Resist material, resist material for dry etching, pattern formation method, and structure

Abstract

To provide a resist material, a resist material for dry etching, a pattern formation method, a structure, and a patterned structure, all of which are novel.SOLUTION: A resist material contains metal oxo acid anion and onium cation.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resist material, a resist material for dry etching, a pattern forming method, and a structure. [Background technology]

[0002] In recent years, advances in lithography technologies such as immersion lithography and EUV lithography have led to the advancement of finer circuit patterns. As lithography technology advances, new resist materials are needed to accommodate these advances.

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

[0004] For example, Patent Document 1 discloses a nanoparticle polymer resist containing nanoparticles containing ZrO2, HfO2, TiO2, or the like in the core, and a polymer. Patent Document 2 also discloses a nanoparticle polymer resist containing an alkyl tin cluster (t-BuSn) 12 O 14 Resists based on (OH)6(HCO2)2 are disclosed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 9,696,624 [Patent Document 2] WO2019 / 195522 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a novel resist material, a resist material for dry etching, a pattern forming method, and a structure. [Means for solving the problem]

[0007] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that by using a resist material containing a metal oxo acid anion and an onium cation, it is possible to provide a novel resist material, a dry etching resist material, a pattern formation method, and a structure, and have completed the present invention.

[0008] That is, the present invention relates to the following inventions. <1> A structure having a substrate and a resist film on a surface of the substrate, the resist film contains a metal element derived from a metal oxo acid anion and an S or I element derived from an onium cation, the resist film has an exposed area and an unexposed area exposed to actinic rays, the molar percentage (x mol%) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the unexposed portion is taken as 100 mol%, and the molar percentage (y mol%) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the exposed portion is taken as 100 mol%, the molar percentage (x mol%) of the S or I element derived from the onium cation contained in the resist film in the exposed portion is reduced by 5 mol% or more (5 mol%≦(xy) mol%) compared to the unexposed portion, structure. <2> the molar percentage (x mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the unexposed portion is taken as 100 mol %, and the molar percentage (y mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the exposed portion is taken as 100 mol %, the molar percentage (x mol %) of the S or I element derived from the onium cation contained in the resist film in the exposed portion is reduced by 10 to 100 mol % (10 mol %≦(xy) mol %≦100 mol %) compared to the unexposed portion, <1> The structure described in <3> the metal element derived from the metal oxo acid anion is at least one element selected from the group consisting of Mo, W, V, Nb, Ta, Zr, Cr, Mn, Se, Te, As, Ni, Sb, and Ge; <1> The structure described in <4> The metal oxo acid anion is MoO4 2- , WO4 2- , VO4 3- , NbO3 - , NbO4 3- , TaO3 2- , ZrO3 2- , CrO4 2- , MnO4 2- , SeO3 2- , SeO4 2- , TeO3 2- , TeO4 2- , AsO3 3- , AsO4 3- , NiO2 - , SbO3 3- , and GeO4 4- At least one selected from the group consisting of <1> The structure described in <5> The onium cation is a sulfonium cation or an iodonium cation. <1> The structure described in <6> forming a resist film using a resist material containing a metal oxo acid anion and an onium cation; exposing the resist film to actinic rays; a post-exposure bake treatment step; A pattern forming method comprising the steps of: <7> After the post-exposure bake treatment step, the resist film is developed using a developer. <6> The pattern forming method according to claim 1. <8> The developer is a developer containing water. <7> The pattern forming method according to claim 1. <9> The actinic ray is UV, DUV, XUV, EUV, an electron beam, or an X-ray. <6> The pattern forming method according to claim 1. <10> a step of exposing the resist film to steam after the post-exposure bake treatment step; <6> The pattern forming method according to claim 1. <11> A resist material containing a metal oxoacid anion and an onium cation. <12> The metal oxo acid anion and the onium cation are a salt of a metal oxo acid anion and an onium cation represented by general formula (I) or a mixture thereof. <11> The resist material according to claim 1. (A m+ ) a (B n+ ) b (C (am+bn)- ) (I) [In formula (I), A m+ are each independently H + , or a metal ion; B n+ each independently represents a sulfonium cation or an iodonium cation; C (am+bn)- represents a metal oxo acid anion; m is an integer of 1 to 3, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.1. <13> containing 0.01 to 5 mass % of a salt of a metal oxo acid anion represented by the general formula (I) and an onium cation or a mixture thereof; <12> The resist material according to claim 1. <14> A dry etching resist material, <11> ~ <13> 10. The resist material according to claim 9, wherein <15> <11> ~ <13> forming a resist film using the resist material according to any one of the preceding claims; exposing the resist film to actinic rays; developing the exposed resist film by dry etching; A pattern forming method comprising the steps of: <16> In the step of developing by dry etching, a gas containing a halogen-containing gas is used as an etching gas. <15> The pattern forming method according to claim 1. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a novel resist material, a resist material for dry etching, a pattern formation method, and a structure. The resist material according to one aspect of the present invention can be suitably used as a resist material for dry etching. Furthermore, when a resist film is formed using a resist material according to another embodiment of the present invention, the resist film is exposed to actinic rays, and then subjected to a post-exposure bake treatment, the molar percentage of S or I elements derived from onium cations when the metal elements derived from metal oxo acid anions in the resist film in the unexposed portions are taken as 100 mol %, and the molar percentage of S or I elements derived from onium cations when the metal elements derived from metal oxo acid anions in the resist film in the exposed portions are taken as 100 mol %, the molar percentage of S or I elements derived from onium cations in the resist film in the exposed portions can be reduced by 5 mol % or more compared to the unexposed portions, thereby enabling the production of a structure in which the molar percentage of a predetermined element in the resist film differs between the unexposed portions and the exposed portions. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a graph showing the relationship between the exposure dose (mJ / cm 2 ) of a KrF excimer laser to a resist film and the film thickness (nm) after post-exposure baking (PEB) treatment. [Figure 2] 1 is a graph showing the relationship between the time (s) that a resist film is immersed in water and the change in film thickness (nm) of the unexposed and exposed portions. [Figure 3] 1 is a graph showing the relationship between the time (s) that a resist film is exposed to water vapor and the change in film thickness (nm) of the unexposed and exposed portions. [Figure 4-1] This is a conceptual diagram of a test in which a resist film is developed by dry etching using an etching gas of 100% CF4. [Figure 4-2] 1 is a graph showing the change in film thickness (nm) of the unexposed portion of the resist film before and after dry etching for 40 seconds using an etching gas containing 100% CF4. [Figure 4-3]1 is a graph showing the change in film thickness (nm) of an exposed portion of a resist film before and after dry etching for 40 seconds using an etching gas containing 100% CF4. DETAILED DESCRIPTION OF THE INVENTION

[0011] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0012] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

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

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

[0015] As used herein, "C 1-18 The term "hydrocarbylene group" refers to a divalent hydrocarbon group generated by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear or branched, or may be partially or entirely cyclic. Hydrocarbylene groups include alkylene groups and arylene groups. Also, "C 1-18 A divalent carbon atom at any position of the "hydrocarbylene group" may be replaced by -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time). "C 1-18The "hydrocarbylene group" is not particularly limited, and examples thereof include "C" groups such as methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadiyl group, cyclohexanediyl group, oxyethane-1,1-diyl group, oxyethane-1,2-diyl group, oxypropane-1,3-diyl group, oxypropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, and oxyethyleneoxyethane-1,1-diyl group. 1-18 alkylene groups such as 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 4,4'-biphenylene, anthracenediyl, phenanthrenediyl, naphthacenediyl, pyrenediyl, perylenediyl, and chrysenediyl groups; 6-18 arylene group" and the like.

[0016] As used herein, "C 1-18 The term "alkyl group" refers to a linear or branched alkyl group having 1 to 18 carbon atoms. Also, "C 1-18 Any divalent carbon atom in the "alkyl group" at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2-, provided that adjacent divalent carbon atoms are not replaced at the same time. "C 1-18The "alkyl group" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an i-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1 Examples of the alkyl group include 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group. "C 1-18 Examples of alkyl groups in which a divalent carbon atom at any position excluding the terminal is replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- include, but are not limited to, a 2-methoxyethoxymethyl group, an ethoxycarbonylmethyl group, and the like.

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

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

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

[0020] As used herein, "C 3-18 The term "alicyclic group" refers to a hydrocarbon group having, in whole or in part, a monocyclic or polycyclic structure having 3 to 18 carbon atoms. Alicyclic groups also include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, and the like. Also, "C 3-18 Any divalent carbon atom in the "alicyclic group" except for the terminal one 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). "C 3-18The "cycloalkyl group" is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-i-propylcyclopentan-1-yl group, a cyclohexyl group, a t-butylcyclohexyl group, a tricyclodecanyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a 2-methyladamantan-2-yl group, a 2-i-propyladamantan-2-yl group, a bornyl group, a norbornyl group, a fenchyl group, a pinanyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a bornylmethyl group, a norbornylmethyl group, an adamantylmethyl group, a 1-methylcyclopentyloxycarbonylmethyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

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

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

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

[0024] As used herein, "C 1-18 The term "hydrocarbyl group" refers to a monovalent group generated 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. Also, "C 1-18 Any divalent carbon atom in the "hydrocarbyl group" at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). This point is explained in the following section "C 1-18 "C" used in the explanation of the definition of "hydrocarbyloxy group" 1-18 The same applies to "hydrocarbyl group" and the like. "C 1-18 The "hydrocarbyl group" is not particularly limited, and examples thereof include "C 1-18 alkyl group," "C 2-18 alkenyl group," "C 2-18 alkynyl group," "C 3-18 “Alicyclic group”, “C 2-18 aryl group," "C 7-18 aralkyl groups, etc.

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

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

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

[0028] As used herein, "C 1-18 "Hydrocarbyloxycarbonyl group" means "C 1-18 It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyloxy group.” "C 1-18 The "hydrocarbyloxycarbonyl group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, an n-pentoxycarbonyl group, and a neopentyloxycarbonyl group.1-18 Alkoxycarbonyl group; 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; phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenanthrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc. 6-18 aryloxycarbonyl group" and the like.

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

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

[0031] As used herein, "DiC 1-18 A "hydrocarbylamino group" is a group consisting of two identical or different "C 1-18 "Hydrocarbyl group" means a group attached to an amino group. "The C 1-18The "hydrocarbylamino group" is not particularly limited, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, an N-ethyl-N-methylamino group, an N-methyl-Nn-propylamino group, an N-isopropyl-N-methylamino group, an Nn-butyl-N-methylamino group, group, N-isobutyl-N-methylamino group, Nt-butyl-N-methylamino group, N-methyl-Nn-pentylamino group, Nn-hexyl-N-methylamino group, N-ethyl-Nn-propylamino group, N-ethyl-N-isopropylamino group, Nn-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, Nt-butyl-N-ethylamino group, N-ethyl-Nn-pentylamino group, N-ethyl-Nn-hexylamino group, and other "di-C" groups. 1-18 alkylamino group; dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. 3-18 Alicyclic amino group; diphenylamino group, phenylnaphthylamino group, etc. 6-18 Arylamino group; N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. 1-18 Alkyl-NC 3-18 Cycloalkylamino group; N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. 1-18 Alkyl-NC 6-18 arylamino group" and the like.

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

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

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

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

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

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

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

[0039] As used herein, "C 1-18"Hydrocarbyloxycarbonylamino group" means "C 1-18 "Hydrocarbyloxycarbonyl group" means a group bonded to an amino group. "C 1-18 The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc. 1-18 alkoxycarbonylamino group; cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. 3-18 Alicyclic oxycarbonylamino group; phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. 6-18 aryloxycarbonylamino group" and the like.

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

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

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

[0043] As used herein, the term "acid-dissociable group" refers to a group that substitutes a hydrogen atom in a polar group such as a hydroxy group (including a phenolic hydroxy group), a carboxy group, an amino group, or a sulfo group, and that dissociates when acted upon by an acid. The compound having the acid-dissociable group can increase the polarity of the compound by dissociating the acid-dissociable group under the action of an acid, thereby generating the polar group. This can change the solubility of the compound in the developer. More specifically, when a developer with high polarity such as an alkaline aqueous solution is used as the developer, the solubility of the compound in the developer relatively increases, while when an organic developer with low polarity is used as the developer, the solubility of the compound in the developer relatively decreases. The polar group is preferably a hydroxy group (including a phenolic hydroxy group) or a carboxy group.

[0044] The acid-dissociable group is not particularly limited, and any known and commonly used acid-dissociable group that can be used in chemically amplified resists can be used. Examples of the acid-dissociable group include acid-dissociable groups G for polar groups represented by the following general formulas (G-1) to (G-4). [ka] [ka] [ka] [ka]

[0045] The acid-dissociable group G is not particularly limited as long as it dissociates under the action of an acid, and any known and commonly used group can be used. Examples of the acid-dissociable group G include "tertiary carbon-type acid-dissociable groups G" represented by the following general formula (g-1): A ", "allyl or benzyl acid-dissociable group G represented by the following general formula (g-2) B ", "acetal-type acid-dissociable group G represented by the following general formula (g-3) C Each of these will be explained in turn below. [ka] [ka] [ka]

[0046] <Tertiary carbon type acid dissociable group G A > The acid-dissociable group G includes a "tertiary carbon-type acid-dissociable group G" represented by the following general formula (g-1): A ", a carbon atom directly bonded to a polar group, and R A g1 ~R A g3 An acid-labile group in which the carbon to which the group is bonded is a tertiary carbon atom can be used. [ka]

[0047] "R A g1 " is an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0048] RA g1 As the C 1-12 Alkyl group, C 3-12 Alicyclic group, C 6-12 an aryl group, or C 7-12 An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 1-12 Alkyl group or C 3-12 Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0049] Also, "R A g2 " and "R A g3 " are each independently optionally substituted C 1-12 a hydrocarbyl group in which any divalent carbon atom except for the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), or R A g2 and R A g3 are combined to form C which may have a substituent. 3-18 It may form an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and a divalent carbon atom at any position except for the terminal may be 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).

[0050] R A g2 and R A g3 As for R A g2 and R A g3 are combined to form C which may have a substituent. 3-18 It is preferable that the group forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and a divalent carbon atom at any position except for a terminal position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), C which may further have the above-mentioned substituent 3-18 It is more preferable that the alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group contains a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, in which a divalent carbon atom at any position except for a terminal 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).

[0051] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1) A Examples of the aryl group include a t-butyl group, a t-amyl group, a 1,1-dimethylpropyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, a 1-methyl-1-cyclohexyl group, a 1-ethyl-1-cyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0052] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1) A Examples of such tertiary carbon-type acid-dissociable groups include the following:

[0053] [ka]

[0054] <<Tertiary carbon type acid dissociable group G A1 and G A2 >> The "tertiary carbon-type acid-dissociable group G" represented by general formula (g-1) A " In R A g2 and R A g3 are combined to form C which may have a substituent. 3-18 In the case where an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, for example, a tertiary carbon-type acid-dissociable group G represented by the following general formula (g-1-1) is A1 and a tertiary carbon-type oxygen-dissociating group G represented by (g-1-2): A2 etc.

[0055] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) A1 >> [ka] A tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1) A1 In R A g11 may have a substituent C 1-12 Alkyl group, C 3-12 Alicyclic group, C 6-12 an aryl group, or C 7-12In an aralkyl group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0056] Also Cy A g1 C which may have a substituent together with the tertiary carbon atom 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 are not replaced at the same time).

[0057] Cy A g1 As the alkyl group, preferred are those which, together with the tertiary carbon atom, form 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, which may have a substituent, and in which a divalent carbon atom at any position except for the terminal may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0058] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1): A1 Examples of such tertiary carbon-type acid-dissociable groups include the following:

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) A2 >> [ka] In the above general formula (g-1-2), R A g21 ~R A g23 are each independently a hydro group or an optionally substituted C 1-12 In the hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), R A g21 and R A g22 , and / or R A g22 and R A g23 are directly or divalently linked to each other by a single bond, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring.

[0064] R A g21 and R A g22, and / or R A g22 and R A g23 Examples of the case where R 1 forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond include the case where R 1 forms a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, or the like, which may have a substituent.

[0065] Also Cy A g2 C which may have a substituent together with the tertiary carbon atom 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 are not replaced at the same time).

[0066] Cy A g2 As the alkyl group, preferred are those which, together with the tertiary carbon atom, form 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, which may have a substituent, and in which a divalent carbon atom at any position except for the terminal may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0067] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2): A2 Examples of such tertiary carbon-type acid-dissociable groups include the following:

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] Allyl or benzyl acid-dissociable group G B > The acid-dissociable group G is an allyl or benzyl acid-dissociable group G represented by the following general formula (g-2): B An acid-labile group in which the carbon atom directly bonded to the polar group is at an allylic or benzyl position, such as: [ka]

[0072] "R B g1 " is an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0073] R B g1 As the C 1-12 Alkyl group, C 3-12 Alicyclic group, C 6-12 an aryl group, or C 7-12An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 1-12 Alkyl group or C 3-12 Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0074] Also, "R B g2 " ~ "R B g4 " each independently represents a hydro group or an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0075] R B g1 and R B g2 , R B g2 and R B g3 , and / or R B g3 and R B g4 are directly or divalently linked to each other by a single bond, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring.

[0076] An 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 forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond, examples of which include the formation of an optionally substituted cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexylideneethenyl group, benzyl group, and 2,3-dihydro-1H-indanyl group.

[0077] An allyl or benzyl acid-dissociable group G represented by general formula (g-2): B Examples of the acid-dissociable group include the following allyl or benzyl acid-dissociable groups:

[0078] [ka]

[0079] <Acetal-type acid-dissociable group G C > The acid-dissociable group G is an acetal-type acid-dissociable group G represented by the following general formula (g-3): C An acid-dissociable group in which an oxygen atom is bonded to a carbon atom directly bonded to a polar group, such as [ka]

[0080] "R C g1 " and "R C g3 " each independently represents a hydro group or an optionally substituted C 1-12Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0081] R C g1 and R C g3 is a hydro group or an optionally substituted C 1-12 Alkyl group or C 3-12 An alicyclic group in which any divalent carbon atom excluding a terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Hydro group or optionally substituted C 1-6 Alkyl group or C 3-8 Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0082] Also, "R C g2 " is an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0083] R C g2 As the C 1-12 Alkyl group or C 3-12An alicyclic group in which any divalent carbon atom excluding a terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 1-6 Alkyl group or C 3-8 Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0084] An acetal-type acid-dissociable group G represented by general formula (g-3) C Examples of the alkoxy group include a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, an n-butoxymethoxy group, a 2,2-dimethylpropoxymethoxy group, a 2,2-dimethylbutoxymethoxy group, a cyclohexyloxymethoxy group, a 1-ethoxyethoxy group, a 1-n-butoxyethoxy group, and a 1-cyclohexyloxyethoxy group.

[0085] As used herein, the term "hydroxy group or carboxy group having a protecting group" refers to a hydroxy group (including a phenolic hydroxy group) or a carboxy group that is protected with an ether-based protecting group, a silyl ether-based protecting group, an acyl-based protecting group, an aminocarbonyl-based protecting group, or the like.

[0086] The ether-based protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, and a di(p-methoxyphenyl)phenylmethyl group. The silyl ether protecting group is not particularly limited, and examples thereof include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), and a t-butyldiphenylsilyl group (TBDPS). The acyl protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, and a benzoyl group. The aminocarbonyl protecting group is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.

[0087] In this specification, the term "optionally having a substituent" is not particularly limited as long as it is chemically permissible and has the effect of the present invention. Examples of the "substituent" include (1) a halogen atom, (2) a haloalkyl group, (3) a hydroxy group, (4) a thiol group, (5) a nitro group, (6) a cyano group, (7) a carboxy group, (8) an amino group, (9) a sulfo group, (10) a vinyl group, (11) an allyl group, (12) a (meth)acryloyl group, (13) a (meth)acryloyloxy group, (14) a (meth)acrylamide group, (15) a styryl group, (16) an epoxy group, (17) a glycidyl group, (18) an amide group, (19) a hydroxy group or a carboxy group having a protecting group, (20) a polar group having an acid-dissociable group, or (21) a C group in which at least a part of the hydrogen atoms may be substituted with the above (1) to (20). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, C 1-18 Hydrocarbylthio group, C 1-18 Hydrocarbylsulfinyl group, C 1-18 Examples of the hydrocarbylsulfonyl group include a hydrocarbylsulfonyl group in which a divalent carbon atom at any position excluding the terminal of the substituent may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0088] [1. Resist materials] The resist material according to this embodiment contains a metal oxo acid anion and an onium cation. The metal oxo acid anion and the onium cation may form an ionic bond.

[0089] [1-1. Metal oxoacid anions] The metal oxo acid anion according to this embodiment is not particularly limited, and any known and commonly used metal oxo acid anion can be used. Examples of the metal oxo acid anion include MoO4 2- , WO4 2- , VO4 3- , NbO3 - , NbO4 3- , TaO3 2- , ZrO3 2- , CrO4 2- , MnO4 2- , SeO3 2- , SeO4 2- , TeO3 2- , TeO4 2- , AsO3 3- , AsO4 3- , NiO2 - , SbO33- , GeO4 4- etc. The metal oxo acid anions may be used singly or in combination of two or more.

[0090] The metal oxo acid anion according to this embodiment is MoO4 2- , WO4 2- , VO4 3- , NbO3 - , NbO4 3- , TaO3 2- , ZrO3 2- , CrO4 2- , MnO4 2- , SeO3 2- , SeO4 2- , TeO3 2- , TeO4 2- , AsO3 3- , AsO4 3- , NiO2 - , SbO3 3- , and GeO4 4- At least one selected from the group consisting of:

[0091] Metal oxo acid anions include MoO4 2- , WO4 2- , VO4 3- , NbO3 - , NbO4 3- , TaO3 2- Preferably, MoO4 2- , WO4 2- , VO4 3- , TaO3 2- More preferably, MoO4 2- , WO4 2- It is more preferable that:

[0092] [1-2. Oxonium cation] The oxonium cation according to this embodiment is not particularly limited, and any known or commonly used oxonium cation can be used. Examples of the onium cation include a sulfonium cation and an iodonium cation. These onium cations may be used alone or in combination of two or more.

[0093] The onium cation is preferably a sulfonium cation or an iodonium cation, from the viewpoint of providing a building block that generates an acid when exposed to DUV, XUV, EUV, an electron beam, or the like.

[0094] [1-2-1. Sulfonium cation] The sulfonium cation is not particularly limited, and any known or commonly used sulfonium cation can be used. Examples of the sulfonium cation include organic sulfonium cations represented by the following general formula (II-1): [ka]

[0095] In general formula (II-1), R 1A ~R 1C each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 1A ~R 1C a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 1A ~R 1CThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino 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 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted 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); Further R 1A ~R 1CAny two of these are directly connected to each other by a single bond, or are a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the sulfur atom in general formula (II-1).

[0096] Above R 1A ~R 1C C which may have a substituent, each independently 1-18 is a hydrocarbyl group; 1A ~R 1C a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); 1A ~R 1C The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18may be substituted with a hydrocarbylthio group, and a divalent carbon atom at any position of these substituents excluding the terminals may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO- (provided that adjacent divalent carbon atoms are not substituted at the same time), is preferred; Optionally substituted C 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 is an aralkyl group; 1A ~R 1C a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); 1A ~R 1C The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18It may be substituted with a hydrocarbylthio group, and a divalent carbon atom at any position of these substituents excluding the terminals may be substituted 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 substituted at the same time).

[0097] Also R 1A ~R 1C Any two of these are directly connected to each other by a single bond, or are a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 Examples of the case where the alkylene group is linked to form a ring together with the sulfur atom in general formula (II-1) include a thian-1-ium skeleton, a thiophen-1-ium skeleton, a 1,4-oxathiane-4-ium skeleton, a 1,4-dithian-1-ium skeleton, a 1H-thiophen-1-ium skeleton, a benzo[b]thiophen-1-ium skeleton, a dibenzothiophenium skeleton, a 9,10-dihydrothioxanthylium skeleton, a 10H-phenoxathiane-10-ium skeleton, and a 5H-thianthren-5-ium skeleton, and the like, and examples thereof include the following. Note that * indicates that the R is not involved in the formation of a ring. 1A , R 1B or R 1C It means the junction with.

[0098] [ka]

[0099] The organic sulfonium cation represented by the general formula (II-1) is not particularly limited, and examples thereof include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalen-1-yl)hexahydrothiopyrylium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrylium cation, di(naphthalen-1-yl)(phenyl)sulfonium cation, phenylbis(2-(trifluoromethyl)phenyl)sulfonium cation, phenylbis(2-(trifluoromethyl)phenyl)sulfonium cation), ... )phenyl)sulfonium cation, mesitylbis(2-(trifluoromethyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(phenyl)sulfonium cation, tris(3,5-difluorophenyl)sulfonium cation, (4-(dodecanoyloxy-3,5-dimethylphenyl))diphenylsulfonium cation, diphenyl(3-(trifluoromethoxy)phenyl)sulfonium cation, (4-(1-adamantylcarbonyloxy)phenyl)diphenylsulfonium cation, (4-phenylthiophenyl)diphenylsulfonium cation, 5-phenyl-5H-thianthren-5-ium cation, 5-(2,5-dimethylphenyl)thianthren-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophen-5-ium cation, 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,d]thiophen-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b]thiophen-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, (2-bromoethyl)diphenylsulfonium cation, dimesityl(trifluoromethyl)sulfonium cation, tri-p-tolyl sulfonium cation, and the like.

[0100] [1-2-2. Iodonium cation] The iodonium cation is not particularly limited, and any known and commonly used iodonium cation can be used. Examples of the iodonium cation include organic iodonium cations represented by the following general formula (II-2): [ka]

[0101] In general formula (II-2), R 2A and R 2B each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 2A and R 2B a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 2A and R 2BThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino 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 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted 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); Further R 2A and R 2Bare directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the iodine atom in general formula (II-2).

[0102] R 2A and R 2B As the C 1-18 is a hydrocarbyl group; 2A and R 2B a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); 2A and R 2B The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18may be substituted with a hydrocarbylthio group, and a divalent carbon atom at any position of these substituents excluding the terminals may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO- (provided that adjacent divalent carbon atoms are not substituted at the same time), is preferred; Optionally substituted C 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 is an aralkyl group; 2A and R 2B a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); 2A and R 2B The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18It may be substituted with a hydrocarbylthio group, and a divalent carbon atom at any position of these substituents excluding the terminals may be substituted 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 substituted at the same time).

[0103] The organic iodonium cation represented by the general formula (II-2) is not particularly limited, and examples thereof include ethynyl(phenyl)iodonium cation, bis(pyridine)iodonium cation, bis(2,4,6-trimethylpyridine)iodonium cation, diphenyliodonium cation, bis(4-(t-butyl)phenyl)iodonium cation, (2-carboxyphenyl)(phenyl)iodonium cation, (4-nitrophenyl)(phenyl)iodonium cation, (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4' -methyldiphenyliodonium cation, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4-trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, phenyl(2,4,6-trimethoxyphenyl)iodonium cation, and the like.

[0104] [1-3. Salts of metal oxoacid anions and onium cations or mixtures thereof] The oxo acid anion and onium cation according to another embodiment may be a salt of a metal oxo acid anion represented by the following general formula (I) and an onium cation, or a mixture thereof. (A m+ ) a (B n+ ) b (C (am+bn)- ) (I) [In formula (I), A m+ are each independently H + , or a metal ion; B n+ each independently represents a sulfonium cation or an iodonium cation; C (am+bn)- represents a metal oxo acid anion; m is an integer of 1 to 3, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.1.

[0105] In the salt of a metal oxo acid anion and an onium cation represented by the above general formula (I), or a mixture thereof, the "metal oxo acid anion," "sulfonium cation," and "iodonium cation" may be any of those described above, as appropriate.

[0106] [1-3-1. Metal ions] The metal ions according to the present embodiment are not particularly limited, and known and commonly used ions can be used. Examples of the metal ions include Li + , Na + , K. + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Al 3+ , Co 3+ , Bi 3+ etc. Metal ions include Li + , Na + , K. + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Al3+ , Co 3+ is preferred, and Na + , K. + , Rb + , Cs + , Ca 2+ , Al 3+ , Co 3+ is more preferred. These metal ions may be used alone or in combination of two or more.

[0107] [1-3-2. Constitution of the salt represented by general formula (I) or its mixture] The salt represented by general formula (I) or a mixture thereof may contain A m+ and B n+ The salts may contain a plurality of salts having different ratios (a:b) of a:b. In this case, the values ​​of a and b can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0108] The ratio of a to b (a:b) varies depending on the types of metal oxo acid anion and onium cation, but is preferably a:b=0-8:1-10, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of am+bn is an integer of 2 to 4 and m and n are 1, it is preferable that a is a real number of 0 to 3.9 and b is a real number of 0.1 to 4, and it is more preferable that a is a real number of 0 to 3.5 and b is a real number of 0.5 to 4.

[0109] [1-3-3. Content of the salt represented by general formula (I) or a mixture thereof] The content of the salt represented by general formula (I) or a mixture thereof in the resist material is not particularly limited and can be appropriately set depending on the method for applying the resist material to a substrate or the like, the thickness of the applied film, etc. From the perspective of achieving a difference in the molar ratio of metal oxo acid anions to onium cations between exposed and unexposed areas, or for suitable use as a dry etching resist material, the content of the salt represented by general formula (I) or a mixture thereof in the resist material is preferably 0.005 to 8% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.05 to 4% by mass, based on 100% by mass of the resist material.

[0110] [1-4. Water and / or organic solvent] The resist material according to this embodiment may further contain water and / or an organic solvent. The water is not particularly limited, and any known or commonly used water can be used. The organic solvent is not particularly limited, and any known or commonly used organic solvent can be used.

[0111] The organic solvent is preferably an organic solvent that can uniformly dissolve or disperse the metal oxo acid anion and the onium cation when they are prepared.

[0112] Examples of organic solvents include polar solvents such as alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, nitrile solvents, and aprotic polar solvents, and nonpolar solvents such as hydrocarbon solvents. These organic solvents may be used alone or in combination of two or more.

[0113] Specific examples of the polar solvent include: 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 solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); Nitrile solvents such as acetonitrile, propionitrile, and benzonitrile: Examples of the solvent include aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. Examples of non-polar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. The organic solvents may be used alone or in combination of two or more.

[0114] The organic solvent contained in the resist material according to this embodiment is preferably a polar solvent in terms of coatability, and more preferably an amide solvent, an ester solvent, an alcohol solvent, or a ketone solvent in terms of solubility. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. Furthermore, the ester solvent or alcohol solvent preferably has an ester bond and / or a hydroxyl group in terms of solubility, and among the above, at least one selected from the group consisting of propylene glycol monomethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, and propylene glycol monomethyl ether acetate is preferred.

[0115] The amount of water and / or organic solvent in the resist material is not particularly limited and can be appropriately set depending on the method for applying the resist material to a substrate, the thickness of the applied film, etc. The amount of water and / or organic solvent in the resist material is preferably such that the solids concentration of the resist material is 0.01 to 20 mass%, more preferably 0.05 to 15 mass%, even more preferably 0.1 to 10 mass%, and even more preferably 0.1 to 8 mass%.

[0116] [1-5.Other] The resist material according to this embodiment may further contain, as desired, miscible additives, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, etc. The resist material according to this embodiment may also contain an acid generator, an acid diffusion controller, etc. The resist material according to this embodiment preferably does not contain an epoxy resin, and also preferably does not contain hydrogen peroxide.

[0117] [2. Pattern formation method] The pattern forming method according to this embodiment includes the steps of applying a resist material to a substrate, exposing the resist film formed by the application step to actinic rays, and developing the exposed resist film. It is also preferable to have a step of performing post-exposure bake treatment after exposing the resist film formed in the coating step to actinic rays. Furthermore, after the step of exposing the resist film formed by the coating step to actinic rays, the method may further include a step of developing the resist film with a developer containing water or a step of exposing the resist film to steam. Note that the step of developing the exposed resist film with a developer containing water or the step of exposing the exposed resist film to steam may be performed on a resist film that has been subjected to a post-exposure heat treatment.

[0118] [2-1. Coating process] The pattern forming method according to this embodiment includes a step of applying a resist material to a substrate.

[0119] <Substrate> The substrate used in this embodiment is not particularly limited, and any known and commonly used substrate can be used. For example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed may be used. The material of the substrate is not particularly limited, and examples thereof include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and substrates made of inorganic materials such as glass, titanium oxide, and silicon dioxide. The size, shape, etc. of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or may be a thin plate-shaped substrate.

[0120] The surface of the substrate may be subjected to a surface treatment as necessary. In the case of a substrate having hydroxyl groups on its surface layer, the surface of the substrate can be treated with a silane coupling agent capable of reacting with the hydroxyl groups, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the resist film containing a metal element. Examples of the silane coupling agent include hexamethyldisilazane (HMDS).

[0121] <Application method> The method for applying the resist material to the substrate is not particularly limited, and any known or commonly used method can be used. Examples of dry application methods include CVD (chemical vapor deposition) methods such as thermal CVD, plasma CVD, and photo-CVD; and PVD (physical vapor deposition) methods such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Examples of wet application methods include spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0122] As a method for applying the resist material according to this embodiment to a substrate, a wet method such as spin coating or screen printing is preferably used, and spin coating is more preferable, from the viewpoint of forming a uniform film thickness, etc. After forming the coating film, a backside rinse, an edge bead removal step, etc. may be performed to remove the edge bead.

[0123] The method for drying the resist film formed by applying the resist material to the substrate is not particularly limited, and can be carried out using, for example, a heating device such as a hot plate (post-apply bake (PAB)), a pressure reducing device, or the like. The baking conditions are not particularly limited and can be set appropriately depending on the type of resist film, the 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.

[0124] 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.

[0125] [2-2. Exposure process] The pattern forming method according to this embodiment includes a step of exposing the resist film formed in the above coating step.

[0126] The exposure device used in the exposure step of the resist film may be, for example, an ArF exposure device, an electron beam lithography device, an EUV exposure device, etc. In the exposure step, exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by lithography using direct irradiation with an electron beam without using a mask pattern.

[0127] The actinic radiation used for exposure is not particularly limited, and may be, for example, UV, DUV, XUV, EUV, electron beam, X-ray, or the like. 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.

[0128] The exposure dose on the resist film is 1 to 200 mJ / cm in the case of an ArF excimer laser or a KrF excimer laser. 2 is preferably 20 to 60 mJ / cm 2 In the case of extreme ultraviolet rays, the exposure dose is, for example, 500 mJ / cm 2 2 or less, 0.1 to 200 mJ / cm 2 is preferably 3 to 100 mJ / cm 2 More preferably, it is 5 to 50 mJ / cm 2 It is more preferable that: For electron beams, 3 μC / cm at 50 kV 2 ~2mC / cm 2 It is preferable to expose at a dose of 10 μC / cm 2 ~1.5mC / cm 2 It is more preferable to expose at a dose of 1000 ppm.

[0129] Here, regarding the differences in the chemical and physical properties between the unexposed portion and the exposed portion of the resist film, for example, the value of X% represented as follows can be used as an index by the number of atoms u in the metal oxoacid anion and the number of atoms v excluding hydrogen atoms contained in the metal oxide formed of an onium cation or the like ionically bonded to the metal oxoacid anion. X% = (u) / (v) × 100

[0130] More specifically, the X(exposed portion)% of the exposed portion has a larger value than the X(unexposed portion)% of the unexposed portion (X(unexposed portion)% < X(exposed portion)%). It is more preferable that X(exposed portion)% is larger than X(unexposed portion)% by 1% or more, even more preferable by 3% or more, and even more preferable by 5% or more.

[0131] The X(unexposed portion)% and X(exposed portion)% are not particularly limited, and can be obtained, for example, using XRF analysis, XPF analysis, etc. described later.

[0132] [2-3. Post-exposure heat treatment step] After exposing the resist film, post-exposure heating (post-exposure bake (PEB)) treatment may or may not be performed. By performing post-exposure heat treatment (PEB), the contrast of the etching selectivity between the exposed portion and the unexposed portion can be increased. Although the mechanism is not clear, by performing heat treatment (PEB) after exposure, in the acid environment after exposure, WO 2- undergoes dehydration condensation reaction or the like and the structure changes, or the sulfide generated by exposure vaporizes and evaporates, or the water or residual water generated by the dehydration condensation reaction or the like of the above WO 2- vaporizes and evaporates, etc. are considered to have an impact.

[0133] More specifically, by performing a post-exposure bake treatment, when the molar percentage (x mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion in the unexposed portion of the resist film is taken as 100 mol %, and the molar percentage (y mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion in the exposed portion of the resist film is taken as 100 mol %, the molar percentage can be reduced ((xy) mol %) of the S or I element derived from the onium cation in the exposed portion of the resist film compared to the unexposed portion, thereby creating differences in chemical and physical properties between the unexposed and exposed portions of the resist film. Furthermore, since the film thickness of the exposed part of the resist film is reduced by the post-exposure heat treatment, it is speculated that the heat treatment causes the vaporization or evaporation of substances derived from the onium cation, although the mechanism is not clear.

[0134] The degree of decrease in mole percent of the onium cation-derived S or I element contained in the resist film in the exposed portion compared to the unexposed portion can be changed by conditions such as the baking temperature and baking time of the post-exposure heat treatment, and (xy) mole percent is preferably 5 mole percent or more, more preferably 10 mole percent or more, and even more preferably 15 mole percent or more. Also, (xy) mole percent is preferably 100 mole percent or less, more preferably 90 mole percent or less, and even more preferably 80 mole percent or less.

[0135] The metal element derived from the metal oxo acid anion is at least one element selected from the group consisting of Mo, W, V, Nb, Ta, Zr, Cr, Mn, Se, Te, As, Ni, Sb, and Ge.

[0136] When the metal element derived from the metal oxo acid anion contained in the resist film is taken as 100 mol %, the mol % of the S or I element derived from the onium cation can be determined by XRF or XPS analysis.

[0137] For the XRF analysis, a known, commonly used method can be used. For example, the molar ratio of the above metal element to the element S or I contained in the resist film can be determined by SQX analysis using a calibration curve method or a fundamental parameter (FP) method.

[0138] Furthermore, known and commonly used methods can be used for XPS analysis. For example, when the metal element is W and the element derived from the onium cation is S, the atomic percentage of each element can be determined based on the peak areas of W4f and S2p, thereby determining the molar ratio of the metal element to the element S or I contained in the resist film.

[0139] The mechanism by which post-exposure bake treatment results in differences in the chemical and physical properties between the exposed and unexposed areas of the resist film is unclear, but it is speculated that post-exposure bake treatment promotes further crosslinking of the metal elements derived from the metal oxo acid anions, which in turn makes it easier for the onium cations to be removed from the crosslinked network of the metal elements.

[0140] The baking conditions for the post-exposure bake treatment are not particularly limited and can be set appropriately depending on the type of resist material, 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, using a heating device such as a hot plate. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0141] [2-4. Development process] The pattern forming method according to this embodiment includes a step of developing the exposed resist film. In the development step, a pattern can be formed by developing the exposed resist film with a developer. A negative pattern formation process is one in which the exposed region remains as a pattern after development, while a positive pattern formation process is one in which the exposed region is removed after development. Whether a positive or negative pattern is formed can be appropriately selected depending on the resist material or the developer. After the development, the resist film may be washed with a rinse solution and then dried, and in some cases, a baking treatment may be further performed.

[0142] The developer used in this embodiment may be a developer containing water for a water development process, or a developer containing an organic solvent (organic developer) for an organic solvent development process.

[0143] <Water development process> With conventional metal oxide resist materials, it has been difficult to form positive-tone patterns with good resolution using a water development process. In contrast, the resist material according to this embodiment can be used to form a pattern with good resolution using a developer containing water.

[0144] The water-containing developer used in the water development process is not particularly limited, and any known and commonly used developer can be used. Pure water can be used as the developer.

[0145] The method for developing the exposed resist film using the water-containing developer is not particularly limited, and any known or commonly used method can be used. Examples of the method for developing using the developer include a method of immersing a substrate having an exposed resist film in the developer for a certain period of time (dip method), a method of spraying the developer onto the surface of the exposed resist film (spray method), and a method of discharging the developer at a constant speed from a discharge nozzle toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispense method).

[0146] Furthermore, pure water can be used as a rinse liquid in the water development process.

[0147] <Organic solvent development process> Examples of developers used in the organic solvent development process include developers containing one or more organic solvents such as polar solvents, such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, and hydrocarbon-based solvents.

[0148] Specific examples of organic solvents include: ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), 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); Nitrile solvents such as acetonitrile, propionitrile, and benzonitrile: Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; Hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene; These may be used alone or in combination of two or more.

[0149] Among these, the organic solvent used in the developer is preferably a polar solvent, and preferably contains an amide solvent, an alcohol solvent, or an ester solvent, and more preferably contains an amide solvent or an ester solvent and an alcohol solvent. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester solvent is preferably at least one selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate. The alcohol-based solvent is preferably at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol.

[0150] When the developer contains both an amide solvent or an ester solvent and an alcohol solvent, the blending ratio (weight ratio) of the amide solvent or the ester solvent to the alcohol solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0151] The method for developing the exposed resist film using the developer is not particularly limited, and any known or commonly used method can be used. Examples of the method for developing using the developer include a method of immersing a substrate having an exposed resist film in the developer for a certain period of time (dip method), a method of spraying the developer onto the surface of the exposed resist film (spray method), and a method of discharging the developer at a constant speed from a discharge nozzle toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispense method).

[0152] After development with the developer, a step of washing with a rinse liquid may be included. The rinse liquid is not particularly limited, and any known or commonly used one can be used. As the rinse liquid, an organic solvent that does not easily dissolve the resist pattern can be appropriately selected from the organic solvents contained in the developer.

[0153] The rinse liquid is not particularly limited, and may be, for example, at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Among these, it is preferable to use at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents as the rinse liquid, it is more preferable to use at least one solvent selected from the group consisting of alcohol solvents and ester solvents, and it is even more preferable to use at least one alcohol solvent.

[0154] The alcohol-based solvent used in the rinse liquid is preferably a monohydric alcohol having 2 to 8 carbon atoms, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples of the monohydric alcohol include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. These organic solvents may be used alone or in combination of two or more.

[0155] The method for cleaning the resist pattern with the rinse liquid is not particularly limited, and any known or commonly used method can be used. Examples of the cleaning method using the rinse liquid include a method of immersing the resist pattern in the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid onto the surface of the resist pattern (spray method), and a method of discharging the rinse liquid at a constant speed from a discharge nozzle toward the surface of the resist pattern rotating at a constant speed (dynamic dispense method).

[0156] <Processes involving exposure to steam> After the resist film is exposed to light, the exposed resist film may or may not be subjected to a treatment of exposing it to steam. By exposing the film to steam, it is possible to selectively reduce the film thickness in the unexposed areas. Although the mechanism by which this phenomenon occurs is unclear, it is presumed to be due to a reaction between the metal element derived from the metal oxo acid anion and water molecules.

[0157] Here, the vapor may be water vapor, or may be vapor of an alcohol-based solvent, a ketone-based solvent, water, or a solvent containing an acid or the like. As the alcohol-based solvent, methanol, ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), etc. are preferred. As the ketone solvent, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc. are preferred. The acid is preferably HCl, HBr, HI, formic acid, or the like.

[0158] The "vapor" may be in a gaseous state or in a liquid state in the form of a fine mist that can be carried by a carrier gas (eg, an inert gas such as N2 or Ar).

[0159] The method for exposing the exposed resist film to steam is not particularly limited, and examples thereof include leaving the resist film in a steam atmosphere, placing the resist film in a steam stream, spraying an inert gas containing steam onto the resist film, etc. A simple method for exposing the resist film to steam includes, for example, placing the surface layer of the resist film on the substrate facing the hot water bath so that the surface layer is exposed to the steam generated from the hot water bath.

[0160] The conditions for exposing the resist film to the vapor (substrate temperature, exposure time, pressure, gas flow rate, etc.) can be appropriately set depending on the type and application of the resist material, the type of vapor, the method of exposure to the vapor, etc. The "temperature of the substrate" may refer to the temperature of at least a portion of the substrate including the resist film, or the temperature of the surface of the resist film. The temperature of the substrate is not particularly limited, but is preferably 1 to 80°C, more preferably 10 to 60°C, and even more preferably 15 to 50°C. The "exposure time" refers to the time for which the resist film is exposed to steam, and can be set appropriately depending on the method for exposing to steam, etc. The exposure time is preferably 5 to 300 seconds, more preferably 10 to 250 seconds, and even more preferably 15 to 200 seconds.

[0161] <Development by dry etching> After the resist film is exposed or subjected to post-exposure bake (PEB), it may be developed by dry etching to form a pattern. Development by anisotropic dry etching reduces the amount of side etching and enables finer processing.

[0162] The development method by dry etching is not particularly limited, and any known and commonly used method can be used, such as chemical etching, physical sputtering, reactive ion etching (RIE), etc. Among these, reactive ion etching (RIE) is preferably used as the dry etching, since it can provide a high etching ratio.

[0163] The reactive ion etching apparatus may be a plasma etching apparatus of a type such as capacitively coupled plasma (CCP), electron cyclotron resonance plasma (ECP), helicon wave excited plasma (HWP), inductively coupled plasma (ICP), microwave excited surface wave plasma (SWP), etc. Among these, an inductively coupled plasma etching apparatus or a capacitively coupled plasma etching apparatus is preferably used as the plasma etching apparatus.

[0164] Dry etching can be performed in a chamber provided in a plasma etching apparatus using a resist film after the above-mentioned exposure, or after the post-exposure heat treatment and / or the post-exposure treatment of exposure to water vapor.

[0165] The etching rate can be adjusted by using a halogen-containing gas such as a fluorocarbon, hydrofluorocarbon, fluorine-based gas, chlorine-based gas, or bromide-based gas as the etching gas. Examples of fluorocarbons include CF, C2F6, C3F6, and C4F8, and examples of hydrofluorocarbons include, but are not limited to, CF3H, CF2H2, CF4H2, C2F5H, C3F7H, C3F6H2, C3F5H3, C3F4H4, and C3F3H5. Examples of fluorine-based gases include SF6, NF3, F2, etc., examples of chlorine-based gases include Cl2, CHCl3, SiCl4, CCl4, BCl3, etc., and examples of bromide-based gases include Br2, HBr, etc., but are not limited to these. These halogen-containing gases may be used alone or in combination of two or more.

[0166] The etching gas may contain an oxidizing gas or an inert gas as an additive gas. Examples of the oxidizing gas include O2, O3, CO, CO2, COCl2, COF2, NO, NO2, SO, and SO 2、 Examples of the inert gas include, but are not limited to, COS, etc. Examples of the inert gas include, but are not limited to, N, He, Ar, Ne, Kr, Xe, etc. The etching rate can be adjusted by adding an oxidizing gas, and the safety of handling the etching gas can be improved by adding an inert gas.

[0167] The ratio of the halogen-containing gas to the additive gas (oxidizing gas and / or inert gas) in the etching gas is not particularly limited and may be 0-10:0-10, preferably 1-10:1-10, and more preferably 1-5:1-5.

[0168] The processing conditions for development by dry etching can be appropriately set depending on the type of apparatus used, the type of etching gas, the type of polyacid salt in the resist film, etc., so that the selectivity of the etching rate between the unexposed area and the exposed area is optimized. The flow rate of the etching gas is preferably 3 to 1000 sccm, and more preferably 5 to 800 sccm. The temperature during dry etching is not particularly limited, and is preferably -50 to 300°C, more preferably -20 to 200°C, and even more preferably -10 to 100°C, for example. The pressure inside the chamber is not particularly limited, and is preferably 0.01 to 300 Pa, more preferably 0.05 to 100 Pa, and even more preferably 0.1 to 30 Pa, for example. The radio frequency (RF) power is preferably 50 to 1500W, and more preferably 150 to 1000W. The bias power is preferably 10 to 1000 W, and more preferably 20 to 500 W.

[0169] The dry etching time can be appropriately set within a range of over-etching so as not to leave any etching residue or cause side etching in the through-holes. The dry etching time is, for example, preferably 5 to 150 seconds, more preferably 8 to 125 seconds, and even more preferably 10 to 100 seconds. In particular, the etching ratio between the unexposed and exposed portions of the resist film formed using the resist material according to this embodiment was good within the range of 10 to 100 seconds, and the etching ratio tended to decrease when dry etching was performed for a longer period of time.

[0170] The selectivity (etching ratio) between the exposed and unexposed portions of the resist film in dry etching can be expressed by the following formula. (Selectivity)=(Etching rate in unexposed area) / (Etching rate in exposed area) The etching rate in the unexposed or exposed areas can be expressed as (etching rate (nm / min) = Δh × (60 / t), where Δh (nm) is the difference in film thickness before and after dry etching for t seconds. In the above case, the selectivity is preferably 1.1 or more, more preferably 1.2 or more, and even more preferably 1.5 or more.

[0171] [3. Dry Etching Resist Materials] When a resist film formed using the resist material according to this embodiment is subjected to a step of exposure to actinic rays and then dry-etched between the unexposed and exposed areas of the resist film, a significant selectivity (etching ratio) is observed between the unexposed and exposed areas. Therefore, the resist material according to this embodiment can be suitably used as a resist material for dry etching.

[0172] [4.Structure] In a resist film formed using the resist material according to this embodiment, by performing a post-exposure bake treatment after the step of exposing the resist film to actinic rays, it is possible to obtain a structure in which the unexposed and exposed areas of the resist film have different chemical and physical properties.

[0173] That is, when the molar percentage (x mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the unexposed portion is taken as 100 mol %, and the molar percentage (y mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the exposed portion is taken as 100 mol %, a structure can be provided in which the molar percentage (5 mol %≦(xy) mol %) of the S or I element derived from the onium cation contained in the resist film in the exposed portion is reduced compared to the unexposed portion.

[0174] Furthermore, the degree of decrease in the molar percentage of the onium cation-derived S or I element contained in the resist film in the exposed portion compared to the unexposed portion can be changed by adjusting conditions such as the baking temperature and baking time of the post-exposure heat treatment, and the (xy) molar percentage can be adjusted to within a range of 5 to 100 molar%, 10 to 90 molar%, 15 to 80 molar%, etc.

[0175] The method for determining the molar ratio of the metal element derived from the metal oxo acid anion, the predetermined metal element contained in the resist film, and the S or I element is as described above.

[0176] [5. Patterned Structure] The patterned structure according to this embodiment can be obtained by forming a pattern of the resist material on a substrate using the pattern formation method.

[0177] The average thickness of part or all of the patterned structure according to this embodiment is not particularly limited and can be appropriately set depending on the intended use, etc. The patterned structure preferably has portions with an average thickness of 1 to 100 nm, more preferably 5 to 75 nm, and even more preferably 10 to 60 nm.

[0178] Furthermore, the pitch of part or all of the patterned structure according to this embodiment is not particularly limited and can be set appropriately depending on the intended use, etc. The patterned structure preferably has a portion with a pitch of 100 nm or less, more preferably has a portion with a pitch of 50 nm or less, and even more preferably has a portion with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the patterning 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.

[0179] [6. Electron beam or EUV resist materials] The resist material according to this embodiment contains a metal oxo acid anion and an onium cation, and therefore has good reactivity with electron beams, EUV, and the like, making it suitable for use as a resist material for electron beams or EUV. [Example]

[0180] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0181] [1. Synthesis and Differential Thermal / Thermogravimetric Measurements of Salts of Metal Oxoanions and Onium Cations] A salt (A-1) of a metal oxo acid anion and an onium cation was synthesized by the following method.

[0182] <Synthesis Example: Bis(triphenylsulfonium)tungstate(IV) (A-1)> [ka] 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=7.93-7.88(m,12H), 7.88-7.82(m,6H), 7.82-7.74(m,12H). ESI-MS: POSITIVE m / z 263.4 ([C 18 H 15 S] + ) NEGATIVE m / z 123.9 (median) ([WO4] 2- )

[0183] 2. Preparation of Test Resist Materials A test resist material (R-1) was prepared by mixing 2 parts by mass of the salt (A-1) synthesized above and 98 parts by mass of a solvent consisting of water and an organic solvent (water:diacetylacetone=97:3 (w / w%)).

[0184] [3. Formation of resist film and XPS analysis of unexposed and exposed areas after post-exposure bake treatment] <Resist film formation> Resist material (R-1) was applied using a spinner to an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then post-applied bake (PAB) was performed on a hot plate at 120°C for 60 seconds, followed by drying to form a 50-nm-thick resist film. The thickness of the formed film was measured using a film thickness measuring device (JA Woollam's "M-2000D").

[0185] <Consideration of exposure amount> The resist film was selectively irradiated with a KrF excimer laser (248 nm) at a predetermined exposure dose using an exposure system NSR-S203B (Nikon Corporation, NA (numerical aperture) = 0.60, σ = 0.68), followed by post-exposure baking (PEB) at 120°C for 60 seconds. KrF excimer laser exposure dose to resist film (mJ / cm 2)The relationship with the film thickness (nm) after post-exposure heat treatment is shown in Fig. 1. From the PEB shrinkage curve in Fig. 1, in the resist film formed from the resist material (R-1), at an exposure dose of 50 - 60 mJ / cm 2 , it was considered that the reaction in the exposed part of the resist film was almost completed. Therefore, in the following XPS analysis, the exposure dose of the KrF excimer laser was set to 100 (mJ / cm 2 ).

[0186] <XPS Analysis> The formed resist film was irradiated with a KrF excimer laser at 100 (mJ / cm 2 ), and then post-exposure bake (PEB) treatment was performed at 120 °C for 60 seconds. Quantitative analysis was performed by X-ray photoelectron spectroscopy (XPS) on the elements of W, S, C, and O contained in the unexposed and exposed parts of the resist film. As the XPS analyzer, K-ALPHA manufactured by Thermofisherscientific was used. The results of obtaining the Atomic% of each element based on the peak areas of W4f, S2p, C1s, and O1s under the following conditions are shown in Table 1. X-ray source: Monochromatic AlKα ray Voltage: 15 kV Beam diameter: 100 μm Photoelectron extraction angle: 45° Scan range: 15.5 - 1100 eV

[0187]

Table 1

[0188] From the results of the quantitative analysis by the above XPS, it can be seen that when the metal element W derived from the metal oxo acid anion contained in the unexposed part of the resist film is 100 mol%, 128.4 mol% of S derived from the onium cation is contained. On the other hand, when the metal element W derived from the metal oxo acid anion contained in the exposed part of the resist film is 100 mol%, it can be seen that 58.9 mol% of S derived from the onium cation is contained. Therefore, it can be seen that the amount of S derived from onium cations is reduced by 69.5 mol % in the exposed area compared to the unexposed area of ​​the resist film.

[0189] [4. Water development] A resist film was formed using the resist material (R-1) in the same manner as above. The resist film was irradiated with a KrF excimer laser at 100 (mJ / cm 2 ) and then subjected to post-exposure baking (PEB) at 120°C for 60 seconds.

[0190] After post-exposure bake treatment, the resist film was immersed in pure water for a specified time and then dried by N2 blow. The relationship between the immersion time in pure water (s), the change in film thickness between the unexposed and exposed parts of the resist film, and the film reduction rate (%) is shown in Table 2 below and Figure 2. The film reduction rate can be calculated using the following formula, where m1 is the film thickness before immersion in pure water, and m2 is the film thickness after immersion in pure water. (Film reduction rate)=((m1-m2) / m1)×100(%)

[0191] [Table 2]

[0192] The results in Table 2 and Figure 2 show that by exposing a resist film formed from the resist material (R-1) to light and then subjecting it to a heat treatment, the unexposed portions can be selectively dissolved and the film reduced by immersing it in water.

[0193] 5. Vapor Exposure A resist film was formed using the resist material (R-1) in the same manner as above. The resist film was irradiated with a KrF excimer laser at 100 (mJ / cm 2 ) and then subjected to post-exposure baking (PEB) at 120°C for 60 seconds. The water bath was then set to 85°C, and the surface of the resist film on the substrate was exposed to water vapor with the surface facing downward toward the water bath. The resist film was then dried by blowing N2. The relationship between the exposure time (s) to water vapor, the changes in the film thickness of the unexposed and exposed portions of the resist film, and the film reduction rate (%) is shown in Table 3 and FIG. 3 below.

[0194]

Table 3

[0195] From the results of Table 3 and FIG. 3, it can be seen that by exposing the resist film formed from the resist material (R-1), performing heat treatment, and then exposing it to water vapor, the unexposed portion can be selectively reduced in film thickness.

[0196] [6. Development by Dry Etching] A resist film was formed in the same manner as above using the resist material (R-1). The resist film was irradiated with a KrF excimer laser at 100 (mJ / cm 2 ), and then post-exposure bake (PEB) treatment was performed at 120 °C for 60 seconds.

[0197] [Development with an Etching Gas of 100% CF4] The resist film after the above post-exposure bake treatment was developed using an etching gas of 100% CF4 (CF4 / O2 = 100 / 0). For development by dry etching, an inductively coupled plasma (ICP) plasma etching apparatus was used.

[0198] The above development by dry etching was adjusted so that the total gas flow rate was 100 sccm and was performed under the conditions of a high-frequency (RF) power of 100 W, a bias power of 25 W, a stage temperature of 0 °C, and a processing pressure of 2.4 Pa.

[0199] The film thickness of the unexposed and exposed parts of the resist film was measured before dry etching. The resist film was then developed by dry etching for 40 seconds under the above conditions. The film thickness of the unexposed and exposed parts of the resist film after development by dry etching was measured. Figure 4-1 shows a conceptual diagram of the above test, and Figures 4-2 and 4-3 show the change in film thickness of the unexposed and exposed parts of the resist film before and after development by dry etching.

[0200] 4-2 and 4-3 show that a resist film formed using the resist material (R-1) can be developed by positive dry etching.

Claims

1. A structure having a substrate and a resist film on a surface of the substrate, the resist film contains a metal element derived from a metal oxo acid anion and an S or I element derived from an onium cation, the resist film has an exposed area and an unexposed area exposed to actinic rays, the mol % of the S or I element derived from the onium cation (x mol %) when the metal element derived from the metal oxo acid anion contained in the resist film in the unexposed portion is taken as 100 mol % is compared with the mol % of the S or I element derived from the onium cation (y mol %) when the metal element derived from the metal oxo acid anion contained in the resist film in the exposed portion is taken as 100 mol %, and the mol % of the S or I element derived from the onium cation contained in the resist film in the exposed portion is reduced by 5 mol % or more (5 mol %≦(x−y) mol %) compared to the unexposed portion; structure.

2. 2. The structure according to claim 1, wherein, when the mol % (x mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the unexposed portion is taken as 100 mol %, and the mol % (y mol %) of the S or I element derived from the onium cation when the metal element derived from the metal oxo acid anion contained in the resist film in the exposed portion is taken as 100 mol %, the mol % of the S or I element derived from the onium cation contained in the resist film in the exposed portion is reduced by 10 to 100 mol % (10 mol %≦(x−y) mol %≦100 mol %) compared to the unexposed portion.

3. 2. The structure according to claim 1, wherein the metal element derived from the metal oxo acid anion is at least one element selected from the group consisting of Mo, W, V, Nb, Ta, Zr, Cr, Mn, Se, Te, As, Ni, Sb, and Ge.

4. The metal oxo acid anion is MoO ４ ２－ , W.O. ４ ２－ , V.O. ４ ３－ , NbO ３ － , NbO ４ ３－ , TaO ３ ２－ , ZrO ３ ２－ , CrO ４ ２－ , MnO ４ ２－ , SeO ３ ２－ , SeO ４ ２－ , TeO ３ ２－ , TeO ４ ２－ , AsO ３ ３－ , AsO ４ ３－ , NiO ２ － , SbO ３ ３－ , and GeO ４ ４－ The structure according to claim 1, wherein the at least one selected from the group consisting of:

5. 2. The structure according to claim 1, wherein the onium cation is a sulfonium cation or an iodonium cation.

6. forming a resist film using a resist material containing a metal oxo acid anion and an onium cation; exposing the resist film to actinic rays; a post-exposure bake treatment step; A pattern forming method comprising the steps of:

7. 7. The pattern forming method according to claim 6, further comprising the step of developing the resist film using a developer after the post-exposure bake treatment step.

8. 8. The pattern forming method according to claim 7, wherein the developer contains water.

9. The pattern formation method according to claim 6 , wherein the actinic radiation is UV, DUV, XUV, EUV, an electron beam, or an X-ray.

10. The pattern forming method according to claim 6 , further comprising a step of exposing the resist film to steam after the step of post-exposure bake treatment.

11. A resist material containing a metal oxoacid anion and an onium cation.

12. 12. The resist material according to claim 11, wherein the metal oxo acid anion and the onium cation are a salt of a metal oxo acid anion and an onium cation represented by general formula (I) or a mixture thereof. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [In formula (I), A ｍ＋ are each independently H ＋ or a metal ion; B ｎ＋ each independently represents a sulfonium cation or an iodonium cation; C （ａｍ＋ｂｎ）－ represents a metal oxoacid anion; m is an integer of 1 to 3, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

1.

13. 13. The resist material according to claim 12, comprising 0.01 to 5 mass % of the salt of the metal oxo acid anion represented by general formula (A) and the onium cation, or a mixture thereof.

14. The resist material according to any one of claims 11 to 13, which is a resist material for dry etching.

15. A step of forming a resist film using the resist material according to any one of claims 11 to 13; exposing the resist film to actinic rays; developing the exposed resist film by dry etching; A pattern forming method comprising the steps of:

16. 16. The pattern formation method according to claim 15, wherein a gas containing a halogen-containing gas is used as an etching gas in the step of developing by dry etching.

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