Resist material, pattern formation method, and patterned structure

Abstract

The purpose of this invention is to provide: a novel resist material containing (A) a polyacid salt having one or more polar groups having an acid dissociable group, or a mixture thereof, and (B) a polymer; and a corresponding pattern formation method and patterned structure.

Description

Resist material, pattern forming method, and patterned structure

[0001] The present invention relates to a resist material, a patterning method, and a patterned structure.

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

[0003] The physicochemical properties of polyacids, such as oxidation-reduction ability, reactivity to actinic rays, and acidity, can be changed depending on the combination of their constituent elements, their structure, the type of counter cation, and the like.

[0004] Patent Document 1 discloses an invention relating to a transfer method, which includes the steps of providing a layer of radiation-sensitive material containing a mixture of an organic compound such as polyvinyl alcohol and a polyoxometalate on a second material, exposing selected regions of the radiation-sensitive material layer to radiation to form a pattern in the layer, and then transferring the pattern into the second material underneath.

[0005] U.S. Pat. No. 5,178,989

[0006] An object of the present invention is to provide a novel resist material, a patterning method, and a patterned structure.

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that a novel resist material can be provided, in which the solubility of the resist material in a developer can be changed by the action of an acid, by using a resist material containing (A) a polyacid salt or a mixture thereof having one or more polar groups each having an acid-dissociable group, and (B) a polymer, and have thereby completed the present invention.

[0008] That is, the present invention relates to the following inventions. <1> A resist material containing (A) a polyacid salt or a mixture thereof having one or more polar groups having an acid dissociable group, and (B) a polymer. <2> The resist material according to <1>, wherein the anion moiety of the (A) polyacid salt or mixture thereof having one or more polar groups having an acid dissociable group is an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having defect sites, in which the defect sites have been modified. <3> The resist material according to <2>, wherein the isopolyacid anion is an isopolyoxomolybdate anion, an isopolyoxotungstate anion, an isopolyoxoniobate anion, or an isopolyoxotantalate anion. <4> The resist material according to <2>, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge. <5> The resist material according to <2>, wherein the heteropolyacid anion having a deficiency site is a deficiency Keggin-type heteropolyacid anion or a deficiency Dawson-type heteropolyacid anion. <6> The resist material according to <2>, wherein the modification is achieved by bonding a group having one or more heteroatoms P, Si, Ge, or Sn, to which one or more organic groups are bonded, to the heteropolyacid anion having a deficiency site via some or all of the heteroatoms. <7> The resist material according to <6>, wherein the organic group has one or more polar groups having an acid-dissociable group. <8> The resist material according to <7>, wherein the acid-dissociable group is a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group. <9> The resist material according to <8>, wherein the cation moiety of the (A) polyacid salt or mixture thereof having one or more polar groups having an acid-dissociable group is H ＋, a metal ion, an onium cation, or an onium dication. <10> The resist material according to <9>, wherein the onium cation or onium dication is an ammonium cation, an ammonium dication, a phosphonium cation, a phosphonium dication, a sulfonium cation, a sulfonium dication, or an iodonium cation. <11> The resist material according to <9>, wherein the onium cation or onium dication has one or more polar groups having an acid dissociable group. <12> The resist material according to <11>, wherein the acid dissociable group is a tertiary carbon acid dissociable group, an allyl or benzyl acid dissociable group, or an acetal acid dissociable group. <13> The resist material according to <1>, wherein the (A) polyacid salt having one or more polar groups having an acid dissociable group or a mixture thereof is a polyacid salt having one or more polar groups having an acid dissociable group represented by general formula (I) or a mixture thereof. (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [wherein A ｍ＋ are each independently H ＋ , a metal ion, an onium cation, or an onium dication; C （ａｍ）－ represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having a defect site, the defect site of which has been modified; ｍ＋ and / or C （ａｍ）－ has one or more polar groups having an acid dissociable group; m is an integer of 1 to 5, and a is a real number greater than 0.] <14> The resist material according to <1>, wherein the (A) polyacid salt having one or more polar groups having an acid dissociable group or a mixture thereof is a polyacid salt having one or more polar groups having an acid dissociable group represented by general formula (I') or a mixture thereof. (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C'(a'm'+bn)-) (I') [wherein A' ｍ’＋ are each independently H ＋, a metal ion, an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B ｎ＋ each independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C'(a'm'+bn)- represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having a defective site, the defective site of which has been modified; ｍ’＋ , B ｎ＋ and / or C'(a'm'+bn)- has one or more polar groups having an acid-dissociable group; m' is an integer from 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0.] <15> The resist material according to <1>, wherein the (B) polymer contains one or more structural units selected from the group consisting of a structural unit having a phenolic hydroxy group, a structural unit that adjusts the solubility in a developer, and a structural unit that has a fluorine atom. <16> The resist material according to <1>, wherein the content of the (B) polymer is 0.1 to 200 parts by mass relative to 100 parts by mass of the (A) polyacid salt or mixture thereof having one or more polar groups having an acid-dissociable group. <17> The resist material according to <15>, wherein the structural unit that adjusts the solubility in a developer is a structural unit represented by general formula (VIII-2) or (VIII-3). [In formula (VIII-2), R α represents a hydrogen atom, a halogen atom, or C １－３ an alkyl group or C １－３ represents a haloalkyl group; Ｂ ｂ１１ represents a single bond or an optionally substituted C １－８ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２- which may be substituted by - (provided that adjacent divalent carbon atoms are not simultaneously substituted); G represents a tertiary carbon type acid-dissociable group, an allyl or benzyl type acid-dissociable group, or an acetal type acid-dissociable group. [In formula (VIII-3), R α represents a hydrogen atom, a halogen atom, or C １－３ an alkyl group or C １－３ represents a haloalkyl group; Ｂ ｂ１２ represents a single bond or an optionally substituted C １－８ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ Ar represents a group which may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time); Ｂ ｂ１２ is an optionally substituted C ６－１８ G represents a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group.] <18> The resist material according to <15>, wherein the structural unit having a fluorine atom is a structural unit represented by general formula (VIII-5) or (VIII-6): [In formula (VIII-5), R α represents a hydrogen atom, a halogen atom, or C １－３ an alkyl group or C １－３ represents a haloalkyl group; Ｃ ｂ１１ represents a single bond, —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ represents -; Ｃ ｂ１２ represents a single bond or an optionally substituted C １－８ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); Ｃ ｂ１１ is an optionally substituted C １－８ represents a hydrocarbyl group in which at least one hydrogen atom is substituted with a fluorine atom. [In formula (VIII-6), R α represents a hydrogen atom, a halogen atom, or C １－３ an alkyl group or C １－３ represents a haloalkyl group; Ｃ ｂ２１ represents a single bond, —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ represents -; R Ｃ ｂ２１ represents a hydrogen atom, a fluorine atom, or a C １－４ an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom; α and L Ｃ ｂ２１ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ may be linked via an alkylene group to form a ring; Ｃ ｂ２１ and R Ｃ ｂ２１ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ The resist material may be linked via an alkylene group to form a ring.] <19> A pattern forming method comprising: forming a resist film using the resist material according to any one of <1> to <18>; exposing the resist film; and developing the exposed resist film using a developer. <20> The step of exposing the resist film is performed by exposing the resist film to light at a concentration of 2 mC / cm２ Electron beam or 200 mJ / cm ２ The pattern forming method according to <19>, comprising the step of exposing to extreme ultraviolet light:

[0009] <21> A patterned structure obtained by patterning the resist material according to any one of <1> to <18>.

[0010] The present invention provides a novel resist material, a pattern formation method, and a patterned structure. The (A) polyacid salt or a mixture thereof contained in the resist material of the present invention contains at least one polar group having an acid-dissociable group. This allows for the provision of a resist material whose solubility in a developer can be changed by the action of an acid, for example. The anion portion of component (A) may include an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having a deficiency site, in which the deficiency site has been modified, and the cation portion may include an onium cation or an onium dication. This allows for the resist material to have good sensitivity to light sources such as DUV, XUV, EUV, and electron beams. Furthermore, by introducing a sulfonium cation, sulfonium dication, or iodonium cation into the cation portion of component (A), a resist material can be provided that generates an acid upon exposure to DUV, XUV, EUV, electron beams, or the like.

[0011] The resist material according to the present invention contains a polymer (B) in addition to the component (A), and therefore the component (A) provides etching resistance, while the component (B) increases the EL margin.

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

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

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

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

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

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

[0018] As used herein, "C １－１８ The term "haloalkyl group" refers to "C １－１８ "C" means a group in which one or more hydrogen atoms of an "alkyl group" are substituted with halogen atoms. １－１８The "haloalkyl group" is not particularly limited, and examples thereof include a dichloromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 3,3,3-trifluoropropyl group.

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

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

[0021] As used herein, "C ３－１８ The term "alicyclic group" refers to a hydrocarbon group having, in whole or in part, a monocyclic or polycyclic structure having 3 to 18 carbon atoms. Alicyclic groups also include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc. ３－１８ A divalent carbon atom at any position excluding the terminals contained in the "alicyclic group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO ２- may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). ３－１８ The "cycloalkyl group" is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-i-propylcyclopentan-1-yl group, a cyclohexyl group, a t-butylcyclohexyl group, a tricyclodecanyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a 2-methyladamantan-2-yl group, a 2-i-propyladamantan-2-yl group, a bornyl group, a norbornyl group, a fenchyl group, a pinanyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a bornylmethyl group, a norbornylmethyl group, an adamantylmethyl group, a 1-methylcyclopentyloxycarbonylmethyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0054]

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

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

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

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

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

[0060]

[0061]

[0062]

[0063]

[0064] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) Ａ２ >> In the above general formula (g-1-2), R Ａ ｇ２１ ~R Ａ ｇ２３ are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), R Ａ ｇ２１ and R Ａｇ２２ , and / or R Ａ ｇ２２ and R Ａ ｇ２３ are directly connected to each other by a single bond or are divalently connected to each other by -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring.

[0065] R Ａ ｇ２１ and R Ａ ｇ２２ , and / or R Ａ ｇ２２ and R Ａ ｇ２３ Examples of the case where 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.

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

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

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

[0069]

[0070]

[0071]

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

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

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

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

[0076] R Ｂ ｇ１ and R Ｂ ｇ２ , R Ｂ ｇ２ and R Ｂ ｇ３ , and / or R Ｂ ｇ３ and R Ｂ ｇ４are directly connected to each other by a single bond or are divalently connected to each other by -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring.

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

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

[0079]

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

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

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

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

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

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

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

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

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

[0089] [1. Resist Material] The resist material according to this embodiment contains (A) a polyacid salt or a mixture thereof having one or more polar groups each having an acid-dissociable group, and (B) a polymer. The resist material according to this embodiment may also contain optional components such as an organic solvent and other components.

[0090] [1-1. (A) Polyacid salt having one or more polar groups having an acid dissociable group, or a mixture thereof] The anion moiety of the (A) polyacid salt having one or more polar groups having an acid dissociable group, or a mixture thereof, according to this embodiment, is composed of an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having a defect site, the defect site of which has been modified. The cation moiety of the component (A) is H ＋ , a metal ion, an onium cation, or an onium dication.

[0091] The polar group having one or more acid-dissociable groups may be contained in the anion moiety, the cation moiety, or both the anion moiety and the cation moiety of component (A). When component (A) contains one or more polar groups having an acid-dissociable group in the anion moiety and / or the cation moiety, the acid-dissociable group dissociates under the action of acid, making it possible to significantly change the solubility in a developer.

[0092] [1-1-1. Anion Moiety of Component (A)] As the anion moiety of component (A) according to this embodiment, an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having defect sites in which the defect sites have been modified may be used.

[0093] [1-1-1-1. Isopolyacid Anion] The isopolyacid anion according to this embodiment is not particularly limited, and examples thereof include an isopolyoxomolybdate anion, an isopolyoxotungstate anion, an isopolyoxovanadate anion, an isopolyoxoniobate anion, and an isopolyoxotantalate anion.

[0094] Examples of the isopolyoxomolybdate anion include [MoO ４ ] ２－ , [Mo ７ O ２４ ] ６－ , [Mo ８ O ２６ ] ４－ Examples of the isopolyoxotungstate anion include [W ４ O １３ ] ２－ , [W ５ O １６ ] ２－ , [W ６ O １９ ] ２－ , [W ７ O ２２ ] ２－ , [W ７ O ２４ ] ６－ , [H ｚ W １２ O ４０ ]－（８－ｚ） (wherein z represents an integer of 1 to 4), [W １０ O ３２ ] ４－ , [H ４ W １１ O ３８ ] ６－ , [H ７ W １１ O ４０ ] ７－ , [HW ５ O １９ ] ７－ , [H ３ W １１ O ２２ ] ５－ Examples of the isopolyoxovanadate anion include [V ４ O １２ ] ４－ , [V １０ O ２８ ] ６－ Examples of the isopolyoxoniobate anion include [Nb ６ O １９ ] ８－ , [Nb １０ O ２８ ] ６－ Examples of the isopolyoxotantalate anion include [Ta ６ O １９ ] ８－ , [Ta ８ O ２１ ] ２－ etc.

[0095] The above-mentioned isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, and isopolyoxotantalate anion include various isomers.

[0096] The isopolyoxotungstate anion may be selected from the group consisting of [W ４ O １３ ] ２－ , [W ５ O １６ ] ２－ , [W ６ O １９ ] ２－ , [W７ O ２２ ] ２－ , [W ７ O ２４ ] ６－ , [W １０ O ３２ ] ４－ , [H ｚ W １２ O ４０ ] －（８－ｚ） (wherein z represents an integer of 1 to 4), [H ４ W １１ O ３８ ] ６－ , [H ７ W １１ O ４０ ] ７－ , [HW ５ O １９ ] ７－ , [H ３ W １１ O ２２ ] ５－ , [H ４ W ２２ O ７４ ] １２－ , or [H １０ W ３４ O １１６ ] １８－ It is preferable that [W ６ O １９ ] ２－ , [W ７ O ２４ ] ６－ , [W １０ O ３２ ] ４－ , [H ｚ W １２ O ４０ ] －（８－ｚ） (where z represents an integer of 1 to 4), and more preferably [W ６ O １９ ] ２－ , [W ７ O ２４ ] ６－ , [W １０ O ３２ ] ４－ , [H ２ W １２ O ４０ ] ６－ , [H ３ W １２ O４０ ] ５－ It is more preferable that:

[0097] [1-1-1-2. Heteropolyacid Anion] Examples of the heteropolyacid anion according to this embodiment include heteropolyoxomolybdate anion, heteropolyoxotungstate anion, heteropolyoxovanadate anion, heteropolyoxoniobate anion, heteropolyoxotantalate anion, etc. The polyatom of the heteropolyacid anion is preferably Mo, W, V, Nb, or Ta, and more preferably Mo or W.

[0098] Examples of the heteropolyoxomolybdate anion include phosphomolybdate anion, silicomolybdate anion, boromolybdate anion, sulfur molybdate anion, phosphotungstomolybdate anion, cobalt molybdate anion, arsenic molybdate anion, germanium molybdate anion, etc. Examples of the heteropolyoxotungstate anion include phosphotungstate anion, silicotungstate anion, borotungstate anion, sulfur tungstate anion, cobalt tungstate anion, arsenic tungstate anion, germanium tungstate anion, etc. Examples of the heteropolyoxovanadate anion include phosphomolybdovanadate anion, boromolybdovanadate anion, boromolybdotungstovanadate anion, etc. The heteroatom of the heteropolyacid anion is preferably P, Si, Ge, B, S, Co or As, and more preferably P, Si, B, S or Ge.

[0099] The heteropolyoxomolybdate anion, heteropolyoxotungstate anion, heteropolyoxovanadate anion, etc. include Keggin type, Dawson type, Anderson type, and isomers thereof.

[0100] The heteropolyoxotungstate anion may be [PW １２ O ４０ ] ３－, [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ , [SW １２ O ４０ ] ２－ , [P ２ W １８ O ６２ ] ６－ , [Si ２ W １８ O ６２ ] ８－ It is preferable that:

[0101] [1-1-1-3. Heteropolyacid Anion Having Modified Defect Sites] As the heteropolyacid anion having defect sites according to this embodiment, a heteropolyacid anion having modified defect sites can be used, which is obtained by reacting a terminal oxygen atom at the defect site of a heteropolyacid anion having defect sites with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups.

[0102] [1-1-1-3-1. Heteropolyacid anion having a defect site] The heteropolyacid anion having a defect site according to this embodiment is not particularly limited, and may be a defect species in which a part of the basic skeleton of the heteropolyacid anion is defective, and any of a one-defect species, a two-defect species, a three-defect species, etc. Examples of the heteropolyacid anion having a defect site include a defective Keggin-type heteropolyacid anion and a defective Dawson-type heteropolyacid anion.

[0103] [1-1-1-3-1-1. Deficient Keggin type heteropolyacid anion] Examples of the defective Keggin type heteropolyacid anion include a mono-deficient Keggin type heteropolyacid anion represented by the following general formula (II-1), a di-deficient Keggin type heteropolyacid anion represented by the following general formula (II-2), and a tri-deficient Keggin type heteropolyacid anion represented by the following general formula (II-3): [XM １１ O ３９ ] ｃ１１－ (II-1) [XM １０ O３６ ] ｃ１２－ (II-2) [XM ９ O ３４ ] ｃ１３－ (II-3) (wherein, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.)

[0104] In the general formulas (II-1) to (II-3), the values ​​of c11 to c13 vary depending on the types of X and M. For example, in the general formula (II-1), when X is P and M is Mo or W, c11 is 7 ([PMo １１ O ３９ ] ７－ , [P.W. １１ O ３９ ] ７－ ) and when X is Si and M is Mo or W, c11 is 8 ([SiMo １１ O ３９ ] ８－ , [SiW １１ O ３９ ] ８－ ) and when X is S and M is Mo or W, c11 is 6 ([SMo １１ O ３９ ] ６－ , [SW １１ O ３９ ] ６－ ) and when X is B and M is Mo or W, c11 is 9 ([BMo １１ O ３９ ] ９－ , [B.W. １１ O ３９ ] ９－ ) and when X is Ge and M is Mo or W, c11 is 8 ([GeMo １１ O ３９ ] ８－ , [GeW １１ O ３９ ] ８－ In addition, in the general formula (II-2), when X is P and M is Mo or W, c12 is 7 ([PMo １０ O ３６ ] ７－ , [P.W. １０ O ３６ ] ７－) and when X is Si and M is Mo or W, c12 is 8 ([SiMo １０ O ３６ ] ８－ , [SiW １０ O ３６ ] ８－ ) and when X is B and M is Mo or W, c12 is 9 ([BMo １０ O ３６ ] ９－ , [B.W. １０ O ３６ ] ９－ ) and when X is Ge and M is Mo or W, c12 is 8 ([GeMo １０ O ３６ ] ８－ , [GeW １０ O ３６ ] ８－ Furthermore, in the general formula (II-3), for example, when X is P and M is Mo or W, c13 is 9 ([PMo ９ O ３４ ] ９－ , [P.W. ９ O ３４ ] ９－ ) and when X is Si and M is Mo or W, c13 is 10 ([SiMo ９ O ３４ ] １０－ , [SiW ９ O ３４ ] １０－ ) and when X is S and M is Mo or W, c13 is 8 ([SMo ９ O ３４ ] ８－ , [SW ９ O ３４ ] ８－ ) and when X is Ge and M is Mo or W, c13 is 10 ([GeMo ９ O ３４ ] １０－ , [GeW ９ O ３４ ] １０－ )

[0105] The defect Keggin type heteropoly acid anion preferably has an isomeric structure of α-, β-, or γ-form. The isomeric structure of the one defect Keggin type heteropoly acid anion represented by the general formula (II-1) is preferably [α-PW １１ O３９ ] ７－ , [β-PW １１ O ３９ ] ７－ , [γ-PW １１ O ３９ ] ７－ , [α-PMo １１ O ３９ ] ７－ , [β-PMo １１ O ３９ ] ７－ , [γ-PW １１ O ３９ ] ７－ , [α-SiW １１ O ３９ ] ８－ , [β-SiW １１ O ３９ ] ８－ , [γ-SiW １１ O ３９ ] ８－ , [α-SiMo １１ O ３９ ] ８－ , [β-SiMo １１ O ３９ ] ８－ , [γ-SiW １１ O ３９ ] ８－ is preferred, and [α-PW １１ O ３９ ] ７－ , [α-PMo １１ O ３９ ] ７－ , [α-SiW １１ O ３９ ] ８－ , [α-SiMo １１ O ３９ ] ８－ The isomer structure of the two-deficient Keggin type heteropoly acid anion represented by the general formula (II-1) is preferably [α-PW １０ O ３６ ] ７－ , [β-PW １０ O ３６ ] ７－ , [γ-PW １０ O ３６ ] ７－ , [α-PMo １０ O ３６ ] ７－ , [β-PMo１０ O ３６ ] ７－ , [γ-PW １０ O ３６ ] ７－ , [α-SiW １０ O ３６ ] ８－ , [β-SiW １０ O ３６ ] ８－ , [γ-SiW １０ O ３６ ] ８－ , [α-SiMo １０ O ３６ ] ８－ , [β-SiMo １０ O ３６ ] ８－ , [γ-SiW １０ O ３６ ] ８－ is preferred, and [γ-PW １０ O ３６ ] ７－ , [γ-PMo １０ O ３６ ] ７－ , [γ-SiW １０ O ３６ ] ８－ , [γ-SiMo １０ O ３６ ] ８－ Further, the isomeric structure of the 3-deficient Keggin type heteropoly acid anion represented by the general formula (III-1) is preferably [α-PW ９ O ３４ ] ９－ , [β-PW ９ O ３４ ] ９－ , [γ-PW ９ O ３４ ] ９－ , [α-PMo ９ O ３４ ] ９－ , [β-PMo ９ O ３４ ] ９－ , [γ-PW ９ O ３４ ] ９－ , [α-SiW ９ O ３４ ] １０－ , [β-SiW ９ O ３４ ]１０－ , [γ-SiW ９ O ３４ ] １０－ , [α-SiMo ９ O ３４ ] １０－ , [β-SiMo ９ O ３４ ] １０－ , [γ-SiW ９ O ３４ ] １０－ is preferred.

[0106] [1-1-1-3-1-2. Deficient Dawson type heteropolyacid anion] Examples of the deficient Dawson type heteropolyacid anion include a mono-deficient Dawson type heteropolyacid anion represented by the following general formula (III-1), a di-deficient Dawson type heteropolyacid anion represented by the following general formula (III-2), and a tri-deficient Dawson type heteropolyacid anion represented by the following general formula (III-3): [X ２ M １７ O ６１ ] ｃ２１－ (III-1) [X ２ M １６ O ５８ ] ｃ２２－ (III-2) [X ２ M １５ O ５６ ] ｃ２３－ (III-3) (wherein X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.)

[0107] In the general formulas (III-1) to (III-3), the values ​​of c21 to c23 vary depending on the types of X and M. For example, in the general formula (III-1), when X is P and M is Mo or W, c21 is 10 ([P ２ Mo １７ O ６１ ] １０－ , [P ２ W １７ O ６１ ] １０－ ), and if X is S and M is W, c21 is 8([S ２ W １７ O６１ ] ８－ In addition, in the general formula (III-2), when X is Ge and M is Mo, c22 is 12 ([Ge ２ Mo １６ O ５８ ] １２－ Furthermore, in the general formula (III-3), when X is P and M is Mo or W, c23 is 12 ([P ２ Mo １５ O ５６ ] １２－ , [P ２ W １５ O ５６ ] １２－ )

[0108] The deficient Dawson type heteropoly acid anion preferably has an isomeric structure of α-, β-, or γ-form. The isomeric structures of the deficient Dawson type heteropoly acid anions represented by the general formulae (III-1) to (III-3) include [α-P ２ W １７ O ６１ ] １０－ , [α-P ２ W １５ O ５６ ] １２－ , [α-S ２ W １７ O ６１ ] ８－ etc. can be suitably used.

[0109] [1-1-1-3-1-3. Modification of Defect Sites] The defect sites of the heteropolyanion having the defect sites according to this embodiment can be modified by reacting a terminal oxygen atom at the defect site with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups to modify the defect site. Through this reaction, the terminal oxygen atom at the defect site of the heteropolyanion bonds to a group having a P, Si, Ge, or Sn heteroatom to which one or more organic groups are bonded, and the defect site is modified by bonding to some or all of the heteroatom.

[0110] [1-1-1-3-1-4. Bonding Form of Defect Site and Its Notation] In the heteropolyacid anion modified at a defect site according to this embodiment, the terminal oxygen atom at the defect site of the heteropolyacid anion having a defect site is modified with a group having a heteroatom of P, Si, Ge, or Sn bonded to one or more organic groups.

[0111] The bonding form between the terminal oxygen atom at the vacant site of the heteropolyacid anion and the group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded is not particularly limited, and can be represented, for example, by the following general formulas (IV-1) to (IV-5). [In formulas (IV-1) to (IV-5), X′ represents Si or Ge; X″ represents a heteroatom of Si, Ge, or Sn; R １Ａ１ ~R １Ｅ１ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ１ ~R １Ｅ１ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １Ａ１ ~R １Ｅ１The hydrogen atoms contained in may be replaced by (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, or (t) polar groups having an acid-dissociable group; * represents the terminal oxygen atom of the defect site.]

[0112] In this specification, for convenience, a heteropoly acid anion in which a deficiency site is modified by a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-1) can be represented by the following general formula (V-1): [X ｗ M ｘ O ｙ (R １Ａ１ X') (R １Ａ２ X')O] ｃ－ (V-1) (wherein w, x, y, and c are all natural numbers, and X, M, X′, and R １Ａ１ and R １Ａ２ is the same as above.) Also, R １Ａ１ and R １Ａ２ If they are the same, call this R １Ａ can be expressed as in the following general formula (V-1'): [X ｗ M ｘ O ｙ (R １Ａ X') ２ O] ｃ－ (V-1′)

[0113] The heteropolyacid anion having a modified defect site represented by general formula (V-1) or (V-1′) is not particularly limited, and may be, for example, a heteropolyacid anion having a defect site and (R １Ａ ) X'Y ３ (Y represents a leaving group, for example, a halogen atom, a hydroxy group, an alkoxy group (C １－４ An alkoxy group is preferred, and C １－２An alkoxy group is more preferred.), an alkylcarbonyloxy group (C １－４ alkylcarbonyloxy group), hydrocarbylsulfonyloxy group (C １－６ Alkyl or C ７－１０ An aralkylsulfonyloxy group is preferred. Examples include a methanesulfonyloxy group and a p-toluenesulfonyloxy group.

[0114] Similarly, in this specification, a heteropoly acid anion in which the vacant site is modified with a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-2) can be represented for convenience as in the following general formula (V-2): [X ｗ M ｘ O ｙ (R １Ｂ１ R １Ｂ２ X') (R １Ｂ３ R １Ｂ４ Si)] ｃ－ (V-2) (wherein w, x, y, and c are all natural numbers, and X, M, X′, and R １Ｂ１ , R １Ｂ２ , R １Ｂ３ and R １Ｂ４ is the same as above.) Also, R １Ｂ１ R １Ｂ２ and R １Ｂ３ R １Ｂ４ are the same, it can be expressed as in the following general formula (V-2'): ｗ M ｘ O ｙ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ－ (V-2′)

[0115] The heteropolyacid anion having a modified defect site represented by general formula (V-2) or (V-2′) is not particularly limited, and may be, for example, a heteropolyacid anion having a defect site and (R １Ｂ１ ) (R １Ｂ２ ) X'Y ２ (wherein Y represents a leaving group as above) to obtain the compound.

[0116] In this specification, for convenience, a heteropoly acid anion in which the vacant site is modified by a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-3) can be represented by the following general formula (V-3): [X ｗ M ｘ O ｙ (R １Ｃ１ X'O) (R １Ｃ２ X'O) (R １Ｃ３ X'O) (R １Ｃ４ X'O)] ｃ－ (V-3) (wherein w, x, y, and c are all natural numbers, and X, M, X′, and R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ is the same as above.) Also, R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ If they are the same, call this R １Ｃ can be expressed as in the following general formula (V-3'): [X ｗ M ｘ O ｙ (R １Ｃ X'O) ４ ] ｃ－ (V-3′)

[0117] The heteropoly acid anion having modified defect sites represented by general formula (V-3) or (V-3′) is not particularly limited, and may be, for example, a heteropoly acid anion of two defect Keggin type or Dawson type and R １Ｃ X'Y ３ (wherein Y represents a leaving group as above) to obtain the compound.

[0118] In this specification, for convenience, a heteropoly acid anion in which a deficiency site is modified by a group having a heteroatom P bonded to one or more organic groups represented by general formula (IV-4) can be represented by the following general formula (V-4): [X ｗ M ｘ O ｙ (R １Ｄ１ P=O)(R １Ｄ２ P=O)] ｃ－(V-4) (wherein w, x, y, and c are all natural numbers, and X, M, and R １Ｄ１ and R １Ｄ２ is the same as above.) Also, R １Ｄ１ and R １Ｄ２ If they are the same, call this R １Ｄ can be expressed as in the following general formula (V-4'): [X ｗ M ｘ O ｙ (R １Ｄ P=O) ２ )] ｃ－ (V-4')

[0119] The heteropolyacid anion having a modified defect site represented by general formula (V-4) or (V-4′) is not particularly limited, and for example, a heteropolyacid anion having a defect site and R １Ｄ P(=O)Y ２ (wherein Y represents a leaving group as above) to obtain the compound.

[0120] In this specification, for convenience, a heteropoly acid anion in which the vacant site is modified by a group having a heteroatom Si, Ge, or Sn bonded to one or more organic groups represented by general formula (IV-5) can be represented by the following general formula (V-5): [X ｗ M ｘ O ｙ (R １Ｅ１ X'') ｃ－ (V-5) (wherein w, x, y, and c are all natural numbers, and X, M, X″, and R １Ｅ１ The above (V-5) may be expressed as the following general formula (V-5') in some cases. １Ｅ is R １Ｅ１ The same definition is used as for [X ｗ M ｘ O ｙ (R １Ｅ X'') ｃ－ (V-5')

[0121] The heteropolyacid anion having a modified defect site represented by general formula (V-5) or (V-5′) is not particularly limited, and for example, a heteropolyacid anion having a defect site and R１Ｅ X''Y ３ (wherein Y represents a leaving group as above) to obtain the compound.

[0122] Among the heteropolyacid anions having modified defect sites represented by the general formulae (V-1) to (V-5) and (V-1') to (V-5'), heteropolyacid anions having modified defect sites represented by the following general formulae (VI-1) to (VI-12) are preferred, from the viewpoint of being relatively stable and capable of controlling the reactivity. [XM １１ O ３９ (R １Ａ X') ２ O] ｃ３１－ (VI-1) [XM １１ O ３９ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３１－ (VI-2) [XM １１ O ３９ (R １Ｄ P=O) ２ ] ｃ３１－ (VI-3) [XM １１ O ３９ (R １Ｅ X'') ｃ３１－ (VI-4) [XM １０ O ３６ (R １Ａ X') ２ O] ｃ３２－ (VI-5) [XM １０ O ３６ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３２－ (VI-6) [XM １０ O ３６ (R １Ｃ X'O) ４ ] ｃ３２－ (VI-7) [XM １０ O ３６ (R １Ｄ P=O) ２ ] ｃ３２－ (VI-8) [X ２ M １７ O ６１ (R １Ａ X')２ O] ｃ３３－ (VI-9) [X ２ M １７ O ６１ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ３３－ (VI-10) [X ２ M １７ O ６１ (R １Ｄ P=O) ２ ] ｃ３３－ (VI-11) [X ２ M １７ O ６１ (R １Ｅ X'') ｃ３３－ (VI-12) (wherein, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; X' represents a heteroatom of Si or Ge; X'' represents a heteroatom of Si, Ge, or Sn; R １Ａ ~R １Ｅ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １Ｅ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １Ａ ~R １Ｅ The hydrogen atom contained in the １－３(c) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; c31, c32, and c33 are natural numbers.)

[0123] In a heteropolyacid anion in which the vacant site is modified, four terminal oxygen atoms of the vacant site are modified, so that the value of c31 is usually c11 - 4, the value of c32 is c12 - 4, and the value of c33 is c21 - 4. On the other hand, for example, when the organic group contains an amino group which is protonated to form an ammonium cation, or when the organic group contains a carboxy group which is formed into a carboxy anion, the values ​​of c31 to c33 will differ from the above values.

[0124] [1-1-1-3-2. Organic group] The above R １Ａ , R １Ｂ１ Or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ The organic group represented by the formula (I) is not particularly limited, and any known or commonly used organic group can be used. From the viewpoint of providing a functional building block, it is preferable to use, as the organic group, an organic group having one or more substituents such as a hydroxy group, a halogen atom, or an epoxy group, an organic group having one or more ethylenically unsaturated double bonds, or an organic group having one or more polar groups having an acid-dissociable group.

[0125] <Organic group having one or more substituents such as a hydroxy group, a halogen atom, an epoxy group, etc.> １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ As the organic group represented by R１Ａ ~R １Ｅ C which may have a substituent １－１８ is a hydrocarbyl group; １Ａ ~R １Ｅ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ and one or more hydrogen atoms contained in the group represented by the formula (I) are replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (p) an epoxy group, (q) a glycidyl group, or (r) an amide group. １－１８ Alkyl group, C ３－１８ Alicyclic group, C ７－１８ an aralkyl group; １Ａ１ ~R １Ｅ１ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ More preferably, one or more of the hydrogen atoms contained in the above formula (I) are replaced with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (p) an epoxy group, (q) a glycidyl group, or (r) an amide group.

[0126] The above R １Ａ ~R １ＥSpecific examples of the group include, but are not limited to, a 1-glycidyloxypropan-3-yl group, a 1-glycidyloxy-n-octan-8-yl group, a 1-aminopropan-3-yl group, a 1-(2-aminoethylamino)-propan-3-yl group, a 3,3,3-trifluoropropan-1-yl group, a chloromethyl group, a 1-chloropropan-3-yl group, a 1-bromopropan-3-yl group, and a 1-iodopropan-3-yl group.

[0127] <Organic group having one or more ethylenically unsaturated double bonds> The above R １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ In order to have a building block reactive to actinic rays, the organic group represented by the formula (I) preferably contains one or more ethylenically unsaturated double bonds.

[0128] In the above case, R １Ａ ~R １Ｅ C which may have a substituent １－１８ is a hydrocarbyl group; １Ａ ~R １Ｅ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ and one or more hydrogen atoms contained in the group represented by the formula (I) are replaced by a (j) vinyl group, a (k) allyl group, a (l) (meth)acryloyl group, a (m) (meth)acryloyloxy group, a (n) (meth)acrylamide group, or a (o) styryl group. １－１８ Alkyl group, C ３－１８ Alicyclic group, C ７－１８ an aralkyl group; １Ａ ~R １ＥAny divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ More preferred are those in which one or more hydrogen atoms contained in the above are substituted with (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, or (o) a styryl group.

[0129] The organic group R having an ethylenically unsaturated double bond １Ａ ~R １Ｅ Specific examples of the alkyl group include, but are not limited to, a vinyl group, an allyl group, a 5-hexen-1-yl group, a 6-hepten-1-yl group, a 7-octen-1-yl group, a 1-acryloyloxypropan-3-yl group, a 1-methacryloyloxypropan-3-yl group, and a 1-vinylbenzene-4-yl group.

[0130] <Organic group having one or more polar groups having an acid-dissociable group> １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ From the viewpoint of providing a building block whose solubility in a developer can be changed by the action of an acid or the like, it is preferable that the organic group represented by the formula (I) contains one or more polar groups having an acid-dissociable group.

[0131] The organic group R having one or more polar groups having the acid-dissociable group １Ａ ~R １Ｅ The C １－１８ is a hydrocarbyl group; １Ａ ~R １Ｅ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ a hydrogen atom contained in the above R may be substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ In the formula (I), at least one hydrogen atom is replaced by a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group (t), and C optionally having a substituent is preferred. １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; １Ａ ~R １Ｅ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅa hydrogen atom contained in the above R may be substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ In the formula (I), at least one hydrogen atom is replaced by a polar group having an acid-dissociable group (t), and C １－１８ Alkyl group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; １Ａ ~R １Ｅ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ More preferably, at least one hydrogen atom of the formula (I) is replaced by a polar group having an acid-dissociable group.

[0132] The above R １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅis characterized by having one or more polar groups having an acid-dissociable group, and for example, a polar group such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group is introduced. Examples of the acid-dissociable group include a tertiary carbon-type acid-dissociable group G Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ and the like. R having one or more of the above acid-dissociable groups １Ａ , R １Ｂ１ or R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ For example, the following can be exemplified:

[0133] [* denotes a bond to a heteroatom P, Si, Ge, or Sn to which an organic group having a polar group having one or more acid-dissociable groups is bonded.]

[0134] [1-1-2. Cationic Moiety of Component (A)] The cationic moiety of the component (A) according to this embodiment may contain H ＋ , metal ions, onium cations, or onium dications can be used. The onium cations or onium dications may function as photoacid generators. Furthermore, polar groups having one or more acid-dissociable groups may be contained in the cation moiety of component (A). In this case, the cation moiety of component (A) contains an onium cation or onium dication having one or more polar groups having an acid-dissociable group.

[0135] [1-1-2-1. Metal Ion] The metal ion that can be used as the cation moiety of the heteropolyacid salt or mixture thereof whose defect site is modified is not particularly limited, and for example, Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co ３＋ , Bi３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ Metal ions include Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co ３＋ is preferred, and Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Ca ２＋ , Al ３＋ , Co ３＋ These metal ions may be used alone or in combination of two or more.

[0136] [1-1-2-2. Onium Cation or Onium Dication] The onium cation or onium dication that can be used as the cation moiety of the heteropolyacid salt or mixture thereof whose defect sites have been modified is not particularly limited, and known and commonly used ones can be used. Examples of the onium cation or onium dication include ammonium cation, ammonium dication, phosphonium cation, phosphonium dication, sulfonium cation, sulfonium dication, and iodonium cation. These onium cations or onium dications may be used alone or in combination of two or more.

[0137] The onium cation or onium dication is preferably a sulfonium cation, a sulfonium dication, or an iodonium cation, from the viewpoint of providing a building block that generates an acid when exposed to DUV, XUV, EUV, an electron beam, or the like.

[0138] [1-1-2-2-1. Ammonium cation] The ammonium cation is not particularly limited, and known and commonly used ammonium cations can be used. The ammonium cation is not particularly limited, and examples thereof include ammonium ion (NH ４ ＋ ), primary ammonium cation (NH ３ (R ２Ａ ) ＋ )), secondary ammonium cation (NH ２ (R ２Ａ ) (R ２Ｂ )) ＋ ), tertiary ammonium cation (NH(R ２Ａ ) (R ２Ｂ ) (R ２Ｃ ) ＋ ), quaternary ammonium cation (N(R ２Ａ ) (R ２Ｂ ) (R ２Ｃ ) (R ２Ｄ ) ＋ ) can be mentioned. ２Ａ ~R ２Ｄ shall represent the same as defined below.

[0139] The ammonium cation is ammonium ion (NH ４ ＋ ), and quaternary ammonium cations are preferred, and in particular, ammonium ions (NH ４ ＋ ), and organic quaternary ammonium cations represented by the following general formula (VII-1) are more preferred.

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

[0141] R in the organic quaternary ammonium cation represented by the general formula (VII-1) ２Ａ ~R ２Ｄ Each of the C groups independently represents an optionally substituted C group. １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ２Ａ ~R ２Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ ~R ２Ｄ wherein a hydrogen atom contained in the formula (I) may be substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group, and １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ２Ａ ~R２Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ ~R ２Ｄ The hydrogen atoms contained in １－３ More preferred are those optionally substituted with a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group.

[0142] Specific examples of the organic quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, tetraheptylammonium cation, trimethylethylammonium cation, dimethyldiethylammonium cation, dimethylethylpropylammonium cation, methylethylpropylbutylammonium cation, trimethylphenylammonium cation, triethylhexylammonium cation, triethylcyclohexylammonium cation, dodecyltrimethylammonium cation, diallyldimethylammonium cation, (3-acrylamidopropyl)trimethylammonium cation, trimethyl-2-methacryloyloxyethylammonium cation, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation, Examples thereof include ammonium cation, trimethylvinylammonium cation, N-4-vinylbenzyltriallylammonium cation, 3-hydroxypropyltriallylammonium cation, 2-trifluoromethylbenzyltriallylammonium cation, di-2-(N-methylacrylamide)ethyldimethylammonium cation, allyltrimethylammonium cation, butyl(2-methacryloyloxyethyl)dimethylammonium cation, ethoxycarbonylmethyltriethylammonium cation, 2-hydroxyethyltrimethylammonium cation, 2-acetylethyltrimethylammonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)trimethylammonium cation, (4-(methacryloyloxy)phenyl)trimethylammonium cation, trimethyl(4-(nonanoyloxy)phenyl)ammonium cation, and the like.

[0143] <Organic Quaternary Ammonium Cation Having One or More Substituents> From the viewpoint of providing a functional building block, the organic quaternary ammonium cation represented by the general formula (VII-1) is preferably an organic quaternary ammonium cation having one or more substituents, R ２Ａ ~R ２Ｄ each independently represents an optionally substituted C １－１８represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ２Ａ ~R ２Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ ~R ２Ｄ It is more preferable that at least one hydrogen atom contained in the optionally substituted C is replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group. １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ２Ａ ~R ２Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ ~R ２Ｄ At least one hydrogen atom of the formula (I) is (a) a halogen atom, (b) C １－３It is more preferable that the substituted group is a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group.

[0144] R having one or more substituents ２Ａ ~R ２Ｄ is not particularly limited, and examples thereof include C alkyl groups having a hydroxy group or a glycidyl group, such as a 2-trifluoromethylbenzyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, or a 1-glycidyloxypropan-3-yl group. １－１８ Hydrocarbyl groups: C groups having an ethylenically unsaturated group such as a vinyl group, an allyl group, a vinylbenzyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an acryloylethyl group, an acryloylpropyl group, a methacryloylethyl group, a methacryloylpropyl group, an acryloyloxyethyl group, an acryloyloxypropyl group, a methacryloyloxyethyl group, a methacryloyloxypropyl group, an acryloylaminoethyl group, an acryloylaminopropyl group, a methacryloylaminoethyl group, a methacryloylaminopropyl group, or a styryl group １－１８Hydrocarbyl groups: C groups having an acid-dissociable group such as a 4-methoxymethoxyphenyl group, a methoxymethyl group, an ethoxyethyl group, a methoxyethoxymethyl group, a t-butoxycarbonyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-phenylcyclopentyl group, a 1-tolylcyclopentyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 1-phenylcyclohexyl group, a 1-tolylcyclohexyl group, a 1-(naphthalen-2-yl)cyclohexyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-phenyladamantan-2-yl group, a diethylaminocarbonyl group, or a diisopropylaminocarbonyl group １－１８ Hydrocarbyl groups and the like.

[0145] <Organic Quaternary Ammonium Cation Having One or More Polar Groups Having an Acid-Dissociable Group> From the viewpoint of providing a building block that changes the solubility in a developer or the like by the action of an acid or the like as the organic quaternary ammonium cation represented by the above general formula (VII-1), ２Ａ ~R ２Ｄ It is preferable that at least one of the above contains a polar group having an acid-dissociable group.

[0146] In the above case, in general formula (VII-2), R ２Ａ ~R ２Ｄ each independently represents an optionally substituted C １－１８ is a hydrocarbyl group; ２Ａ ~R ２Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ ~R ２Ｄat least one hydrogen atom of C is preferably substituted by (t) a polar group having an acid-dissociable group, １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ２Ａ ~R ２Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ２Ａ ~R ２Ｄ It is more preferable that at least one hydrogen atom of (t) is replaced by a polar group having an acid-dissociable group.

[0147] R having one or more polar groups having an acid-dissociable group ２Ａ ~R ２Ｄ Examples of the acid-dissociable group include those into which a polar group such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group has been introduced. Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ etc.

[0148] [1-1-2-2-2. Ammonium dication] The ammonium dication is not particularly limited, and any known or commonly used ammonium dication can be used. Examples of the ammonium dication include organic quaternary ammonium dications represented by the following general formula (VII-2):

[0149] In general formula (VII-2), R ３Ａ ~R ３Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ３Ａ ~R３Ｆ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ３ is an optionally substituted C １－１８ represents a hydrocarbylene group, ３ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ３Ａ ~R ３Ｆ and L ３ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ３Ａ ~R ３Ｆ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the nitrogen atom in formula (VII-2).

[0150] The organic quaternary ammonium dication represented by general formula (VII-2) is not particularly limited, and examples thereof include 1,4-diallyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1,4-di(2-(meth)acryloyloxyethyl)-1,4-diazabicyclo[2.2.2]octane-1.4-diium, and 1,4-bis(2-(meth)acrylamidoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium.

[0151] [1-1-2-2-3. Phosphonium Cation] The phosphonium cation is not particularly limited, and any known or commonly used phosphonium cation can be used. Examples of the phosphonium cation include organic quaternary phosphonium cations represented by the following general formula (VII-3):

[0152] In general formula (VII-3), R ４Ａ ~R ４Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ４Ａ ~R ４Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４Ｄ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４Ｄ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the phosphorus atom in formula (VII-3).

[0153] <Organic Quaternary Phosphonium Cation Having One or More Substituents> From the viewpoint of providing a functional building block, the organic quaternary phosphonium cation represented by the general formula (VII-3) is preferably an organic quaternary phosphonium cation having one or more substituents, R ４Ａ ~R ４Ｄ each independently represents an optionally substituted C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ４Ａ ~R ４Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４Ｄat least one hydrogen atom of the optionally substituted C is preferably replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ４Ａ ~R ４Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４Ｄ At least one hydrogen atom of the formula (I) is (a) a halogen atom, (b) C １－３ It is more preferable that the substituted group is a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group.

[0154] R having one or more substituents ４Ａ ~R ４Ｄis not particularly limited, and examples thereof include C alkyl groups having a halogen atom, a hydroxy group, a glycidyl group, etc., such as a 2-trifluoromethylbenzyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, and a 1-glycidyloxypropan-3-yl group. １－１８ Hydrocarbyl groups: C groups having an ethylenically unsaturated double bond such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an acryloylethyl group, an acryloylpropyl group, a methacryloylethyl group, a methacryloylpropyl group, an acryloyloxyethyl group, an acryloyloxypropyl group, a methacryloyloxyethyl group, a methacryloyloxypropyl group, an acryloylaminoethyl group, an acryloylaminopropyl group, a methacryloylaminoethyl group, a methacryloylaminopropyl group, or a styryl group; １－１８ Hydrocarbyl groups: C having an acid-dissociable group such as a methoxymethyl group, an ethoxyethyl group, a methoxyethoxymethyl group, a t-butoxycarbonyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-phenylcyclopentyl group, a 1-tolylcyclopentyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 1-phenylcyclohexyl group, a 1-tolylcyclohexyl group, a 1-(naphthalen-2-yl)cyclohexyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-phenyladamantan-2-yl group, a diethylaminocarbonyl group, or a diisopropylaminocarbonyl group １－１８ Hydrocarbyl groups and the like.

[0155] The organic quaternary phosphonium cation represented by the general formula (VII-3) is not particularly limited, and examples thereof include tributylcyanomethylphosphonium cation, methyltriphenylphosphonium cation, ethyltriphenylphosphonium cation, cyanomethyltriphenylphosphonium cation, formylmethyltriphenylphosphonium cation, methoxymethyltriphenylphosphonium cation, chloromethyltriphenylphosphonium cation, acetonyltriphenylphosphonium cation, tributyl-1,3-dioxan-2-ylmethylphosphonium cation, triphenylpropargylphosphonium cation, allyltriphenyl Examples of such cations include phosphonium cation, cyclopropyltriphenylphosphonium cation, benzyltriphenylphosphonium cation, tetrakis(hydroxymethyl)phosphonium cation, 2-carboxyethyltriphenylphosphonium cation, methoxycarbonylmethyltriphenylphosphonium cation, t-butoxycarbonylmethyltriphenylphosphonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)triphenylphosphonium cation, (4-(methacryloyloxy)phenyl)triphenylphosphonium cation, and triphenyl(4-(nonanoyloxy)phenyl)phosphonium cation.

[0156] <Organic Quaternary Phosphonium Cation Having One or More Polar Groups Having an Acid-Dissociable Group> From the viewpoint of providing a building block that changes the solubility in a developer or the like by the action of an acid or the like as the organic quaternary phosphonium cation represented by the above general formula (VII-3), ４Ａ ~R ４Ｄ It is preferable that at least one of the above contains a polar group having an acid-dissociable group.

[0157] In the above case, in general formula (VII-3), R ４Ａ ~R ４Ｄ each independently represents an optionally substituted C １－１８ is a hydrocarbyl group; ４Ａ ~R ４ＤThe divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４Ｄ at least one hydrogen atom of C is preferably substituted by (t) a polar group having an acid-dissociable group, １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ４Ａ ~R ４Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ４Ａ ~R ４Ｄ It is more preferable that at least one hydrogen atom of (t) is replaced by a polar group having an acid-dissociable group.

[0158] R having one or more polar groups having an acid-dissociable group ４Ａ ~R ４Ｄ Examples of the acid-dissociable group include those into which a polar group such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group has been introduced. Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ etc.

[0159] [1-1-2-2-4. Phosphonium dication] The phosphonium dication is not particularly limited, and any known or commonly used phosphonium dication can be used. Examples of the phosphonium dication include organic quaternary phosphonium dications represented by the following general formula (VII-4):

[0160] In general formula (VII-4), R ５Ａ ~R ５Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ５Ａ ~R ５Ｆ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), L ５ is an optionally substituted C １－１８ represents a hydrocarbylene group, ５ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ５Ａ ~R ５Ｆ and L ５ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C１－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ５Ａ ~R ５Ｆ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the phosphorus atom in formula (VII-4).

[0161] The organic quaternary phosphonium dication represented by general formula (VII-4) is not particularly limited, and examples thereof include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylenebis(triphenylphosphonium) dication, and pentamethylenebis(triphenylphosphonium) dication.

[0162] [1-1-2-2-5. Sulfonium Cation] The sulfonium cation is not particularly limited, and any known or commonly used sulfonium cation can be used. Examples of the sulfonium cation include organic sulfonium cations represented by the following general formula (VII-5):

[0163] In general formula (VII-5), R ６Ａ , R ６Ｂ and R ６Ｃ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ６Ａ , R ６Ｂ and R ６Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ , R ６Ｂ and R ６Ｃ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C１－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ , R ６Ｂ and R ６Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the sulfur atom in formula (VII-5).

[0164] The above R ６Ａ , R ６Ｂ and R ６Ｃ Each of the C groups independently has a substituent. １－１８ is a hydrocarbyl group; ６Ａ , R ６Ｂ and R ６Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ , R ６Ｂ and R ６Ｃ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ６Ａ , R ６Ｂ and R ６Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ , R ６Ｂ and R ６Ｃ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0165] Also R ６Ａ , R ６Ｂ and R ６Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３Examples of the case where R is linked via an alkylene group to form a ring together with the sulfur atom in formula (VII-5) include those having a thian-1-ium skeleton, a thiophen-1-ium skeleton, a 1,4-oxathiane-4-ium skeleton, a 1,4-dithian-1-ium skeleton, a 1H-thiophen-1-ium skeleton, a benzo[b]thiophen-1-ium skeleton, a dibenzothiophenium skeleton, a 9,10-dihydrothioxanthylium skeleton, a 10H-phenoxathiane-10-ium skeleton, and a 5H-thianthren-5-ium skeleton, and the following can be mentioned as examples. Note that * indicates that R is not involved in ring formation. ６Ａ , R ６Ｂ or R ６Ｃ It means the junction with.

[0166]

[0167] Examples of the organic sulfonium cation include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalen-1-yl)hexahydrothiopyrylium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrylium cation, di(naphthalen-1-yl)(phenyl)sulfonium cation, phenylbis(2-(trifluoromethyl)phenyl)sulfonium cation, mesitylbis(2-(trifluoromethyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(phenyl)sulfonium cation, tris(3,5-difluorophenyl)sulfonium cation, (4-(dodecanoyloxy-3,5-dimethylphenyl))diphenylsulfonium cation, diphenyl(3-(trifluoromethoxy)phenyl)sulfonium cation, (4-(1-adamantylcarbonyloxy)phenyl)diphenylsulfonium cation, (4-phenylthiophenyl)diphenylsulfonium cation, 5-phenyl-5H-thianthren-5-ium cation, 5-(2,5-dimethylphenyl)thianthren-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophen-5-ium cation, 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,d]thiophen-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b]thiophen-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, (2-bromoethyl)diphenylsulfonium cation, dimesityl(trifluoromethyl)sulfonium cation, tri-p-tolyl sulfonium cation, and the like.

[0168] <Organic sulfonium cation having one or more polar groups having an acid-dissociable group> From the viewpoint of providing a building block that changes the solubility in a developer or the like by the action of an acid or the like, the organic sulfonium cation represented by the general formula (VII-5) may be selected from the group consisting of the above R ６Ａ ~R ６Ｃ It is preferable that at least one of the above contains a polar group having an acid-dissociable group.

[0169] In the above case, R having one or more polar groups having an acid-dissociable group ６Ａ ~R ６Ｃ With respect to each of the groups, C which may have a substituent independently １－１８ is a hydrocarbyl group; ６Ａ ~R ６Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ ~R ６Ｃ at least one hydrogen atom of C is preferably substituted by (t) a polar group having an acid-dissociable group, １－１８Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ６Ａ ~R ６Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ ~R ６Ｃ It is more preferable that at least one hydrogen atom of (t) is replaced by a polar group having an acid-dissociable group.

[0170] R having one or more polar groups having an acid-dissociable group ６Ａ ~R ６Ｃ Examples of the acid-dissociable group include those into which a polar group such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group has been introduced. Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ etc.

[0171] Examples of the organic sulfonium cation having one or more polar groups having an acid-dissociable group include (3,5-dimethyl-4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl)diphenylsulfonium cation, (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, (3,5-dimethyl-4-(2-((1-methylcyclopentyl)oxy)-2-oxoethoxy)phenyl)diphenylsulfonium cation, (4-(2-(t-butoxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, (3,5-dimethyl-4-(2-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)-2-oxoethoxy)phenyl)diphenylsulfonium cation, (3,5-dimethyl-4-(2-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl)diphenylsulfonium cation, 5-(3,5-dimethyl-4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl (4-(2-((1-ethylcyclohexyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, 1-(4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)naphthalen-1-yl)tetrahydro-1H-thiophen-1-ium cation, (4-(t-butoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, -((diisopropylcarbamoyl)oxy)phenyl)dimethylsulfonium cation, 1-(4-methoxymethoxy)naphthalen-1-yl)tetrahydro-1H-thiophen-1-ium cation, 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)tetrahydro-1H-thiophen-1-ium cation, 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)hexahydrothiopyrylium cation, and the like.

[0172] Examples of the organic sulfonium cation having one or more polar groups having an acid-dissociable group include the following.

[0173]

[0174] The sulfonium dication is not particularly limited, and any known or commonly used sulfonium dication can be used. Examples of the sulfonium dication include organic sulfonium dications represented by the following general formula (VII-6):

[0175] In general formula (VII-6), R ７Ａ , R ７Ｂ , R ７Ｃ and R ７Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ７Ａ , R ７Ｂ , R ７Ｃ and R ７Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); K ７Ａ , K. ７Ｂ and L ７ each independently represents a C １－１８ represents a hydrocarbylene group, ７Ａ , K. ７Ｂ and L ７ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ , R ７Ｂ , R ７Ｃ , R ７Ｄ , K. ７Ａ , K. ７Ｂ and L ７The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ A divalent carbon atom at any position excluding the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ７Ａ , R ７Ｂ and K.７Ａ and / or R ７Ｃ , R ７Ｄ and K. ７Ｂ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the sulfur atom in formula (VII-6).

[0176] The above R ７Ａ ~R ７Ｄ Each of the C groups independently has a substituent. １－１８ is a hydrocarbyl group; ７Ａ ~R ７Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ ~R ７Ｄ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ７Ａ ~R ７Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ ~R ７Ｄ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0177] Above K ７Ａ , K. ７Ｂ and L ７ Each of the C groups independently has a substituent. １－１８ Alkylene group or C １－１８ represents an arylene group; ７Ａ , K. ７Ｂ and L ７ The divalent carbon atom at any position in ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ７Ａ , K. ７Ｂ and L ７ Preferably, the hydrogen atoms contained in the above may be substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group.

[0178] [1-1-2-2-7. Iodonium cation] The iodonium cation is not particularly limited, and any known or commonly used iodonium cation can be used. Examples of the iodonium cation include organic iodonium cations represented by the following general formula (VII-7):

[0179] In general formula (VII-7), R ８Ａ and R ８Ｂ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ８Ａ and R ８Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ and R ８Ｂ The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ and R ８Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (VII-7).

[0180] R ８Ａ and R ８Ｂ As the C １－１８ is a hydrocarbyl group; ８Ａ and R ８Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ and R ８ＢThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ８Ａ and R ８Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ and R ８ＢThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C groups in which at least a portion of the hydrogen atoms may be substituted with any of the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ a hydrocarbyloxycarbonyloxy group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0181] <Organic iodonium cation having one or more polar groups having an acid-dissociable group> From the viewpoint of providing a building block that changes the solubility in a developer or the like by the action of an acid or the like, the organic iodonium cation represented by the general formula (VII-7) is ８Ａ and R ８Ｂ It is preferable that at least one of the above contains a polar group having an acid-dissociable group.

[0182] In the above case, R having one or more polar groups having an acid-dissociable group ８Ａ or R ８Ｂ With respect to each of the groups, C which may have a substituent independently １－１８is a hydrocarbyl group; ８Ａ or R ８Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ or R ８Ｂ at least one hydrogen atom of C is preferably substituted by (t) a polar group having an acid-dissociable group, １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ８Ａ or R ８Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ８Ａ or R ８Ｂ It is more preferable that at least one hydrogen atom of (t) is replaced by a polar group having an acid-dissociable group.

[0183] R having one or more polar groups having an acid-dissociable group ８Ａ or R ８Ｂ Examples of the acid-dissociable group include those into which a polar group such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group has been introduced. Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ etc.

[0184] [1-1-3. Polyacid salts having one or more polar groups having an acid dissociable group or mixtures thereof] <Polyacid salts having one or more polar groups having an acid dissociable group represented by general formula (I) or mixtures thereof> As the polyacid salts having one or more polar groups having an acid dissociable group according to this embodiment or mixtures thereof, polyacid salts having one or more polar groups having an acid dissociable group represented by the following general formula (I) or mixtures thereof can be used. (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [wherein A ｍ＋ are each independently H ＋ , a metal ion, an onium cation or an onium dication; （ａｍ）－ represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having a defect site, the defect site of which has been modified; ｍ＋ and / or C （ａｍ）－ has one or more polar groups having an acid-dissociable group; m is an integer of 1 to 5, and a is a real number greater than 0.

[0185] In the polyacid salt having one or more polar groups having an acid-dissociable group represented by the general formula (I) above, or a mixture thereof, the "metal ion," "onium cation or onium dication," "isopolyacid anion," "heteropolyacid anion," and "heteropolyacid anion having defective sites, in which the defective sites have been modified" may be appropriately selected from those described above.

[0186] The polyacid salt represented by the general formula (I) or the mixture thereof is characterized in that a polar group having an acid-dissociable group is introduced into either an onium cation or an onium dication, or a heteropolyacid anion having a defect site and in which the defect site is modified. Examples of the acid-dissociable group include a tertiary carbon-type acid-dissociable group G Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ etc.

[0187] The mixture of polyacid salts represented by general formula (I) contains a plurality of types of A ｍ＋ In the above case, multiple types of A may be included. ｍ＋ The content ratio can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0188] <Polyacid salt having one or more polar groups having an acid-dissociable group represented by general formula (I') or a mixture thereof> As a polyacid salt having one or more polar groups having an acid-dissociable group according to another embodiment of the present invention, a polyacid salt having one or more polar groups having an acid-dissociable group represented by the following general formula (I') or a mixture thereof can be used. (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C'(a'm'+bn)-) (I') [wherein A' ｍ’＋ are each independently H ＋ , a metal ion, an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B ｎ＋ each independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C'(a'm'+bn)- represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion having a defective site, the defective site of which has been modified; ｍ’＋ , B ｎ＋ and / or C'(a'm'+bn)- has one or more polar groups having an acid-dissociable group; m' is an integer of 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0.

[0189] In the polyacid salt having one or more polar groups having an acid-dissociable group represented by the general formula (I') above or a mixture thereof, the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "sulfonium cation," "sulfonium dication," "iodonium cation," "isopolyacid anion," "heteropolyacid anion," and "heteropolyacid anion having defective sites, in which the defective sites are modified" may be appropriately selected from those described above.

[0190] The polyacid salt having one or more polar groups having an acid-dissociable group represented by the above general formula (I') or a mixture thereof has a sulfonium cation, a sulfonium dication, or an iodonium cation in the cation moiety, and therefore can be given the function of generating an acid by exposure to DUV, XUV, EUV, an electron beam, or the like.

[0191] The polyacid salt represented by the general formula (I') or a mixture thereof is characterized in that a polar group having an acid-dissociable group is introduced into either an ammonium cation, an ammonium dication, a phosphonium cation, a phosphonium dication, a sulfonium cation, a sulfonium dication, or an iodonium cation, or into a heteropolyacid anion having a defect site and in which the defect site is modified. Examples of the acid-dissociable group include a tertiary carbon-type acid-dissociable group G Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ etc.

[0192] The mixture of polyacid salts having one or more polar groups having an acid-dissociable group represented by general formula (I') contains A' ｍ’＋ and B ｎ＋ In this case, the values ​​of a′ and b can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0193] The ratio of a' to b is as follows: polyacid anion, C'(a'm'+bn)-, A' ｍ’＋ , B ｎ＋ Although it depends on the types of compounds, a':b is preferably 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a'm'+bn is an integer of 2-8 and m' and n are 1, it is preferable that a' is a real number of 0-7 and b is a real number of 1-8, and it is more preferable that a' is a real number of 0-4 and b is a real number of 2-8.

[0194] [1-1-4. Content of Component (A)] There are no particular limitations on the content of component (A) in the resist material, and it can be set appropriately depending on the method for applying the resist material to a substrate or the like, the thickness of the applied film, etc. The content of component (A) in the resist material is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.2 to 10 mass%, based on the resist material being 100 mass%.

[0195] [1-2. (B) Polymer] The resist material according to this embodiment contains a (B) polymer in addition to the (A) component. The (B) component is not particularly limited, and any known or commonly used polymer in the field of chemically amplified resist materials can be used. The (B) polymer contains a structural unit B having a phenolic hydroxy group. Ａ , a structural unit B that adjusts solubility in a developer Ｂ and a structural unit B having a fluorine atom. Ｃ It is possible to suitably use a polymer containing one or more structural units selected from the group consisting of: The polymer of component (B) may contain structural units other than those mentioned above.

[0196] [1-2-1. Structural unit B having a phenolic hydroxy group Ａ Structural unit B having a phenolic hydroxy group Ａ (B) A structural unit B having a phenolic hydroxyl group in the polymer is not particularly limited, and any known or commonly used structural unit can be used. ＡBy including the structural unit B, it is possible to improve the etching resistance and the contrast in developer solubility between the exposed and unexposed areas. Ａ Examples of the structural unit include those represented by the following formula (VIII-1):

[0197] In general formula (VIII-1), “R α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group. α is preferably a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a trifluoromethyl group.

[0198] "L Ａ ｂ " represents a single bond, -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, -SO ２ - or optionally substituted C １－８ A hydrocarbylene group in which a divalent carbon atom at any position including the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - represents something that may be replaced by .

[0199] L Ａ ｂ Examples thereof include a single bond, —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —S—, and —SO ２ - or optionally substituted C １－８ An alkylene group in which a divalent carbon atom at any position including the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ Those which may be substituted with - are preferred, and -C(=O)-, -C(=O)O-, -OCO-, or -CONH- is preferred, and a single bond, -C(=O)O-, or -OCO- is more preferred.

[0200] "Ar Ａ ｂ " is an optionally substituted C ６－１８ represents an arylene group. ６－１８ The arylene group means an aromatic hydrocarbon cyclic group or aromatic heterocyclic group having 6 to 18 carbon atoms and having two bonding sites. The aromatic heterocyclic group may form a cyclic conjugated system having 4n+2 π electrons including heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms in addition to carbon atoms. Examples of the aromatic heterocyclic group include those having a pyridine ring, a thiophene ring, a furan ring, a pyrrole ring, a benzofuran ring, a benzothiophene ring, an indole ring, a quinoline ring, an isoquinoline ring, etc. C which may have a substituent ６－１８ The arylene group is not particularly limited, and examples thereof include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,8-naphthylene group, a 4,4′-biphenylene group, an anthracenediyl group, a phenanthrenediyl group, a naphthacenediyl group, a pyrenediyl group, a perylenediyl group, and a chrysenediyl group. ６－１８ The hydrogen atoms on the arylene group may be substituted with a substituent. Examples of the substituent include a halogen atom, a haloalkyl group, a hydroxy group, and a C １－１８ Hydrocarbyl group, C １－１８ Examples thereof include a hydrocarbyloxy group.

[0201] "OH" represents a phenolic hydroxy group, and Ar Ａ ｂ It is also bonded to "n Ａ " is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably 1, 2 or 3, and particularly preferably 1 or 2.

[0202] Structural unit B having a phenolic hydroxy group Ａ is not particularly limited, and examples thereof include the structural units shown below. α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３represents a haloalkyl group.

[0203]

[0204] Structural unit B having a phenolic hydroxy group Ａ can be obtained by polymerizing, for example, 4-vinylphenol, 4-(1-methylvinyl)phenol, 3-vinylphenol, 2-methyl-4-vinylphenol, 2-methoxy-4-vinylphenol, 4-vinylnaphthalen-1-ol, 4-hydroxyphenyl(meth)acrylate, 4-hydroxy-3-methylphenyl(meth)acrylate, 3,4-dihydroxyphenyl(meth)acrylate, 4-hydroxy-3-methoxyphenyl(meth)acrylate, or the like, by a known, commonly used method.

[0205] [1-2-2. Structural unit B for adjusting solubility in developer Ｂ Structural unit B for adjusting solubility in a developer Ｂ The structural unit B is not particularly limited, and any known or commonly used structural unit can be used. Ｂ Examples of the structural unit B having an acid-dissociable group include Ｂ１ Structural unit B having a lactone skeleton, a sultone skeleton, a sulfolane skeleton, a lactam skeleton, or a sultam skeleton Ｂ２ and the like. When the polymer (B) contains a structural unit having an acid-dissociable group, the acid-dissociable group is eliminated by the action of an acid to generate a polar group, thereby making it possible to greatly change the solubility of the exposed and unexposed portions in a developer. Furthermore, when the polymer (B) contains a structural unit having a lactone skeleton or the like, it is possible to finely adjust the solubility in a developer.

[0206] [1-2-2-1. Structural unit B having an acid-dissociable group Ｂ１ Structural unit B having an acid-dissociable group Ｂ１ The structural unit B is not particularly limited, and any known or commonly used structural unit can be used. Ｂ１ Examples of the structural unit B represented by the following formula (VIII-2) or (VIII-3) include: Ｂ１－１ or B Ｂ１－２ Examples include:

[0207] <Structural unit B having an acid-dissociable group represented by general formula (VIII-2) Ｂ１－１ > A structural unit B represented by the following general formula (VIII-2): Ｂ１－１ has a structure in which the hydrogen atom of the carboxy group is substituted with an acid-dissociable group G.

[0208] In general formula (VIII-2), “R α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0209] "L Ｂ ｂ１１ " is a single bond or an optionally substituted C １－８ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0210] L Ｂ ｂ１１ is a single bond or C which may have a substituent. １－８ An alkanediyl group in which any divalent carbon atom, including the terminal carbon atom, is —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0211] "G" represents an acid-dissociable group G, and is not particularly limited as long as it dissociates under the action of an acid, and any known or commonly used group can be used. The acid-dissociable group G includes a tertiary carbon-type acid-dissociable group G Ａ , an allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group G Ｃ etc. can be suitably used.

[0212] Structural unit B having an acid-dissociable group Ｂ１－１ is not particularly limited, and examples thereof include the structural units shown below. α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220] <Structural unit B having an acid-dissociable group represented by general formula (VIII-3) Ｂ１－２ > A structural unit B represented by the following general formula (VIII-3): Ｂ１－２ has a structure in which the hydrogen atom of the phenolic hydroxy group is substituted with an acid-dissociable group G.

[0221] In general formula (VIII-3), “R α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0222] "L Ｂ ｂ１２ " is a single bond or an optionally substituted C １－８ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0223] L Ｂｂ１２ is a single bond or an optionally substituted C １－８ An alkanediyl group in which any divalent carbon atom, including the terminal carbon atom, is —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ Preferably, it may be replaced by - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and more preferably it is a single bond, -C(=O)-O-, or -CONH-.

[0224] "Ar Ｂ ｂ１２ " is an optionally substituted C ６－１８ Represents an arylene group.

[0225] Structural unit B having an acid-dissociable group Ｂ１－２ is not particularly limited, and examples thereof include the structural units shown below. α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0226]

[0227] [1-2-2-2. Structural unit B having a lactone skeleton or the like Ｂ２ Structural unit B having a lactone skeleton or the like Ｂ２ The structural unit B is not particularly limited, and any known or commonly used structural unit can be used. Ｂ２ has a lactone skeleton (containing a CO—O— group in part of the ring: for example, β-propylolactone, γ-butyrolactone, δ-valerolactone, adamantane lactone, etc.), a sultone skeleton (containing SO ２ -O- group), sulfolane skeleton (containing -SO ２ - group), lactam skeleton (containing a -C(OH)=N- group in part of the ring), sultam skeleton (containing a -SO ２ The ring may be a monocyclic ring, a polycyclic ring, or a fused ring.

[0228] Structural unit B Ｂ２Examples of the structural unit include the structural unit represented by the following formula (VIII-4).

[0229] In general formula (VIII-4), “R α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0230] "L Ｂ ｂ２１ " is a single bond or an optionally substituted C １－４ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0231] L Ｂ ｂ２１ is a single bond or an optionally substituted C １－４ An alkanediyl group in which any divalent carbon atom, including the terminal carbon atom, is —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ Preferably, it may be replaced by - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and more preferably it is a single bond, -C(=O)-O-, or -CONH-.

[0232] "L Ｂ ｂ２２ " is a single bond or an optionally substituted C １－８ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0233] L Ｂｂ２２ is a single bond or an optionally substituted C １－８ An alkanediyl group in which any divalent carbon atom, including the terminal carbon atom, is —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－８ An alkanediyl group in which one or more divalent carbon atoms including the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)-O-, or -O-C(=O)- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0234] "Cy Ｂ ｂ２１ " represents a monocyclic, polycyclic or fused ring containing a lactone skeleton, a sultone skeleton, a sulfolane skeleton, a lactam skeleton or a sultam skeleton, which may have a substituent.

[0235] Cy Ｂ ｂ２１ The alkyl group is preferably a monocyclic, polycyclic or fused ring structure containing a lactone skeleton, a sultone skeleton or a sulfolane skeleton, which may have a substituent, and more preferably a monocyclic, polycyclic or fused ring structure containing a lactone skeleton or a sultone skeleton, which may have a substituent.

[0236] Cy Ｂ ｂ２１ As the ring structure, for example, a monocyclic ring, a polycyclic ring, or a fused ring having a lactone skeleton, a sultone skeleton, or a sulfolane skeleton shown below can be used, and * represents L Ｂ ｂ２２ Any hydrogen atom on the ring may be substituted with a substituent.

[0237]

[0238]

[0239] Structural unit B having a lactone skeleton or the like Ｂ２is not particularly limited, and examples thereof include the structural units shown below. α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0240]

[0241] [1-2-3. Structural unit B having a fluorine atom Ｃ ] Structural unit B having a fluorine atom Ｃ The structural unit B is not particularly limited, and any known or commonly used structural unit can be used. When the structural unit B contains a fluorine atom having water repellency and oil repellency, the distribution of the polymer B in the resist material and pattern can be controlled, and the occurrence of bubble defects in the pattern can be suppressed. Ｃ Examples of the structural unit B represented by the following formula (VIII-5) or (VIII-6) include: Ｃ１ or B Ｃ２ etc.

[0242] [1-2-3-1. Structural unit B having a fluorine atom Ｃ１ ] Structural unit B having a fluorine atom Ｃ１ The structural unit B is not particularly limited, and any known or commonly used structural unit can be used. Ｃ１ Examples of the structural unit include those represented by the following formula (VIII-5):

[0243] In general formula (VIII-5), “R α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0244] "L Ｃ ｂ１１ " represents a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S- or -SO ２ - represents. Ｃ ｂ１１is preferably a single bond, —C(═O)—, —C(═O)O—, or —CONH—, and more preferably a single bond or —C(═O)O—.

[0245] "L Ｃ ｂ１２ " is a single bond or an optionally substituted C １－８ In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0246] L Ｃ ｂ１２ is a single bond or an optionally substituted C １－８ An alkanediyl group in which any divalent carbon atom, including the terminal carbon atom, is —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－８ An alkanediyl group in which one or more divalent carbon atoms including the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)-O-, or -O-C(=O)- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0247] "R Ｃ ｂ１１ " is an optionally substituted C １－８ It represents a hydrocarbyl group in which at least one hydrogen atom has been replaced by a fluorine atom.

[0248] R Ｃ ｂ１１ The C １－８A hydrocarbyl group in which one-fourth or more of the hydrogen atoms are substituted with fluorine atoms is preferred, and C optionally having a substituent １－８ An alkyl group in which half or more of the hydrogen atoms have been substituted with fluorine atoms is more preferred.

[0249] Structural unit B having a fluorine atom Ｃ１ is not particularly limited, and examples thereof include the structural units shown below. α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0250]

[0251] [1-2-3-2. Structural unit B having a fluorine atom Ｃ２ ] Structural unit B having a fluorine atom Ｃ２ The structural unit B is not particularly limited, and any known or commonly used structural unit can be used. Ｃ２ Examples of the structural unit include those represented by the following formula (VIII-6):

[0252] In general formula (VIII-6), “R α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0253] "L Ｃ ｂ２１ " represents a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S- or -SO ２ - represents. Ｃ ｂ２１ is preferably a single bond, —C(═O)—, —C(═O)O—, or —CONH—, and more preferably a single bond or —C(═O)O—.

[0254] "L Ｃ ｂ２２ " is a single bond or an optionally substituted C １－８In a hydrocarbylene group, any divalent carbon atom, including the terminal one, may be —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0255] L Ｃ ｂ２２ is a single bond or an optionally substituted C １－８ An alkanediyl group in which any divalent carbon atom, including the terminal carbon atom, is —O—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —CONH—, —NH(C═O)—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－８ An alkanediyl group in which one or more divalent carbon atoms including the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)-O-, or -O-C(=O)- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0256] "R Ｃ ｂ２１ " is a hydrogen atom, a fluorine atom, or a C １－４ It represents an alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom.

[0257] R Ｃ ｂ２１ The alkyl group may be a fluorine atom or a C １－４ An alkyl group in which half or more of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is preferred, and １－４ A perfluoroalkyl group is more preferred, and a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group is even more preferred.

[0258] The above R α and LＣ ｂ２１ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring.

[0259] Also, the above L Ｃ ｂ２２ and R Ｃ ｂ２１ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring.

[0260] Structural unit B having a fluorine atom Ｃ２ is not particularly limited, and examples thereof include the structural units shown below. α " is a hydrogen atom, a halogen atom, C １－３ an alkyl group or C １－３ represents a haloalkyl group.

[0261]

[0262] [1-2-4. Other structural units] The polymer (B) may contain the above structural unit B Ａ ~B Ｃ The other structural units may contain any other structural units. The other structural units are not particularly limited, and examples thereof include a structural unit having (meth)acrylic acid or a (meth)acrylic acid ester derivative, a structural unit having styrene or a styrene derivative, and a structural unit having an alicyclic group including a carbonate skeleton, a carbamate skeleton, or the like.

[0263] [1-2-5. Blending ratio, etc.] The (B) polymer contains a structural unit B having a phenolic hydroxy group. Ａ , a structural unit B that adjusts solubility in a developer Ｂ and a structural unit B having a fluorine atom. ＣThe polymer (B) contains one or more structural units selected from the group consisting of: Ａ , a structural unit B that adjusts solubility in a developer Ｂ and a structural unit B having a fluorine atom. Ｃ The polymer (B) preferably contains two or more structural units selected from the group consisting of: Ａ , a structural unit B that adjusts solubility in a developer Ｂ and a structural unit B having a fluorine atom. Ｃ It is more preferable that it contains

[0264] (B) A structural unit B having a phenolic hydroxy group in the polymer Ａ When the component (B) is contained, the structural unit B Ａ is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 70 parts by mass.

[0265] (B) A structural unit B having a phenolic hydroxy group in the polymer Ａ and a structural unit B that adjusts the solubility in a developer. Ｂ When the structural unit B Ａ and structural unit B Ｂ The molar ratio is preferably 2-8:2-8, more preferably 3-7:3-7, and even more preferably 4-6:4-6.

[0266] (B) A structural unit B in the polymer that adjusts the solubility in the developer Ｂ and a structural unit B having a fluorine atom. Ｃ When the structural unit B Ｂ and structural unit B Ｃ The molar ratio is preferably 1-9:1-9, more preferably 1-8:1-8, and even more preferably 1-7:1-7.

[0267] (B) A structural unit B having a phenolic hydroxy group in the polymer Ａand a structural unit B having a fluorine atom. Ｃ When the structural unit B Ａ and structural unit B Ｃ The molar ratio is preferably 1-10:1-5, more preferably 3-10:1-4, and even more preferably 5-10:1-3.

[0268] The synthesis method of the (B) polymer is not particularly limited, and any known or commonly used synthesis method can be used. Examples of the synthesis method of the (B) polymer include a synthesis method in which monomers that derive each structural unit are dissolved in a polymerization solvent, and a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate is added thereto to polymerize the monomers.

[0269] The weight average molecular weight (Mw) of the (B) polymer (based on polystyrene standards measured by gel permeation chromatography (GPC)) is not particularly limited, and the lower limit is preferably 1,000, more preferably 2,000, and even more preferably 3,000. The upper limit of Mw is preferably 50,000, more preferably 40,000, and even more preferably 30,000. When the Mw of the (B) component is equal to or greater than the lower limit, the EL margin and sensitivity can be improved, and when the Mw is equal to or less than the upper limit, the solubility of the (B) component can be maintained.

[0270] The polydispersity (Mw / Mn) of the (B) polymer is not particularly limited, and is, for example, preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. Here, Mn refers to the number average molecular weight. By ensuring that the polydispersity of the (B) component falls within the above range and narrowing the molecular weight distribution, the reactivity of the resist composition can be made uniform.

[0271] The content of the polymer (B) in the total solid components of the resist composition is preferably from 0.1 to 20 mass%, more preferably from 0.2 to 15 mass%, and even more preferably from 0.5 to 10 mass%. Here, "total solid components" refers to all components of the resist composition other than the organic solvent.

[0272] The content of the (B) polymer in the resist material according to this embodiment is not particularly limited and can be selected appropriately depending on the content and type of the (A) component, etc. From the viewpoint of achieving both etching resistance and an EL margin of the resist material, the content of the (B) polymer in the resist material is preferably 0.01 to 200 parts by mass, more preferably 0.01 to 100 parts by mass, even more preferably 0.05 to 75 parts by mass, even more preferably 0.05 to 50 parts by mass, and particularly preferably 0.1 to 25% by mass, per 100 parts by mass of the (A) component.

[0273] [1-3. Organic Solvent] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and any known or commonly used organic solvent can be used. The organic solvent is preferably an organic solvent that can uniformly dissolve or disperse (A) a polyacid salt or a mixture thereof having one or more polar groups each having an acid-dissociable group, and (B) a polymer when they are prepared.

[0274] Examples of the organic solvent include polar solvents such as alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, nitrile solvents, and aprotic polar solvents, and nonpolar solvents such as hydrocarbon solvents. These organic solvents may be used alone or in combination of two or more.

[0275] 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-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Amide-based solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ester-based solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); nitrile-based solvents such as acetonitrile, propionitrile, and benzonitrile; aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea; and nonpolar solvents such as hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. The above organic solvents may be used alone or in combination of two or more.

[0276] 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.

[0277] The amount of organic solvent in the resist material is not particularly limited and can be set appropriately depending on the method for applying the resist material to a substrate, the thickness of the applied film, etc. The amount of organic solvent in the resist material is preferably such that the solids concentration of the resist material is 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.2 to 10 mass%.

[0278] [1-4. Others] The resist material according to this embodiment may further contain, as desired, miscible additives, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, etc. 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. It is also preferable that the resist material according to this embodiment does not contain hydrogen peroxide.

[0279] [2. Pattern Forming Method] The pattern forming method according to this embodiment includes the steps of applying a resist material to a substrate, exposing the resist film formed by the application step, and developing the exposed resist film.

[0280] [2-1. Coating Step] The pattern forming method according to this embodiment includes a step of coating a substrate with a resist material.

[0281] <Substrate> The substrate used in this embodiment is not particularly limited, and known and commonly used substrates can be used. For example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed may be used. The material of the substrate is not particularly limited, and examples thereof include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and inorganic substrates such as glass, titanium oxide, and silicon dioxide. The size, shape, and the like of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or may be a flake-shaped substrate.

[0282] The surface of the substrate may be subjected to a surface treatment as necessary. In the case of a substrate having hydroxyl groups on its surface layer, the surface of the substrate is treated with a silane coupling agent capable of reacting with the hydroxyl groups, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane coupling agent include hexamethyldisilazane (HMDS).

[0283] <Coating Method> The method for applying the resist material onto the substrate is not particularly limited, and any known or commonly used method can be used. Examples of dry coating methods include CVD (chemical vapor deposition) methods such as thermal CVD, plasma CVD, and photo-CVD; and PVD (physical vapor deposition) methods such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Examples of wet coating methods include spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0284] 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.

[0285] The method for drying the resist film formed by applying a resist material to a substrate is not particularly limited, and can be performed using, for example, a heating device such as a hot plate (post-applied bake (PAB)), a pressure reducing device, or the like. The baking conditions are not particularly limited, and can be set appropriately depending on the type of resist film, application, etc. The baking temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0286] 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.

[0287] [2-2. Exposure Step] The pattern formation method according to this embodiment includes a step of exposing the resist film formed in the above-described coating step.

[0288] As an exposure apparatus in the exposure step of the resist film, for example, an ArF exposure apparatus, an electron beam lithography apparatus, an EUV exposure apparatus, etc. Furthermore, in the exposure step, exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by lithography using direct irradiation with an electron beam without using a mask pattern.

[0289] The wavelength used for exposure is not particularly limited, and examples thereof include ArF excimer laser (wavelength 193 nm), KrF excimer laser (248 nm), F ２Radiation such as excimer laser (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, or soft X-ray may also be used.

[0290] 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 or less, and 0.1 to 200 mJ / cm ２ is preferably 3 to 100 mJ / cm ２ More preferably, it is 5 to 50 mJ / cm ２ In the case of an electron beam, it is more preferable that the concentration is 3 μC / cm at 50 kV. ２ ~2mC / cm ２ It is preferable to expose with a dose of 10 μC / cm ２ ~1.5mC / cm ２ It is more preferable to expose at a dose of 1000 ppm.

[0291] After the resist film is exposed to light, it may or may not be baked (post-exposure bake (PEB)). The baking conditions are not particularly limited and can be set appropriately depending on the type of resist film, its intended use, etc. The baking temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C, using a heating device such as a hot plate. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0292] [2-3. Development Step] The pattern formation method according to this embodiment includes a step of developing the exposed resist film. In the development step, a pattern can be formed by developing the exposed resist film with a developer. A negative pattern formation process is one in which the exposed region remains as a pattern after development, while a positive pattern formation process is one in which the exposed region is removed after development. Whether a positive or negative pattern is formed can be appropriately selected depending on the resist material or the developer. After the development, the resist film may be washed with a rinse solution and then dried, and in some cases, a baking treatment may be further performed.

[0293] The developer used in this embodiment may be an alkaline developer for an alkaline development process, or a developer containing an organic solvent (organic developer) for an organic solvent development process.

[0294] <Alkaline Development Process> With conventional metal oxide resist materials, it has been difficult to form a positive-tone pattern with good resolution using an alkaline development process. In contrast, the resist material of this embodiment uses (A) a polyacid salt or a mixture thereof having one or more polar groups with an acid-dissociable group, in which the cation moiety has an onium cation or an onium dication. Therefore, when the resist material of this embodiment is exposed to DUV, XUV, EUV, an electron beam, or the like, an acid is generated, and the acid-dissociable group is dissociated by the action of the acid, thereby changing the solubility in a developer, particularly an alkaline developer, and enabling the formation of a pattern with good resolution.

[0295] The alkaline developer used in the alkaline development process is not particularly limited, and any known or commonly used one can be used. Examples of the alkaline developer include aqueous solutions containing one or more of quaternary ammonium salts such as tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide, inorganic alkalis such as sodium hydroxide and potassium hydroxide, and alkanolamines such as dimethylethanolamine and triethanolamine.

[0296] Furthermore, pure water can be used as a rinse liquid in the alkaline development process.

[0297] <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.

[0298] Specific examples of organic solvents include: ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; ester-based solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), 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); and nitrile-based solvents such as acetonitrile, propionitrile, and benzonitrile. Examples of the solvent include amide-based solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; and hydrocarbon-based solvents such as n-pentane, n-hexane, toluene, and xylene. These may be used alone or in combination of two or more.

[0299] Among these, the organic solvent used in the developer is preferably a polar solvent, and preferably contains an amide solvent, an alcohol solvent, or an ester solvent, and more preferably contains an amide solvent or an ester solvent and an alcohol solvent. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester solvent is preferably at least one selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate. The alcohol solvent is preferably at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol.

[0300] 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.

[0301] 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).

[0302] After development with the developer, a step of washing with a rinse liquid may be included. The rinse liquid is not particularly limited, and any known or commonly used liquid may be used. As the rinse liquid, water or an organic solvent contained in the developer that does not easily dissolve the resist pattern may be appropriately selected and used.

[0303] 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.

[0304] The alcohol-based solvent used in the rinse solution is preferably a monohydric alcohol having 2 to 8 carbon atoms, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples of the monohydric alcohol include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. These organic solvents may be used alone or in combination of two or more.

[0305] The method for cleaning the resist pattern with the rinse liquid is not particularly limited, and any known or commonly used method can be used. Examples of the cleaning method using the rinse liquid include a method of immersing the resist pattern in the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid onto the surface of the resist pattern (spray method), and a method of discharging the rinse liquid at a constant speed from a discharge nozzle toward the surface of the resist pattern that is rotating at a constant speed (dynamic dispense method).

[0306] 3. Patterned Structure The patterned structure according to this embodiment can be obtained by forming a pattern of the resist material on a substrate using the pattern formation method described above.

[0307] The average thickness of part or all of the patterned structure according to this embodiment is not particularly limited and can be set appropriately depending on the intended use, etc. The patterned structure preferably has portions with an average thickness of 1 to 100 nm, more preferably 5 to 75 nm, and even more preferably 10 to 60 nm.

[0308] The pitch of part or all of the patterned structure according to this embodiment is not particularly limited and can be set appropriately depending on the purpose of use, etc. In the patterned structure, it is preferable to have a part with a pitch of 100 nm or less, more preferably a part with a pitch of 50 nm or less, and even more preferably a part with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the above-mentioned pattern formation method, it is possible to create parts with pitches of 50 nm, 20 nm, or 15 nm in part or all of the patterned structure.

[0309] [4. Resist Material for Electron Beam or EUV] The resist material according to this embodiment contains (A) a polyacid salt or a mixture thereof having one or more polar groups each having an acid-dissociable group, and (B) a polymer. Therefore, the acid-dissociable groups in the resist material according to this embodiment dissociate under the action of acid, changing the solubility in a developer and enabling pattern formation with good resolution. The inclusion of component (A) in the resist material improves etching resistance. Furthermore, the inclusion of the polymer (B) in the resist material improves the EL margin.

[0310] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0311] [1. Synthesis of Polyacid Salts Having a Polar Group Having an Acid-Dissociable Group] Polyacid salts (A-1) and (A-7) were each synthesized by the following method.

[0312] <Production Example: Potassium undecatungstosilicate (α-K ８ [SiW １１ O ３９ ])>Tungstosilicic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ４ [SiW １２ O ４０ ]・xH ２ To 63 g of 1M acetic acid (C10), 380 g was added, and the reaction solution was heated to 45 ° C. Potassium bicarbonate (52 g) was added so that the pH was 6.0. The reaction solution was then cooled to room temperature and filtered off by suction, yielding 56 g of a crude product. 216 g of purified water was added to the resulting crude product, which was then redissolved by heating to 73 ° C. The solution was cooled at 4 ° C. for 16 hours to recrystallize, which was then filtered off by suction and dried in vacuo to yield 34 g of the target compound. ２９ Si-NMR (119.22MHz, D ２ O): δ (ppm) = -84.6 (s, 1Si). １８３ W-NMR (20.84MHz, D ２ O): δ (ppm) = -101.85 (s, 2W), -116.26 (s, 2W), -119.29 (s, 1W), -125.62 (s, 2W), -140.85 (s, 2W), -174.53 (s, 2W).

[0313] <Synthesis Example 1: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-di(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-1))> To a mixed solvent of 402 g of acetonitrile and 184 g of pure water, 3.8 g (10.9 mmol) of (3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyl)trimethoxysilane was added, and the mono-deficient Keggin-type potassium undecatungstosilicate (α-K８ [SiW １１ O ３９ ]) was added. The pH was adjusted to 1.8 using 1 M hydrochloric acid. After stirring for 2 hours, the unreacted powder was filtered off by suction, and the filtrate was concentrated to approximately 200 g using a rotary evaporator. A solution of 9.9 g (18.2 mmol) of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide in 40 g of methanol was added to this concentrated solution to precipitate a powder. The precipitated powder was separated by suction filtration and washed three times each with 180 mL of pure water, 180 mL of methanol, and 180 mL of methyl t-butyl ether. The obtained powder was then dispersed and washed with 160 g of methanol for 3 hours, filtered off by suction filtration again, and washed three times with 160 g of methanol. Further thorough vacuum drying yielded 15.4 g of the target compound, polyacid salt (A-1), as a white powder. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 0.77-0.81 (t, 12H), 1.48-1.75 (m, 46H), 1.90-1.93 (m, 16H), 1.99 -2.08 (m, 4H), 2.29 (m, 24H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 4.55 (s, 8H), 7.59 (s, 8H), 7.76-7.82 (m, 40H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 461.2 ([C ２９ H ３３ O ３ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0314] <Synthesis Example 2: Tetrakis(triphenylsulfonium)silicotungstate (polyacid salt (A-2))> 27.95 g of triphenylsulfonium chloride was dissolved in 50 g of cyclohexanone, and silicotungstic acid (H ４ [SiW １２ O ４０ ]・26H ２ 41.97 g of methyl 2-hydroxybenzoate (A-2) was added, and the reaction solution was stirred at room temperature for 2 hours. The reaction solution was filtered, and the obtained powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized at room temperature using dichloromethane and acetonitrile to obtain the target compound, polyacid salt (A-2). １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.74-7.90 (m, 60H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis S:W (molar ratio of S to W) = 4:12

[0315] <Synthesis Example 3: Tetrakis(triphenylsulfonium)(1,3-bis(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-3))> The target compound, polyacid salt (A-3), was obtained in the same manner as above, except that triphenylsulfonium chloride was used instead of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide as the raw material compound in Synthesis Example 1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.49 (s, 6H), 1.54-1.71 (m, 16H) , 1.99-2.08 (m, 4H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 7.78-7.87 (m, 60H). ２９Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0316] <Synthesis Example 4: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)silicate (Polyacid Salt (A-4))> 35.47 g of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium chloride was dissolved in 50 g of cyclohexanone, and tungstosilicic acid (H ４ [SiW １２ O ４０ ]・26H ２ 41.06 g of methyl 2-hydroxybenzoate (A-4) was added, and the reaction solution was stirred at room temperature for 2 hours. The reaction solution was filtered, and the obtained powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized at room temperature using dichloromethane and acetonitrile to obtain polyacid salt (A-4). １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.76-7.82 (m, 40H), 7.59 (s, 8H), 4.55 (s, 8 H), 2.29 (m, 24H), 1.90-1.93 (m, 16H), 1.48-1.75 (m, 24H), 0.77-0.81 (t, 12H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis S:W (molar ratio of S to W) = 4:12

[0317] <Synthesis Example 5: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-di(2-((1-methylcyclopentyl)oxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-5))> The target compound, polyacid salt (A-5), was obtained in the same manner as above, except that in Synthesis Example 1, 2-((1-methylcyclopentyl)oxycarbonyl)ethyltrimethoxysilane was used instead of (3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyl)trimethoxysilane as the raw material compound. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 16H), 1.48-1.93 (m, 62H), 2. 29 (m, 24H), 2.37-2.42 (m, 4H), 4.55 (s, 8H), 7.59 (s, 8H), 7.76-7.82 (m, 40H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 461.2 ([C ２９ H ３３ O ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0318] <Synthesis Example 6: Tetrakis((3,5-dimethyl-4-((2-methyladamantan-2-yl)oxycarbonylmethyloxy)phenyl)diphenylsulfonium)(1,3-di(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-6))> The target compound, polyacid salt (A-6), was obtained in the same manner as above, except that (3,5-dimethyl-4-((2-methyladamantan-2-yl)oxycarbonylmethyloxy)phenyl)diphenylsulfonium chloride was used instead of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide as the raw material compound in Synthesis Example 1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.49-2.08 (m, 94H), 2.31 (s, 24H), 2 .49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 4.62 (s, 8H), 7.61 (s, 8H), 7.75-7.86 (m, 40H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 513.2 ([C ３３ H ３７ O ３ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0319] <Synthesis Example 7: Tetrakis((4-(t-butyloxycarbonylmethyloxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-di(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-7))> The target compound, polyacid salt (A-7), was obtained in the same manner as above, except that (4-(t-butyloxycarbonylmethyloxy)-3,5-dimethylphenyl)diphenylsulfonium chloride was used instead of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide as the raw material compound in Synthesis Example 1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.42 (s, 36H), 1.49 (s, 6H), 1.54-1.71 (m, 16H), 1.99-2.08 ( m, 4H), 2.15 (s, 24H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 4.99 (s, 8H), 7.11 (s, 8H), 7.33-7.36 (m, 40H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 421.2 ([C ２６ H ２９ O ３ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0320] [2. Preparation of Test Resist Materials] Test resist materials (R-1) to (R-25) were prepared by blending the polyacid salts (A-1) to (A-7) synthesized above with polymers (B-1) to (B-7) shown in Tables 1 and 2 below, and an organic solvent in the amounts (unit: parts by mass) shown in Tables 1 and 2 below. Details of polymers (B-1) to (B-7) shown in Tables 1 and 2 are as follows.

[0321] Polymer (B-1): A polymer obtained by copolymerizing 4-vinylphenol, which provides a structural unit having a phenolic hydroxy group, and 1-phenylcyclopentyl methacrylate, which provides a structural unit that adjusts the solubility in a developer, represented by the following formula (B-1) (molar ratio: 40:60; weight average molecular weight (Mw) calculated in terms of standard polystyrene obtained by GPC measurement: 5,000).

[0322] Polymer (B-2): A polymer obtained by polymerizing 4-vinylphenol to give a structural unit having a phenolic hydroxy group, represented by the following formula (B-2) (weight average molecular weight (Mw) calculated as standard polystyrene by GPC measurement: 8,000).

[0323] Polymer (B-3): A polymer represented by the following formula (B-3), obtained by copolymerizing 1-ethylcyclooctyl methacrylate, which provides a structural unit that adjusts the solubility in a developer, 2-oxo-2-(2,2,2-trifluoroethoxy)ethyl methacrylate, which provides a structural unit having a fluorine atom, and methacrylic acid, which provides other structural units (molar ratio of 20:70:10; weight average molecular weight (Mw) of 27,000 in terms of standard polystyrene obtained by GPC measurement).

[0324] Polymer (B-4): A polymer represented by the following formula (B-4), obtained by copolymerizing 5-oxotetrahydrofuran-3-yl methacrylate, which provides a structural unit that adjusts the solubility in a developer, and 5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl methacrylate, which provides a structural unit having a fluorine atom (molar ratio of 20:80; weight average molecular weight (Mw) calculated in terms of standard polystyrene obtained by GPC measurement is 8,000).

[0325] Polymer (B-5): A polymer represented by the following formula (B-5), obtained by copolymerizing 4-vinylphenol, which provides a structural unit having a phenolic hydroxy group, 1-ethylcyclooctyl methacrylate, which provides a structural unit that adjusts solubility in a developer, and 2-oxo-2-(2,2,2-trifluoroethoxy)ethyl methacrylate, which provides a structural unit having a fluorine atom (molar ratio of 10:20:70; weight average molecular weight (Mw) calculated in terms of standard polystyrene obtained by GPC measurement is 23,000).

[0326] Polymer (B-6): A polymer represented by the following formula (B-6), obtained by copolymerizing 4-vinylphenol, which provides a structural unit having a phenolic hydroxy group, and 2-oxo-2-(2,2,2-trifluoroethoxy)ethyl methacrylate, which provides a structural unit having a fluorine atom (molar ratio: 20:80; weight average molecular weight (Mw) calculated as standard polystyrene by GPC measurement: 20,000).

[0327] Polymer (B-7): A polymer represented by the following formula (B-7), obtained by copolymerizing 1-ethylcyclooctyl methacrylate, which provides a structural unit that adjusts the solubility in a developer, and 5,5,5-trifluoro-4-hydroxy-4-(trifluoromethyl)pentan-2-yl methacrylate, which provides a structural unit having a fluorine atom (molar ratio of 20:80; weight average molecular weight (Mw) calculated in terms of standard polystyrene obtained by GPC measurement is 20,000).

[0328]

[0329]

[0330] [3. Evaluation of Sensitivity and EL Margin] <Formation of LS Pattern> Resist materials R-1 to R-5 were applied using a spinner to an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then post-applied bake (PAB) treatment was performed on a hot plate at a temperature of 120°C for 60 seconds, followed by drying to form a resist film with a thickness of 50 nm. The thickness of the formed film was measured using a film thickness measurement device ("M-2000D" manufactured by J.A. Woollam Co.).

[0331] The resist film was subjected to exposure (writing) using an electron beam lithography system F7000S-VD2 (manufactured by Advantest Corporation) at an acceleration voltage of 50 kV, with a target size of a 1:1 line and space pattern (hereinafter also referred to as "LS pattern") with a line width of 50 nm. Thereafter, a post-exposure bake (PEB) treatment was performed at 90°C for 60 seconds. Next, development was performed for 60 seconds at 23°C using a developer (NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.)), and then rinsing was performed with pure water for 60 seconds. As a result, a 1:1 LS pattern with a line width of 50 nm was formed, and LS patterns (LS-1) to (LS-18) corresponding to the resist materials (R-1) to (R-18) were obtained. Note that the LS patterns (LS-1) to (LS-18) are all positive-tone patterns.

[0332] <Sensitivity Evaluation> The optimum exposure dose Eop (μC / cm) for forming a 1:1 LS pattern with a line width of 50 nm by the above LS pattern formation method was ２ The results are shown in Table 2.

[0333] <Evaluation of EL Margin> In forming the above LS pattern, the EL margin (unit: %) was calculated from the exposure dose required to form LS patterns of 45 nm and 55 nm, which are ±10% of the space width of 50 nm, according to the following formula. Note that a larger EL margin value indicates a smaller change in pattern dimension due to fluctuations in exposure dose. Eop: Optimum exposure dose to give an LS pattern with a line width of 50 nm and a pitch of 100 nm E1: Optimum exposure dose to give an LS pattern with a line width of 45 nm and a pitch of 100 nm E2: Optimum exposure dose to give an LS pattern with a line width of 55 nm and a pitch of 100 nm EL margin (%) = (|E1 - E2| / Eop) x 100

[0334] The EL margin was evaluated according to the following criteria. The results are shown in Table 3. A: EL margin value is 15% or more. B: EL margin value is 10% or more and less than 15%. C: EL margin value is 5% or more and less than 10%. D: EL margin value is less than 5%.

[0335]

[0336] The results in Table 3 show that the LS patterns (LS-1) to (LS-17) formed using resist materials (R-1) to (R-17) containing either the polymers (B-1) to (B-7) in addition to the polyacid salts (A-1) or (A-3) to (A-7) have large EL margin values ​​and are all evaluated as good. A large EL margin value is preferable because it reduces the amount of change in pattern dimension due to fluctuations in exposure dose, providing process latitude.

[0337] [5. Evaluation of Etching Resistance] Resist materials (R-19) to (R-25) were applied using a spinner onto an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then post-applied bake (PAB) treatment was performed on a hot plate at a temperature of 120°C for 60 seconds, followed by drying to form resist films (M-19) to M-25) with a thickness of 40 nm. The resist films were then dry-etched (O ) using plasma obtained from oxygen gas under the following conditions. ２ Plasma etching was performed.

[0338] <O２ Plasma Etching Conditions> For each resist film with a thickness of 40 nm, a dry etching apparatus TCA-3822 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. ４ A dry etching process was performed for 60 seconds using a gas. The remaining film amount was determined from the film thickness of the resist film before and after this dry etching process. The remaining film amount of the resist films (M-19) to (M-24) formed using the resist materials (R-19) to (R-24) was expressed as a relative value when the remaining film amount of the resist film (M-25) formed using the resist material (R-25) was set to 1.00, and this value is shown in Table 4 as "etching resistance." The larger this relative value, the larger the remaining film amount, which means that film loss is suppressed and etching resistance is high.

[0339]

[0340] The results in Table 4 show that the resist films (M-19) to (M-24) formed using resist materials (R-19) to (R-24) containing the polyacid salt (A-1) all have improved etching resistance compared to the resist film (M-25) formed using the resist material (R-25) not containing the polyacid salt. Here, the resist materials (R-19) to (R-24) contain an increasing amount of polymer (B-1) in the resist material in this order, and the relative content of the polyacid salt (A-1) in the resist material decreases. Furthermore, Table 4 shows that as the relative content of the polyacid salt (A-1) in the resist material decreases, the etching resistance decreases.

Claims

1. A resist material containing (A) a polyacid salt having one or more polar groups having an acid-dissociable group or a mixture thereof, and (B) a polymer.

2. The resist material according to claim 1, wherein the anion part of the polyacid salt having one or more polar groups having an acid-dissociable group in (A) or a mixture thereof is an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion in which the defect site in a heteropolyacid anion having a defect site is modified.

3. The resist material according to claim 2, wherein the isopolyacid anion is an isopolymolybdic acid anion, an isopolytungstic acid anion, an isopolymolybdovanadic acid anion, or an isopolytantalic acid anion.

4. The resist material according to claim 2, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb or Ta, and the heteroatom is P, Si, B, S or Ge.

5. The resist material according to claim 2, wherein the heteropolyacid anion having a defect site is a defective Keggin-type heteropolyacid anion or a defective Dawson-type heteropolyacid anion.

6. The resist material according to claim 2, wherein the modification is made by a group having one or more heteroatoms P, Si, Ge or Sn to which one or more organic groups are bonded being bonded to the heteropolyacid anion having a defect site through part or all of the heteroatoms.

7. The resist material according to claim 6, wherein the organic group has one or more polar groups having an acid-dissociable group.

8. The resist material according to claim 7, wherein the acid-dissociable group is a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group.

9. The cationic part of the polyacid salt having one or more polar groups having an acid-dissociable group (A) or a mixture thereof is H ＋ , a resist material according to claim 1, having a metal ion, an onium cation or an onium dication.

10. The resist material according to claim 9, wherein the onium cation or onium dication is an ammonium cation, an ammonium dication, a phosphonium cation, a phosphonium dication, a sulfonium cation, a sulfonium dication, or an iodonium cation.

11. The resist material according to claim 9, wherein the onium cation or onium dication has one or more polar groups having an acid-dissociable group.

12. The resist material according to claim 11, wherein the acid-dissociable group is a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group.

13. The resist material according to claim 1, wherein the polyacid salt or a mixture thereof having at least one polar group having an acid-dissociable group (A) is a polyacid salt or a mixture thereof having at least one polar group having an acid-dissociable group represented by the general formula (I). (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In formula (I), A ｍ＋ each independently represents H ＋ , a metal ion, an onium cation, or an onium dication; C （ａｍ）－ represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion in which the defect site in the heteropolyacid anion having a defect site is modified; the above A ｍ＋ and / or C （ａｍ）－ has at least one polar group having an acid-dissociable group; m is an integer of 1 to 5, and a is a real number greater than 0.] 14. The resist material according to claim 1, wherein the polyacid salt having one or more polar groups having an acid-dissociable group (A) or a mixture thereof is a polyacid salt having one or more polar groups having an acid-dissociable group represented by the general formula (I') or a mixture thereof. (A' ｍ’＋ ). ａ’ (B ｎ＋ ). ｂ (C' （ａ’ｍ’＋ｂｎ）－ ) (I') [In the formula (I'), A' ｍ’＋ each independently represents H ＋ , a metal ion, an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B ｎ＋ each independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C' （ａ’ｍ’＋ｂｎ）－ represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion in which the defect site in the heteropolyacid anion having a defect site is modified; the A' ｍ’＋ , B ｎ＋ and / or C' （ａ’ｍ’＋ｂｎ）－ has one or more polar groups having an acid-dissociable group; m' is an integer of 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0.] 15. The resist material according to claim 1, wherein the (B) polymer contains at least one structural unit selected from the group consisting of a structural unit having a phenolic hydroxy group, a structural unit for adjusting solubility in a developer, and a structural unit having a fluorine atom.

16. The resist material according to claim 1, wherein the content ratio of the (B) polymer is 0.1 to 200 parts by mass when the blending amount of the polyacid salt having at least one polar group having an acid dissociable group (A) or a mixture thereof is 100 parts by mass.

17. The resist material according to claim 15, wherein the structural unit for adjusting the solubility in the developer is a structural unit represented by general formula (VIII-2) or (VIII-3). [In formula (VIII-2), R α represents a hydrogen atom, a halogen atom, a C １－３ alkyl group, or a C １－３ haloalkyl group; L Ｂ ｂ１１ represents a single bond or an optionally substituted C １－８ hydrocarbylene group, wherein any divalent carbon atom including the terminal may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S- or -SO ２ -(provided that adjacent divalent carbon atoms are not simultaneously replaced).); G represents a tertiary carbon type acid dissociable group, an allyl type or benzyl type acid dissociable group, or an acetal type acid dissociable group. ] [In formula (VIII-3), R α represents a hydrogen atom, a halogen atom, a C １－３ alkyl group, or a C １－３ haloalkyl group; L Ｂ ｂ１２ represents a single bond or an optionally substituted C １－８ hydrocarbylene group, wherein any divalent carbon atom including the terminal may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S- or -SO ２ -(provided that adjacent divalent carbon atoms are not simultaneously replaced).); Ar Ｂ ｂ１２ represents an optionally substituted C ６－１８ arylene group; G represents a tertiary carbon type acid dissociable group, an allyl type or benzyl type acid dissociable group, or an acetal type acid dissociable group. ] 18. The resist material according to claim 15, wherein the structural unit having a fluorine atom is a structural unit represented by the general formula (VIII-5) or (VIII-6). [In formula (VIII-5), R α represents a hydrogen atom, a halogen atom, a C １－３ alkyl group, or a C １－３ haloalkyl group; L Ｃ ｂ１１ represents a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S- or -SO ２ -; L Ｃ ｂ１２ represents a single bond or a C １－８ hydrocarbylene group which may have a substituent, and any divalent carbon atom including the terminal may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); R Ｃ ｂ１１ represents a C １－８ hydrocarbyl group which may have a substituent, and at least one or more hydrogen atoms are replaced by fluorine atoms. ] [In formula (VIII-6), R α represents a hydrogen atom, a halogen atom, a C １－３ alkyl group, or a C １－３ haloalkyl group; L Ｃ ｂ２１ represents a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NH(C=O)-, -S- or -SO ２ -; R Ｃ ｂ２１ represents a hydrogen atom, a fluorine atom, or a C １－４ alkyl group which may have a substituent, and at least one or more hydrogen atoms are replaced by fluorine atoms; the said R α and L Ｃ ｂ２１ are directly bonded 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 and may be linked via an alkylene group to form a ring; said L Ｃ ｂ２１ and R Ｃ ｂ２１ are directly bonded 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 and may be linked via an alkylene group to form a ring. ] 19. A pattern forming method comprising: a step of forming a resist film using the resist material according to any one of claims 1 to 18; a step of exposing the resist film; and a step of developing the exposed resist film using a developer.

20. The step of exposing the resist film includes exposing the resist film with an electron beam having a dose of 2 mC / cm ２ or less or extreme ultraviolet light having a dose of 200 mJ / cm ２ or less. The pattern forming method according to claim 19

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