18 R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. 6A , R 6B , R 6C and R 6D Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time); L 6 C may have substituents. 1-18 Represents a hydrocarbylene group, and the above L 6Any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time); the above R 6A , R 6B , R 6C , R 6D , and L 6 The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C 1-18The hydrocarbylthio group may be replaced, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously); R 6A , R 6B and L 6 Any two of the following, and / or R 6C , R 6D and L 6 Any two of these are directly linked by a single bond, or 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 alkylene groups to form a ring together with the sulfur atoms in formula (VI-6).

[0243] [1-2-4-2-2-7. Iodonium Cations] The iodonium cation is not particularly limited, and known and commonly used ones can be used. Examples of iodonium cations include the organic iodonium cation represented by the following general formula (VI-7).

[0244] In general formula (VI-7), R 7A and R 7B Each of these may independently have substituents. 1-18 R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. 7A and R 7B Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time); the above R 7A and R 7BThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be replaced by a hydrocarbylthio group, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Furthermore R 7A and R 7BThese are directly linked by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via alkylene groups, forming a ring together with the iodine atom in formula (VI-7).

[0245] In the organic iodonium cation represented by the general formula (VI-7), R 7A and R 7B For example, R 7A and R 7B However, each C may independently have substituents. 1-18 It is a hydrocarbyl group; the above R 7A and R 7B It is preferable that the divalent carbon atoms at any position other than the terminals are replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time). 7A and R 7B However, each C may independently have substituents. 1-18 alkyl group, C 3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18 It is an aralkyl group; the above R 7A and R 7B It is more preferable that any divalent carbon atom at any position other than the terminals of R may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). 7A and R 7B However, each C may independently have substituents. 6-18 It is an aryl group; the above R 7A and R 7BThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is preferable that these substituents may be replaced by hydrocarbylthio groups, and that the divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0246] Examples of the above organic iodonium cations 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, and (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl) ) Iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4 (Trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-methylphenyl) Examples include (2,4,6-trimethylphenyl)iodonium cation, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, phenyl(2,4,6-trimethoxyphenyl)iodonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)(phenyl)iodonium cation, (4-(methacryloyloxy)phenyl)(phenyl)iodonium cation, and (4-(nonanoyloxy)phenyl)(phenyl)iodonium cation.

[0247] [1-2-4-3. Polyate or Mixture thereof] As the polyate or mixture thereof according to this embodiment, a polyate or mixture thereof represented by the following general formula (VII-1) or (VII-2) can be used. (A m+ ) a (C (am)- ) (VII-1) (A' m’+ ) a’ (B n+ ) b (C'(a'm'+bn)-) (VII-2)

[0248] <Polysate or mixture thereof represented by general formula (VII-1)> In this embodiment, the polysate or mixture thereof represented by the following general formula (VII-1) may be used. (A m+ ) a (C (am)- ) (VII-1) [In formula (VII-1), A m+ Each of them independently, H + , metal ions, NH4 + , represents an onium cation or onium dication; C (am)- [where m represents an isopolyate anion or heteropolyate anion, m is an integer from 1 to 5, and a is a real number greater than 0.]

[0249] In the polysalt or mixture thereof represented by the above general formula (VII-1), the "metal ion," "onium cation," "onium dication," "isopolyate anion," and "heteropolyate anion" can be those described above as appropriate.

[0250] The mixture of polysalts represented by the above general formula (VII-1) contains several types of A m+ It may include multiple types of A. m+ The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0251] <Polysate or mixture thereof represented by general formula (VII-2)> Another polysate or mixture thereof according to this embodiment may be represented by the following general formula (VII-2). (A' m’+ )a’ (B n+ ) b (C'(a'm'+bn)-) (VII-2) [In formula (VII-2), A' m’+ Each of them independently, H + , metal ions, or NH4 + Represents; B n+ Each of these independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents an isopolyate anion or a heteropolyate anion, where 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.

[0252] In the polysalt or mixture thereof represented by the above general formula (VII-2), the "metal ion," "onium cation," "onium dication," "isopolyate anion," and "heteropolyate anion" can be those described above as appropriate.

[0253] The polysalt represented by the above general formula (VII-2) or a mixture thereof has a sulfonium cation, sulfonium dication, or iodonium cation in its cation portion, and therefore can be given the function of generating acid by exposure with DUV, XUV, EUV, electron beam, etc.

[0254] A mixture of polysalts represented by the general formula (VII-2) contains A' m’+ and B n+ Multiple polysalts with different ratios may be included. In this case, the values ​​of a' and b can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0255] The ratio of a' to b is polyacid anion, A' m’+ , B n+Depending on the type, etc., it is preferable that a':b = 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 from 2 to 8, and m' and n are 1, it is preferable that a' is a real number from 0 to 7 and b is a real number from 1 to 8, and more preferably that a' is a real number from 0 to 4 and b is a real number from 2 to 8.

[0256] [1-2-5. Content of Component (B)] The content of component (B) in the resist material is not particularly limited and can be appropriately set depending on the type and content of component (A), the type of component (B), the method of applying the resist material to the substrate, the film thickness to be applied, etc. The content of component (B) in the resist material is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 10% by mass, when the resist material is considered to be 100% by mass.

[0257] [1-3. (C) Acid Generator] In addition to components (A) and (B), the resist material according to this embodiment may also contain an optional component (C) an acid generator. The acid generator is not particularly limited, and any known and commonly used acid generator in the field of chemically amplified resist materials can be used. The acid generator has the function of generating acid by exposure such as DUV, XUV, EUV, or electron beam.

[0258] Examples of acid generators include ionic acid generators such as sulfonium salts, iodonium salts, ammonium salts, and other onium salts; and nonionic acid generators such as imidosulfonates, oximesulfonates, and sulfonyldiazomethanes. From the viewpoint of resolution and sensitivity, it is preferable to use ionic acid generators as the acid generator.

[0259] [1-3-1. Ionic Acid Generator] The anion portion of the ionic acid generator is not particularly limited and may consist of, for example, a sulfonate anion, a sulfonamide anion, a sulfonimide anion, a methide anion, etc. The cation portion of the ionic acid generator is not particularly limited and may consist of, for example, an onium cation or a dication.

[0260] Examples of acid generators include "sulfonate compound C1" represented by the following general formula (VIII-1), "sulfonamide or sulfonimide salt compound C2" represented by the following general formula (VIII-2), and "methide salt compound C3" represented by the following general formula (VIII-3). Hereinafter, sulfonate anion, sulfonylamide anion, sulfonimide anion, methide anion, onium cation or onium dication (D p+ ) will be explained in detail.

[0261] [1-3-1-1. Sulfonate Compound C1] As an acid generator, "sulfonate compound C1" represented by the following general formula (VIII-1) consists of a sulfonate anion and an onium cation or dication (D p+ ) and salt can be used.

[0262] "R C1 1 " may have substituents 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 except terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0263] R C1 1 C may have substituents. 1-18A hydrocarbyl group is preferred in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the C may have substituents. 1-18 alkyl group, C 3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18 An aralkyl group is more preferably one in which any divalent carbon atom other than the terminal is replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and one or more hydrogen atoms are substituted with halogen atoms. 1-12 C, which may have an alkyl group or substituent. 3-18 Alicyclic group, or C 6-18 It is even more preferable that the group be an aryl group.

[0264] C may have substituents. 3-18 Alicyclic group, or C 6-18 The aryl group is not particularly limited and can be, for example, a C having a benzene skeleton, naphthalene skeleton, anthracene skeleton, phenanthrene skeleton, or biphenyl skeleton. 6-18 C having an aryl group; cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, tricyclodecene skeleton, bicyclo[2.2.1]heptane skeleton, bicyclo[2.2.2]octane skeleton, 9,10-dihydro-9,10-ethanoanthracene skeleton, 9,10-dihydro-9,10-[1,2]benzenoanthracene skeleton 3-18 Examples include alicyclic groups.

[0265] R C11 Specific examples include, for instance, trifluoromethyl group, perfluoroethyl group, perfluorobutyl group, perfluoropentyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, azlenyl group, acenaphthyl group, phenantrenyl group, anthracenyl group, cyclopentyl group, cyclopenta-1-en-1-yl group, 2-methylcyclopenta-1-en-1-yl group, cyclohexa-1-en-1-yl group, adamantan-1-yl group, adamantan-2-yl group, bicyclo[2.2.1]heptanyl group, bicyclo[2.2.2]octanyl group, Examples include the bicyclo[2.2.1]heptenyl group, the bicyclo[2.2.2]octenyl group, the 9,10-dihydro-9,10-ethanoanthracene-11-yl group, the 9,10-dihydro-9,10-ethanoanthracene-12-yl group, the 9,10-dihydro-9,10-ethanoanthracene-9-yl group, the 9,10-dihydro-9,10-ethanoanthracene-10-yl group, the 9,10-dihydro-9,10-[1,2]benzenoanthracene-9-yl group, and the 9,10-dihydro-9,10-[1,2]benzenoanthracene-10-yl group.

[0266] "L C1 1 " is a single bond or a C which may have a substituent 1-12 In a hydrocarbylene group, any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0267] L C1 1 This may consist of a single bond or a C that may have a substituent. 1-12The hydrocarbylene group is preferably such that any divalent carbon atom, excluding the terminals other than the bond, may be replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). The C may have a single bond or a substituent. 1-12 Alkanediyl group, C 6-12 The arenediyl group is more preferably one in which any divalent carbon atom other than the terminals other than the bond is replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time), and may have substituents. 1-12 More preferably, the alkanediyl group is one in which at least one or more divalent carbon atoms, excluding the terminals other than the bond, are replaced with -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0268] "L C1 2 " is a C in which at least one hydrogen atom is replaced by a halogen atom. 1-6 This represents a hydrocarbylene group.

[0269] L C1 2 For example, C in which at least one hydrogen atom is replaced by a halogen atom. 1-6 Preferably a hydrocarbylene group, and at least one hydrogen atom is substituted with a halogen atom. 1-6 Alkanediyl group or C 1-6 It is more preferably an arylene group, in which at least one hydrogen atom of the carbon atom at the α position relative to the sulfonic acid group is substituted with a halogen atom. 1-6 C is either an alkanediyl group or a group in which at least one hydrogen atom is replaced by a fluorine atom. 1-6C is either an alkanediyl group or a C in which two or more hydrogen atoms are substituted with fluorine atoms. 1-6 It is even more preferable that the group is an arylene group, wherein at least one hydrogen atom of the carbon atom at the α position relative to the sulfonic acid group is substituted with a fluorine atom. 1-5 C 1-6 A carbon atom in the γ position relative to an alkanediyl group or a sulfonic acid group, where two or more hydrogen atoms are substituted with fluorine atoms. 1-6 C is either an alkanediyl group or a C in which three or more hydrogen atoms are replaced by fluorine atoms. 1-6 It is even more preferable that the group be an arylene group.

[0270] The above sulfonic acid anions are not particularly limited and include, for example, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid anion, 2-((cyclohexanecarbonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonic acid anion, 2-((cyclohexanecarbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion, 2-((decahydronaphthalene-2-carbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion, 2-((decahydronaphthalene-2-carbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion, 2-((decahydronaphthalene-2-carbonyl)oxy) Bonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate anion, 2-((bicyclo[2.2.1]heptane-2-carbonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate anion, 2-((bicyclo[2.2.1]heptane-2-carbonyl)oxy)-1,1-difluoroethane-1-sulfonate anion, 2-(bicyclo[2.2.1]heptane-2-yl)-1,1,2,2-tetrafluoroethane-1-sulfonate anion, 2-(benzoyloxy)-1,1,3,3 ,3-pentafluoropropane-1-sulfonate anion, 2-(benzoyloxy)-1,1-difluoroethane-1-sulfonate anion, 2-(benzoyloxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate anion, 1,1-difluoro-2-oxo-2-phenoxyethane-1-sulfonate anion, 1,1-difluoro-2-phenoxyethane-1-sulfonate anion, 2-((adamantane-1-carbonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate anion Honate anion, 2-((adamantan-1-carbonyl)oxy)-1,1-difluoroethane-1-sulfonate anion, 2-(adamantan-1-yl)-1,1-difluoroethane-1-sulfonate anion, 2-(((adamantan-1-yl)oxy)carbonyl)-1,1,1,3,3,3-hexafluoropropane-2-sulfonate anion, 2-((adamantan-1-yl)oxy)-1,1-difluoro-2-oxoethane-1-sulfonate anion, 6-((adamantan-1-carbonyl)oxy)-1,1,2,Examples include 2-tetrafluorohexane-1-sulfonic acid anion, 2-(2-((adamantane-1-carbonyl)oxy)ethoxy)-1,1-difluoro-2-oxoethane-1-sulfonic acid anion, 4-((adamantane-1-carbonyl)oxy)-1,1,2-trifluorobutane-1-sulfonic acid anion, 1,1-difluoro-2-(2-((2-methyladamantane-2-yl)oxy)-2-oxoethoxy)-2-oxoethane-1-sulfonic acid anion, and 2-((9,10-dihydro-9,10-ethanoanthracene-12-carbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion.

[0271]

[0272]

[0273] [1-3-1-2. Sulfonamide or Sulfonimide Compound C2] As an acid generator, a "sulfonamide or sulfonimide compound C2" represented by the following general formula (VIII-2) is used, which consists of a sulfonamide anion or sulfonimide anion and an onium cation or dication (D p+ ) and salt can be used.

[0274] "R C2 1 " and "R C2 2 Each of these may independently have a cyano group or a substituent. 1-12 A hydrocarbyl group in which any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously), or R C2 1 and R C2 2 However, C may be directly linked by a single bond, or by a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C which may have a substituent. 1-3They may be linked via alkylene groups and form a ring together with the nitrogen atom in formula (VIII-2).

[0275] R C2 1 and R C2 2 Each of these may independently have a cyano group or a substituent. 1-12 A hydrocarbyl group is preferred in which divalent carbon atoms at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). A cyano group or a C group in which at least one hydrogen atom is replaced with a halogen atom is preferred. 1-12 Alkyl or C 6-12 An aryl group is more preferably one in which a divalent carbon atom at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time), and a cyano group or a C group in which at least two hydrogen atoms are replaced with fluorine atoms. 1-12 Alkyl or C 6-12 An aryl group is more preferably one in which divalent carbon atoms at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0276] Also R C2 1 and R C2 2 However, C may be directly linked by a single bond, or by a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C which may have a substituent. 1-3 Linked via an alkylene group, the nitrogen atom in formula (VIII-2), R C 1 , R C22 , L C2 1 In the case where a ring is formed with -S(=O)2-, it is preferable that a 5- to 7-membered ring is formed overall and one or more hydrogen atoms are substituted with halogen atoms, and it is more preferable that a 6-membered ring is formed and two or more hydrogen atoms are substituted with fluorine atoms.

[0277] "L C2 1 " is a single bond or a C which may have a substituent 1-3 In a hydrocarbylene group, any divalent carbon atom other than the terminals other than the bond may be replaced with -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0278] L C2 1 This may consist of a single bond or a C that may have a substituent. 1-3 The hydrocarbylene group is preferably such that any divalent carbon atoms, excluding the terminals other than the bond, may be replaced with -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). It is more preferably a single bond or -C(=O)-, -C(=O)-O-, -CONH-, or -SO2-, and even more preferably a single bond or -C(=O)- or -SO2-.

[0279] The above-mentioned sulfonamide anions or sulfonimide anions are not particularly limited and include, for example, (4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-oid 1,1,3,3-tetraoxide) anions, (4,4,5,5,6,6-hexafluoro-3-oxo-1,2-thiadinane-2-oid 1,1-dioxide) anions, and (3,3,4,4,5,5,6,6-octafluoro-1,2-thiadinane-2-oid Examples include 1,1-dioxide anions, bis((trifluoromethyl)sulfonyl)amide anions, (phenylsulfonyl)((trifluoromethyl)sulfonyl)amide anions, ((perfluoroethyl)sulfonyl)(phenylsulfonyl)amide anions, ((perfluorobutyl)sulfonyl)((trifluoromethyl)sulfonyl)amide anions, and bis((perfluorobutyl)sulfonyl)amide anions.

[0280]

[0281] [1-2-1-3. Methylated salt compound C3] As an acid generator, as shown in the general formula (VIII-3) below, "methylated salt compound C3" consists of a methyl anion and an onium cation or dication (D p+ ) and salt can be used.

[0282] "R C3 1 "R" C3 2 " and "R C3 3 Each of these may independently have a cyano group or a substituent. 1-12 A hydrocarbyl group in which any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously), or R C3 1 , R C3 2 and R C3 3Any two of these may be directly linked by a single bond, or may have divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C(=O)O- which may have substituents. 1-3 Linked via an alkylene group, the methide (C) in formula (VIII-3) - They may form a ring together.

[0283] R C3 1 , R C3 2 and R C3 3 Each of these may independently have a cyano group or a substituent. 1-12 A hydrocarbyl group is preferred in which divalent carbon atoms at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). A cyano group or a C group in which at least one hydrogen atom is replaced with a halogen atom is preferred. 1-12 Alkyl or C 6-12 An aryl group in which divalent carbon atoms at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time) is more preferable, and a cyano group or a C group in which at least two hydrogen atoms are replaced with fluorine atoms. 1-12 Alkyl or C 6-12 It is even more preferable that the aryl group has divalent carbon atoms at any position other than the terminals replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0284] Also R C3 1 , R C3 2 and R C33 Any two of these may be directly linked by a single bond, or may have divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C(=O)O- which may have substituents. 1-3 Linked via an alkylene group, the methide (C) in formula (VIII-3) - When a ring is formed together with the other elements, it is preferable that the ring forms a total of 5 to 7 members and one or more hydrogen atoms are substituted with halogen atoms, and it is more preferable that the ring forms a 6-membered ring and two or more hydrogen atoms are substituted with fluorine atoms.

[0285] "L C3 1 "L C3 2 " and "L C3 3 Each of these may independently have a single bond or a substituent. 1-3 In a hydrocarbylene group, any divalent carbon atom other than the terminals other than the bond may be replaced with -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0286] L C3 1 , L C3 2 and L C3 3 This may consist of a single bond or a C that may have a substituent. 1-3 The hydrocarbylene group is preferably such that any divalent carbon atoms, excluding the terminals other than the bond, may be replaced with -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). It is more preferably a single bond or -C(=O)-, -C(=O)-O-, -CONH-, or -SO2-, and even more preferably a single bond or -C(=O)- or -SO2-.

[0287] The above-mentioned metanide anions are not particularly limited and include, for example, tris(methylsulfonyl)methionine, tris((trifluoromethyl)sulfonyl)methionine, tris((perfluoroethyl)sulfonyl)methionine, tris(phenylsulfonyl)methionine, dicyano((trifluoromethyl)sulfonyl)methionine, and the like.

[0288]

[0289] [1-3-1-4. Onium cation or onium dication (D p+ )] The cation portion of the above (B) acid generator may be an onium cation or a dication (D p+ ) can be used. Here, the general formulas (VIII-1) to (VIII-3) represent "(D p+ ) 1 / p In this expression, D represents an onium cation or dication, and p represents an integer of 1 or 2.

[0290] The above-mentioned onium cation or dication is not particularly limited, and sulfonium cations, sulfonium dications, iodonium cations, etc., can be used.

[0291] The above onium cation or dication (D p+ It is preferable to use an organic sulfonium cation represented by the general formula (VI-5) above, an organic sulfonium dication represented by the general formula (VI-6) above, or an organic iodonium cation represented by the general formula (VI-7) above as the above-mentioned components.

[0292] [1-3-2. Content of Component (C)] The content of the acid generator (C) contained in the resist material according to this embodiment is not particularly limited and can be appropriately set depending on the type and content of components (A) and (B). The content of component (C) in the resist material is preferably 0.1 to 30 parts by mass, preferably 0.2 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (B).

[0293] [1-4. Organic Solvents] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and known and commonly used solvents can be used. The organic solvent is preferably one that can uniformly dissolve or disperse when prepared with components (A) and (B).

[0294] Examples of organic solvents include polar solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, nitrile-based solvents, and aproton-based polar solvents, and examples of non-polar solvents such as hydrocarbon-based solvents. These organic solvents may be used individually or in combination of two or more.

[0295] Specific examples of the above polar solvents include, for example, alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), 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, methylisopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Examples of organic solvents include: amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; and aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. Nonpolar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. The above organic solvents may be used individually or in combination of two or more.

[0296] The organic solvent to be included in the resist material according to this embodiment is preferably a polar solvent in terms of coatability, and more preferably an amide solvent, ester solvent, alcohol solvent, or 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. The ester solvent or alcohol solvent is preferably one having an ester bond and / or a hydroxyl group in terms of solubility, and among the above, it is preferably at least one selected from the group consisting of propylene glycol monomethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, and propylene glycol monomethyl ether acetate.

[0297] The content of the organic solvent in the resist material is not particularly limited and can be appropriately set depending on the type and content of components (A) and (B), the method of applying the resist material to the substrate, the film thickness to be applied, etc. Preferably, the solid content of the resist material is 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 10% by mass.

[0298] [1-5. Others] The resist material according to this embodiment may further contain, if desired, miscible additives such as additional resins to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.

[0299] [2. Pattern Forming Method] The pattern forming method according to this embodiment comprises 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.

[0300] [2-1. Coating Process] The pattern formation method according to this embodiment includes a step of coating a resist material onto a substrate.

[0301] <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 with a predetermined wiring pattern formed on it may be used. The material of the substrate is not particularly limited, and examples 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 and shape of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or it may be a thin, flake-shaped substrate.

[0302] The surface of the substrate may be surface-treated as needed. In the case of a substrate having hydroxyl groups on its surface, surface treatment of the substrate using a silane-based coupling agent that reacts with hydroxyl groups can change the surface of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane-based coupling agent include hexamethyldisilazane (HMDS).

[0303] <Coating Method> The method for coating the resist material onto the substrate is not particularly limited, and known and conventional methods can be used. Dry coating methods include, for example, CVD methods (chemical vapor deposition) such as thermal CVD, plasma CVD, and photo-CVD; and PVD methods (physical vapor deposition) such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Wet coating methods include, for example, spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0304] As a method for applying the resist material according to this embodiment onto a substrate, it is preferable to use a wet method such as spin coating or screen printing, and more preferably to use spin coating, from the viewpoint of forming a uniform film thickness. After forming the coated film, backside rinsing, edge bead removal steps, etc., can be performed to remove edge beads.

[0305] The method for drying the resist film formed by coating a resist material onto a substrate is not particularly limited and can be carried out using, for example, a heating device such as a hot plate (post-application bake (PAB)), a vacuum device, etc. The baking conditions are not particularly limited and can be set appropriately according to 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.

[0306] 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.

[0307] [2-2. Exposure Step] The pattern formation method according to this embodiment includes a step of exposing the resist film formed by the coating step described above.

[0308] For example, an ArF exposure apparatus, electron beam lithography apparatus, EUV exposure apparatus, etc., can be used as the exposure apparatus in the resist film exposure process. In the exposure process, exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by direct irradiation with an electron beam or the like without using a mask pattern.

[0309] The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser (wavelength 193 nm), KrF excimer laser (248 nm), F2 excimer laser (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays may be used.

[0310] For ArF or KrF excimer lasers, the exposure dose to the resist film is 1 to 200 mJ / cm². 2 Preferably, the concentration is 20 to 60 mJ / cm². 2 It is more preferable that this be the case. Also, in the case of extreme ultraviolet light, the exposure dose is, for example, 500 mJ / cm². 2 The following applies: 0.1 to 200 mJ / cm² 2 Preferably, it is 3 to 100 mJ / cm². 2 It is more preferable that the concentration be 5 to 50 mJ / cm². 2 It is even more preferable that this be the case. In the case of an electron beam, 3 μC / cm at 50 kV. 2 ~2 mC / cm 2 It is preferable to expose with a dose of 10 μC / cm². 2 ~1.5 mC / cm 2 Exposure at this dose is more preferable.

[0311] After exposure to the resist film, a bake (post-exposure bake (PEB)) treatment may or may not be performed. The bake conditions are not particularly limited and can be set appropriately depending on the type of resist film, application, etc. The bake 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 bake time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0312] [2-3. Development Process] The pattern formation method according to this embodiment includes a step of developing the exposed resist film. In the development process, a pattern can be formed by developing the exposed resist film with a developer. When the exposed area remains as a pattern after development, it is a negative-type pattern formation process, and when the exposed area is removed after development, it is a positive-type pattern formation process. Whether to form a positive or negative pattern can be appropriately selected depending on the resist material or developer. After development, the film may be washed with a rinsing solution and then dried, and in some cases, a baking process may be performed further.

[0313] The developer used in this embodiment may be an alkaline developer for the alkaline development process, or a developer containing an organic solvent (organic developer) for the organic solvent development process.

[0314] <Alkaline Development Process> With conventional metal oxide resist materials, it has been difficult to form positive-type patterns with good resolution using the alkaline development process. In contrast, the resist material according to this embodiment can form patterns with good resolution using a water-containing developer.

[0315] The alkaline developer used in the alkaline development process is not particularly limited, and any known and commonly used one may be used. Examples of the above-mentioned alkaline developer include quaternary ammonium salts such as tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and aqueous solutions containing one or more alkanolamines such as dimethylethanolamine and triethanolamine.

[0316] The method for developing the exposed resist film using the above-mentioned alkaline developer is not particularly limited, and known and conventional methods can be used. Examples of methods for developing using the above-mentioned developer include immersing the substrate having the exposed resist film in the developer for a certain period of time (dip method), spraying the developer onto the surface of the exposed resist film (spray method), and dispensing the developer from a discharge nozzle at a constant speed toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispensing method).

[0317] Furthermore, pure water can be used as the rinsing solution in the alkaline development process.

[0318] <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 like ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, or hydrocarbon solvents.

[0319] Specific examples of organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); alcohol 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 solvents such as acetonitrile, propionitrile, and benzonitrile. Examples include amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; and hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. These may be used individually or in combination of two or more.

[0320] Among these, the organic solvent used in the developer is preferably a polar solvent, and more preferably contains amide solvents, alcohol solvents, ester solvents, and ketone solvents. 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 one or more selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl 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. Furthermore, the ketone solvent is preferably at least one selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, and 2-heptanone.

[0321] When the developer contains either an amide-based solvent or an ester-based solvent and an alcohol-based solvent, the mixing ratio (by weight) of the amide-based solvent or ester-based solvent to the alcohol-based solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0322] The method for developing the exposed resist film using the above-mentioned developer is not particularly limited, and known and conventional methods can be used. Examples of methods for developing using the above-mentioned developer include immersing the substrate having the exposed resist film in the developer for a certain period of time (dip method), spraying the developer onto the surface of the exposed resist film (spray method), and dispensing the developer from a discharge nozzle at a constant speed toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispensing method).

[0323] The process may include a step of washing with a rinsing solution after development with the above-mentioned developer solution. The rinsing solution is not particularly limited, and any known and commonly used solution can be used. As the rinsing solution, a suitable choice can be made from the water or organic solvent contained in the above-mentioned developer solution that does not easily dissolve the resist pattern.

[0324] The rinsing solution is not particularly limited, and 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 can be used. 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 rinsing solution, more preferably at least one selected from the group consisting of alcohol solvents and ester solvents, and even more preferably at least one alcohol solvent.

[0325] As the alcohol-based solvent used in the rinsing solution, a monohydric alcohol having 2 to 8 carbon atoms is preferred, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples of the above monohydric alcohols 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, benzyl alcohol, and the like. These organic solvents may be used individually or in combination of two or more.

[0326] The method for cleaning the resist pattern with the above-mentioned rinsing solution is not particularly limited, and known and conventional methods can be used. Examples of methods for cleaning using the above-mentioned rinsing solution include immersing the resist pattern in the rinsing solution for a certain period of time (dip method), spraying the rinsing solution onto the surface of the resist pattern (spray method), and dispensing the rinsing solution from a discharge nozzle at a constant speed toward the surface of a resist pattern rotating at a constant speed (dynamic dispensing method).

[0327] [3. Patterned Structure] The patterned structure according to this embodiment is obtained by forming a pattern on a substrate using the pattern formation method described above.

[0328] The average thickness of part or all of the patterned structure according to this embodiment is not particularly limited and can be set as appropriate depending on the intended use. The patterned structure preferably has an average thickness portion of 1 to 100 nm, more preferably a portion of 5 to 75 nm, and even more preferably a portion of 10 to 60 nm.

[0329] Furthermore, the pitch of part or all of the patterned structure according to this embodiment is not particularly limited and can be set as appropriate depending on the intended use. It is preferable that the patterned structure has a portion with a pitch of 100 nm or less, more preferably a portion with a pitch of 50 nm or less, and even more preferably a portion with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the pattern formation method described above, it is possible to create portions with pitches of 50 nm, 20 nm, and 15 nm in part or all of the patterned structure.

[0330] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0331] [1. (A) Synthesis of Polymers] The polymers (A-1) to (A-6) shown below were obtained by radical polymerization of monomers that induce the constituent units of each polymer. Below, for polymers (A-1) to (A-6), the weight-average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) on a standard polystyrene basis, determined by GPC measurement, are described, 13 The copolymerization composition ratios (molar ratios of each constituent unit in the polymer) determined by C-NMR are shown below.

[0332] <Polymer (A-1)> Polymer (A-1) was obtained by copolymerizing 3,4,5-trifluorophenyl methacrylate, which gives a structural unit having a fluorine atom represented by the following formula (A-1), with 1-ethylcyclopentyl methacrylate, which gives a structural unit that adjusts the solubility in the developer. In polymer (A-1), Mw = 11000, Mw / Mn = 1.3, and the molar ratio of 3,4,5-trifluorophenyl methacrylate to 1-ethylcyclopentyl methacrylate was 70:30.

[0333] <Polymer (A-2)> Polymer (A-2) was obtained by copolymerizing 1-(2,3,4,5,6-pentafluorophenyl)ethyl methacrylate, which gives a structural unit having a fluorine atom represented by the following formula (A-2), 1-ethylcyclopentyl methacrylate, which gives a structural unit that adjusts the solubility in the developer, and methacrylic acid, which gives other structural units. In polymer (A-2), Mw = 13300, Mw / Mn = 1.5, and the molar ratio of 1-(2,3,4,5,6-pentafluorophenyl)ethyl methacrylate, 1-ethylcyclopentyl methacrylate, and methacrylic acid was 20:30:50.

[0334] <Polymer (A-3)> Polymer (A-3) was obtained by copolymerizing 2,3,4,5,6-pentafluorophenyl-2,3,5,6-tetrafluoro-4-(isopropenylcarbonyloxy)benzoate, which gives a structural unit having a fluorine atom represented by the following formula (A-3), with 1-ethylcyclooctyl methacrylate, which gives a structural unit that adjusts the solubility in the developer. In polymer (A-3), Mw = 13000, Mw / Mn = 1.4, and the molar ratio of 2,3,4,5,6-pentafluorophenyl-2,3,5,6-tetrafluoro-4-(isopropenylcarbonyloxy)benzoate to 1-ethylcyclooctyl methacrylate was 20:80.

[0335] <Polymer (A-4)> Polymer (A-4) was obtained by copolymerizing 1,2,3,4,5-pentafluoro-6-isopropenylbenzene, which gives a structural unit having a fluorine atom represented by the following formula (A-4), with 1-ethylcyclopentyl methacrylate, which gives a structural unit that adjusts the solubility in the developer. In polymer (A-4), Mw = 8700, Mw / Mn = 1.6, and the molar ratio of 1,2,3,4,5-pentafluoro-6-isopropenylbenzene to 1-ethylcyclopentyl methacrylate was 50:50.

[0336] <Polymer (A-5)> Polymer (A-5) was obtained by copolymerizing 2,2,3,3,3-pentafluoropropyl (6-vinyl-2-naphthyloxy) acetate, represented by the following formula (A-5), with 1-ethylcyclooctyl methacrylate. In polymer (A-5), Mw = 12500, Mw / Mn = 1.5, and the molar ratio of 2,2,3,3,3-pentafluoropropyl (6-vinyl-2-naphthyloxy) acetate to 1-ethylcyclooctyl methacrylate was 75:25.

[0337] <Polymer (A-6)> Polymer (A-6) was obtained by copolymerizing 2,2,2-trifluoro-1-(trifluoromethyl)ethyl methacrylate, represented by the following formula (A-6), with 1-methylcyclopentyl methacrylate. In polymer (A-6), Mw = 8600, Mw / Mn = 1.62, and the molar ratio of 2,2,2-trifluoro-1-(trifluoromethyl)ethyl methacrylate to 1-methylcyclopentyl methacrylate was 60:40.

[0338] [2. (B) Synthesis of Metal Compounds] <Production Example 1: Production of Tris(ethylcarbonyloxy)stannylpropanoate (Compound A)> 20 g of tetraphenyltin was added to 60 mL of propionic acid, heated under reflux for 24 hours, and then unreacted propionic acid was removed under reduced pressure to obtain 15 g of compound A.

[0339] <Synthesis Example 1: Synthesis of bis(ethylcarbonyloxy)(ethylsulfanyl)stannylpropanoate (metal compound (B-1))> After adding 50 mL of anhydrous toluene to compound A (5 g), 0.8 g of ethanethiol dissolved in 20 mL of anhydrous toluene was gradually added dropwise for 15 minutes while stirring at room temperature, and then the mixture was stirred at room temperature for 24 hours. The volatile solvent was removed under reduced pressure to obtain 2.9 g of metal compound (B-1).

[0340] <Manufacturing Example 2: Manufacturing of Trichloro(2,2-dimethylpropyl) stannane (Compound B)> 20 g of triphenyltin chloride was mixed with 70 mL of THF, cooled to 0°C, and then 62.3 mL of 1 M solution of 2,2-dimethylpropylmagnesium chloride in THF was gradually added dropwise. After the addition was complete, the mixture was stirred at 25°C for 12 hours to obtain 15.6 g of triphenyl(2,2-dimethylpropyl)stannane. 9.7 g of triphenyl(2,2-dimethylpropyl)stannane was dissolved in 50 mL of CH2Cl2, and 7.5 mL of 2 M HCl diethyl ether solution was gradually added dropwise at -78°C. After stirring at 25°C for 12 hours, the solvent was concentrated and the mixture was subjected to vacuum distillation to obtain 17 g of compound B.

[0341] <Synthesis Example 2: Synthesis of (2,2-dimethylpropyl)di(ethylcarbonyloxy)stannylpropanoate (metal compound (B-2))> 10 g of compound B was gradually mixed with 25 mL of propionic acid at 25°C, and then heated under reflux at 110°C for 12 hours. The mixture was then heated to 25°C, and the propionic acid was removed by distillation under reduced pressure to obtain 3.8 g of metal compound (B-2).

[0342] <Synthesis Example 3: [(t-BuSn) 12 O 14Synthesis of (OH)6](OH)2 (metal compound (B-3)) > 0.209 g of monobutyltin oxide hydrate was mixed with 10 mL of 4-methyl-2-pentanol and stirred at room temperature for 24 hours. The resulting mixture was centrifuged at 4000 rpm for 15 minutes and filtered through a 0.45 μm PTFE syringe filter. Low-boiling point substances in the filtrate were removed by vacuum distillation to obtain 1.7 g of metal compound (B-3).

[0343] <Manufacturing Example 3: Manufacturing of Triphenyl(propan-2-yl) stannan (Compound C)> Triphenyltin chloride (20 g) was dissolved in THF (70 mL) and cooled to 0°C. Then, isopropyl magnesium chloride (2.4 M in THF, 31 mL) was gradually added dropwise. After the addition was complete, the temperature was raised to 25°C and stirred for 12 hours to obtain 18 g of compound C.

[0344] <Synthesis Example 4: Dicarbonyloxy(propan-2-yl) stannylformate (Synthesis of Metal Compound (B-4))> Compound C (10 g) was dissolved in formic acid (25 mL), and the mixture was heated under reflux at 100°C for 24 hours. After cooling to 25°C, the formic acid was removed by distillation under reduced pressure to obtain 6.7 g of metal compound (B-4).

[0345] <Synthesis Example 5: Tetrakis(bis(3,5-difluorophenyl)(phenyl)sulfonium) keitangstate(metal compound (B-5))> Dissolve 6.68 g of bis(3,5-difluorophenyl)(phenyl)sulfonium chloride in 99.36 g of pure water, and prepare ammonium metatungstate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: ammonium metatungstate hydrate ((NH4)6[H2W) 12 O 40 6.88 g of ]・xH2O) was added, and the reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was filtered, and the resulting powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was dissolved in 100 g of dimethylformamide, and then 335 g of methanol was added. Crystallization was carried out at room temperature to obtain the metal compound (B-5). 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.75-7.96 (m, 66H), 5.97 (s, 2H). ESI-MS: POSITIVE m / z 335.1 ([C 18 H 11 F4S] + ) NEGATIVE m / z 712.3 (median) ([H4W 12 O 40 ] 4- )

[0346] [3. Preparation of Test Resist Materials] Test resist materials (R-1) to (R-12) were prepared by blending the above polymers (A-1) to (A-6), the above metal compounds (B-1) to (B-5), the metal compounds (B-6) and (B-7) shown below, the acid generator (C-1) shown below, and an organic solvent in the amounts shown in Table 1 (unit: parts by mass).

[0347] The following metal compounds were used as (B-6) and (B-7) as listed in Table 1: • (B-6): Tetrakis(acetylacetonato)hafnium(IV) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • (B-7): Tetrakis(2,4-pentanedionato)titanium(IV) (manufactured by Tokyo Chemical Industries, Ltd.)

[0348] Furthermore, as the acid generator (C-1) listed in Table 1, the acid generator represented by the following formula was used.

[0349]

[0350] [4. Formation of Test LS Patterns] On an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS), resist materials (R-1) to (R-12) were applied using a spinner. A post-application bake (PAB) treatment was performed on a hot plate at a temperature of 120°C for 60 seconds, and the substrate was dried to form a resist film with a thickness of 50 nm. The thickness of the formed film was measured using a film thickness measuring device (J.A. Wollam's "M-2000D").

[0351] The above resist film was subjected to lithography (exposure) using an electron beam lithography system F7000S-VD2 (manufactured by Advantest Corporation) at an acceleration voltage of 50 kV, creating a 1:1 line-and-space pattern (hereinafter also referred to as "LS pattern") with a target size of 50 nm line width. Subsequently, a post-exposure baking (PEB) treatment was performed at 180°C for 860 seconds.

[0352] Next, at 23°C, development was performed for 60 seconds using the developer solutions shown in Table 2, followed by rinsing with the solvent used for development for 60 seconds. As a result, 1:1 test LS patterns (LS-1) to (LS-12) with a line width of 50 nm were formed. Note that all test LS patterns (LS-1) to (LS-12) are negative type patterns. In Table 2, for (R-5) and (R-8) to (R-12), developer solutions were used that were formulated to contain the organic solvents shown in Table 2 in the amounts indicated (unit: parts by mass).

[0353]

[0354] <Evaluation of Optimal Exposure Dose (Eop)> In forming the above test LS pattern, the optimal exposure dose Eop (mJ / cm²) for forming an LS pattern of the target size is determined. 2 The values ​​were calculated for each of the following: Eop(mJ / cm²). 2 This is shown in Table 3.

[0355] <Evaluation of LS Pattern Shape> The shapes of the above LS patterns (LS-1) to (LS-12) were observed using a measuring SEM (scanning electron microscope, accelerating voltage 10kV, product name: SU-5000, manufactured by Hitachi High-Technologies Corporation), and the shapes were evaluated according to the following criteria. The results are shown in Table 3. A: The LS pattern in the SEM image shows almost no trailing and has excellent resolution. B: A slight trailing is observed in part of the LS pattern in the SEM image. C: The LS pattern is not formed (not resolved) in the entire SEM image.

[0356] Table 3, under the "PFAS" column, indicates whether each test resist material contains PFAS (perfluoroalkyl compounds and polyfluoroalkyl compounds) in the broad sense.

[0357]

[0358] Table 3 shows that even when using resist materials (R-1) to (R-10) that do not contain the component corresponding to PFAS, LS patterns with excellent sensitivity and resolution can be obtained. In particular, the shapes of the LS patterns (LS-2) to (LS-5) and (LS-8) to (LS-10) formed using resist materials that do not contain the component corresponding to PFAS showed superior resolution and almost no trailing compared to the LS patterns (LS-11) and (LS-12) formed using conventional resist materials containing the component corresponding to PFAS, resulting in excellent LS patterns. Furthermore, as can be seen from Table 3, when comparing polymers (A-1) to (A-6) based on the shapes of the LS patterns (LS-5) and (LS-8) to (LS-12) given by resist materials (R-5) and (R-8) to (R-12) using the same metal compound, it can be seen that the shapes of the LS patterns (LS-5) and (LS-8) to (LS-10) formed using polymers (A-1) to (A-4) containing a fluorine atom structural unit having a monovalent or divalent aromatic hydrocarbon cyclic group in which at least two hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms, yield better results and reduce environmental impact than the shapes of the LS patterns (LS-11) and (LS-12) formed using polymers (A-5) and (A-6) containing components corresponding to conventional PFAS.

Claims

A resist material containing (A) a polymer and (B) a metal compound, The above component (A) includes a structural unit having a fluorine atom, A resist material characterized in that the structural unit having a fluorine atom is a monovalent or divalent aromatic hydrocarbon cyclic group, wherein at least two or more hydrogen atoms on the aromatic hydrocarbon cyclic group are substituted with fluorine atoms. 　 The resist material according to claim 1, wherein the structural unit having a fluorine atom is a structural unit having a fluorine atom represented by the following general formula (I). [In formula (I), R α represents a hydrogen atom, a halogen atom, or an alkyl group; L A1 1 represents a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2-; R A1 1 This represents a monovalent organic group having a monovalent or divalent aromatic hydrocarbon cyclic group in which at least two or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by fluorine atoms, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted by substituents. The resist material according to claim 1 or 2, wherein the monovalent or divalent aromatic hydrocarbon cyclic group is a phenyl group, phenylene group, naphthyl group, naphthylene group, phenantrenyl group, phenanthrylene group, anthryl group, anthreylene group, pyrrolyl group, imidazolyl group, pyridyl group, pyridylene group, pyrazinyl group, pyramidinyl group, indolyl group, isoindolyl group, quinolyl group, or isoquinolyl group. 　 The group in which at least two hydrogen atoms on the monovalent or divalent aromatic hydrocarbon cyclic group are substituted with fluorine atoms is a 2,3-difluorobenzene-1-yl group, a 2,4-difluorobenzene-1-yl group, a 2,5-difluorobenzene-1-yl group, a 2,6-difluorobenzene-1-yl group, a 3,4-difluorobenzene-1-yl group, a 3,5-difluorobenzene-1-yl group, a 3,5-difluoro-4-nitrobenzene-1-yl group, a 3,5-difluoro-4-cyanobenzene-1-yl group, a 2,3,4-trifluorobenzene- 1-yl group, 2,3,5-trifluorobenzene-1-yl group, 2,3,6-trifluorobenzene-1-yl group, 2,4,5-trifluorobenzene-1-yl group, 2,4,6-trifluorobenzene-1-yl group, 3,4,5-trifluorobenzene-1-yl group, 2,3,4,5-tetrafluorobenzene-1-yl group, 2,3,4,6-tetrafluorobenzene-1-yl group, 2,3,5,6-tetrafluorobenzene-1-yl group, 2,2',3,3',4,4',5,5',6-nonafluoro-1,1'-biphenyl-6 -yl group, 2,3-difluorobenzene-1,4-diyl group, 2,5-difluorobenzene-1,4-diyl group, 2,6-difluorobenzene-1,4-diyl group, 2,3,5-trifluorobenzene-1,4-diyl group, 2,3,6-trifluorobenzene-1,4-diyl group, 2,3,5,6-tetrafluorobenzene-1,4-diyl group, 2,4-difluorobenzene-1,3-diyl group, 2,5-difluorobenzene-1,3-diyl group, 2,6-difluorobenzene-1,3-diyl group, 2,4,5-trifluorobenzene The resist material according to claim 1 or 2, wherein the group is n-1,3-diyl group, 2,4,6-trifluorobenzene-1,3-diyl group, 2,4,5,6-tetrafluorobenzene-1,3-diyl group, 3,4-difluorobenzene-1,2-diyl group, 3,5-difluorobenzene-1,2-diyl group, 3,6-difluorobenzene-1,2-diyl group, 3,4,5-trifluorobenzene-1,2-diyl group, 3,4,6-trifluorobenzene-1,2-diyl group, or 3,4,5,6-tetrafluorobenzene-1,2-diyl group. 　 The resist material according to claim 1 or 2, wherein component (A) includes a structural unit that adjusts solubility in a developer. 　 The resist material according to claim 1 or 2, characterized in that the component (A) does not contain a trifluoromethyl group other than a trifluoromethyl group having the structure represented by the following general formula (F-1), or a trifluoromethylene group other than a trifluoromethylene group having the structure represented by the following general formula (F-2) or (F-3). [In formula (F-1), X f1 is -L f1 -O-, -L f1 -N(R f1 )- or -L f1 -N(L f2 )-; L f1 and L f2 Each independently represents a methylene group, a optionally substituted divalent aromatic hydrocarbon cyclic group, or a carbonyl group; R f1 C may have substituents other than hydrogen atoms and fluorine atoms. 1-6 This represents a hydrocarbyl group, or a monovalent aromatic hydrocarbon cyclic group which may have substituents. [In formula (F-2), X f1 is, -L f1 -O-, -L f1 -N(R) f1 ) - or - L f1 -N(L) f2 -)- represents; L f1 and L f2 Each independently represents a methylene group, a optionally substituted divalent aromatic hydrocarbon cyclic group, or a carbonyl group; R f1 C may have substituents other than hydrogen atoms and fluorine atoms. 1-6 Represents a hydrocarbyl group, or a monovalent aromatic hydrocarbon cyclic group which may have substituents. X f2 C may have substituents other than fluorine atoms. 1-6 Hydrocarbyl group, optionally substituted monovalent aromatic hydrocarbon cyclic group, -O-R f2 , -S-R f2 , -N(R f2 ) (Caution f3 ) represents; R f2 and R f3 Each of these C atoms may independently have substituents other than hydrogen and fluorine atoms. 1-6 This represents a hydrocarbyl group, or a monovalent aromatic hydrocarbon cyclic group which may have substituents. [In formula (F-3), X f1 is, -L f1 -O-, -L f1 -N(R) f1 ) - or - L f1 -N(L) f2 -)- represents; L f1 and L f2 Each independently represents a methylene group, a optionally substituted divalent aromatic hydrocarbon cyclic group, or a carbonyl group; R f1 C may have substituents other than hydrogen atoms and fluorine atoms. 1-6 Represents a hydrocarbyl group, or a monovalent aromatic hydrocarbon cyclic group which may have substituents. X f3 This includes a methylene group, a divalent aromatic hydrocarbon group which may have substituents, a carbonyl group, and -O-L f3 -, -S-L f3 -, -N(R f4 )-L f3 -, -N(L f3 -) L f4 - represents; L f3 and L f4 Each independently represents a methylene group, a optionally substituted divalent aromatic hydrocarbon cyclic group, or a carbonyl group; R f4 C may have substituents other than hydrogen atoms and fluorine atoms. 1-6 This represents a hydrocarbyl group, or a monovalent aromatic hydrocarbon cyclic group which may have substituents. The resist material according to claim 1 or 2, wherein the (B) component is an organometallic compound B1 represented by the following general formula (IV), or an organometallic compound B2 represented by the following general formula (V). M B1 (X B1 R B1 1 ) n (R B1 2 ) 4-n (IV) [In formula (IV), M B1 represents a metal atom or metal oxide; X B1 represents -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2-; R B1 1 Each of these independently contains a hydrogen atom or a C which may have a substituent. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously); R B1 2 Each of these is independently a C which may have substituents. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously); n is an integer between 0 and 4. [(R B2 1 -Sn) 12 O 14 (OH)6] 2+ (Y - )2 (V) [In formula (V), R B2 1 Each of these is independently a C which may have substituents. 1-12 A hydrocarbyl group is represented where any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously); Y - Each of these independently represents a monovalent anion. The resist material according to claim 1 or 2, wherein the (B) component is a polyate represented by the following general formula (VII-1) or (VII-2) or a mixture thereof. () m+ ) a (| (am)- ) ((|).)) [In formula (VII-1), A m+ Each of them independently, H + , metal ions, NH4 + , represents an onium cation or onium dication; C (am)- This represents an isopolyate anion or a heteropolyate anion. m is an integer between 1 and 5, and a is a real number greater than 0. (A' m’+ ) a’ (B n+ ) b (C'(a'm'+bn)-) (VII-2) [In formula (VII-2), A' m’+ Each of them independently, H + , metal ions, or NH4 + It represents; B n+ Each of these independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents an isopolyate anion or a heteropolyate anion. m' is an integer between 1 and 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 according to claim 1 or 2, further comprising (C) an acid generator. 　 A step of forming a resist film using the resist material described in claim 1 or 2, The steps include: exposing the resist film, The process involves developing the exposed resist film using a developer solution, A pattern formation method including the following.

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