Resist material and pattern formation method

Abstract

The present invention provides a resist material comprising (A) a heteropolyacid salt having a modified defect site or a mixture thereof, and (B) an acid diffusion control agent, wherein the acid diffusion control agent (B) is (B1) a photodegradable base having an iodine atom.

Description

Resist material and pattern formation method

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

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

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

[0004] Compared to conventional organic photoresists, metal resists utilize metal atoms with high electron emission cross-sections, making them more adept at absorbing active light such as EUV rays, thus enabling higher sensitivity. Furthermore, because metal resists contain metal atoms, they have high etching resistance, allowing them to be used in thin films and reducing the risk of pattern collapse.

[0005] It has been reported that in conventional chemically amplified resists, high sensitivity and low CDU and LWR can be achieved by using a base polymer containing iodine atoms that readily absorb active light such as EUV, an acid generator, an acid diffusion control agent, etc. (for example, Patent Document 1). More specifically, Patent Document 1 discloses that the strong absorption of active light by iodine atoms contained in the base polymer generates secondary electrons from the base polymer during exposure, and this energy is transferred to the acid generator, increasing the efficiency of acid generation. It also discloses that an iodized benzene ring-containing quencher absorbs active light, generates secondary electrons, and promotes the decomposition of the acid generator.

[0006] On the other hand, while introducing iodine atoms into base polymers or acid diffusion control agents can increase the absorption coefficient for active light such as EUV, it has also been observed that this tends to decrease the acid generation efficiency of the acid generator itself. Furthermore, the general effects of coexisting an acid diffusion control agent containing iodine atoms that further absorb active light such as EUV in a metal resist with high absorption of active light such as EUV are not known.

[0007] U.S. Patent No. 1,1774,853

[0008] Therefore, the present invention aims to provide a novel resist material and pattern formation method that offer good performance in both the sensitivity of the resist material and the roughness of the LS pattern, which were previously in a trade-off relationship in conventional chemically amplified resists, by incorporating a photodecayable base having an iodine atom into a predetermined metal resist.

[0009] As a result of diligent research to solve the above problems, the present inventors have found that by providing a resist material containing (A) a heteropolyate or a mixture thereof with modified defect sites, and (B) an acid diffusion control agent, wherein the (B) acid diffusion control agent is a photodecayable base having (B1) an iodine atom, the sensitivity of the resist material is good, and the roughness of the LS pattern formed using the resist material can be kept within a good range, thus completing the present invention.

[0010] In other words, the present invention relates to the following inventions: <1> A resist material comprising (A) a heteropolyate or mixture thereof modified with a defect site, and (B) an acid diffusion control agent, wherein the (B) acid diffusion control agent is (B1) a photodecayable base having an iodine atom. <2> The resist material according to <1>, wherein the (B1) photodecayable base having an iodine atom is a photodecayable base having an aromatic hydrocarbon cyclic group having an iodine atom. <3> The photodecayable base having an aromatic hydrocarbon cyclic group having an iodine atom is a photodecayable base B represented by the following general formula (IX-1-1). １Ａ , photodecayable base B represented by the following general formula (IX-1-2)１Ｂ and a photodegradable base B represented by the following general formula (IX-1-3) １Ｃ or a photodegradable base B represented by the following general formula (IX-1-4) １Ｄ The resist material according to <2>. [In the general formula (IX-1-1), Ar Ｂ１ａ represents a monovalent aromatic hydrocarbon cyclic group which may have a substituent, at least one or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by iodine atoms, and further the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be replaced by substituents; D ｐ＋ represents an onium cation or an onium dication; p represents an integer of 1 or 2. ] [In the general formula (IX-1-2), Ar Ｂ１ｂ represents a monovalent aromatic hydrocarbon cyclic group which may have a substituent, at least one or more hydrogen atoms on the aromatic hydrocarbon cyclic group are replaced by iodine atoms, and further the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be replaced by substituents; L Ｂ１ｂ represents a C １－１８ hydrocarbylene group which may have a substituent, and any divalent carbon atoms except the terminals other than the bonding part may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S- or -SO ２ -(provided that adjacent divalent carbon atoms are not simultaneously replaced).; D ｐ＋ represents an onium cation or an onium dication; p represents an integer of 1 or 2. ] [In the general formula (IX-1-3), Ar Ｂ１ｃ １ represents a divalent aromatic hydrocarbon cyclic group which may have a substituent; Ar Ｂ１ｃ ２ represents a monovalent aromatic hydrocarbon cyclic group which may have a substituent; Ar Ｂ１ｃ １ or Ar Ｂ１ｃ ２At least one hydrogen atom on the aromatic hydroxyl group is replaced by an iodine atom; L Ｂ１ｃ C may have a single bond or a substituent. １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ - Represents a component that may be replaced by (however, adjacent divalent carbon atoms cannot be replaced simultaneously); D ｐ＋ [where p represents an onium cation or onium dication; where p represents an integer of 1 or 2.] [In general formula (IX-1-4), Ar Ｂ１ｄ １ represents a divalent aromatic hydrocarbon cyclic group which may have substituents; Ar Ｂ１ｄ ２ represents a monovalent aromatic hydrocarbon cyclic group which may have substituents; Ar Ｂ１ｄ １ or Ar Ｂ１ｄ ２ At least one hydrogen atom on the aromatic hydroxyl group is replaced by an iodine atom; L Ｂ１ｄ １ C may have substituents. １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ - Represents a component that may be replaced by (however, adjacent divalent carbon atoms cannot be replaced simultaneously); L Ｂ１ｄ ２ C may have a single bond or a substituent. １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２- Represents a component that may be replaced by (however, adjacent divalent carbon atoms cannot be replaced simultaneously); D ｐ＋ [where p represents an onium cation or onium dication; where p represents an integer of 1 or 2.]

[0011] <4> The resist material according to <1>, wherein the anionic portion and / or cation portion of the heteropolyate salt modified with the (A) defect portion has one or more polar groups having an acid-dissociable group. <5> The resist material according to <4>, wherein the resist material generates acid upon exposure and its solubility in a developer changes due to the action of the acid. <6> The resist material according to <4>, 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. <7> The resist material according to <1>, wherein the anionic portion of the heteropolyate salt modified with the (A) defect portion is a heteropolyate anion having a defect portion in which the defect portion is modified, and 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, bonding to the terminal oxygen atom of the heteropolyate anion having the defect portion via some or all of the heteroatoms. <8> The organic group may have substituents. １－１８ A hydrocarbyl group, which may have the aforementioned substituents. １－１８ Any divalent carbon atom other than the terminal of the hydrocarbyl group is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and may have the substituent C １－１８ The resist material according to <7>, wherein one or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group. <9> The resist material according to <7>, wherein the organic group is represented by general formula (VII-1). (VII-1) [In general formula (VII-1), L ２Ａ１C may have substituents. １－１２ In a hydrocarbyl group, one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are R ２Ａ１ Represents a group substituted with the L ２Ａ１ The terminal and R ２Ａ１ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ２Ａ１ Each of these independently represents a polar group having an acid-dissociable group; x represents an integer from 1 to 6; and * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn.

[0012] <10> The resist material according to <1>, wherein the (A) modified heteropolyate or mixture thereof is a heteropolyate or mixture thereof that is modified with a defect represented by general formula (I). (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In general formula (I), A ｍ＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C （ａｍ）－ A represents a heteropoly acid anion in which the defective site has been modified; A ｍ＋ and / or C （ａｍ）－ (A') has at least one polar group having an acid-dissociable group; m is an integer from 1 to 5, and a is a real number greater than 0. ] <11> The resist material according to <1>, wherein the (A) modified heteropolyate or mixture thereof is a heteropolyate or mixture thereof that has a modified defect represented by general formula (I'). (A') ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ(C'(a'm'+bn)-) (I') [In general formula (I'), A' ｍ’＋ Each of them independently, H ＋ , metal ions, or NH ４ ＋ Represents; B ｎ＋ Each of these independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents a heteropoly acid anion in which the missing site is modified in a heteropoly acid anion having a missing site; the B ｎ＋ and / or C'(a'm'+bn)- has at least one polar group 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. ] <12> A pattern forming method comprising: forming a resist film using a resist material described in any of <1> to <11>; exposing the resist film; and developing the exposed resist film using a developer.

[0013] <13> The resist material according to <11>, wherein the poly atom of the heteropoly acid anion is Mo, W, V, Nb, or Ta, and the hetero atom is P, Si, B, S, or Ge. <14> The resist material according to <11>, wherein the heteropoly acid anion having the defect is a defective Keggin-type heteropoly acid anion or a defective Dawson-type heteropoly acid anion. <15> The resist material according to <11>, wherein the defective Keggin-type heteropoly acid anion is represented by the general formula (II-1), (II-2), or (II-3). [XM １１ O ３９ ] ｃ１１－ (II-1) [XM １０ O ３６ ] ｃ１２－ (II-2) [XM ９ O ３４ ] ｃ１３－(II-3) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.) <16> The resist material according to <11>, wherein the defective Dawson-type heteropolyacid anion is represented by the general formula (III-1), (III-2), or (III-3). [X ２ M １７ O ６１ ｃ２１－ ｃ２１－ (III-1) [X ２ M １６ O ５８ ｃ２２－ ｃ２２－ (III-2) [X ２ M １５ O ５６ ｃ２３－ ｃ２３－ (III-3) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.) <17> The resist material according to <11>, wherein the onium cation or onium dication is an organic sulfonium cation, an organic sulfonium dication, or an organic iodonium cation. <18> The resist material according to <1>, further containing an organic solvent.

[0014] According to the present invention, it is possible to provide a novel resist material and a patterning method in which both sensitivity and roughness, which have been in a trade-off relationship in conventional chemically amplified resists and the like, are good.

[0015] Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0016] In this specification, the "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0017] In this specification, the "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0018] In this specification, for example, "C１－６ Terms such as "etc." mean the number of carbon atoms in the parent nucleus group.

[0019] In this specification, "C １－１８ "hydrocarbylene group" means a divalent hydrocarbon group formed by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear, branched, or partially or wholly cyclic. The hydrocarbylene group includes an alkylene group, an arylene group, etc. Also, "C １－１８ "hydrocarbylene group", the divalent carbon atoms at any position may be replaced by -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO ２ - (provided that adjacent divalent carbon atoms are not replaced simultaneously). "C １－１８ "hydrocarbylene group" is not particularly limited, and for example, methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadienyl 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, oxyethyleneoxyethane-1,1-diyl group, etc. of "C 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. of "C ６－１８ "arylene group", etc. may be mentioned.

[0020] In this specification, "C １－１８ "alkyl group" means a linear or branched alkyl group having 1 to 18 carbon atoms. Also, "C １－１８ "alkyl group", the divalent carbon atoms at any position except the terminal contained therein may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO２ - may be replaced. However, adjacent divalent carbon atoms cannot be replaced at the same time. １－１８ The "alkyl group" is not particularly limited and includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, i-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1 Examples include 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. １－１８ The divalent carbon atoms at any position in the alkyl group, excluding the terminals, are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ The substitutes for the hyphen are not particularly limited, and examples include the 2-methoxyethoxymethyl group and the ethoxycarbonylmethyl group.

[0021] In this specification, "C １－１８ "Haloalkyl group" refers to "C １－１８ "Alkyl group" refers to a group in which one or more hydrogen atoms are substituted with halogen atoms. １－１８ The term "haloalkyl group" is not particularly limited and includes, for example, dichloromethyl group, trifluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, etc.

[0022] In this specification, "C ２－１８An "alkenyl group" is a group with two or more carbon atoms. １－１８ "Alkyl group" refers to an alkenyl group having one or more double bonds, and includes alkadinyl groups, alkatrienyl groups, etc. ２－１８ The "alkenyl group" is not particularly limited and includes, for example, vinyl group (ethenyl group), allyl group (2-propenyl group), 1-propenyl group, isopropenyl group (1-methylvinyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc.

[0023] In this specification, "C ２－１８ An "alkynyl group" is a group with two or more carbon atoms. １－１８ "Alkyl group" refers to an alkynyl group having one or more triple bonds. ２－１８ The "alkynyl group" is not particularly limited and includes, for example, ethynyl group, 1-propynyl group, 2-propynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, desynyl group, undecynyl group, dodecynyl group, etc.

[0024] In this specification, "C ３－１８ A "cycloalicyclic group" refers to a hydrocarbon group that has a monocyclic or polycyclic cyclic structure with 3 to 18 carbon atoms, either entirely or partially. Cyclocyclic groups include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc. ３－１８ A divalent carbon atom at any position in an alicyclic group, excluding the terminals, is either -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time). ３－１８The term "cycloalkyl group" is not particularly limited and includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-i-propylcyclopentan-1-yl group, cyclohexyl group, t-butylcyclohexyl group, tricyclodecanyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, 2-methyladamantan-2-yl group, 2-i-propyladamantan-2-yl group, bornyl group, norbonyl group, fenquil group, pinanyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, bornylmethyl group, norbornylmethyl group, adamantylmethyl group, 1-methylcyclopentyloxycarbonylmethyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, and the like.

[0025] In this specification, "3- to 18-membered non-aromatic heterocyclic group" means a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and may be monocyclic, polycyclic, or fused, and may be saturated or partially unsaturated. The "3- to 18-membered ring non-aromatic heterocyclic group" is not particularly limited and includes, for example, aziridinyl group, azetidyl group, pyrrolidinyl group, pyrrolyl group, piperidinyl group, piperazinyl group, morpholinyl group, thiomorpholinyl group, tetrahydrofuryl group, tetrahydropyranyl group, oxetanyl group, tetrahydrofuryl group, tetrahydropyranyl group, imidazolinyl group, oxazolinyl group, 2,5-diazabicyclo[2.2.1]heptyl group, 2,5-diazabicyclo[2.2.2]octyl group, 3,8-diazabicyclo[3.2.1]octyl group, 1,4-diazabicyclo[4.3.0]nonyl group, 1-azadamantyl group, 2-azadamantyl group, etc.

[0026] In this specification, "C ２－１８An "aryl group" refers to an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 2 to 10 carbon atoms. In the case of an aromatic heterocyclic group, a ring is formed by a carbon atom with 2 to 10 carbon atoms and one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and each ring may be monocyclic, polycyclic, or fused. ２－１８ The "aryl group" is not particularly limited and includes, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, azlenyl group, pentarenyl group, heptarenyl group, indacenyl group, acenaphthyl group, phenantrenyl group, anthracenyl group, etc.

[0027] In this specification, "C ７－１８ "Aralkyl group" refers to "C １－１２ The substituted portion in the alkyl group is the above "C ２－１２ This refers to a group that has been substituted with an aryl group. ７－１８ The "aralkyl group" is not particularly limited and examples include benzyl group, phenethyl group, 3-phenylpropyl group, 4-phenylbutyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0028] In this specification, "C １－１８ A "hydrocarbyl group" refers to a monovalent group produced by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, and aralkyl groups. １－１８ A divalent carbon atom at any position in the hydrocarbyl group, excluding the terminals, can be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time). This point is explained below in "C １－１８ The term "C" is used in the explanation of the definition of "hydrocarbyl oxy group," etc. １－１８ The same applies to "hydrocarbyl group," etc. １－１８ The term "hydrocarbyl group" is not particularly limited; for example, "C １－１８"Alkyl alkyl group", "C ２－１８ "Alkenyl group", "C ２－１８ "Alkynyl group", "C ３－１８ “Alicyclic group”, “C ２－１８ "Aryl group", "C ７－１８ Examples include the "aralkyl group."

[0029] In this specification, "C １－１８ "Hydrocarbyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group". １－１８ The term "hydrocarbyloxy group" is not particularly limited and includes, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, i-pentoxy group, sec-pentoxy group, n-hexoxy group, i-hexoxy group, 1,1-dimethylpropyloxy group, 1,2-dimethylpropyloxy group, 2,2-dimethylpropyloxy group, 1-methyl- C １－１８ "Alkoxy group"; such as cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-methylcyclopentyloxycarbonylmethoxy group, 1-ethylcyclohexyloxycarbonylmethoxy group, 1-methyladamantyloxycarbonylmethoxy group, etc. ３－１８ "Alicyclic oxy group"; phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, azulenyloxy group, pentarenyloxy group, heptarenyloxy group, indacenyloxy group, acenaphthyloxy group, phenantrenyloxy group, anthracenyloxy group, etc. ６－１８ Examples include "aryloxy group".１－１８ As for the "hydrocarbyl oxy group", C １－１８ It is preferable that the divalent carbon atoms at any position other than the terminals in the "hydrocarbyl group" are replaced with -O-, -C(=O)-, and / or -C(=O)O-. １－１８ A "hydrocarbyloxycarbonylalkyloxy group" is more preferred, and from the viewpoint of solubility, it is even more preferred that the carbon bonded to the oxygen atom of the hydrocarbyloxy is a tertiary carbon. Specific examples of the hydrocarbyloxy include substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, etc.

[0030] In this specification, "C １－１８ The term "hydrocarbyl carbonyl group" refers to "C １－１８ This refers to a group in which a carbonyl group (-C(=O)-) is bonded to a hydrocarbyl group. １－１８ The "hydrocarbyl carbonyl group" is not particularly limited and includes, for example, acetyl group, propionyl group, isopropionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pentanoyl group, 3-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanol group, etc. １－１８ "Alkyl carbonyl group"; cyclopropyl carbonyl group, cyclobutyl carbonyl group, cyclopentyl carbonyl group, 2-methylcyclopentyl carbonyl group, 3-methylcyclopentyl carbonyl group, cyclohexyl carbonyl group, 2-methylcyclohexyl carbonyl group, 3-methylcyclohexyl carbonyl group, 4-methylcyclohexyl carbonyl group, adamantyl carbonyl group, etc. ３－１８ "Alicyclic carbonyl group"; "C" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. ６－１８ Examples include "arylcarbonyl group," etc.

[0031] In this specification, "C １－１８ "Hydrocarbylcarbonyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group". １－１８The "hydrocarbylcarbonyloxy group" is not particularly limited and includes, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, hexylcarbonyloxy group, etc. １－１８ "Alkyl carbonyloxy group"; such as cyclopropyl carbonyloxy group, cyclobutyl carbonyloxy group, cyclopentyl carbonyloxy group, cyclohexyl carbonyloxy group, etc. ３－１８ "Alicyclic carbonyloxy group"; such as phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenantrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc. ６－１８ Examples include "arylcarbonyloxy group," etc.

[0032] In this specification, "C １－１８ The term "hydrocarbyloxycarbonyl group" refers to "C １－１８ This refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbyloxy group". １－１８ The "hydrocarbyloxycarbonyl group" is not particularly limited and includes, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, neopentyloxycarbonyl group, etc. １－１８ "Alkoxycarbonyl group"; such as cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 2-methylcyclopentyloxycarbonyl group, 3-methylcyclopentyloxycarbonyl group, 2-methylcyclohexyloxycarbonyl group, 3-methylcyclohexyloxycarbonyl group, 4-methylcyclohexyloxycarbonyl group, etc. ３－１８"Alicyclic oxycarbonyl group"; such as phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenantrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc. ６－１８ Examples include "aryloxycarbonyl group," etc.

[0033] In this specification, "C １－１８ The term "hydrocarbyloxycarbonyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group". １－１８ The "hydrocarbyloxycarbonyloxy group" is not particularly limited and includes, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propyloxycarbonyloxy group, i-propyloxycarbonyloxy group, n-butoxycarbonyloxy group, i-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, t-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, i-pentyloxycarbonyloxy group, n-hexyloxycarbonyloxy group, etc. １－１８ "Alkoxycarbonyloxy group"; such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. ３－１８ "Alicyclic oxycarbonyloxy group"; such as phenoxycarbonyloxy group, naphthoxycarbonyloxy group, acenaphthyloxycarbonyloxy group, phenantrenyloxycarbonyloxy group, anthracenyloxycarbonyloxy group, etc. ６－１８ Examples include "aryloxycarbonyloxy group".

[0034] In this specification, "C １－１８ A "hydrocarbylamino group" is a single "C" １－１８ A "hydrocarbyl group" refers to a group in which an amino group is bonded. １－１８The "hydrocarbylamino group" is not particularly limited and includes, for example, methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, sec-butylamino group, t-butylamino group, n-pentylamino group, i-pentylamino group, neopentylamino group, n-hexylamino group, etc. １－１８ "Alkylamino group"; cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, 2-methylcyclopentylamino group, 3-methylcyclopentylamino group, cyclohexylamino group, 2-methylcyclohexylamino group, 3-methylcyclohexylamino group, 4-methylcyclohexylamino group, etc. ３－１８ "Alicyclic amino group"; such as phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. ６－１８ Examples include "arylamino group," etc.

[0035] In this specification, "Di C １－１８ A "hydrocarbylamino group" is two identical or different "C" groups. １－１８ "Hydrocarbyl group" refers to a group in which a hydroxyl group is bonded to an amino group. １－１８ The term "hydrocarbylamino group" is not particularly limited and includes, for example, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-t-butylamino group, di-n-pentylamino group, di-n-hexylamino group, N-ethyl-N-methylamino group, N-methyl-N-n-propylamino group, N-isopropyl-N-methylamino group, N-n-butyl-N-methylamino group, N DiC groups such as -isobutyl-N-methylamino group, N-t-butyl-N-methylamino group, N-methyl-N-n-pentylamino group, N-n-hexyl-N-methylamino group, N-ethyl-N-n-propylamino group, N-ethyl-N-isopropylamino group, N-n-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, N-t-butyl-N-ethylamino group, N-ethyl-N-n-pentylamino group, N-ethyl-N-n-hexylamino group, etc. １－１８"Alkylamino group"; dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. ３－１８ "Alicyclic amino group"; such as diphenylamino group, phenylnaphthylamino group, etc. ６－１８ "Arylamino group"; "N-C" such as N-methylcyclopentaneamino group and N-methylcyclohexylamino group. １－１８ Alkyl-N-C ３－１８ "Cycloalkylamino group"; "N-C" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group １－１８ Alkyl-N-C ６－１８ Examples include "arylamino group," etc.

[0036] In this specification, "C １－１８ "Hydrocarbylaminocarbonyl group" refers to "C １－１８ This refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group". １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited and includes, for example, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, t-butylaminocarbonyl group, n-pentylaminocarbonyl group, 2-pentylaminocarbonyl group, neopentylaminocarbonyl group, 4-methyl-2-pentylaminocarbonyl group, n-hexylaminocarbonyl group, 3-methyl-n-pentylaminocarbonyl group, etc. １－１８ "Alkylaminocarbonyl group"; cyclopropylaminocarbonyl group, cyclobutylaminocarbonyl group, cyclopentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-methylcyclopentylaminocarbonyl group, 3-methylcyclopentylaminocarbonyl group, 2-methylcyclohexylaminocarbonyl group, 3-methylcyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group, etc. ３－１８ "Alicyclic aminocarbonyl group"; such as phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc.６－１８ An example is the "arylaminocarbonyl group."

[0037] In this specification, "Di C １－１８ "Hydrocarbylaminocarbonyl group" refers to "diC １－１８ This refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group". １－１８ The term "hydrocarbylaminocarbonyl group" is not particularly limited and includes, for example, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, diisopropylaminocarbonyl group, di-n-butylaminocarbonyl group, diisobutylaminocarbonyl group, di-t-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, N-ethyl-N-methylaminocarbonyl group, N-methyl-N-n-propylaminocarbonyl group, N-isopropyl-N-methylaminocarbonyl group, N-n-butyl-N-methylaminocarbonyl group, N-isobutyl-N-methylaminocarbonyl group, N-t-butyl-N-methylaminocarbonyl group, N-methyl-N-n-pentylaminocarbonyl group, N-n-hexyl-N-methylaminocarbonyl group DiC groups such as N-ethyl-N-n-propylaminocarbonyl group, N-ethyl-N-isopropylaminocarbonyl group, N-n-butyl-N-ethylaminocarbonyl group, N-ethyl-N-isobutylaminocarbonyl group, N-t-butyl-N-ethylaminocarbonyl group, N-ethyl-N-n-pentylaminocarbonyl group, N-ethyl-N-n-hexylaminocarbonyl group, etc. １－１８ "Alkylamino group"; such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. ３－１８ "Alicyclic aminocarbonyl group"; "DiC" such as diphenylaminocarbonyl group and phenylnaphthylaminocarbonyl group. ６－１８ Examples include "arylaminocarbonyl group," etc.

[0038] In this specification, "C １－１８ "Hydrocarbylcarbonylamino group" refers to "C １－１８This refers to a group in which an amino group is bonded to a "hydrocarbyl carbonyl group". １－１８ The "hydrocarbonylamino group" is not particularly limited and includes, for example, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, n-hexylcarbonylamino group, etc. １－１８ "Alkylcarbonylamino group"; such as cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. ３－１８ "Alicyclic carbonylamino group"; such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenantrenylcarbonylamino group, anthracenylcarbonylamino group, etc. ６－１８ Examples include "arylcarbonylamino group," etc.

[0039] In this specification, "C １－１８ "Hydrocarbylaminocarbonyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group". １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited and includes, for example, methylaminocarbonyloxy group, ethylaminocarbonyloxy group, n-propylaminocarbonyloxy group, etc. １－１８ "Alkylaminocarbonyloxy group"; "C" such as cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. ３－１８ "Alicyclic aminocarbonyloxy group"; "C" such as phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group ６－１８ Examples include "arylaminocarbonyloxy group".

[0040] In this specification, "Di C １－１８ "Hydrocarbylaminocarbonyloxy group" is a "diC １－１８This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group". １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited and includes, for example, dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, di-n-propylaminocarbonyloxy group, etc. １－１８ Examples include "alkylaminocarbonyloxy group," etc.

[0041] In this specification, "C １－１８ "Hydrocarbylaminocarbonylamino group" refers to "C １－１８ "Hydrocarbylaminocarbonyl group" refers to a group in which an amino group is bonded. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited and includes, for example, methylaminocarbonylamino group, ethylaminocarbonyloxy group, n-propylaminocarbonylamino group, etc. １－１８ "Alkylaminocarbonylamino group"; "C" such as cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. ３－１８ "Alicyclic aminocarbonylamino group"; "C" such as phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. ６－１８ Examples include "arylaminocarbonylamino group," etc.

[0042] In this specification, "Di C １－１８ "Hydrocarbylaminocarbonylamino group" refers to "diC １－１８ "DiC" refers to a group in which a "hydrocarbylaminocarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited and includes, for example, dimethylaminocarbonylamino group, diethylaminocarbonylamino group, di-n-propylaminocarbonylamino group, etc. １－１８ Examples include "alkylaminocarbonylamino group," etc.

[0043] In this specification, "C １－１８ "Hydrocarbyloxycarbonylamino group" is "C １－１８This refers to a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbyloxycarbonylamino group" is not particularly limited and includes, for example, methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc. １－１８ "Alkoxycarbonylamino group"; "C" such as cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. ３－１８ "Alicyclic oxycarbonylamino group"; "C" such as phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. ６－１８ Examples include "aryloxycarbonylamino group," etc.

[0044] In this specification, "C １－１８ A "hydrocarbylthio group" is a "C １－１８ This refers to a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group". １－１８ The "hydrocarbylthio group" is not particularly limited and includes, for example, methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, etc. １－１８ "Alkylthio group"; cyclopropylthio group, cyclobutylthio group, cyclopentylthio group, cyclohexylthio group, 2-methylcyclopentylthio group, 3-methylcyclopentylthio group, 2-methylcyclohexylthio group, 3-methylcyclohexylthio group, 4-methylcyclohexylthio group, etc. ３－１８ "Alicyclic thio group"; such as phenylthio group, 1-naphthylthio group, 2-naphthylthio group, acenaphthylthio group, phenantrenylthio group, anthracenylthio group, etc. ６－１８ Examples include "arylthio group," etc.

[0045] In this specification, "C １－１８ The term "hydrocarbyl sulfinyl group" refers to "C １－１８ This refers to a group in which a sulfinyl group (-S (=O)-) is bonded to a hydrocarbyl group.１－１８ The "hydrocarbyl sulfinyl group" is not particularly limited and includes, for example, methyl sulfinyl group, ethyl sulfinyl group, n-propyl sulfinyl group, i-propyl sulfinyl group, n-butyl sulfinyl group, t-butyl sulfinyl group, pentyl sulfinyl group, hexyl sulfinyl group, etc. １－１８ "Alkyl sulfinyl group"; cyclopropyl sulfinyl group, cyclobutyl sulfinyl group, cyclopentyl sulfinyl group, cyclohexyl sulfinyl group, 2-methylcyclopentyl sulfinyl group, 3-methylcyclopentyl sulfinyl group, 2-methylcyclohexyl sulfinyl group, 3-methylcyclohexyl sulfinyl group, 4-methylcyclohexyl sulfinyl group, etc. ３－１８ "Alicyclic sulfinyl group"; such as phenylsulfinyl group, naphthylsulfinyl group, acenaphthylsulfinyl group, phenantrenylsulfinyl group, anthracenylsulfinyl group, etc. ６－１８ Examples include "aryl sulfinyl group," etc.

[0046] In this specification, "C １－１８ The term "hydrocarbyl sulfonyl group" refers to "C １－１８ A sulfonyl group (-SO) attached to a hydrocarbyl group. ２ It means a group to which -) is attached. １－１８ The "hydrocarbyl sulfonyl group" is not particularly limited and includes, for example, methyl sulfonyl group, ethyl sulfonyl group, n-propyl sulfonyl group, i-propyl sulfonyl group, n-butyl sulfonyl group, t-butyl sulfonyl group, pentyl sulfonyl group, etc. １－１８ "Alkyl sulfonyl group"; cyclopropyl sulfonyl group, cyclobutyl sulfonyl group, cyclopentyl sulfonyl group, cyclohexyl sulfonyl group, 2-methylcyclopentyl sulfonyl group, 3-methylcyclopentyl sulfonyl group, 2-methylcyclohexyl sulfonyl group, 3-methylcyclohexyl sulfonyl group, 4-methylcyclohexyl group, etc. ３－１８ "Alicyclic sulfonyl group"; such as phenylsulfonyl group, naphthylsulfonyl group, acenaphthylsulfonyl group, phenantrenylsulfonyl group, anthracenylsulfonyl group, etc. ６－１８Examples include "aryl sulfonyl group," etc.

[0047] In this specification, "acid-dissociable group" means a polar group that substitutes a hydrogen atom, such as a hydroxyl group (including phenolic hydroxyl groups, etc.), a carboxyl group, an amino group, or a sulfo group, which dissociates upon the action of an acid. Compounds having a polar group having the above-mentioned acid-dissociable group can increase their polarity by dissociating the acid-dissociable group upon the action of an acid, thereby generating the above-mentioned polar group. This can change the solubility of the compound in a developer. More specifically, when a highly polar developer such as an alkaline aqueous solution is used as the developer, the solubility of the compound in the developer increases relatively, while when a less polar organic developer is used as the developer, the solubility of the compound in the developer decreases relatively. Hydroxyl groups (including phenolic hydroxyl groups, etc.) and carboxyl groups are preferred as the above-mentioned polar groups.

[0048] The above-mentioned acid-dissociable group is not particularly limited, and any known and conventional acid-dissociable group usable in chemically amplified resists can be used. Examples of acid-dissociable groups include the acid-dissociable group G for polar groups having an acid-dissociable group represented by the following general formulas (G-1) to (G-4).

[0049] The above-mentioned acid-dissociable group G is not particularly limited as long as it dissociates upon the action of an acid, and known and commonly used groups can be used. For example, the acid-dissociable group G is the "tertiary carbon type acid-dissociable group G" represented by the following general formula (g-1). Ａ ", and "allyl-type or benzyl-type acid-dissociating group G" represented by the following general formula (g-2) Ｂ " and "acetal-type acid-dissociating group G" represented by the following general formula (g-3) Ｃ These are some examples. Each of these will be explained in turn below.

[0050] <Tertiary carbon type acid dissociable group G Ａ> The above acid-dissociating group G is the "tertiary carbon type acid-dissociating group G" represented by the following general formula (g-1) Ａ As shown above, the carbon is directly bonded to a polar group, and R Ａ ｇ１ ~R Ａ ｇ３ An acid-dissociable group can be used in which the bonded carbon is a tertiary carbon atom.

[0051] "R Ａ ｇ１ " may have substituents C １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0052] R Ａ ｇ１ C may have substituents. １－１２ alkyl group, C ３－１２ Alicyclic group, C ６－１２ Aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１２ Alkyl alkyl group, or C ３－１２ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0053] Also, "R Ａ ｇ２ " and "R Ａ ｇ３Each of these C atoms may independently have substituents. １－１２ A hydrocarbyl group in which the divalent carbon atoms at any position except the terminals are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms may not be replaced at the same time), or R Ａ ｇ２ and R Ａ ｇ３ These are combined and may have substituents. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0054] R Ａ ｇ２ and R Ａ ｇ３ For example, R Ａ ｇ２ and R Ａ ｇ３ These are combined and may have substituents. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atom may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously), and furthermore, it may have the above substituent. ３－１８The alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group includes a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, and tricyclodecene skeleton, and the divalent carbon atoms at any position except the terminals are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0055] Tertiary carbon type acid-dissociable group G represented by general formula (g-1) Ａ Examples include t-butyl group, t-amyl group, 1,1-dimethylpropyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0056] Tertiary carbon type acid-dissociable group G represented by general formula (g-1) Ａ Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0057]

[0058] <<Tertiary carbon type acid dissociable group G Ａ１ and G Ａ２ >> Also, the "tertiary carbon type acid-dissociable group G" represented by the general formula (g-1) Ａ In ", R Ａ ｇ２ and R Ａ ｇ３ These are combined and may have substituents. ３－１８In cases where an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, for example, a tertiary carbon-type acid-dissociable group G represented by the following general formula (g-1-1) Ａ１ , and the tertiary carbon-type oxygen dissociable group G represented by (g-1-2) Ａ２ These are some examples.

[0059] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) Ａ１ >> The tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1) Ａ１ In R Ａ ｇ１１ C may have substituents. １－１２ alkyl group, C ３－１２ Alicyclic group, C ６－１２ Aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0060] Also CC Ａ ｇ１ This is a C atom that may have substituents, along with the tertiary carbon atom mentioned above. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0061] Cy Ａ ｇ１As such, together with the above tertiary carbon atoms, they may form a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton, and any divalent carbon atoms at any position except the terminals are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the atoms may be replaced by ⁻ (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0062] The tertiary carbon type acid-dissociable group G, represented by the general formula (g-1-1). Ａ１ Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0063]

[0064]

[0065]

[0066]

[0067] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) Ａ２ >> In the above general formula (g-1-2), R Ａ ｇ２１ ~R Ａ ｇ２３ Each of these may independently have a hydro group or a substituent. １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time), R Ａ ｇ２１ and R Ａｇ２２ , and / or, R Ａ ｇ２２ and R Ａ ｇ２３ These are linked directly by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring.

[0068] R Ａ ｇ２１ and R Ａ ｇ２２ , and / or, R Ａ ｇ２２ and R Ａ ｇ２３ Examples of cases where a ring is formed together with the carbon atom included in the ethylenically unsaturated double bond include the formation of a cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexyllideneethenyl group, etc., which may have substituents.

[0069] Also CC Ａ ｇ２ This is a C atom that may have substituents, along with the tertiary carbon atom mentioned above. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0070] Cy Ａ ｇ２As such, together with the above tertiary carbon atoms, they may form a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton, and any divalent carbon atoms at any position except the terminals are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the atoms may be replaced by ⁻ (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0071] Tertiary carbon type acid-dissociable group G represented by general formula (g-1-2) Ａ２ Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0072]

[0073]

[0074]

[0075] <Allyl or benzyl acid-dissociating group G> Ｂ > The above acid-dissociating group G is an "allyl-type or benzyl-type acid-dissociating group G" represented by the following general formula (g-2). Ｂ As shown above, an acid-dissociable group can be used in which the carbon directly bonded to the polar group is located at the allylic or benzyl position.

[0076] "R Ｂ ｇ１ " may have substituents C １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0077] R Ｂ ｇ１ C may have substituents. １－１２ alkyl group, C ３－１２ Alicyclic group, C ６－１２ Aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１２ Alkyl alkyl group, or C ３－１２ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0078] Also, "R Ｂ ｇ２ "~"R Ｂ ｇ４ Each of these may independently have a hydro group or a substituent. １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0079] R Ｂ ｇ１ and R Ｂ ｇ２ , R Ｂ ｇ２ and R Ｂ ｇ３ , and / or, R Ｂ ｇ３ and R Ｂ ｇ４These are linked directly by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring.

[0080] Allyl or benzyl acid-dissociable group G represented by general formula (g-2) Ｂ In R Ｂ ｇ１ and R Ｂ ｇ２ , R Ｂ ｇ２ and R Ｂ ｇ３ , and / or, R Ｂ ｇ３ and R Ｂ ｇ４ Examples of cases where a ring is formed together with the carbon atom included in the ethylenically unsaturated double bond include cases where a cyclic cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexyllideneethenyl group, benzyl group, or 2,3-dihydro-1H-indanyl group, which may have substituents, are formed.

[0081] Allyl or benzyl acid-dissociable group G represented by general formula (g-2) Ｂ Examples include the following allyl or benzyl acid-dissociating groups.

[0082]

[0083] <Acetal-type acid-dissociating group G> Ｃ > The above acid-dissociating group G is the "acetal-type acid-dissociating group G" represented by the following general formula (g-3). Ｃ As shown above, an acid-dissociable group can be used in which an oxygen atom is bonded to a carbon atom that is directly bonded to the polar group.

[0084] "R Ｃ ｇ１ " and "R Ｃ ｇ３ Each of these may independently have a hydro group or a substituent. １－１２A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0085] R Ｃ ｇ１ and R Ｃ ｇ３ This may include a hydro group or a C which may have a substituent. １－１２ Alkyl or C ３－１２ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the C group may be replaced by a ⁻ (however, adjacent divalent carbon atoms may not be replaced simultaneously), and may have a hydro group or substituent. １－６ Alkyl or C ３－８ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0086] Also, "R Ｃ ｇ２ " may have substituents C １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0087] R Ｃ ｇ２ C may have substituents. １－１２ Alkyl alkyl group or C ３－１２In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－６ Alkyl alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0088] Acetal-type acid-dissociable group G represented by general formula (g-3) Ｃ Examples include methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, n-butoxymethoxy group, 2,2-dimethylpropoxymethoxy group, 2,2-dimethylbutoxymethoxy group, cyclohexyloxymethoxy group, 1-ethoxyethoxy group, 1-n-butoxyethoxy group, and 1-cyclohexyloxyethoxy group.

[0089] In this specification, "hydroxyl group or carboxyl group having a protecting group" means a hydroxyl group (including phenolic hydroxyl group) or carboxyl group that is protected by an ether protecting group, a silyl ether protecting group, an acyl protecting group, an aminocarbonyl protecting group, or the like.

[0090] Examples of ether protecting groups are not particularly limited and include methyl group, benzyl group, p-methoxybenzyl group, t-butyl group, triphenylmethyl group, p-methoxyphenyldiphenylmethyl group, and di(p-methoxyphenyl)phenylmethyl group. Examples of silyl ether protecting groups are not particularly limited and include t-butyldimethylsilyl group (TBS), triisopropylsilyl group (TIPS), trimethylsilyl group (TMS), triethylsilyl group (TES), and t-butyldiphenylsilyl group (TBDPS). Examples of acyl protecting groups are not particularly limited and include acetyl group, pivaloyl group, and benzoyl group. Examples of aminocarbonyl protecting groups are not particularly limited and include dimethylaminocarbonyl group, diethylaminocarbonyl group, diisopropylaminocarbonyl group, and N-phenyl-N-methylaminocarbonyl group.

[0091] In this specification, "may have substituents," "may be substituted with substituents," "may be replaced by substituents," etc., are not particularly limited as long as they are chemically acceptable and have the effects of the present invention. Examples of "substituents" are: (1) halogen atoms, (2) haloalkyl groups, (3) hydroxyl groups, (4) thiol groups, (5) nitro groups, (6) cyano groups, (7) carboxyl groups, (8) amino groups, (9) sulfo groups, (10) vinyl groups, (11) allyl groups, (12) (meth)acryloyl groups, (13) (meth)acryloyloxy groups, (14) (meth)acrylamide groups, (15) styryl groups, (16) epoxy groups, (17) glycidyl groups, (18) amide groups, (19) hydroxyl or carboxyl groups having a protecting group, (20) polar groups having an acid-dissociable group, or (21) C in which at least one part of the hydrogen atoms is substituted with (1) to (20) above. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C１－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ Hydrocarbyl sulfinyl group, C １－１８ A hydrocarbyl sulfonyl group in which the divalent carbon atoms at any position other than the terminals of the substituent are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ Examples include the possibility of substitution with - (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0092] [1. Resist Material] The resist material according to this embodiment is a resist material containing (A) a heteropolyate salt or a mixture thereof modified with defects, and (B) an acid diffusion control agent, wherein the (B) acid diffusion control agent is (B1) a photodecayable base having an iodine atom. The resist material according to this embodiment may also contain an organic solvent, an acid generator, or other components as optional components.

[0093] [1-1. (A) Heteropolyate salt or mixture thereof with modified defect sites] The anionic portion of the (A) heteropolyate salt or mixture thereof with modified defect sites according to this embodiment is composed of heteropolyate anions having a defect site, in which the defect site is modified. Furthermore, the cation portion of the above (A) component is H ＋ It is composed of metal ions, onium cations, or onium dications.

[0094] The inclusion of one or more acid-dissociable polar groups in component (A) allows for the dissociation of these acid-dissociable groups by the action of an acid, thereby altering the solubility in the developer. The acid-dissociable polar groups may be contained in the anionic portion of component (A), in the cationic portion, or in both the anionic and cationic portions of component (A).

[0095] Furthermore, by including multiple polar groups having acid-dissociable groups in component (A), that is, two or more polar groups having acid-dissociable groups, the multiple acid-dissociable groups can be dissociated by the action of acid, drastically changing the solubility in the developer. For this reason, it is preferable that component (A) contains one or more polar groups having acid-dissociable groups, more preferably two to ten, and even more preferably four to eight. It is preferable that one or more of the above-mentioned polar groups having acid-dissociable groups are included in the cationic and / or anionic portion of component (A), more preferably two or more in the anionic portion of component (A), and even more preferably four or more in the anionic portion of component (A).

[0096] Furthermore, by adjusting the bulkiness, hydrophobicity, and lipid solubility of the acid-dissociable group, the range of changes in physical properties such as solubility in the developer between the exposed and unexposed areas can be appropriately adjusted.

[0097] In the following, the anionic and cationic portions of the heteropoly salt or mixture thereof modified with the (A) defect site according to this embodiment will be described, respectively.

[0098] [1-1-1. Anionic portion of component (A)] The anionic portion of the heteropoly acid salt or mixture thereof modified with a defect site according to this embodiment is obtained by reacting the terminal oxygen atom at the defect site of the heteropoly acid anion having the defect site with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups. The heteropoly acid anion having a defect site and the modification of the defect site will be described below.

[0099] [1-1-1-1. Heteropoly acid anions having a defect] The heteropoly acid anion having a defect according to this embodiment is not particularly limited, and a defective species in which a part of the basic skeleton of the heteropoly acid anion is missing can be used, and any of the 1-defective species, 2-defective species, 3-defective species, etc., may be used. Examples of the heteropoly acid anion having the above-mentioned defect include a defective Keggin-type heteropoly acid anion and a defective Dawson-type heteropoly acid anion.

[0100] <Deficient Keggin-type heteropoly acid anions> Examples of the above-mentioned deficient Keggin-type heteropoly acid anions include the 1-deficient Keggin-type heteropoly acid anion represented by the following general formula (II-1), the 2-deficient Keggin-type heteropoly acid anion represented by the following general formula (II-2), and the 3-deficient Keggin-type heteropoly acid anion represented by the following general formula (II-3). [XM １１ O ３９ ] ｃ１１－ (II-1) [XM １０ O ３６ ] ｃ１２－ (II-2) [XM ９ O ３４ ] ｃ１３－ (II-3) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the negative charge number, and c11- to c13 are natural numbers.)

[0101] In general formulas (II-1) to (II-3), the values ​​of c11 to c13 change depending on the types of X and M. For example, in general formula (II-1), when X is P and M is Mo or W, c11 is 7 ([PMo １１ O ３９ ] ７－ [PW 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 if X is S and M is Mo or W, then c11 is 6 ([SMo １１ O ３９ ] ６－ [SW １１ O ３９ ] ６－ ) and if X is B and M is Mo or W, then c11 is 9 ([BMo １１ O ３９ ] ９－ [BW １１ O ３９ ] ９－ ) and if X is Ge and M is Mo or W, then c11 is 8 ([GeMo １１ O ３９ ] ８－ [GeW １１ O ３９ ] ８－ ) becomes. Also, in general formula (II-2), when X is P and M is Mo or W, c12 is 7 ([PMo １０ O ３６ ] ７－ [PW 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 if X is B and M is Mo or W, then c12 is 9 ([BMo １０ O ３６ ] ９－ [BW １０ O ３６ ] ９－ ) and if X is Ge and M is Mo or W, then c12 is 8 ([GeMo １０ O ３６ ] ８－ [GeW １０ O ３６ ] ８－ Furthermore, in general formula (II-3), for example, when X is P and M is Mo or W, c13 is 9 ([PMo ９ O ３４ ] ９－ [PW 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 if X is S and M is Mo or W, then c13 is 8 ([SMo ９ O ３４ ] ８－ [SW ９ O ３４ ] ８－ ) and if X is Ge and M is Mo or W, then c13 is 10([GeMo ９ O ３４ ] １０－ [GeW ９ O ３４ ] １０－ )

[0102] The above-mentioned deficient Keggin-type heteropoly acid anion is preferably an isomer structure of the α-form, β-form, or γ-form. The isomer structure of the 1-deficient Keggin-type heteropoly acid anion represented by general formula (II-1) is [α-PW １１ O ３９ ] ７－ [β-PW １１ O ３９ ] ７－ [γ-PW １１ O ３９ ] ７－ [α-PMo １１ O ３９ ] ７－ [β-PMo １１ O ３９ ] ７－ [γ-PW １１ O ３９ ] ７－ [α-SiW] １１ O ３９ ] ８－ [β-SiW] １１ O ３９ ] ８－ [γ-SiW １１ O ３９ ] ８－ [α-SiMo １１ O ３９ ] ８－ [β-SiMo １１ O ３９ ]８－ [γ-SiW １１ O ３９ ] ８－ Preferably, [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 more preferable is the isomer structure of the two-deficient Keggin-type heteropoly acid anion represented by the general formula (II-1), which is [α-PW １０ O ３６ ] ７－ [β-PW １０ O ３６ ] ７－ [γ-PW １０ O ３６ ] ７－ [α-PMo １０ O ３６ ] ７－ [β-PMo １０ O ３６ ] ７－ [γ-PW １０ O ３６ ] ７－ [α-SiW] １０ O ３６ ] ８－ [β-SiW] １０ O ３６ ] ８－ [γ-SiW １０ O ３６ ] ８－ [α-SiMo １０ O ３６ ] ８－ [β-SiMo １０ O ３６ ] ８－ [γ-SiW １０ O ３６ ] ８－ Preferably, [γ-PW １０ O ３６ ] ７－ [γ-PMo １０ O ３６ ] ７－ [γ-SiW １０O ３６ ] ８－ [γ-SiMo １０ O ３６ ] ８－ The more preferable is the isomer structure of the 3-deficient Keggin-type heteropoly acid anion represented by the general formula (III-1), which is [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－ It is preferable.

[0103] <Deficient Dawson-type heteropoly acid anions> Examples of deficient Dawson-type heteropoly acid anions include the 1-deficient Dawson-type heteropoly acid anion represented by the following general formula (III-1), the 2-deficient Dawson-type heteropoly acid anion represented by the following general formula (III-2), and the 3-deficient Dawson-type heteropoly acid anion represented by the following general formula (III-3). [X ２ M １７ O ６１ ] ｃ２１－ (III-1) [X ２ M １６ O５８ ] ｃ２２－ (III-2) [X ２ M １５ O ５６ ] ｃ２３－ (III-3) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the negative charge number, and c21- to c23 are natural numbers.)

[0104] In general formulas (III-1) to (III-3), the values ​​of c21 to c23 change depending on the types of X and M. For example, in 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, then c21 is 8([S ２ W １７ O ６１ ] ８－ ) And in general formula (III-2), when X is Ge and M is Mo, c22 is 12([Ge ２ Mo １６ O ５８ ] １２－ Furthermore, in 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－ )

[0105] The above-mentioned deficient Dawson-type heteropoly acid anion is preferably an isomer structure of the α-form, β-form, or γ-form. The isomer structure of the deficient Dawson-type heteropoly acid anion represented by general formulas (III-1) to (III-3) is [α-P ２ W １７ O ６１ ] １０－ [α-P ２ W１５ O ５６ ] １２－ [α-S ２ W １７ O ６１ ] ８－ These can be suitably used.

[0106] [1-1-1-2. Modification of Defect Sites] The modification of the defective site in the heteropoly acid anion having a defective site according to this embodiment is performed by reacting the terminal oxygen atom at the defective site of the heteropoly acid anion with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups to modify the defective site. Through the above reaction, the terminal carbon atom of the defective site of the heteropoly acid anion is bonded to a group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded, via some or all of the heteroatom, thereby modifying the defective site.

[0107] [1-1-1-2-1. Bonding form of the defective site and its notation] In the heteropoly acid anion modified with a defective site according to this embodiment, the terminal oxygen atom of the defective site of the heteropoly acid anion having a defective site is modified by a group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded.

[0108] The bonding configuration between the terminal oxygen atom of the vacant site of the above-mentioned heteropoly acid anion and a 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 of these may independently have substituents. １－１８ Represents a hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group, and the above R １Ａ１ ~R １Ｅ１Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and the above R １Ａ１ ~R １Ｅ１ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups with protecting groups, or (t) polar groups with acid-dissociable groups; * indicates the bond with the terminal oxygen atom of the missing site in a heteropoly acid anion having a missing site.

[0109] In this specification, for convenience, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having a heteroatom Si or Ge to which one or more organic groups represented by general formula (IV-1) are bonded may be represented as shown in the following general formula (V-1). [X ｗ M ｘ O ｙ (R １Ａ１ X') (R １Ａ２ X')O] ｃ－ (V-1) (wherein w, x, y, and c are all natural numbers, X, M, X', R １Ａ１ and R １Ａ２ (This is the same as above.) Also, R １Ａ１ and R １Ａ２ If they are the same, then R １Ａ It can be expressed as follows: [X ｗ M ｘ O ｙ (R １Ａ X') ２ O] ｃ－ (V-1')

[0110] A heteropoly acid anion modified with a defect site represented by the general formula (V-1) or (V-1') is not particularly limited, and for example, a heteropoly acid anion having a defect site and (R １Ａ ) X'Y ３ (Y represents a leaving group, for example, a halogen atom, a hydroxyl group, an alkoxy group (C) １－４ It is preferably an alkoxy group, C １－２ It is more preferable that it be an alkoxy group, (C) alkylcarbonyloxy group １－４ Preferably, it is an alkylcarbonyloxy group.), hydrocarbyl sulfonyloxy group (C １－６ Alkyl or C ７－１０ It is preferable that it be an aralkylsulfonyloxy group. Examples include a methanesulfonyloxy group and a p-toluenesulfonyloxy group. It can be obtained by reacting it with ().

[0111] Similarly, in this specification, for the convenience of use, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having a heteroatom Si or Ge to which one or more organic groups represented by general formula (IV-2) are bonded may be expressed as shown in the following general formula (V-2). [X ｗ M ｘ O ｙ (R １Ｂ１ R １Ｂ２ X') (R １Ｂ３ R １Ｂ４ X') ｃ－ (V-2) (wherein w, x, y, and c are all natural numbers, X, M, X', R １Ｂ１ , R １Ｂ２ , R １Ｂ３ and R １Ｂ４ (This is the same as above.) Also, R １Ｂ１ R １Ｂ２ and R １Ｂ３ R １Ｂ４ If they are the same, they can be expressed as shown in the following general formula (V-2'). [X ｗ M ｘ O ｙ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ－(V-2')

[0112] A heteropoly acid anion modified with a defect site represented by the general formula (V-2) or (V-2') is not particularly limited, and for example, a heteropoly acid anion having a defect site and (R １Ｂ１ ) (Caution １Ｂ２ ) X'Y ２ It can be obtained by reacting it with (Y represents a leaving group as described above).

[0113] In this specification, for convenience, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having a heteroatom Si or Ge to which one or more organic groups represented by general formula (IV-3) are bonded may be represented as shown in the following general formula (V-3). [X ｗ M ｘ O ｙ (R １Ｃ１ X'O) (R １Ｃ２ X'O) (R １Ｃ３ X'O) (R １Ｃ４ X'O) ｃ－ (V-3) (In the formula, w, x, y, and c are all natural numbers, and X, M, X', R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ (This is the same as above.) Also, R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ If they are the same, then R １Ｃ It can be expressed as follows: [X ｗ M ｘ O ｙ (R １Ｃ X'O) ４ ] ｃ－ (V-3')

[0114] The heteropoly acid anions modified by the deletion site represented by the general formula (V-3) or (V-3') are not particularly limited, and for example, two-deleted Keggin-type or Dawson-type heteropoly acid anions and R １Ｃ X'Y ３ It can be obtained by reacting it with (Y represents a leaving group as described above).

[0115] In this specification, for convenience, heteropoly acid anions in which the deficiency site of the heteropoly acid anion is modified by a group having a heteroatom P to which one or more organic groups represented by general formula (IV-4) are bonded may be represented as shown in the following general formula (V-4). [X ｗ M ｘ O ｙ (R １Ｄ１ P = O) (R １Ｄ２ P = O) ｃ－ (V-4) (In the formula, w, x, y, and c are all natural numbers, and X, M, R １Ｄ１ and R １Ｄ２ (This is the same as above.) Also, R １Ｄ１ and R １Ｄ２ If they are the same, then R １Ｄ It can be expressed as follows: [X ｗ M ｘ O ｙ (R １Ｄ P = O) ２ )] ｃ－ (V-4')

[0116] A heteropoly acid anion modified with a defect site represented by the general formula (V-4) or (V-4') is not particularly limited, and for example, a heteropoly acid anion having a defect site and R １Ｄ P(=O)Y ２ It can be obtained by reacting it with (Y represents a leaving group as described above).

[0117] In this specification, for convenience, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having one or more organic groups represented by general formula (IV-5) bonded to a heteroatom Si, Ge, or Sn may be represented as shown in the following general formula (V-5). [X ｗ M ｘ O ｙ (R １Ｅ１ X'')] ｃ－ (V-5) (wherein w, x, y, and c are all natural numbers, and X, M, X'' and R １Ｅ１The same applies as above.) Also, the above (V-5) may be expressed as the general formula (V-5') below in some cases. Note that R １Ｅ is R １Ｅ１ The same definition is used. [X ｗ M ｘ O ｙ (R １Ｅ X'')] ｃ－ (V-5')

[0118] A heteropoly acid anion modified with a defect site represented by the general formula (V-5) or (V-5') is not particularly limited, and for example, a heteropoly acid anion having a defect site and R １Ｅ X''Y ３ It can be obtained by reacting it with (Y represents a leaving group as described above).

[0119] Among heteropoly acid anions modified with the defect sites represented by general formulas (V-1) to (V-5) and (V-1') to (V-5'), heteropoly acid anions modified with the defect sites represented by the following general formulas (VI-1) to (VI-12) are particularly preferred from the viewpoint of being relatively stable and allowing for controllable 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 R１Ｂ２ X') ２ ｃ３２－ (VI-6) [XM １０ O ３６ (R １Ｃ XO) 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 hydrocarbyl group which may have a substituent, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, and any divalent carbon atom at a position other than the terminal of the above R １Ａ ~R １Ｅ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ ​​​​​- may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and the above R １Ａ ~R １Ｅ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups with protecting groups, or (t) polar groups with acid-dissociable groups; c31, c32, and c33 are natural numbers.

[0120] In heteropolyacid anions with modified defect sites, the four terminal oxygen atoms of the defect site are modified. Therefore, the value of c31 is usually c11-4 (where c11 represents the absolute value of the number of negative charges in a one-defective Keggin-type heteropolyacid anion represented by general formula (II-1)), the value of c32 is c12-4 (where c12 represents the absolute value of the number of negative charges in a two-defective Keggin-type heteropolyacid anion represented by general formula (II-2)), and the value of c33 is c21-4 (where c21 represents the absolute value of the number of negative charges in a one-defective Dawson-type heteropolyacid anion represented by general formula (III-1)). On the other hand, for example, if the organic group contains an amino group which is protonated to form an ammonium cation, or if the organic group contains a carboxyl group which is formed to form a carboxyl anion, the values ​​of c31 to c33 will differ from the above values.

[0121] [1-1-1-2-2. Organic group] The above R １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and also, R １Ｅ The organic group represented by is not particularly limited, and any known and commonly used one can be used. １Ａ ~R １Ｅ As an example of an organic group represented by R,１Ａ ~R １Ｅ However, C may have substituents. １－１８ Represents a hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in C may preferably be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group, and C may have substituents. １－１８ It is a hydrocarbyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom excluding the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １ＥThe hydrogen atoms contained in C may more preferably be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group, and C may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom excluding the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in are more preferably replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group.

[0122] Also, the above R １Ａ ~R １ＥFrom the viewpoint of providing a functional building block in which the physical properties such as solubility in developing solutions differ between the exposed and unexposed portions of the active light, the organic group represented is preferably an organic group having one or more polar groups having acid-dissociable groups. The number of polar groups having acid-dissociable groups included in the above organic group is not particularly limited, but for example, it is preferably 1 to 6, more preferably 1 to 5, and even more preferably 1 to 4.

[0123] <Organic group having one or more polar groups with acid-dissociable groups> The above R １Ａ ~R １Ｅ From the viewpoint of changing the solubility in the developing solution by the action of an acid, etc., it is preferable that the organic group represented by the above contains one or more polar groups having an acid-dissociable group.

[0124] R is an organic group having one or more of the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, R １Ａ ~R １Ｅ However, C may have substituents. １－１８ It is a hydrocarbyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R １Ａ ~R１Ｅ It is preferable that at least one or more hydrogen atoms thereof are replaced with a polar group having a (t) acid dissociable group, and it may have a substituent, and a C １－１８ alkyl group, C ３－１８ alicyclic group, C ６－１８ aryl group, or a C ７－１８ aralkyl group; any divalent carbon atom at a position other than the ends of the above R １Ａ to R １Ｅ may be replaced with -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); the hydrogen atoms contained in the above R １Ａ to R １Ｅ may be 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, (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; it is more preferable that at least one or more hydrogen atoms of the above R １Ａ to R １Ｅ are replaced with a polar group having a (t) acid dissociable group, and it may have a substituent, and a C １－１８ alkyl group, C ６－１８ aryl group, or a C ７－１８ aralkyl group; any divalent carbon atom at a position other than the ends of the above R １Ａ to R １Ｅ may be replaced with -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); the hydrogen atoms contained in the above R １Ａ to R １ＥIt is even more preferable that at least one hydrogen atom is replaced by a polar group having a (t) acid-dissociable group.

[0125] The above R １Ａ ~R １Ｅ It is characterized by having one or more polar groups having acid-dissociable groups, for example, polar groups such as a hydroxyl group, carboxyl group, amino group, or sulfo group having acid-dissociable groups are introduced. Examples of the above acid-dissociable groups include tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ Examples include R having one or more polar groups having the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, the following can be cited:

[0126] [* indicates a bond between a heteroatom P, Si, Ge, or Sn to an organic group having one or more acid-dissociable groups.]

[0127] Furthermore, the organic group having one or more polar groups having acid-dissociable groups according to another embodiment is not particularly limited, and examples include the organic group represented by general formula (VII-1).

[0128] (VII-1) [In general formula (VII-1), L ２Ａ１ C may have substituents. １－１２ In a hydrocarbyl group, one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are R ２Ａ１ Represents a group substituted with the L ２Ａ１ The terminal and R ２Ａ１ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ２Ａ１Each of these independently represents a polar group having an acid-dissociable group; x represents an integer from 1 to 6; and * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn.

[0129] L in an organic group represented by general formula (VII-1) ２Ａ１ L ２Ａ１ However, C may have substituents. ２－１０ In a hydrocarbyl group, one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are R ２Ｂ The group substituted for: the above L ２Ａ１ The terminal and R ２Ａ１ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), L ２Ａ１ However, C may have substituents. ２－１０ alkyl group, C ３－１０ Alicyclic group, C ６－１０ Aryl group, or C ６－１０ In an aralkyl group, one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminals are R ２Ａ１ The group substituted for: the above L ２Ａ１ The terminal and R ２Ａ１ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), L ２Ａ１ However, C may have substituents. ２－８ alkyl group, C ３－８ Alicyclic group, C ６－８ Aryl group, or C ６－８ In an aralkyl group, one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminals are each R２Ａ１ The group substituted for: the above L ２Ａ１ The terminal and R ２Ａ１ It is even more preferable that any divalent carbon atoms at any position other than the carbon atom to which the compound is bonded may be replaced with -O- or -S- (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0130] R in an organic group represented by general formula (VII-1) ２Ａ１ For example, R ２Ａ１ However, each is preferably independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group, R ２Ａ１ However, each is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; and the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ Allyl or benzyl acid-dissociating group G Ｂ , or acetal-type acid-dissociating group G Ｃ It is more preferable that R ２Ａ１ However, each is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; and the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ It is even more preferable that this be the case.

[0131] The x represented by the general formula (VII-1) is preferably an integer from 1 to 6, and may also be an integer from 2 to 4. The organic group represented by the general formula (VII-1) is R ２Ａ１ It contains one or more of the following: R ２Ａ１ When two or more of these are included, the R ２Ａ１ These may all be polar groups having the same acid-dissociating group, or they may each be polar groups having different acid-dissociating groups.

[0132] <Organic group having two or more polar groups with acid-dissociable groups> The above R １Ａ ~R １Ｅ From the viewpoint of drastically changing the solubility in the developing solution through the action of an acid, etc., it is preferable that the organic group represented by the above contains two or more polar groups having acid-dissociable groups.

[0133] R is an organic group having two or more of the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, R １Ａ ~R １Ｅ However, C may have substituents. １－１８ It is a hydrocarbyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R １Ａ ~R １Ｅ Preferably, at least two hydrogen atoms of the C are replaced by polar groups having (t) acid-dissociable groups, and the C may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １ＥThe hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R １Ａ ~R １Ｅ It is more preferable that at least two hydrogen atoms of the C are replaced by polar groups having (t) acid-dissociable groups, and the C may have substituents. １－１８ alkyl group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ It is even more preferable that at least two hydrogen atoms are replaced by polar groups having (t) acid-dissociable groups.

[0134] The above R １Ａ ~R １Ｅ It is characterized by having two or more polar groups having acid-dissociable groups, for example, polar groups such as a hydroxyl group, carboxyl group, amino group, or sulfo group having acid-dissociable groups are introduced. Examples of the above acid-dissociable groups include a tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ Examples include R having two or more polar groups having the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, the following can be cited:

[0135] [G represents an acid-dissociable group G, and * indicates the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0136] [* indicates organic group R] １Ａ ~R １Ｅ This refers to the bond with the heteroatom P, Si, Ge, or Sn to which it is bonded.

[0137] The organic group having two or more polar groups with acid-dissociable groups according to another embodiment is not particularly limited, and examples include the organic group represented by general formula (VII-2). (VII-2) [In formula (VII-2), L ２Ａ２ C may have substituents. １－１２ In the hydrocarbyl group, hydrogen atoms on carbon atoms at any position including the terminals are each R ２Ａ２ and R ２Ｂ２ Represents a group substituted with the L ２Ａ２ A divalent carbon atom at any position other than the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ２Ａ２ and R ２Ｂ２ Each of these independently represents a polar group having an acid-dissociable group, and * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn.

[0138] L in an organic group represented by general formula (VII-2) ２Ａ２ L ２Ａ２ However, C may have substituents. ２－１０ In the hydrocarbyl group, hydrogen atoms on carbon atoms at any position including the terminals are each R ２Ａ and R ２Ｂ The group substituted for: the above L ２Ａ２ The terminal and R ２Ａ２ or R ２Ｂ２A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), L ２Ａ２ However, C may have substituents. ２－１０ alkyl group, C ３－１０ Alicyclic group, C ６－１０ Aryl group, or C ６－１０ In an aralkyl group, hydrogen atoms on carbon atoms at any position, including terminals, are each R ２Ａ２ and R ２Ｂ２ The group substituted for: the above L ２Ａ２ The terminal and R ２Ａ２ or R ２Ｂ２ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), L ２Ａ２ However, C may have substituents. ２－８ alkyl group, C ３－８ Alicyclic group, C ６－８ Aryl group, or C ６－８ In an aralkyl group, hydrogen atoms on carbon atoms at any position, including terminals, are each R ２Ａ２ and R ２Ｂ２ The group substituted for: the above L ２Ａ The terminal and R ２Ａ２ or R ２Ｂ２ It is even more preferable that any divalent carbon atoms at any position other than the carbon atom to which the compound is bonded may be replaced with -O- or -S- (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0139] R in an organic group represented by general formula (VII-2) ２Ａ２ and R ２Ｂ２ For example, R ２Ａ２ and R２Ｂ２ Each of these is preferably an acid-dissociable hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group, R ２Ａ２ and R ２Ｂ２ Each of these is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; and the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ Allyl or benzyl acid-dissociating group G Ｂ , or acetal-type acid-dissociating group G Ｃ It is more preferable that R ２Ａ２ and R ２Ｂ２ Each of these is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ It is even more preferable that this be the case.

[0140] [1-1-2. (A) Cationic portion of component] As the cation portion of the heteropolyate or mixture thereof modified with the defective portion according to this embodiment, H ＋ Metal ions, onium cations, or onium dications can be used.

[0141] [1-1-2-1. Metal Ions] The metal ions that can be used as the cation portion of a heteropolyate or mixture thereof modified with a defect site are not particularly limited, for example, Li ＋ Na ＋ _K ＋ , Rb ＋ , Cs ＋ Be ２＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ Al ３＋ Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ Examples include Li ＋ Na ＋ _K ＋ , Rb ＋ , Cs ＋ Mg２＋ Ca ２＋ , Sr ２＋ Ba ２＋ Al ３＋ Co ３＋ Na is preferred. ＋ _K ＋ , Rb ＋ , Cs ＋ Ca ２＋ Al ３＋ Co ３＋ This is more preferable. These metal ions may be present individually or in combination of two or more.

[0142] [1-1-2-2. Onium Cation or Onium Dication] The onium cation or onium dication that can be used as the cation portion of a heteropolyate or mixture thereof modified with a defect site is not particularly limited, and known and commonly used ones can be used. Examples of the above onium cation or onium dication include sulfonium cation, sulfonium dication, iodonium cation, etc.

[0143] [1-1-2-2-1. Sulfonium Cations] The sulfonium cation is not particularly limited, and known and commonly used ones can be used. Examples of sulfonium cations include the organic sulfonium cation represented by the following general formula (VIII-1).

[0144] In general formula (VIII-1), R ３Ａ , R ３Ｂ and R ３Ｃ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ３Ａ , R ３Ｂ and R ３Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２- may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３Ａ , R ３Ｂ and R ３Ｃ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time); further R ３Ａ , R ３Ｂ and R ３Ｃ Any two of these are directly linked 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 alkylene groups and form a ring together with the sulfur atoms in formula (VIII-1).

[0145] In an organic sulfonium cation represented by general formula (VIII-1), the above R ３Ａ , R ３Ｂ and R ３Ｃ For example, R ３Ａ , R ３Ｂ and R ３Ｃ However, each C may independently have substituents. １－１８ It is a hydrocarbyl group; the above R ３Ａ , R ３Ｂ and R ３Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), R ３Ａ , R ３Ｂ and R ３Ｃ However, each C may independently have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ３Ａ , R ３Ｂ and R ３Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２It is more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), R ３Ａ , R ３Ｂ and R ３Ｃ However, each C may independently have substituents. ６－１８ It is an aryl group; the above R ３Ａ , R ３Ｂ and R ３Ｃ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is even more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0146] Also R ３Ａ , R ３Ｂ and R ３Ｃ Any two of these are directly linked by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)２ -, -C(=O)O-, or C １－３ Examples of structures that are linked via alkylene groups and form a ring with the sulfur atom in formula (VIII-5) include those having the thian-1-ium skeleton, thiophene-1-ium skeleton, 1,4-oxatian-4-ium skeleton, 1,4-dithiane-1-ium skeleton, 1H-thiophene-1-ium skeleton, benzo[b]thiophene-1-ium skeleton, dibenzothiophenium skeleton, 9,10-dihydrothioxanthilium skeleton, 10H-phenoxathiyne-10-ium skeleton, 5H-thiantrene-5-ium skeleton, and the following are examples. Note that * indicates that R is not involved in ring formation. ３Ａ , R ３Ｂ or R ３Ｃ It means the connection point.

[0147]

[0148] Examples of the above organic sulfonium cations include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalene-1-yl)hexahydrothiopyrillium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrillium cation, di(naphthalene-1-yl)(phenyl)sulfonium cation, and phenylbis(2-(trifluoromethyl)phenyl)sulfonium Mu cation, mesitylbis(2-(trifluoromethyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(phenyl)sulfonium cation, tris(3,5-difluorophenyl)sulfonium cation, (4-(dodecanoyloxy-3,5-dimethylphenyl))diphenylsulfonium cation, diphenyl(3-(trifluoromethoxy)phenyl)sulfonium cation, (4-(1-adamantylcarbonyloxy)phenyl)diphenylsulfonium cation, (4-phenylthiophenyl)diphenylsulfonium cation, 5-phenyl-5H-thianthrene-5-ium cation, 5-(2,5-dimethylphenyl)thianthrene-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophene-5-ium cation, 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,Examples include [d] thiophene-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b] thiophene-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, (2-bromoethyl)diphenylsulfonium cation, dimethyl(trifluoromethyl)sulfonium cation, tri-p-tolylsulfonium cation, etc.

[0149] <Organosulfonium cations having one or more polar groups with acid-dissociable groups> As sulfonium cations, from the viewpoint of providing building blocks whose solubility in the developer can be changed by the action of an acid, etc., organosulfonium cations having one or more polar groups with acid-dissociable groups may be used.

[0150] As an organosulfonium cation having one or more polar groups with acid-dissociable groups, in general formula (VIII-1), R ３Ａ , R ３Ｂ and R ３Ｃ However, each C may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ３Ａ , R ３Ｂ and R ３Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３Ａ , R ３Ｂ and R ３ＣThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); also, the above R ３Ａ One or more hydrogen atoms contained in are replaced by polar groups having (t) acid-dissociable groups, and further R ３Ａ , R ３Ｂ and R ３Ｃ Any two of these are directly linked 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 alkylene groups and form a ring together with the sulfur atoms in formula (VIII-1).

[0151] R having one or more polar groups having the above-mentioned acid-dissociable groups ３Ａ C may have substituents. １－１８It is a hydrocarbyl group; the above R ３Ａ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３Ａ Preferably, at least one hydrogen atom of the C is replaced by a polar group having a (t) acid-dissociable group, and the C may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ３Ａ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３Ａ It is more preferable that at least one hydrogen atom of the C is replaced by a polar group having an acid-dissociable group, and the C may have substituents. ６－１８ Aryl group or C ７－１８ It is an aralkyl group; the above R ３Ａ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３Ａ It is even more preferable that at least one hydrogen atom is replaced by a polar group having a (t) acid-dissociable group.

[0152] The above R ３ＡIt is characterized by having one or more polar groups having acid-dissociable groups, for example, polar groups such as a hydroxyl group, carboxyl group, amino group, or sulfo group having acid-dissociable groups are introduced. Examples of the above acid-dissociable groups include tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ These are some examples.

[0153] R having one or more polar groups having the above-mentioned acid-dissociable groups ３Ａ For example, the following can be cited. Note that * indicates the bond with the sulfur atom in general formula (VII-1).

[0154]

[0155] R ３Ｂ and R ３Ｃ Each of these may independently have substituents. １－１８ It is a hydrocarbyl group; the above R ３Ｂ and R ３Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３Ｂ and R ３Ｃ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ３Ｂ and R ３Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３Ｂ and R ３Ｃ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C１－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0156] Examples of sulfonium cations having one or more polar groups having the above acid-dissociable groups 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) Toxy)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, 5-(3,5-dimethyl-4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl )-5H-dibenzo[b,d]thiophene-5-ium cation, (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-thiophene-1-ium cation, (4-(t-butoxy)-3,5dimethylphenyl)diphenylsulfonium cation, (4- Examples include ((diisopropylcarbamoyl)oxy)phenyl)dimethylsulfonium cation, 1-(4-methoxymethoxy)naphthalen-1-yl)tetrahydro-1H-thiophene-1-ium cation, 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)tetrahydro-1H-thiophene-1-ium cation, and 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)hexahydrothiopyrillium cation.

[0157] Examples of organosulfonium cations having one or more of the above-mentioned acid-dissociable groups include the following:

[0158]

[0159] [1-1-2-2-2. Sulfonium Dication] The sulfonium dication is not particularly limited, and known and commonly used ones can be used. Examples of sulfonium dications include the organic sulfonium dication represented by the following general formula (VIII-2).

[0160] In general formula (VIII-2), R ４Ａ , R ４Ｂ , R ４Ｃ and R ４Ｄ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ４Ａ , R ４Ｂ , R ４Ｃ and R ４Ｄ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); L ４ C may have substituents. １－１８ Represents a hydrocarbylene group, and the above L ４ The divalent carbon atoms at any position are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ４Ａ , R ４Ｂ , R ４Ｃ , R ４Ｄ , and L ４The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ４Ａ , R ４Ｂ and L４ Any two of the following, and / or R ４Ｃ , R ４Ｄ and L ４ Any two of these are directly linked by a single bond, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring with the sulfur atoms in formula (VIII-2).

[0161] <Organosulfonium dications having one or more polar groups with acid-dissociable groups> As a sulfonium dication, an organosulfonium dication having one or more polar groups with acid-dissociable groups may be used, from the viewpoint that its solubility in the developer can be changed by the action of an acid, etc.

[0162] As an organic sulfonium dication having one or more polar groups with acid-dissociable groups, in general formula (VIII-2), R ４Ａ , R ４Ｂ , R ４Ｃ , R ４Ｄ , and L ４ Examples include those in which at least one hydrogen atom contained therein is replaced by a polar group having a (t) acid-dissociable group.

[0163] R having one or more polar groups with acid-dissociable groups ４Ａ , R ４Ｂ , R ４Ｃ , R ４Ｄ , and / or, L ４ Examples include those in which polar groups such as hydroxyl groups, carboxyl groups, amino groups, or sulfo groups having acid-dissociable groups are introduced. Furthermore, examples of the above-mentioned acid-dissociable groups include tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ Examples include R having one or more of the above acid-dissociable groups. ４Ａ ~R ４Ｄ For example, R has one or more polar groups that have acid-dissociable groups. ３Ａ Examples similar to those exemplified above can be given.

[0164] [1-1-2-2-3. Iodonium Cations] The iodonium cation is not particularly limited, and known and commonly used ones can be used. Examples of iodonium cations include the organic iodonium cation represented by the following general formula (VIII-3).

[0165] In general formula (VIII-3), R ５Ａ and R ５Ｂ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ５Ａ and R ５Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ５Ａ and R ５Ｂ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time); further R ５Ａ and R ５Ｂ These are linked directly by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups and form a ring together with the iodine atom in formula (VIII-3).

[0166] In the organic iodonium cation represented by the general formula (VIII-3), R ５Ａ and R ５Ｂ For example, R ５Ａ and R ５Ｂ However, each C may independently have substituents. １－１８ It is a hydrocarbyl group; the above R ５Ａ and R ５Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), R ５Ａ and R ５Ｂ However, each C may independently have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ５Ａ and R ５Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), R ５Ａ and R ５Ｂ However, each C may independently have substituents. ６－１８ It is an aryl group; the above R ５Ａ and R ５Ｂ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, or C １－１８The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is even more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0167] Examples of the above organic iodonium cations include ethynyl(phenyl)iodonium cation, bis(pyridine)iodonium cation, bis(2,4,6-trimethylpyridine)iodonium cation, diphenyliodonium cation, bis(4-(t-butyl)phenyl)iodonium cation, (2-carboxyphenyl)(phenyl)iodonium cation, (4-nitrophenyl)(phenyl)iodonium cation, and (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl) ) Iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4 (Trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-methylphenyl) Examples include (2,4,6-trimethylphenyl)iodonium cation, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, phenyl(2,4,6-trimethoxyphenyl)iodonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)(phenyl)iodonium cation, (4-(methacryloyloxy)phenyl)(phenyl)iodonium cation, and (4-(nonanoyloxy)phenyl)(phenyl)iodonium cation.

[0168] <Organiodonium cation having one or more polar groups with acid-dissociable groups> As a sulfonium cation, an organic sulfonium cation having one or more polar groups with acid-dissociable groups may be used, from the viewpoint that its solubility in the developer can be changed by the action of an acid, etc.

[0169] As an organosulfonium cation having one or more polar groups with acid-dissociable groups, in general formula (VIII-3), R ５Ａ and R ５Ｂ However, each C may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ５Ａ and R ５Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ５Ａ and R ５Ｂ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, or C １－１８The groups may be replaced by hydrocarbyloxycarbonyloxy groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); also, the above R ５Ａ One or more hydrogen atoms contained in are replaced by polar groups having (t) acid-dissociable groups, and further R ５Ａ and R ５Ｂ These are linked directly by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups and form a ring together with the iodine atom in formula (VIII-3).

[0170] R having one or more of the above acid-dissociable groups ５Ａ For example, C which may have substituents. １－１８ It is a hydrocarbyl group; the above R ５Ａ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ５Ａ Preferably, at least one hydrogen atom of the C is replaced by a polar group having a (t) acid-dissociable group, and the C may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ５Ａ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２- may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ５Ａ It is more preferable that at least one hydrogen atom of the C is replaced by a polar group having an acid-dissociable group, and the C may have substituents. ６－１８ Aryl group or C ７－１８ It is an aralkyl group; the above R ５Ａ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ５Ａ It is even more preferable that at least one hydrogen atom is replaced by a polar group having a (t) acid-dissociable group.

[0171] The above R ５Ａ It is characterized by having one or more polar groups having acid-dissociable groups, for example, polar groups such as a hydroxyl group, carboxyl group, amino group, or sulfo group having acid-dissociable groups are introduced. Examples of the above acid-dissociable groups include tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ Examples include R having one or more polar groups having the above-mentioned acid-dissociable groups. ５Ａ As an example, R has one or more polar groups having acid-dissociable groups as described above. ３Ａ Examples similar to those given as examples can be provided.

[0172] [1-1-3. Component (A) represented by general formula (I) or (I')] <Component (A) represented by general formula (I)> As a heteropoly salt or mixture thereof modified with the (A) defect site according to this embodiment, the component (A) represented by the following general formula (I) can be used. (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In formula (I), A ｍ＋ Each of them independently, H ＋ , metal ions, NH４ ＋ , represents an onium cation or onium dication; C （ａｍ）－ A represents a heteropoly acid anion in which the defective site has been modified; A ｍ＋ and / or C （ａｍ）－ It has one or more polar groups that have acid-dissociable groups; m is an integer from 1 to 5, and a is a real number greater than 0.

[0173] In heteropolyate salts or mixtures thereof modified with the defect site represented by the above general formula (I), the "metal ion," "onium cation," "onium dication," "heteropolyate anion having a defect site," and "heteropolyate anion having a defect site in which the defect site has been modified" can be any of the above as appropriate.

[0174] The component (A) represented by the above general formula (I) is characterized in that one or more polar groups having an acid-dissociable group are introduced to an onium cation or onium dication and / or a heteropoly acid anion modified with a missing site. Examples of the above acid-dissociable group include a tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ These are some examples.

[0175] The mixture of heteropoly salts modified with the defect site represented by the above general formula (I) contains multiple types of A ｍ＋ It may include multiple types of A. ｍ＋ The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0176] <Component (A) represented by general formula (I')> As a heteropoly salt or mixture thereof modified with the (A) defect site according to another embodiment, component (A) represented by the following general formula (I') can be used. (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ(C'(a'm'+bn)-) (I') [In equation (I'), A' ｍ’＋ Each of them independently, H ＋ , metal ions, or NH ４ ＋ Represents; B ｎ＋ Each of these independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents a heteropoly acid anion in which the missing site is modified in a heteropoly acid anion having a missing site; the B ｎ＋ And / or C'(a'm'+bn)- has one or more polar groups having acid-dissociable groups; 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.

[0177] In heteropoly salts or mixtures thereof modified with a defect site represented by general formula (I'), the "metal ion," "onium cation," "onium dication," "heteropoly acid anion having a defect site," and "heteropoly acid anion having a defect site in which the defect site has been modified" can be any of the above as appropriate.

[0178] A heteropolyate or mixture thereof, modified with the defect site represented by the above general formula (I'), has an onium cation such as a sulfonium cation, sulfonium dication, or iodonium cation in its cation portion, and therefore can be given the function of generating acid by exposure with DUV, XUV, EUV, electron beam, etc.

[0179] In a heteropolyate salt or mixture thereof modified with the vacancy represented by the above general formula (I'), one or more polar groups having an acid-dissociable polar group are introduced into a sulfonium cation, sulfonium dication, or iodonium cation, and / or a heteropolyate anion modified with the vacancy. It is preferable that the cationic or anionic portion of component (A) contains one or more polar groups having an acid-dissociable polar group, and it is more preferable that the cationic and / or anionic portions of component (A) together contain two or more polar groups having an acid-dissociable polar group, or that the anionic portion of component (A) contains two or more polar groups having an acid-dissociable polar group. An example of the above acid-dissociable group is a tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ These are some examples.

[0180] A mixture of heteropoly salts modified with the defect site represented by general formula (I') contains A' ｍ’＋ and B ｎ＋ The heteropoly salt may contain multiple modified defect sites with different ratios. In this case, the values ​​of a' and b can be determined, for example, by NMR analysis, XRF analysis, XPS analysis, etc.

[0181] The ratio of a' to b is a heteropoly acid anion with a modified deletion site (C'(a'm'+bn)-), A' ｍ’＋ , B ｎ＋ Depending on the type, etc., it is preferable that a':b = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a'm' + bn is an integer from 2 to 8, and m' and n are 1, it is preferable that a' is a real number from 0 to 7 and b is a real number from 1 to 8, and more preferably that a' is a real number from 0 to 4 and b is a real number from 2 to 8.

[0182] [1-1-4. Content of Component (A)] The content of component (A) in the resist material is not particularly limited and can be set appropriately depending on the method of applying the resist material to the substrate, the film thickness to be applied, etc. The content of component (A) in the resist material is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 10% by mass, when the resist material is considered to be 100% by mass.

[0183] [1-2. (B) Acid Diffusion Control Agent] The resist material according to this embodiment contains an (B) acid diffusion control agent that traps the acid generated by exposure and controls the diffusion of the acid. The above (B) component is not particularly limited, and known and conventional components can be used. Examples of acid diffusion control agents include (B1) a photodecayable base that decomposes upon exposure and loses its acid diffusion control properties, and which has an iodine atom, and (B2) a photodecayable base that does not fall under (B1), etc. These may be used individually or in combination of two or more.

[0184] [1-2-1. (B1) Photodecayable Base Having an Iodine Atom] The resist material according to this embodiment contains a photodecayable base having an iodine atom (B1). The iodine atom can increase the absorption coefficient for active light such as EUV, making it easier to decompose the photodecayable base during exposure. On the other hand, if the absorption coefficient for active light increases due to the iodine atom, it is possible that the acid generation efficiency of the acid generator itself will decrease. However, component (A) contained in the resist material according to this embodiment contains a heteropoly acid anion with a modified defect site, and has high absorption for active light such as EUV. Furthermore, when the cation portion of component (A) contains an onium cation or onium dication, acid can be efficiently generated by exposing component (A) to active light such as DUV, XUV, EUV, or electron beam. In addition, in the unexposed areas of the active light, component (B1) has the function of controlling the diffusion of the acid, whereas in the exposed areas of the active light, the presence of iodine atoms allows for the efficient decomposition of the photodecayable base of component (B1), enabling the acid to diffuse to a certain extent only in the exposed areas. As a result, it is presumed that the resist material according to this embodiment can produce a state in which both sensitivity and roughness are good.

[0185] (B1) The photodecayable base having an iodine atom is not particularly limited, and known and commonly used bases can be used. For example, the photodecayable base B represented by the following general formula (IX-1) is an example of a photodecayable base having an iodine atom. １ As shown, carboxylic acid anions and onium cations or onium dications (D ｐ＋ ) and salt can be used.

[0186] In general formula (IX-1), “R Ｂ１ " may have substituents C １－１８ A hydrocarbyl group, -C(=O)O － Any divalent carbon atom, excluding the terminals other than the bonding site, is -O-, -C(=O)-, -C(=O)O-, -OCO-, -NH-, -CONH-, -NHCO-, -S-, or -SO ２- may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time); R Ｂ１ This represents a compound in which at least one hydrogen atom is replaced by an iodine atom.

[0187] Furthermore, the above onium cation or onium dication (D ｐ＋ As for (A), the same onium cation or onium dication as the cation portion of component (A) can be used. ｐ＋ The preferred elements are sulfonium cations, sulfonium dications, and iodonium cations; more preferably sulfonium cations and iodonium cations; and even more preferably organic sulfonium cations and organic iodonium cations. ＋ represents the valence of the onium cation or onium dication, and p represents an integer of 1 or 2.

[0188] The above photodecayable base B １The carboxylic acid anions are not particularly limited, and include, for example, iodoacetate anion, 3-iodopropanoate anion, 4-iodobutanoate anion, 5-iodopentanoate anion, 6-iodohexanoate anion, 2-iodopropanoate anion, 2-iodo-2-methylpropanoate anion, 4-iodocyclohexane-1-carboxylic acid anion, 3-iodocyclohexane-1-carboxylic acid anion, 2-iodocyclohexane-1-carboxylic acid anion, iodo(phenyl)acetate anion, 2-iodo-3-butenate anion, 2 -Iodo-3-butyrate anion, cyclohexyl(iodo)acetate anion, cyclopentyl(iodo)acetate anion, iodo(4-methylphenyl)acetate anion, iodo(3-methylphenyl)acetate anion, iodo(2-methylphenyl)acetate anion, 1-iodocyclohexane-1-carboxylate anion, 1-iodocyclopentanecarboxylate anion, 6-iodobicyclo[2.2.1]heptane-2-carboxylate anion, 3-iodobicyclo[2.2.1]heptane-2-carboxylate anion, iodo(2-norbornate Nyl acetate anion, 3-iodo-5-norbornene-2-carboxylate anion, iodo(5-norbornene-2-yl) acetate anion, (2-cyclohexen-1-yl)iodoacetate anion, (2-cyclopenten-1-yl)iodoacetate anion, (3-cyclohexen-1-yl)iodoacetate anion, (3-cyclopenten-1-yl)iodoacetate anion, 2-iodobutanoate anion, 5-iodo-2-cyclohexen-1-carboxylate anion, 6-iodo-2-cyclohexen-1-carboxylate anion, 5-iod -3-Cyclohexene-1-carboxylate anion, 6-Iodo-3-Cyclohexene-1-carboxylate anion, 2-Iodo-2-methylbutanoate anion, 3-Iodo-2-methylpropanoate anion, 2-(iodomethyl)butanoate anion, 3-Iodo-2,2-dimethylpropanoate anion, 2-(iodomethyl)-2-methylbutanoate anion, 2-ethyl-2-iodobutanoate anion, 2-iodo-2-methyl-3-oxobutanoate anion, 2-iodo-2-methyl-3-oxopentanoate anion, 2-iodo-2,4-dimethyl-3-oxopentanoate anion, 2-ethyl-2-(iodomethyl)butanoate anion, 2,3-diiodopropanoate anion, diiodoacetate anion, triiodoacetate anion, 4-(2-(iodomethylcarbonyloxy)ethyloxycarbonyl)benzene-1-carboxylate anion, 4-(2-(1-iodoethylcarbonyloxy)ethyloxycarbonyl)benzene-1-carboxylate anion, 4-(2-(1-iodo-1-methylethylcarbonyloxy)ethyloxycarbonyl)benzene-1-carboxylate anion n, 4-(2-(iodomethylcarbonyloxy)ethyloxycarbonyl)cyclohexane-1-carboxylate anion, 4-(2-(1-iodoethylcarbonyloxy)ethyloxycarbonyl)cyclohexane-1-carboxylate anion, 4-(2-(1-iodo-1-methylethylcarbonyloxy)ethyloxycarbonyl)cyclohexane-1-carboxylate anion, 2-iodo-3-oxobutanoate anion, 2-iodo-3-oxopentanoate anion, 2-iodo-4-methyl-3-oxopentanoate anion, 2-iodo-4,4-dimethyl-3-oxopentanoate anion, 3-cyclopentyl-2-iodo-3-oxopropanoate anion, 3-cyclohexyl-2-iodo-3-oxopropanoate anion, 2-benzoyl-2-iodoacetate anion, iodo(4-nitrophenyl)acetate anion, iodo(3-nitrophenyl)acetate anion, iodo(2-nitrophenyl)acetate anion, (iodomethylcarbonyloxy)acetate anion, (1-iodoethylcarbonyloxy)acetate anion, (1-iodo-1-methylethylcarbonyloxy)acetate anion, (2-iodoethylcarbonyloxy)acetate anion, 2-(iodomethylcarbonyloxy)propanoate anion, 3-(iodomethylcarbonyloxy)propanoate anion Examples include (iodomethylcarbonyloxy)propanoate anion, 4-(iodomethylcarbonyloxy)butanoate anion, 2-(iodomethylcarbonyloxy)-2-methylpropanoate anion, 1-(iodomethylcarbonyloxy)cyclopentane-2-carboxylate anion, 1-(iodomethylcarbonyloxy)cyclohexane-1-carboxylate anion, 5-(iodomethylcarbonyloxy)pentanoate anion, (2-(iodomethylcarbonyloxy)ethyloxy)acetate anion, (2-(1-iodoethylcarbonyloxy)ethyloxy)acetate anion, (2-(1-iodo-1-methylethylcarbonyloxy)ethyloxy)acetate anion, etc.

[0189] The above photodecayable base B １ Examples of carboxylic acid anions include the following:

[0190]

[0191]

[0192]

[0193] Photodecayable base B having an iodine atom represented by the general formula (IX-1) １From the viewpoint of having good absorption to active light and efficiently decomposing photodecayable bases, those having an aromatic hydrocarbon cyclic group containing an iodine atom are preferred. An example of a photodecayable base having the above-mentioned aromatic hydrocarbon cyclic group containing an iodine atom is photodecayable base B represented by the following general formula (IX-1-1). １Ａ , photodecayable base B represented by the following general formula (IX-1-2) １Ｂ , photodecayable base B represented by the following general formula (IX-1-3) １Ｃ , photodecayable base B represented by the following general formula (IX-1-4) １Ｄ These are some examples.

[0194] <Photodecayable base B １Ａ > Photodecayable base B represented by general formula (IX-1-1) １Ａ It is characterized by having an aromatic hydrocarbon cyclic group containing an iodine atom.

[0195] In general formula (IX-1-1), “Ar Ｂ１ａ " represents a monovalent aromatic hydrocarbon cyclic group which may have substituents, wherein at least one hydrogen atom on the aromatic hydrocarbon cyclic group is replaced by an iodine atom, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be replaced by any substituent. In the above monovalent aromatic hydrocarbon cyclic group, it is preferable that at least one hydrogen atom on the aromatic hydrocarbon cyclic group is replaced by an iodine atom, and more preferably that at least two hydrogen atoms are replaced by an iodine atom.

[0196] Examples of monovalent aromatic hydrocarbon cyclic groups include phenyl groups, naphthyl groups, 4,4'-biphenyl groups, phenantrenyl groups, and anthyl groups.

[0197] The above photodecayable base B １ＡThe carboxylic acid anion is not particularly limited, and for example, 2-hydroxy-5-iodobenzoate anion, 2-hydroxy-3,5-diiodobenzoate anion, 2-hydroxy-3,5,6-triiodobenzoate anion, 3,5-diiodobenzoate anion, 2,3,5-triiodobenzoate anion, 2-hydroxy-4,5-diiodobenzoate anion, 3-hydroxy-2,4,6-triiodobenzoate anion, 4-iodobenzoate anion, 3,5-diiodo-2-methoxybenzoate anion, 3,5-diiodo-4-methoxybenzoate anion Anions, 2-ethoxy-3,5-diiodobenzoate anion, 2,3,6-triiodo-5-methoxybenzoate anion, 3-hydroxy-4-iodonaphthalene-2-carboxylate anion, 3-hydroxy-4-iodonaphthalene-1-carboxylate anion, 6-hydroxy-1-iodonaphthalene-2-carboxylate anion, 4-iodo-3-methoxynaphthalene-2-carboxylate anion, 3,4-diiodonaphthalene-2-carboxylate anion, 6-iodoanthracene-2-carboxylate anion, 5,7-diiodonaphthalene-2-carboxylate anion Anions, 5,8-diiodonaphthalene-2-carboxylate anion, 3,7-diiodonaphthalene-2-carboxylate anion, 1,6-diiodonaphthalene-2-carboxylate anion, 6,8-diiodonaphthalene-2-carboxylate anion, 5,7-diiodonaphthalene-1-carboxylate anion, 5,8-diiodonaphthalene-1-carboxylate anion, 3,7-diiodonaphthalene-1-carboxylate anion, 4,7-diiodonaphthalene-1-carboxylate anion, 6,8-diiodonaphthalene-1-carboxylate anion, 1,4,7-triiodona Phthalene-2-carboxylate anion, 1,3,6-triiodonaphthalene-2-carboxylate anion, 4,6,8-triiodonaphthalene-2-carboxylate anion, 5,6,7-triiodonaphthalene-2-carboxylic acid, 2,4,7-triiodonaphthalene-1-carboxylate anion, 5,6,7-triiodonaphthalene-1-carboxylate anion, 3,5,8-triiodonaphthalene-1-carboxylate anion, 3,5,7-triiodonaphthalene-1-carboxylate anion, 1,3,5,7-tetraiodonaphthalene-2-carboxylate anion, 1,3,4,7-tetraiodonaphthalene-2-carboxylate anion, 1,3,5,6,7-pentaiodonaphthalene-2-carboxylate anion, 3-hydroxy-1,5,7-triiodonaphthalene-2-carboxylate anion, 3-hydroxy-1,4,7-triiodonaphthalene-2-carboxylate anion, 6-hydroxy-1,4,7-triiodonaphthalene-2-carboxylate anion, 6-hydroxy-3,5,7-triiodonaphthalene-2-carboxylate anion, 1-hydroxy-4,6,8-triiodonaphthalene-2-carboxylate anion, Examples include 1-hydroxy-3,4,7-triiodonaphthalene-2-carboxylate anion, 1-hydroxy-5,6,7-triiodonaphthalene-2-carboxylate anion, 2-hydroxy-4,6,8-triiodonaphthalene-1-carboxylate anion, 2-hydroxy-5,6,7-triiodonaphthalene-1-carboxylate anion, 1,3,5,7-tetraiodoanthracene-2-carboxylate anion, 1,3,5,6,7-pentaiodoanthracene-2-carboxylate anion, 6-hydroxy-1,3,5,7-tetraiodoanthracene-2-carboxylate anion, 3-hydroxy-1,5,6,7-tetraiodoanthracene-2-carboxylate anion, and 1-hydroxy-3,5,6,7-tetraiodoanthracene-2-carboxylate anion.

[0198] The above photodecayable base B １Ａ Examples of carboxylic acid anions include the following:

[0199]

[0200]

[0201]

[0202]

[0203] <Photodecayable base B １Ｂ > Photodecayable base B represented by general formula (IX-1-2) １Ｂ It is characterized by having an aromatic hydrocarbon cyclic group having an iodine atom, and having a predetermined linker between the carboxylic acid anion and the aromatic hydrocarbon cyclic group.

[0204] In general formula (IX-1-2), “Ar Ｂ１ｂ " is the "Ar" in the above general formula (IX-1-1). Ｂ１ａ This represents something similar to "[...]".

[0205] Also, "L Ｂ１ｂ " may have substituents C １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ This represents a component that may be replaced by a negative (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0206] L Ｂ１ｂ C may have substituents. １－１２ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or preferably -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, or -NH(C=O)-, and may have substituents. １－８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or more preferably -O-, -C(=O)-, -O-C(=O)-, -NH-, -CONH-, or -NH(C=O)-.

[0207] The above photodecayable base B １ＢThe carboxylic acid anion is not particularly limited, and for example, (2,3,5-triiodophenyl)acetate anion, 3-(2,3,5-triiodophenyl)propanoate anion, (2,3,5-triiodophenylcarbonyloxy)acetate anion, ((2,4,6-triiodophenyl)methyloxy)acetate anion, 3-(2,3,5-triiodophenylcarbonyloxy)propanoate anion, 4-(2,3,5-triiodophenylcarbonyloxy)butanoate anion, 5-(2,3,5-triiodophenylcarbonyloxy)pentanoate anion, 6-(2,3,5-triio (2,3,5-triiodophenylcarbonyloxy)hexanoate anion, 7-(2,3,5-triiodophenylcarbonyloxy)heptanoate anion, 4-(2,3,5-triiodophenylcarbonyloxy)cyclohexane-1-carboxylate anion, 5-(2,3,5-triiodophenylcarbonyloxy)bicyclo[2.2.1]heptane-2-carboxylate anion, 3-(2,3,5-triiodophenylcarbonyloxy)adamantane-1-carboxylate anion, 3-(3-(2,3,5-triiodophenylcarbonyloxy) Damantane-1-ylcarbonyloxy)propanoate anion, 6-(2,3,5-triiodophenylcarbonyloxy)bicyclo[2.2.1]heptane-2-carboxylic acid anion, 6-(2,3,5-triiodophenylcarbonyloxy)-7-oxabicyclo[2.2.1]heptane-2-carboxylic acid anion, 3-(2,3,5-triiodophenylcarbonyloxy)cyclohexane-1-carboxylic acid anion, (2,3,5-triiodophenylcarbonylamino)acetate anion, 2-(2,3,5-triiodophenyl (N-methyl(2,3,5-triiodophenyl)carbonylamino) acetate anion, (2,4,6-triiodophenyloxy) acetate anion, (2,4,6-triiodophenyloxycarbonyl) acetate anion, 3-(2,4,6-triiodophenyloxycarbonyl) propanoate anion, 4-(2,4,6-triiodophenyloxycarbonyl) butanoate anion, 5-(2,4,6-triiodophenyloxycarbonyl) pentanoate anion, (E)-3-(2,4,6-triiodophenyloxycarbonyl)acrylate anion, 3-(2,4,6-triiodophenyloxycarbonyl)propiolate anion, 4-(2,4,6-triiodophenyloxycarbonyl)cyclohexane-1-carboxylate anion, 5-(2,4,6-triiodophenyloxycarbonyl)bicyclo[2.2.1]heptane-2-carboxylate anion, 2-(2,4,6-triiodophenylcarbonyl)cyclohexane-1-carboxylate anion, (Z)-3-(2,4,6-triiodophenyloxycarbonyl)acrylate anion, 3-((4-iodophenyl)(aminocal Bonyloxy))propanoate anion, 4-((3-iodophenyl)(aminocarbonyloxy))butanoate anion, 3-((3,4,5-triiodophenyl)(aminocarbonyloxy)propanoate anion, 4-(N-3,4,5-triiodophenylcarbamoyl)butanoate anion, 3-(N-3,4,5-triiodophenylcarbamoyl)propanoate anion, (N-3,4,5-triiodophenylcarbamoyl)acetate anion, 2,4,6-triiodophenyloxycarbonylcarboxylic acid anion, 2-((3-hydroxy-2,4,6-triiodophenyl)methyl)butanoate anion, (4-iodophenyl)(oxo)acetate anion, (3-iodophenyl)(oxo)acetate anion, (2-iodophenyl)(oxo)acetate anion, (2-hydroxy-5-iodophenyl)(oxo)acetate anion, (2-bromo-5-iodophenyl)(oxo)acetate anion, (3-bromo-2-iodophenyl)(oxo)acetate anion, (4-chloro-3-iodophenyl)(oxo)acetate anion, (2-fluoro-5-iodophenyl)(oxo)acetate anion, (2- Chloro-5-iodophenyl)(oxo)acetate anion, N-4-iodophenylcarbamoylcarboxylate anion, N-3-iodo-5-methylphenylcarbamoylcarboxylate anion, N-3-bromo-4-iodophenylcarbamoylcarboxylate anion, (2-hydroxy-4,5-diiodophenyl)(oxo)acetate anion, (4-hydroxy-3,5-diiodophenyl)(oxo)acetate anion, N-3,5-diiodophenylcarbamoylcarboxylate anion, N-2,4-diiodo-6-(methyloxycarbonyl)phenylcarbamoylcarboxylate anion, N-2,4-diiodo-5-(methylcarbonylamino)phenylcarbamoylcarboxylate anion, (3,5-diiodo-4-methoxyphenyl)(oxo)acetate anion, oxo(2,3,5-triiodophenyl)acetate anion, (3-hydroxy-2,4,6-triiodophenyl)(oxo)acetate anion, 3-(4-iodophenyl)-2-oxopropanoate anion, 4-(4-iodophenyl)-2-oxobutanoate anion, 4-(3-hydroxy-4-iodophenyl)-2-oxobutanoate anion, 4-(4-iodo-3-methoxyphenyl)-2-oxobutanoate anion, 3-(4 Examples include (-iodophenyloxy)-2-oxopropanoate anion, 5-(4-iodophenyloxy)-2-oxopentanoate anion, 4-(4-iodophenyl)-2,4-dioxobutanoate anion, 3-(4-iodophenylthio)-2-oxopropanoate anion, 3-(4-hydroxy-3,5-diiodophenyl)-2-oxopropanoate anion, 3-(2-hydroxy-3,5-diiodophenyl)-2-oxopropanoate anion, 3-(3,5-diiodo-4-methoxyphenyl)-2-oxopropanoate anion, 2-oxo-3-(2,3,5-triiodophenyl)propanoate anion, and 2-oxo-4-(2,3,5-triiodophenyl)butanoate anion.

[0208] The above photodecayable base B １Ｂ Examples of carboxylic acid anions include the following:

[0209]

[0210]

[0211]

[0212]

[0213] <Photodecayable base B １Ｃ > Photodecayable base B represented by general formula (IX-1-3) １ＣIt is characterized by having at least two or more aromatic hydrocarbon cyclic groups, having a predetermined linker between the two aromatic hydrocarbon cyclic groups, and having at least one of the two aromatic hydrocarbon cyclic groups having an iodine atom.

[0214] In general formula (IX-1-3), “Ar Ｂ１ｃ １ " represents a divalent aromatic hydrocarbon cyclic group which may have substituents. Examples of divalent aromatic hydrocarbon cyclic groups include phenylene groups (1,2-phenylene, 1,3-phenylene, 1,4-phenylene), naphthylene groups (1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene), phenanthrylene groups, and anthrylene groups. Preferably, at least one hydrogen atom on the above divalent aromatic hydrocarbon cyclic group is replaced by an iodine atom, and more preferably, two or more hydrogen atoms are replaced by hydrogen atoms. Furthermore, any hydrogen atoms other than those mentioned above on the above aromatic hydrocarbon cyclic group may be substituted with any substituent.

[0215] Also, "Ar Ｂ１ｃ ２ " represents a monovalent aromatic hydrocarbon cyclic group which may have substituents. Examples of monovalent aromatic hydrocarbon cyclic groups include phenyl group, naphthyl group, 4,4'-biphenyl group, phenantrenyl group, and anthryl group. Preferably, at least one hydrogen atom on the above monovalent aromatic hydrocarbon cyclic group is replaced by an iodine atom, and more preferably, two or more hydrogen atoms are replaced by hydrogen atoms. Furthermore, any hydrogen atoms other than those mentioned above on the above aromatic hydrocarbon cyclic group may be substituted with any substituent.

[0216] Photodecayable base B represented by general formula (IX-1-3) １Ｃ In "Ar Ｂ１ｃ １ " or "Ar Ｂ１ｃ ２ At least one of the following contains one or more iodine atoms, preferably one or more iodine atoms in each, and more preferably three or more iodine atoms in total.

[0217] Furthermore, "L Ｂ１ｃ " is a single bond or a C which may have a substituent １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ This represents a component that may be replaced by a negative (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0218] L Ｂ１ｃ C may have single bonds or substituents. １－１２ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or preferably -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, or -S-, and may have substituents. １－８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or more preferably -O-, -C(=O)-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, or -S-.

[0219] The above photodecayable base B １ＣThe carboxylic acid anion is not particularly limited, and for example, 5-iodo-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylic acid anion, 4-iodo-5-methyl-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylic acid anion, 2,4-diiodo-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylic acid anion, 2,4,6-triiodo-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylic acid anion, 3-iodo-4-(2,3,5-triiodophenyl Carbonylamino)benzene-1-carboxylate anion, 2-iodo-6-(trifluoromethyl)-4-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-4-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 2,3,5,6-tetraiodo-4-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(4-iodophenylcarbonylamino)benzene-1-carboxylate anion Rubonic acid anion, 3,5-diiodo-2-(2-iodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(3-iodophenylcarbonylamino)benzene-1-carboxylate anion, 2-(3-bromo-5-iodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 3,5-diiodo-2-(2-iodo-6-methylphenylcarbonylamino)benzene-1-carboxylate anion, 2-(3-hydroxy-5-iodophenylcarbonylamino)-3 ,5-diiodobenzene-1-carboxylate anion, 2-(3-amino-5-iodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 2-(3,5-diiodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 6-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 4-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 5-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 4-iodo-6-methyl-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3-chloro-5-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 4-fluoro-5-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion Benzone anion, 4-ethyl-6-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 6-hydroxy-4-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 5-iodo-4-methoxy-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 4-cyano-6-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 4-iodo-5-nitro-2 - (2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 6-bromo-4-iodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,4-diiodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 4,6-diiodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 6-fluoro-3,5-diiodo-2-(2,3,5-triiodophenylcarbonylamino) Benzene-1-carboxylate anion, 3,4,5,6-tetraiodo-2-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 5-iodo-2-(N-(propan-2-yl)(2,3,5-triiodophenyl)carbonylamino)benzene-1-carboxylate anion, 5-iodo-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 4-iodo-5-methyl-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 2,4-diiodo-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 2,4,6-triiodo-3-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3-iodo-4-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 2-iodo-6-(trifluoromethyl)-4-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-4-(2,3,5-triiodo Phenylcarbonylamino)benzene-1-carboxylate anion, 2,3,5,6-tetraiodo-4-(2,3,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(4-iodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(2-iodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(3-iodophenylcarbonylamino)benzene-1-carboxylate anion, 2-(3-bromo-5-iod Phenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 3,5-diiodo-2-(2-iodo-6-methylphenylcarbonylamino)benzene-1-carboxylate anion, 2-(3-hydroxy-5-iodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 2-(3,5-diiodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 2-(2,3-diiodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion On, 3,5-diiodo-2-(2,4,5-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(2,4,6-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(2,3,4-triiodophenylcarbonylamino)benzene-1-carboxylate anion, 3,5-diiodo-2-(2,3,4,6-tetraiodophenylcarbonylamino)benzene-1-carboxylate anion, 2-(3,4-diiodophenylcarbonylamino)-3,5-Diiodobenzene-1-carboxylate anion, 2-(2,4-diiodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 2-(2,5-diiodophenylcarbonylamino)-3,5-diiodobenzene-1-carboxylate anion, 2-((3,5-diiodophenyl)methylcarbonyloxy)-3,5-diiodobenzene-1-carboxylate anion, 2-(2-(3,5-diiodophenyl)ethoxy)-3,5-diiodobenzene-1 Examples include carboxylate anions, 3,5-diiodo-2-(2-(4-iodophenyl)ethylcarbonylamino)benzene-1-carboxylate anions, 2-iodo-5-((2,3,5-triiodophenylcarbonylamino)methyl)benzene-1-carboxylate anions, 3,5-diiodo-2-(phenylcarbonylamino)benzene-1-carboxylate anions, and 3,5-diiodo-2-(naphthalene-2-ylcarbonylamino)benzene-1-carboxylate anions.

[0220] The above photodecayable base B １Ｃ Examples of carboxylic acid anions include the following:

[0221]

[0222]

[0223]

[0224]

[0225] <Photodecayable base B １Ｄ > Photodecayable base B represented by general formula (IX-1-4) １Ｄ The material is characterized by having at least two aromatic hydrocarbon cyclic groups, having a predetermined linker between the carboxylic acid anion and the aromatic hydrocarbon cyclic group, and between the two aromatic hydrocarbon cyclic groups, and having at least one of the two aromatic hydrocarbon cyclic groups having an iodine atom.

[0226] In general formula (IX-1-4), “Ar Ｂ１ｄ １ " and "Ar Ｂ１ｄ２ " are the same as "Ar" in the general formula (IX-1-3) Ｂ１ｃ 1" and "Ar Ｂ１ｃ ２ This represents something similar to . Photodecayable base B, represented by the general formula (IX-1-3). １Ｄ In "Ar Ｂ１ｄ １ " or "Ar Ｂ１ｄ ２ At least one of the following contains one or more iodine atoms, preferably one or more iodine atoms in each, and more preferably three or more iodine atoms in total.

[0227] Also, "L Ｂ１ｄ １ " may have substituents C １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ This represents a component that may be replaced by a negative (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0228] L Ｂ１ｄ １ C may have substituents. １－１２ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or preferably -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, or -NH(C=O)-, and may have substituents. １－８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or more preferably -O-, -C(=O)-, -O-C(=O)-, -NH-, -CONH-, or -NH(C=O)-.

[0229] Furthermore, "L Ｂ１ｄ ２ " is a single bond or a C which may have a substituent １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ This represents a component that may be replaced by a negative (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0230] L Ｂ１ｄ ２ C may have single bonds or substituents. １－１２ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or preferably -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, or -S-, and may have substituents. １－８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), or more preferably -O-, -C(=O)-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, or -S-.

[0231] The above photodecayable base B １Ｄ The carboxylic acid anion is not particularly limited, and for example, (5-iodo-2-(4-iodophenylcarbonyloxy)phenyl)(oxo)acetate anion, (2-(3,5-diiodophenylcarbonyloxy)-5-iodophenyl)(oxo)acetate anion, (5-iodo-2-(2,3,5-triiodophenylcarbonyloxy)phenyl)(oxo)acetate anion, 4-(4-iodo-3-(2,3,5-triiodophenylcarbonyloxy)phenyl)-2-oxobutanoate Examples include anions such as (3,5-diiodo-4-(4-iodophenylcarbonyloxy)phenyl)(oxo)acetate anion, (4-(3,5-diiodophenylcarbonyloxy)-3,5-diiodophenyl)(oxo)acetate anion, (3,5-diiodo-4-(2,3,5-triiodophenylcarbonyloxy)phenyl)(oxo)acetate anion, and (3,5-diiodo-4-(2,3,4,5,6-pentaiodophenylcarbonyloxy)phenyl(oxo)acetate anion.

[0232] The above photodecayable base B １Ｄ Examples of carboxylic acid anions include the following:

[0233]

[0234] [1-2-2. Photodecayable bases not falling under (B2) and (B1)] The resist material according to this embodiment may contain photodecayable bases not falling under (B2) and (B1). The above photodecayable base is not particularly limited, and known and commonly used ones can be used.

[0235] (B2) Examples of photodecayable bases include "carboxylate compound B" represented by the following general formula (IX-2-1). ２Ａ ", represented by the following general formula (IX-2-2), "sulfonate compound B" ２Ｂ ", and "sulfonylamide salt compound B" represented by the following general formula (IX-2-3) ２Ｃ Examples include carboxylic acid anions, sulfonate anions, sulfonylamide anions, onium cations or onium dications (Dｐ＋ The following will be explained in this order.

[0236] [1-2-2-1. Carboxylate Compound B] ２Ａ The above (B2) photodecayable base is "carboxylate compound B" represented by the following general formula (IX-2-1). ２Ａ " and onium cation or onium dication (D ｐ＋ ) and salt can be used.

[0237] "R Ｂ２ａ " may have substituents C １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0238] R Ｂ２ａ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0239] <Carboxylate compound B> ２Ａ１> Carboxylate compound B represented by the above general formula (IX-2-1) ２Ａ This is carboxylate compound B, represented by the following general formula (IX-2-1-1). ２Ａ１ That's fine.

[0240] "X Ｂ２ａ " may have substituents C １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0241] X Ｂ２ａ C may have substituents. ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. ３－１８ Alicyclic group, or C ６－１８ An aryl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0242] "L Ｂ２ａ " is X Ｂ２ａ to-COO － A base that connects and the following general formula (L Ｂ２Ａ -1) to (L Ｂ２Ａ A linking group represented by -7) can be used. [In the formula, L Ｂ２ａ １ and L Ｂ２ａ ２ C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ｂ２ａ The connection part is, *2 is -COO － This represents the connection point.

[0243] L Ｂ２ａ １ and L Ｂ２ａ ２ This may consist of a single bond or a C that may have a substituent. １－８ Alkylene group or C ６－８ It is preferably an arylene group, and may have a single bond or a substituent. １－８ It is more preferable that the group be an alkylene group.

[0244] <Example of a carboxylate anion> The above carboxylate salt compound B ２Ａ or B ２Ａ１ The carboxylic acid anions are not particularly limited, and examples include trifluoroacetate anion, pentafluoropropionate anion, 2-methoxyacetate anion, 2-methoxy-2-methylpropionate anion, 2-hydroxyacetate anion, 2-hydroxy-2-methylpropionate anion, 2-acetoxyacetate anion, adamantane-1-carboxylic acid anion, 9,10-dihydro-9,10-ethanoanthracene-11-carboxylic acid anion, 9,10-dihydro-9,10-[1,2]benzenoanthracene-9-carboxylic acid anion, benzoate anion, salicylate anion, 3-hydroxybenzoate anion, 3-trifluoromethylbenzoate anion, and the like.

[0245]

[0246]

[0247]

[0248] [1-2-2-2. Sulfonate Compound B] ２Ｂ The above (B2) photodecayable base is "sulfonate compound B" represented by the following general formula (IX-2-2). ２Ｂ " and sulfonate anion and onium cation or onium dication (D ｐ＋ ) and salt can be used.

[0249] "R Ｂ２ｂ " may have substituents C １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0250] R Ｂ２ｂ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0251] <Sulfonate compound B> ２Ｂ１ > Sulfonate compound B represented by the above general formula (IX-2) ２Ｂ However, sulfonate compound B, represented by the following general formula (IX-2-2-1) ２Ｂ１That's fine.

[0252] "X Ｂ２ｂ " may have substituents C １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0253] X Ｂ２ｂ C may have substituents. ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. ３－１８ Alicyclic group, or C ６－１８ An aryl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0254] "L Ｂ２ｂ " is X Ｂ２ｂ to-SO ２ -O － A base that connects and the following general formula (L Ｂ２Ｂ -1) to (L Ｂ２Ｂ A linking group represented by -7) can be used. [In the formula, L Ｂ２ｂ １ and L Ｂ２ｂ ２ C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ｂ２ｂ The connection point is, *2 is -SO ２ -O － This represents the connection point.

[0255] L Ｂ２ｂ １ and L Ｂ２ｂ ２ This may consist of a single bond or a C that may have a substituent. １－８ Alkylene group or C ６－８ It is preferably an arylene group, and may have a single bond or a substituent. １－８ It is more preferable that the group be an alkylene group.

[0256] <Example of sulfonate anion> The above sulfonate compound B ２Ｂ or B ２Ｂ１ The sulfonate anions are not particularly limited and include, for example, camphor sulfonate anion, (adamantan-1-yl)methanesulfonate anion, (adamantan-1-carbonyloxy)ethane-1-sulfonate anion, cyclohexanesulfonate anion, 2-(cyclohexanecarbonyloxy)ethane-1-sulfonate anion, bicyclo[2.2.1]heptane-2-sulfonate anion, benzenesulfonate anion, 4-methylbenzenesulfonate anion, and the like.

[0257]

[0258] [1-2-2-3. Sulfonylamide salt compound B] ２Ｃ ] The above (B2) photodecayable base is "sulfonylamide compound B" represented by the following general formula (IX-2-3). ２Ｃ " and sulfonylamide anion and onium cation or onium dication (D ｐ＋ ) and salt can be used.

[0259] "R Ｂ２ｃ １ " may have substituents C １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time). Ｂ２ｃ ２ " may have substituents C １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0260] R Ｂ２ｃ １ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0261] R Ｂ２ｃ ２ C may have substituents. １－１８ alkyl group, C ３－１８In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), C １－１２ It is more preferably a haloalkyl group, C １－５ It is even more preferable that the alkyl group is a fluorinated alkyl group.

[0262] <Sulfonylamide compound B> ２Ｃ１ > Sulfonylamide salt compound B represented by the above general formula (IX-2) ２Ｃ However, sulfonylamide salt compound B, represented by the following general formula (IX-2-3-1) ２Ｃ１ That's fine.

[0263] "X Ｂ２ｃ " may have substituents C １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0264] X Ｂ２ｃ C may have substituents. ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. ３－１８ Alicyclic group, or C ６－１８An aryl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0265] "L Ｂ２ｃ " is X Ｂ２ｃ to-N － -SO ２ -R Ｂ２ｃ ２ A base that connects and the following general formula (L Ｂ２Ｃ -1) to (L Ｂ２Ｃ A linking group represented by -7) can be used. [In the formula, L Ｂ２ｃ １ and L Ｂ２ｃ ２ C may have a single bond or a substituent. １－１２ This represents a hydrocarbylene group, and *1 is X Ｂ２ｃ The connection point is, *2 is -N － -SO ２ -R Ｂ２ｃ ２ This represents the connection point.

[0266] L Ｂ２ｃ １ and L Ｂ２ｃ ２ This may consist of a single bond or a C that may have a substituent. １－１２ Alkylene group, C １－１２ Cycloalkylene group or C ６－１２ It is preferably an arylene group, and may have a single bond or a substituent. １－８ Alkylene group or C １－８ It is more preferable that the group be a cycloalkylene group.

[0267] <Example of sulfonylamide anion> The above sulfonylamide salt compound B Ｃ or B Ｃ１The sulfonylamide anion is not particularly limited, and includes, for example, methyl((trifluoromethyl)sulfonyl)amide anion, i-propyl((trifluoromethyl)sulfonyl)amide anion, methacryloyloxy((trifluoromethyl)sulfonyl)amide anion, 2-(methacryloyloxy)ethyl((trifluoromethyl)sulfonyl)amide anion, cyclohexyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclopentanecarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclohesanylcarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1 Examples include heptane-2-ylmethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1]heptane-7-ylmethyl((trifluoromethyl)sulfonyl)amide anion, 2-((adamantane-1-carbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(adamantane-1-carboxamide)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(4-((adamantane-1-carbonyl)oxy)cyclohexyl)ethyl((trifluoromethyl)sulfonyl)amide anion, and 4-((adamantane-1-carbonyl)oxy)phenyl((trifluoromethyl)sulfonyl)amide anion.

[0268]

[0269]

[0270]

[0271] [1-2-2-4. Onium cation or onium dication (D ｐ＋ )] The cation portion of the above (B1) photodecayable base is an onium cation or an onium dication (D ｐ＋ ) can be used. Note that the above onium cation or onium dication (D ｐ＋ As for (A), the same onium cation or onium dication as the cation portion of component (A) can be used. ｐ＋The onium cation is preferably a sulfonium cation, a sulfonium dication, or an iodonium cation; more preferably a sulfonium cation or an iodonium cation; and even more preferably an organic sulfonium cation or an organic iodonium cation. Furthermore, p+ represents the valence of the onium cation or onium dication, and p represents an integer of 1 or 2.

[0272] [1-2-3. (B1) Photodecayable base having an iodine atom in the cation portion] The photodecayable base having an iodine atom in (B1) according to this embodiment is further described as the above "carboxylate compound B ２Ａ "Sulfonate compound B" ２Ｂ " or "Sulfonylamide salt compound B ２Ｃ This also includes cases where the onium cation or onium dication of the cation portion of the photodecayable base described above in (B1) Photodecayable base having an iodine atom is an onium cation or onium dication having an iodine atom, in which case the anion portion and the cation portion of the photodecayable base will both have an iodine atom. Furthermore, a photodecayable base having an iodine atom in both the anion portion and the cation portion is more preferable from the viewpoint of having a large absorption coefficient for active light such as EUV and causing decomposition of the photodecayable base upon exposure.

[0273] The onium cation or onium dication having the iodine atom is not particularly limited, and known and commonly used ones can be used. As an onium cation having the iodine atom, for example, a triarylsulfonium cation represented by the following general formula (X) can be used.

[0274] In general formula (X), Ar ６Ａ ~Ar ６Ｃ Each of these may independently have substituents. ６－１８ Represents an aryl group, as shown above Ar ６Ａ ~Ar ６ＣAny two of these are directly linked by a single bond, or are divalent linking groups C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ - may be connected via a link and form a ring with the sulfur atom in formula (X), and the above Ar ６Ａ Ar ６Ｂ or Ar ６Ｃ At least one of the hydrogen atoms above is substituted with an iodine atom.

[0275] In the triarylsulfonium cation represented by general formula (X), the above Ar ６Ａ ~Ar ６Ｃ This is not particularly limited, and may include, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenantrenyl group, an anthracenyl group, etc., which may have substituents. ６－１８ It is preferably an aryl group, and more preferably a phenyl group, 1-naphthyl group, or 2-naphthyl group, which may have substituents.

[0276] Furthermore, in the triarylsulfonium cation represented by the general formula (X), the above Ar ６Ａ ~Ar ６Ｃ Any two of these are directly linked by a single bond, or are divalent linking groups C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ Examples of structures where the atoms are linked via a - and form a ring with the sulfur atom in formula (X) include those having a 9-thia-9H-fluorene-9-ium skeleton, a 9-thia-9,10-dihydroanthracene-9-ium skeleton, a 10H-phenoxatiyne-10-ium skeleton, a 5H-thianthrene-5-ium skeleton, a 9-thia-9,10-dihydroanthracene-9-ium-10-one skeleton, and a 5,10-dihydrothianthrene-5-ium-10,10-dione skeleton. More specifically, examples include those having the following skeletons. Note that in the following chemical structural formulas, * indicates Ar that is not involved in ring formation. ６Ａ Ar６Ｂ or Ar ６Ｃ This represents the bond with the sulfur atom in general formula (X).

[0277]

[0278] In the triarylsulfonium cation represented by general formula (X), the above Ar ６Ａ Ar ６Ｂ or Ar ６Ｃ At least one of the hydrogen atoms above is substituted with an iodine atom. From the viewpoint of increasing the absorption coefficient of the triarylsulfonium cation to active light and improving its sensitivity, it is preferable that the triarylsulfonium cation contains one or more iodine atoms, and more preferably two or more.

[0279] Also, the above Ar ６Ａ Ar ６Ｂ and Ar ６Ｃ A C which may have a substituent represented by this C ６－１８ In the aryl group, substituents other than the iodine atom include, for example, a hydroxyl group, a thiol group, an amino group, or a C atom which may have substituents. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, or C １－１８ Electron-donating groups such as hydrocarbylthio groups; fluorine atom, chlorine atom, bromine atom, C １－５ C may have a haloalkyl group, a nitro group, a sulfo group, or a substituent. １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbyl sulfinyl group, or C １－１８Examples include electron-withdrawing groups such as hydrocarbyl sulfonyl groups; polar groups having acid-dissociating groups; and organic groups containing polar groups having acid-dissociating groups. Among these, substituents other than iodine atoms include fluorine atoms, chlorine atoms, bromine atoms, and C １－５ It is preferable that the substituents include a haloalkyl group, a polar group having an acid-dissociable group, or an organic group containing a polar group having an acid-dissociable group.

[0280] Furthermore, organic groups containing polar groups having acid-dissociable groups (hereinafter referred to as "R") ＡＤＧ It is also called ". ) as the above organic group R ＡＤＧ However, C may have substituents. １－１８ A hydrocarbyl group, R ＡＤＧ A divalent carbon atom at any position other than the terminals outside the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time), R ＡＤＧ One example is when at least one hydrogen atom is replaced by a polar group having an acid-dissociable group.

[0281] Organic group R containing the polar group having the above-mentioned acid-dissociating group ＡＤＧ For example, C which may have substituents. １－１８ alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ３ A divalent carbon atom at any position other than the terminals outside the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ＡＤＧ It is more preferable that at least one hydrogen atom of the C is replaced by a polar group having an acid-dissociable group, and the C may have substituents. １－１８ alkyl group, C ６－１８ Aryl group, or C７－１８ It is an aralkyl group; the above R ＡＤＧ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ＡＤＧ It is even more preferable that at least one hydrogen atom is replaced by a polar group having an acid-dissociable group.

[0282] (B1) The photodecayable base having an iodine atom is not particularly limited, and known and commonly used bases can be used. For example, the photodecayable base B represented by the following general formula (IX-1) is an example of a photodecayable base having an iodine atom. １ As shown, carboxylic acid anions and onium cations or onium dications (D ｐ＋ ) and salt can be used.

[0283] [1-2-4. Amount of Blending] The content of the acid diffusion control agent (B) contained in the resist material according to this embodiment is not particularly limited and can be appropriately set depending on the content and type of component (A). The content of component (B) in the resist material is preferably 0.1 to 100 parts by mass, more preferably 0.2 to 75 parts by mass, even more preferably 0.5 to 50 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of component (A).

[0284] [1-3. Organic Solvents] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and known and commonly used solvents can be used. The organic solvent is preferably an organic solvent that can uniformly dissolve or disperse (A) a heteropolyate salt or mixture thereof when prepared.

[0285] Examples of organic solvents include polar solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, nitrile-based solvents, and aproton-based polar solvents, and examples of non-polar solvents such as hydrocarbon-based solvents. These organic solvents may be used individually or in combination of two or more.

[0286] Specific examples of the above polar solvents include, for example, alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methylisopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Examples of organic solvents include: amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; and aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. Nonpolar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. The above organic solvents may be used individually or in combination of two or more.

[0287] The organic solvent to be included in the resist material according to this embodiment is preferably a polar solvent in terms of coatability, and more preferably an amide solvent, ester solvent, alcohol solvent, or ketone solvent in terms of solubility. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester solvent or alcohol solvent is preferably one having an ester bond and / or a hydroxyl group in terms of solubility, and among the above, it is preferably at least one selected from the group consisting of propylene glycol monomethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, and propylene glycol monomethyl ether acetate.

[0288] The content of the organic solvent in the resist material is not particularly limited and can be appropriately set depending on the method of applying the resist material to the substrate, the film thickness to be applied, etc. Preferably, the solid content of the organic solvent in the resist material is 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 10% by mass.

[0289] [1-4. Others] The resist material according to this embodiment may optionally contain additional miscible additives, such as additional resins to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.

[0290] [2. Pattern Forming Method] The pattern forming method according to this embodiment comprises the steps of: applying a resist material to a substrate; exposing the resist film formed by the application step; and developing the exposed resist film.

[0291] [2-1. Coating Process] The pattern formation method according to this embodiment includes a step of coating a resist material onto a substrate.

[0292] <Substrate> The substrate used in this embodiment is not particularly limited, and known and commonly used substrates can be used. For example, a substrate for electronic components or a substrate with a predetermined wiring pattern formed on it may be used. The material of the substrate is not particularly limited, and examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and inorganic substrates such as glass, titanium oxide, and silicon dioxide. The size and shape of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or it may be a thin, flake-shaped substrate.

[0293] The surface of the substrate may be surface-treated as needed. In the case of a substrate having hydroxyl groups on its surface, surface treatment of the substrate using a silane-based coupling agent that reacts with hydroxyl groups can change the surface of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane-based coupling agent include hexamethyldisilazane (HMDS).

[0294] <Coating Method> The method for coating the resist material onto the substrate is not particularly limited, and known and conventional methods can be used. Dry coating methods include, for example, CVD methods (chemical vapor deposition) such as thermal CVD, plasma CVD, and photo-CVD; and PVD methods (physical vapor deposition) such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Wet coating methods include, for example, spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0295] As a method for applying the resist material according to this embodiment onto a substrate, it is preferable to use a wet method such as spin coating or screen printing, and more preferably to use spin coating, from the viewpoint of forming a uniform film thickness. After forming the coated film, backside rinsing, edge bead removal steps, etc., can be performed to remove edge beads.

[0296] The method for drying the resist film formed by coating a resist material onto a substrate is not particularly limited and can be carried out using, for example, a heating device such as a hot plate (post-application bake (PAB)), a vacuum device, etc. The baking conditions are not particularly limited and can be set appropriately according to the type of resist film, application, etc. The baking temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0297] 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.

[0298] [2-2. Exposure Step] The pattern formation method according to this embodiment includes a step of exposing the resist film formed by the coating step described above.

[0299] For example, an ArF exposure apparatus, electron beam lithography apparatus, EUV exposure apparatus, etc., can be used as the exposure apparatus in the resist film exposure process. In the exposure process, exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by direct irradiation with an electron beam or the like without using a mask pattern.

[0300] The wavelength used for exposure is not particularly limited, and includes ArF excimer laser (wavelength 193 nm), KrF excimer laser (248 nm), and F ２ Radiation such as excimer lasers (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays may also be used.

[0301] For ArF or KrF excimer lasers, the exposure dose to the resist film is 1 to 200 mJ / cm². ２ Preferably, the concentration is 20 to 60 mJ / cm². ２It is more preferable that this be the case. Also, in the case of extreme ultraviolet light, the exposure dose is, for example, 500 mJ / cm². ２ The following applies: 0.1 to 200 mJ / cm² ２ Preferably, it is 3 to 100 mJ / cm². ２ It is more preferable that the concentration be 5 to 50 mJ / cm². ２ It is even more preferable that this be the case. In the case of an electron beam, 3 μC / cm at 50 kV. ２ ~2 mC / cm ２ It is preferable to expose with a dose of 10 μC / cm². ２ ~1.5 mC / cm ２ Exposure at this dose is more preferable.

[0302] After exposure to the resist film, a bake (post-exposure bake (PEB)) treatment may or may not be performed. The bake conditions are not particularly limited and can be set appropriately depending on the type of resist film, application, etc. The bake temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C, using a heating device such as a hot plate. The bake time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0303] [2-3. Development Process] The pattern formation method according to this embodiment includes a step of developing the exposed resist film. In the development process, a pattern can be formed by developing the exposed resist film with a developer. When the exposed area remains as a pattern after development, it is a negative-type pattern formation process, and when the exposed area is removed after development, it is a positive-type pattern formation process. Whether to form a positive or negative pattern can be appropriately selected depending on the resist material or developer. After development, the film may be washed with a rinsing solution and then dried, and in some cases, a baking process may be performed further.

[0304] The developer used in this embodiment may be an alkaline developer for the alkaline development process, or a developer containing an organic solvent (organic developer) for the organic solvent development process.

[0305] <Alkaline Development Process> With conventional metal oxide resist materials, it has been difficult to form positive-type patterns with good resolution using the alkaline development process. In contrast, the resist material according to this embodiment can form patterns with good resolution using a water-containing developer.

[0306] The alkaline developer used in the alkaline development process is not particularly limited, and any known and commonly used one may be used. Examples of the above-mentioned alkaline developer include quaternary ammonium salts such as tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and aqueous solutions containing one or more alkanolamines such as dimethylethanolamine and triethanolamine.

[0307] The method for developing the exposed resist film using the above-mentioned alkaline developer is not particularly limited, and known and conventional methods can be used. Examples of methods for developing using the above-mentioned developer include immersing the substrate having the exposed resist film in the developer for a certain period of time (dip method), spraying the developer onto the surface of the exposed resist film (spray method), and dispensing the developer from a discharge nozzle at a constant speed toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispensing method).

[0308] Furthermore, pure water can be used as the rinsing solution in the alkaline development process.

[0309] <Organic Solvent Development Process> Examples of developers used in the organic solvent development process include developers containing one or more organic solvents such as polar solvents like ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, or hydrocarbon solvents.

[0310] Specific examples of organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); alcohol solvents such as methanol, ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); and nitrile solvents such as acetonitrile, propionitrile, and benzonitrile. Examples include amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; and hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. These may be used individually or in combination of two or more.

[0311] Among these, the organic solvent used in the developer is preferably a polar solvent, and more preferably contains amide solvents, alcohol solvents, ester solvents, and ketone solvents. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester solvent is preferably one or more selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate. The alcohol solvent is preferably at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol. Furthermore, the ketone solvent is preferably at least one selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, and 2-heptanone.

[0312] When the developer contains either an amide-based solvent or an ester-based solvent and an alcohol-based solvent, the mixing ratio (by weight) of the amide-based solvent or ester-based solvent to the alcohol-based solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0313] The method for developing the exposed resist film using the above-mentioned developer is not particularly limited, and known and conventional methods can be used. Examples of methods for developing using the above-mentioned developer include immersing the substrate having the exposed resist film in the developer for a certain period of time (dip method), spraying the developer onto the surface of the exposed resist film (spray method), and dispensing the developer from a discharge nozzle at a constant speed toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispensing method).

[0314] The process may include a step of washing with a rinsing solution after development with the above-mentioned developer solution. The rinsing solution is not particularly limited, and any known and commonly used solution can be used. As the rinsing solution, a suitable choice can be made from the water or organic solvent contained in the above-mentioned developer solution that does not easily dissolve the resist pattern.

[0315] The rinsing solution is not particularly limited, and for example, at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents can be used. Among these, it is preferable to use at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents as the rinsing solution, more preferably at least one selected from the group consisting of alcohol solvents and ester solvents, and even more preferably at least one alcohol solvent.

[0316] As the alcohol-based solvent used in the rinsing solution, a monohydric alcohol having 2 to 8 carbon atoms is preferred, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples of the above monohydric alcohols include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, and the like. These organic solvents may be used individually or in combination of two or more.

[0317] The method for cleaning the resist pattern with the above-mentioned rinsing solution is not particularly limited, and known and conventional methods can be used. Examples of methods for cleaning using the above-mentioned rinsing solution include immersing the resist pattern in the rinsing solution for a certain period of time (dip method), spraying the rinsing solution onto the surface of the resist pattern (spray method), and dispensing the rinsing solution from a discharge nozzle at a constant speed toward the surface of a resist pattern rotating at a constant speed (dynamic dispensing method).

[0318] [3. Patterned Structure] The patterned structure according to this embodiment is obtained by forming a pattern on a substrate using the pattern formation method described above.

[0319] The average thickness of part or all of the patterned structure according to this embodiment is not particularly limited and can be set as appropriate depending on the intended use. The patterned structure preferably has an average thickness portion of 1 to 100 nm, more preferably a portion of 5 to 75 nm, and even more preferably a portion of 10 to 60 nm.

[0320] Furthermore, the pitch of part or all of the patterned structure according to this embodiment is not particularly limited and can be set as appropriate depending on the intended use. It is preferable that the patterned structure has a portion with a pitch of 100 nm or less, more preferably a portion with a pitch of 50 nm or less, and even more preferably a portion with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the pattern formation method described above, it is possible to create portions with pitches of 50 nm, 20 nm, and 15 nm in part or all of the patterned structure.

[0321] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0322] [1. Synthesis of heteropolyates with modified defect sites] Heteropolyates (A-1) to (A-25) with modified defect sites (hereinafter also referred to as "polyate (A-1)") were synthesized by the following method.

[0323] <Manufacturing Example 1: Potassium Undecatungus Silicate (α-K ８ [SiW １１ O ３９ Manufacturing of ]) > Silicate tungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ４ [SiW １２ O ４０ ]・xH ２O) 63 g was mixed with 380 g of 1 M acetic acid, and the reaction mixture was heated to 45°C. Potassium bicarbonate was added (52 g) to bring the pH to 6.0. The reaction mixture was then cooled to room temperature and filtered by suction filtration to obtain 56 g of crude product. 216 g of pure water was added to the obtained crude product and heated to 73°C to redissolve it. The solution was cooled at 4°C for 16 hours to recrystallize it, filtered by suction filtration, and vacuum dried to obtain 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).

[0324] <Production Example 2: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanediate (Compound A1)>

[0325] Preparation Example 2-1: Preparation of di(1-phenylcyclopentyl)(2E)-buta-2-engioate (compound a1) 1-phenylcyclopentanol (14.5 g), dichloromethane (60 g), and triethylamine (18.4 g) were charged and cooled with ice while stirring. Fumaryl chloride (5.6 g) was added and stirred for 1 hour. Then, 5% potassium carbonate aqueous solution (75 g) was charged and stirred. After stopping stirring, the aqueous layer was removed and washed with ultrapure water (100 g). The organic layer was concentrated under reduced pressure to obtain 13.7 g of compound a1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.78-1.98 (m, 8H), 2.02-2.21 (m, 4H), 2.37-2.53 (m, 4H), 6.80 (s, 2H), 7.20-7.49 (m, 10H).

[0326] Preparation Example 2-2: Preparation of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanediate (compound A1) Compound a1 (7.5 g), 3-mercaptopropyltrimethoxysilane (7.2 g), methyl ethyl ketone (20 ml), and 1,1'-azobis(cyclohexane-1-carbonitride) (1.8 g) were charged in that order and stirred. Then, the temperature was raised from room temperature to 90°C and stirred for 7 hours. The reaction mixture was removed by distillation and then vacuum dried to obtain 13.2 g of compound A1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 2H), 1.62-1.82 (m, 10H), 1.90-2.10 ( m, 4H), 2.20-2.32 (m, 4H), 2.50-2.80 (m, 4H), 3.45-3.50 (m, 10H), 7.10-7.39 (m, 10H).

[0327] <Manufacturing Example 3: Manufacturing of di(1-methylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanediate (Compound A2)>

[0328] Preparation Example 3-1: Preparation of di(1-methylcyclopentyl)(2E)-buta-2-engioate (compound a2) 1-methylcyclopentanol (14.1 g), dichloromethane (60 g), and triethylamine (21.3 g) were charged and cooled with ice while stirring. Fumaryl chloride (10.3 g) was added and stirred for 1 hour. Then, 5% potassium carbonate aqueous solution (60 g) was charged and stirred. After stopping stirring, the aqueous layer was removed and washed with ultrapure water (60 g). The organic layer was concentrated under reduced pressure to obtain 14.5 g of compound a2.

[0329] Preparation Example 3-2: Preparation of (di(1-methylcyclopentyl) 2-(3-trimethoxysilyl)propylthio)butanediote (compound A2) Compound a2 (7.7 g), 3-mercaptopropyltrimethoxysilane (9.8 g), methyl ethyl ketone (20 ml), and 1,1'-azobis(cyclohexane-1-carbonitride) (0.3 g) were charged in that order and stirred. Then, the temperature was raised from room temperature to 90°C and stirred for 7 hours. The reaction mixture was removed by distillation and then vacuum dried to obtain 16.6 g of compound A2.１ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 2H), 1.38-1.82 (m, 20H), 1.90-2.10 (m, 4H), 2.50-2.80 (m, 4H), 3.45-3.50 (m, 10H).

[0330] <Manufacturing Example 4: Manufacturing of di(1-t-butylcyclopentyl)2-(3-(trimethoxysilyl)propylthio)butanediate (Compound A3)>

[0331] Production Example 4-1: Production of di(1-t-butylcyclopentyl)(2E)-buta-2-engioate (compound a3) In Production Example 2-1, 1-phenylcyclopentanol was replaced with 1-t-butylcyclopentanol to obtain compound a3. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (s, 18H), 1.78-1.98 (m, 8H), 2.12-2.21 (m, 4H), 2.47-2.53 (m, 4H), 6.80 (s, 2H).

[0332] Production Example 4-2: Production of di(1-t-butylcyclopentyl)2-(3-(trimethoxysilyl)propylthio)butanediote (compound A3) In Production Example 2-2, compound a1 was changed to compound a3 to obtain compound A3. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 2H), 0.95 (s, 18H), 1.62-1.82 (m, 10H), 1.90-2.10 (m, 4H), 2.20-2.32 (m, 4H), 2.50-2.80 (m, 4H), 3.45-3.50 (m, 10H).

[0333] <Production Example 5: Production of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane (Compound A4)>

[0334] In Production Example 2-2, compound a1 was replaced with 1-methylcyclopentyl acrylate to obtain compound A4. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 2H), 1.49 (s, 3H), 1.54-1.71 (m, 8H), 1.99-2.08 (m, 2H), 2.49 (t, 2H), 2.58 (t, 2H), 2.67 (t, 2H), 3.50 (s, 9H).

[0335] <Synthesis Example 1: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-1))>

[0336] Adding 5.5 g of compound A1 to a mixed solvent of 402 g of acetonitrile and 184 g of pure water, the monodeficient keging-type potassium undecatungus silicate (α-K) synthesized above is obtained. ８ [SiW １１ O ３９ 9.8 g of ]) was added. The pH was adjusted to 1.8 with 1 M hydrochloric acid, and after stirring for 2 hours, the filtrate after filtration was concentrated to approximately 200 g. To this concentrate, 8.3 g (15.3 mol) of bis(2-trifluoromethylphenyl)phenylsulfonium chloride and 40 g of pure water were added to precipitate the powder. The precipitated powder was filtered off, washed three times with 180 mL of pure water, and filtered off again. Further vacuum drying was performed to obtain 15.8 g of polysulfate (A-1). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2. 20-2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.10-7.39 (m, 20H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0337] <Synthesis Example 2: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-2))>

[0338] Adding 5.6 g of compound A2 to a mixed solvent of 402 g of acetonitrile and 184 g of pure water, the monodeficient Keggin-type potassium undecatungus silicate (α-K) synthesized above is obtained. ８ [SiW １１ O ３９ 10.9 g of bis(2-trifluoromethylphenylphenylsulfonium chloride) was added. The pH was adjusted to 1.8 with 1 M hydrochloric acid, and after stirring for 2 hours, the filtrate after filtration was concentrated to approximately 200 g. To this concentrate, 9.9 g (18.2 mol) of bis(2-trifluoromethylphenylphenylsulfonium chloride) and 40 g of pure water were added to precipitate the powder. The precipitated powder was filtered off, washed three times with 180 mL of pure water, and filtered off again. Further thorough vacuum drying yielded 15.8 g of polysulfate (A-2). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.38-1.82 (m, 40H), 1 90-2.10 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 864.1 (median) ([C ３８H ６２ O ４８ S ２ Si ３ W １１ ] ４－ )

[0339] <Synthesis Example 3: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-t-butylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-3))>

[0340] In Synthesis Example 1, compound A1 was replaced with compound A3 to obtain polysalt (A-3). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 0.95 (s, 36H), 1.62-1.82 (m, 20H), 1.9 0-2.10 (m, 8H), 2.20-2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 906.2 (median) ([C ５０ H ８６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0341] <Synthesis Example 4: Synthesis of Tetrakis((4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-4))>

[0342] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was replaced with (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide to obtain polysulfate (A-4). ESI-MS: POSITIVE m / z 461.2 ([C ２９ H ３３ O ３ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0343] <Synthesis Example 5: Synthesis of Tetrakis(triphenylsulfonium)(1,3-bis(3-(1,2-di(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate (polyate (A-5))>

[0344] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was replaced with triphenylsulfonium chloride to obtain polysodium acid (A-5). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0345] <Synthesis Example 6: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-6))>

[0346] In Synthesis Example 1, compound A1 was replaced with compound A4 to obtain the polysalt (A-6). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.49 (s, 6H), 1.54-1.71 (m, 16H) , 1.99-2.08 (m, 4H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0347] <Synthesis Example 7: Synthesis of Tetrakis((4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-bis(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-7))>

[0348] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was replaced with (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide, and compound A1 was replaced with compound A4 to obtain the polysulfate (A-7). 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－ )

[0349] <Synthesis Example 8: Synthesis of Tetrakis(triphenylsulfonium)(1,3-bis(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-7))>

[0350] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was replaced with triphenylsulfonium chloride, and compound A1 was replaced with compound A4 to obtain the polysulfate (A-8). 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－ )

[0351] <Manufacturing Example 6: Manufacturing of di(2-cyclopenten-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediate (Compound A5)>

[0352] Production Example 6-1: Production of di(2-cyclopenten-1-yl)(2E)-buta-2-engioate (compound a5) In Production Example 2-1, 1-phenylcyclopentanol was replaced with 2-cyclopenten-1-ol to obtain compound a5. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.02-2.33 (m, 8H), 5.45 (m, 2H), 5.60-5.61 (m, 4H), 6.31 (s, 2H).

[0353] Production Example 6-2: Production of di(2-cyclopenten-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediote (compound A5) In Production Example 2-2, compound a1 was changed to compound a5 to obtain compound A5. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.62 (quint, 2H), 2.02-2.33 (m, 8H), 2.60 ( t, 2H), 2.85 (m, 1H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 5.45 (m, 2H), 5.60-5.61 (m, 4H).

[0354] <Synthesis Example 9: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(2-cyclopenten-1-yloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-9))> In Synthesis Example 1, compound A1 was replaced with compound A5, and polysalt (A-9) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62 (quint, 4H), 2.02-2.33 (m, 16H), 2.60 ( t, 4H), 2.85 (m, 2H), 3.10 (m, 2H), 4.00 (t, 2H), 5.45 (m, 4H), 5.60-5.61 (m, 8H), 7.65-8.35 (m, 52H). ２９Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 847.9 (median) ([C ３４ H ４６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0355] <Manufacturing Example 7: Manufacturing of di(1-indanyl)2-(3-(trimethoxysilyl)propylthio)butanediate (Compound A6)>

[0356] Production Example 7-1: Production of di(1-indanyl)(2E)-buta-2-engioate (compound a6) In Production Example 2-1, 1-phenylcyclopentanol was replaced with 1-indanol to obtain compound a6. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.15 (m, 2H), 2.40 (m, 2H), 3.11-3.21 (m, 4H), 6.08 (t, 2H), 6.31 (s, 2H), 7.06-7.26 (m, 8H).

[0357] Production Example 7-2: Production of di(1-indanyl)2-(3-(trimethoxysilyl)propylthio)butanediote (compound A6) In Production Example 2-2, compound a1 was changed to compound a6 to obtain compound A6. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.62 (quint, 2H), 2.15 (m, 2H), 2.40 (m, 2H), 2.60 ( t, 2H), 2.85 (m, 1H), 3.10-3.21 (m, 5H), 3.55 (s, 9H), 4.00 (t, 1H), 6.08 (t, 2H), 7.06-7.26 (m, 8H).

[0358] <Synthesis Example 10: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-indanyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-10))> In Synthesis Example 1, compound A1 was replaced with compound A6, and polysalt (A-10) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62 (quint, 4H), 2.15 (m, 4H), 2.40 (m, 4H), 2.60 (t , 4H), 2.85 (m, 2H), 3.10-3.21 (m, 10H), 4.00 (t, 2H), 6.08 (t, 4H), 7.06-7.26 (m, 16H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 898.4 (median) ([C ５０ H ５４ O ４８ S ２ Si ３ W １１ ] ４－ )

[0359] <Manufacturing Example 8: Potassium undecatungus phosphate (α-K ７ [PW １１ O ３９ ]) Manufacturing > Phosphate tungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ３ [PW １２ O ４０ ]・xH ２O) 63 g of the compound was mixed with 380 g of 1 M acetic acid, and the reaction mixture was heated to 45°C. Sodium bicarbonate was added (43 g) to bring the pH to 4.8. The reaction mixture was then cooled to room temperature. 41 g of potassium chloride was added to the resulting solution and heated to 73°C to redissolve it. The solution was recrystallized by cooling at 4°C for 16 hours, filtered by suction filtration, and vacuum dried to obtain 38 g of the target compound. ３１ P-NMR (242.92MHz, D ２ O): δ (ppm) = 10.08 (s, 1P).

[0360] <Production Example 9: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (Compound A7)>

[0361] Production Example 9-1: Production of di(1-phenylcyclohexyl) (2E)-buta-2-engioate (compound a7) In Production Example 2-1, 1-phenylcyclopentanol was changed to 1-phenylcyclohexanol to obtain compound a7. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.43-1.53 ​​(12H), 1.86 (m, 4H), 2.12 (m, 4H), 6.31 (s, 2H), 7.17 (m, 2H), 7.30 (t, 4H), 7.54 (dd, 4H).

[0362] Production Example 9-2: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (compound A7) In Production Example 2-2, compound a1 was changed to compound a7, and 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane to obtain compound A7. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.43-1.53 ​​(m, 12H), 1.86 (m, 4H), 2.12 (m, 4H), 2.40 (t, 2H), 2.81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 7.17 (m, 2H), 7.30 (t, 4H), 7.54 (dd, 4H).

[0363] <Synthesis Example 11: Synthesis of Tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-11))> In Synthesis Example 1, compound A1 was replaced with compound A7, and potassium undecatungus silicate was replaced with potassium undecatungus phosphate, and polysalt (A-11) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0364] <Production Example 10: Production of di(1-methylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (Compound A8)>

[0365] In Production Example 3-2, 3-mercaptopropyltrimethoxysilane was replaced with (2-(2-mercaptoethylthio)ethyl)trimethoxysilane to obtain compound A8. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.39 (s, 6H), 1.56-1.81 (m, 1 6H), 2.40 (t, 2H), 2.81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H).

[0366] <Synthesis Example 12: Synthesis of Tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-12))> In Synthesis Example 1, compound A1 was replaced with compound A8, and potassium undecatungus silicate was replaced with potassium undecatungus phosphate, and polysalt (A-12) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.39 (s, 12H), 1.56-1.81 (m, 32H) , 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.02 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.75 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1184.2 (median) ([C ４０ H ６６ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0367] <Production Example 11: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (Compound A9)>

[0368] Production Example 11-1: Production of di(1-ethylcyclopentyl)(2E)-buta-2-engioate (compound a9) In Production Example 2-1, 1-phenylcyclopentanol was replaced with 1-ethylcyclopentanol to obtain compound a9. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90 (t, 6H), 1.49-1.81 (m, 20H), 6.31 (s, 2H).

[0369] Production Example 11-2: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (compound A9) In Production Example 2-2, compound a1 was changed to compound a9, and 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane to obtain compound A9. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90-0.95 (m, 8H), 1.49-1.81 (m, 20H) , 2.40 (t, 2H), 2.81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H).

[0370] <Synthesis Example 13: Synthesis of Tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-13))> In Synthesis Example 1, compound A1 was replaced with compound A9, and potassium undecatungus silicate was replaced with potassium undecatungus phosphate, and polysalt (A-13) was obtained by the same method as described above. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90-1.04 (m, 16H), 1.49-1.81 (m, 40H), 2. 40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.05 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.74 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1202.2 (median) ([C ４４ H ７４ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0371] <Production Example 12: Production of di(1-phenylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (Compound A10)> In Production Example 2-2, 3-mercaptopropyltrimethoxysilane was replaced with (2-(2-mercaptoethylthio)ethyl)trimethoxysilane to obtain compound A10. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.63-1.92 (m, 12H), 2.17 (m, 4H), 2.40 (t, 2H), 2. 81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 7.17 (m, 2H), 7.30 (t, 4H), 7.54 (dd, 4H).

[0372] <Synthesis Example 14: Synthesis of Tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-14))> In Synthesis Example 1, compound A1 was replaced with compound A10, and potassium undecatungus silicate was replaced with potassium undecatungus phosphate, and polysalt (A-14) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.63-1.92 (m, 24H), 2.17 (m, 8H), 2.40 (t, 4H), 2.81- 2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.03 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1266.2 (median) ([C ６０ H ７４ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0373] <Production Example 13: Production of di(3-methyl-2-cyclohexen-1-yl)2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (Compound A11)>

[0374] Preparation Example 13-1: Preparation of di(3-methyl-2-cyclohexen-1-yl)(2E)-buta-2-engioate (compound a11) In Preparation Example 2-1, 1-phenylcyclopentanol was replaced with 3-methyl-2-cyclohexen-1-ol to obtain compound a11. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.60-2.01 (m, 18H), 5.13 (q, 2H), 5.37 (d, 2H), 6.31 (s, 2H).

[0375] Production Example 13-2: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanediate (compound A11) In Production Example 2-2, compound a1 was changed to compound a11, and 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane to obtain compound A11. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.60-2.01 (m, 18H), 2.40 (t, 2H), 2 .81-2.85 (m, 5H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 5.13 (q, 2H), 5.37 (t, 2H).

[0376] <Synthesis Example 15: Synthesis of Tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(3-methyl-2-cyclohexen-1-yloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-15))> In Synthesis Example 1, compound A1 was replaced with compound A11, and potassium undecatungus silicate was replaced with potassium undecatungus phosphate, and polyate (A-15) was obtained by the same method as described above. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.60-2.01 (m, 36H), 2.40 (t, 4H), 2.81- 2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 5.13 (q, 4H), 5.37 (t, 4H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.72 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1200.2 (median) ([C ４４ H ６６ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0377] <Production Example 14: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound A12)>

[0378] Preparation Example 14-1: Preparation of tri(1-methylcyclopentyl)(E)-1-propene-1,2,3-tricarboxylate (compound a12) 2.54 g (20.0 mmol) of trans-aconitic acid was dissolved in 20 g of DCM, and a solution of 5.58 g (44.0 mmol) of oxalyl chloride with 0.15 g (2.0 mmol) of DMF was added dropwise at 0°C. The reaction mixture was stirred at room temperature for 12 hours, and the solvent was removed from the resulting reaction mixture under vacuum to obtain a mixture containing trans-aconitic acid chloride. Subsequently, in Preparation Example 3-1, fumaryl chloride was replaced with trans-aconitic acid chloride, and 4.46 g of compound a12 was obtained by the same method. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.39 (s, 9H), 1.63-1.81 (m, 24H), 3.58 (s, 2H), 6.79 (s, 1H).

[0379] Production Example 14-2: Production of tri(1-methylcyclopentyl)1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (compound A12) In Production Example 3-2, compound a2 was changed to compound a12 to obtain compound A12. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.39 (s, 9H), 1.56-1.81 ( m, 26H), 2.60-2.69 (m, 3H), 2.94 (m, 1H), 3.55 (s, 9H), 3.86-3.90 (m, 2H).

[0380] <Synthesis Example 16: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-16))> In Synthesis Example 1, compound A1 was replaced with compound A12, and polysodium chloride (A-16) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.39 (s, 18H), 1.56-1.81 ( m, 52H), 2.60-2.69 (m, 6H), 2.94 (m, 2H), 3.86-3.90 (m, 4H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.02 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 934.7 (median) ([C ５４ H ８６ O ５２ S ２ Si３ W １１ ] ４－ )

[0381] <Production Example 15: Production of tri(1-methylcyclopentyl) 1-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)-1,2,3-propanetricarboxylate (Compound A13)> In Production Example 2-2, compound a1 was changed to compound a12, and 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane to obtain compound A13. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.39 (s, 9H), 1.56-1.81 (m, 24H), 2 .40 (t, 2H), 2.69 (m, 1H), 2.81 (s, 4H), 2.94 (m, 1H), 3.55 (s, 9H), 3.86-3.90 (m, 2H).

[0382] <Synthesis Example 17: Synthesis of Tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-17))> In Synthesis Example 1, compound A1 was replaced with compound A13, and potassium undecatungus silicate was replaced with potassium undecatungus phosphate, and polysodium salt (A-17) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.39 (s, 18H), 1.56-1.81 (m, 48H), 2.40 (t, 4H), 2.69 (m, 2H), 2.81 (s, 8H), 2.94 (m, 2H), 3.86-3.90 (m, 4H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.02 (s, 2Si). ３１P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.74 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1277.6 (median) ([C ５６ H ９０ O ５２ PS ４ Si ２ W １１ ] ３－ )

[0383] <Production Example 16: Production of di(1-phenylcyclohexyl) 2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)-1-(3-(trimethoxysilyl)propylthio)ethylcarbonyloxy)butanediate (Compound A14)>

[0384] Production Example 16-1: Production of di(1,2-bis(methyloxycarbonyl)ethyl) (2E)-buta-2-engioate (compound (a14-1)). In Production Example 2-1, 1-phenylcyclopentanol was replaced with DL-dimethyl malate to obtain compound (a14-1). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 2.75 (m, 2H), 3.00 (m, 2H), 3.60 (s, 6H), 3.70 (s, 6H), 6.13 (t, 2H), 6.31 (s, 2H).

[0385] Preparation Example 16-2: Preparation of di(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyl) (2E)-buta-2-engioate (compound (a14-2)) 8.09 g (20.0 mmol) of compound (a14-1) was dissolved in pure water / 1,4-dioxane (480 mL / 320 mL), and 17.24 g (431.0 mmol) of sodium hydroxide was added. The reaction mixture was stirred at room temperature for 20 hours and washed twice with 200 mL of t-butyl methyl ether. Then, the pH of the aqueous layer was adjusted to 1 with 6 M hydrochloric acid, and the target product was extracted into the organic layer with 400 mL of t-butyl methyl ether. This procedure was repeated five times, and the resulting organic layer was concentrated using a rotary evaporator and dried under vacuum to obtain the carboxylic acid. Subsequently, in Production Example 18-1, Trans-aconitic acid was replaced with the carboxylic acid obtained above, which was then converted into a carboxylic acid chloride. Then, in Production Example 2-1, fumaryl chloride was replaced with the carboxylic acid chloride, and 1-phenylcyclopentanol was replaced with 1-phenylcyclohexanol, and 11.77 g of compound (a14-2) was obtained by the same method. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.75 ( m, 2H), 3.00 (m, 2H), 6.13 (t, 2H), 6.31 (s, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H).

[0386] Production Example 16-3: Production of di(1-phenylcyclohexyl) 2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)-1-(3-(trimethoxysilyl)propylthio)ethylcarbonyloxy)butanediate (compound A14). In Production Example 2-2, compound a1 was changed to compound (a14-2) to obtain compound A14. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.43-1.62 (m, 26H), 1.86 (m, 8H), 2.12 (m, 8H), 2.60 (t, 2H), 2.75 -2.85 (m, 3H), 3.00-3.10 (m, 3H), 3.55 (s, 9H), 4.00 (t, 1H), 6.13 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H).

[0387] <Synthesis Example 18: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-18))> In Synthesis Example 1, compound A1 was replaced with compound A14, and polysodium chloride (A-18) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.43-1.62 (m, 52H), 1.86 (m, 16H), 2.12 (m, 16H), 2.60 (t, 4H), 2.75- 2.85 (m, 6H), 3.00-3.10 (m, 6H), 4.00 (t, 2H), 6.13 (t, 4H), 7.17 (m, 8H), 7.30 (t, 16H), 7.54 (dd, 16H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.03 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1214.8 (median) ([C １２６ H １５０ O ６４ S ２ Si ３ W １１ ] ４－ )

[0388] <Production Example 17: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-(3-(trimethoxysilyl)propylthio)propylthio)butanediote (Compound A15)>

[0389] Production Example 17-1: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-hydroxypropylthio)butanediote (compound a15) In Production Example 2-2, compound a1 was replaced with compound a9, and 3-mercaptopropyltrimethoxysilane was replaced with 2,3-mercapto-1-propanol to obtain compound a15. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90 (t, 12H), 1.49-1.81 (m, 40H), 2.62 (m, 1H) ), 2.81-2.88 (m, 4H), 3.10 (m, 2H), 3.71 (m, 1H), 3.96-4.00 (m, 3H), 6.24 (s, 1H).

[0390] Preparation Example 17-2: Preparation of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-(3-(trimethoxysilyl)propylthio)propylthio)butanediate (compound A15) To a DCM solution of compound A15 and pyridine, tosyl chloride was added dropwise at 0°C. The mixture was then stirred at room temperature for 18 hours, and the resulting crude product was purified by column chromatography. Subsequently, the obtained tosylate ester was reacted with 3-mercaptopropyltrimethoxysilane in a DCM solution in the presence of triethylamine to obtain compound A15. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 0.90 (t, 12H), 1.49-1.81 (m, 42H), 2.60-2.62 (m, 4H), 2.85-2.88 (m, 4H), 3.08-3.10 (m, 3H), 3.55 (s, 9H), 4.00 (t, 2H).

[0391] <Synthesis Example 19: Synthesis of Tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(2,3-bis(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)propylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-19))> In Synthesis Example 1, compound A1 was replaced with compound A15, and potassium undecatungus silicate was replaced with potassium undecatungus phosphate, and polysalt (A-19) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.93 (m, 28H), 1.49-1.81 (m, 84H), 2.60-2 .62 (m, 8H), 2.85-2.88 (m, 8H), 3.08-3.10 (m, 6H), 4.00 (t, 4H), 7.65-8.35 (m, 39H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -58.08 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 399.1 ([[C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1448.7 (median) ([C ８４ H １３８ O ５６ PS ６ Si ２ W １１ ] ３－ )

[0392] <Synthesis Example 20: Synthesis of Tris(Tris(3,5-difluorophenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-20))> In Synthesis Example 1, compound A1 was replaced with compound A7, potassium undecatungus silicate with potassium undecatungus phosphate, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride with tris(3,5-difluorophenyl)sulfonium triflate, and polysulfate (A-20) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H), 7.86-7.96 (m, 27H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 371.0 ([C １８ H ９ F ６ S] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0393] <Synthesis Example 21: Synthesis of Tris(bis(3,5-difluorophenyl)(phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-21))> In Synthesis Example 1, compound A1 was replaced with compound A7, potassium undecatungus silicate with potassium undecatungus phosphate, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride with bis(3,5-difluorophenyl)(phenyl)sulfonium chloride, and polysodium salt (A-21) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.17 (m, 4H), 7.30 (t, 8H), 7.54 (dd, 8H), 7.75-7.96 (m, 33H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 335.1 ([C １８ H １１ F ４ S] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0394] <Synthesis Example 22: Synthesis of Tris(bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-22))> In Synthesis Example 1, compound A1 was replaced with compound A7, potassium undecatungus silicate with potassium undecatungus phosphate, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride with bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium triflate, and polysodium (A-22) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.40 (t, 4H), 2.81-2.8 5 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 6.75-6.81 (m, 18H), 7.10-7.17 (m, 10H), 7.30 (t, 8H), 7.54 (dd, 8H), 7.77 (d, 6H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 460.9 ([C １８ H １０ F ４ IS] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0395] <Synthesis Example 23: Synthesis of Tris((4-iodophenyl)di(2-(trifluoromethyl)phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-23))> In Synthesis Example 1, compound A1 was replaced with compound A7, potassium undecatungus silicate with potassium undecatungus phosphate, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride with (4-iodophenyl)di(2-(trifluoromethyl)phenyl)sulfonium bromide, and polysodium (A-23) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.43-1.53 ​​(m, 24H), 1.86 (m, 8H), 2.12 (m, 8H), 2.40 (t, 4H), 2.8 1-2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 7.10-7.17 (m, 10H), 7.23-7.47 (m, 32H), 7.54 (dd, 8H), 7.77 (d, 6H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 525.0 ([C ２０ H １２ F ６ IS] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0396] <Production Example 18: Bis(3,5-difluorophenyl)(4-((1-methylcyclopentyloxycarbonyl)methyloxy)phenyl)sulfonium bromide> 20.54 g (74.9 mmol) of bis(3,5-difluorophenyl) sulfoxide and 7.05 g (74.9 mmol) of phenol were dissolved in 200 mL of dichloromethane, and Eaton's reagent (100 mL) was added dropwise at 0°C. The reaction was heated to room temperature, stirred for 4 hours, then cooled to 0°C, and 200 mL of water was slowly added to quench the reaction. The reaction temperature was maintained below 20°C. The aqueous layer was extracted with ethyl acetate, and 50 mL of an aqueous solution containing 17.9 g (150 mmol) of potassium bromide was added to the aqueous layer with vigorous stirring. The slurry was stirred at room temperature for 1 hour, filtered, washed with water and methyl-t-butyl ether, and thoroughly vacuum-dried to obtain 11.3 g of bis(3,5-difluorophenyl)(4-hydroxyphenyl)sulfonium bromide as a white solid. 6.73 g (15.6 mmol) of bis(3,5-difluorophenyl)(4-hydroxyphenyl)sulfonium bromide and 10.15 g (31.1 mmol) of cesium carbonate were dissolved in 150 mL of dimethylformamide, and 3.78 g (17.1 mmol) of 1-methylcyclopentyl 2-bromoacetate was added dropwise at 0°C under a nitrogen atmosphere. The solution was gradually warmed to room temperature and stirred for 16 hours, after which 400 mL of water and 400 mL of dichloromethane were added. The organic layer was separated, and the aqueous layer was extracted with dichloromethane. The combined organic layers were extracted with water, dried over sodium sulfate, and concentrated to a volume of 100 mL. When 700 mL of methyl-t-butyl ether was added to this solution, a precipitate formed. The precipitate was filtered off, washed with methyl-t-butyl ether, and thoroughly vacuum-dried to obtain 8.47 g of the target compound as a white solid. ESI-MS: POSITIVE m / z 491.1 ([C ２６ H ２３ F ４ O ３ S] ＋ )

[0397] <Synthesis Example 24: Synthesis of Tris(bis(3,5-difluorophenyl)(4-((1-methylcyclopentyloxycarbonyl)methyloxy)phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-24))> In Synthesis Example 1, compound A1 was replaced with compound A7, potassium undecatungus silicate with potassium undecatungus phosphate, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride with bis(3,5-difluorophenyl)(4-((1-methylcyclopentyloxycarbonyl)methyloxy)phenyl)sulfonium bromide, and polysodium (A-24) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.39-1.86 (m, 65H), 2.12 (m, 8H), 2.40 (t, 4H), 2.81-2.85 (m, 10H), 3. 10 (m, 2H), 4.00 (t, 2H), 4.99 (s, 6H), 6.75-6.81 (m, 18H), 6.96 (d, 6H), 7.17 (m, 4H), 7.30-7.33 (m, 14H), 7.54 (dd, 8H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 491.1 ([C ２６ H ２３ F ４ O ３ S] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0398] <Production Example 19: Bis(3-fluoro-5-(trifluoromethyl)phenyl)(2-iodo-4-((1-methylcyclopentyloxycarbonyl)methyloxy)phenyl)sulfonium bromide> In Production Example 18, the target compound was obtained by the same method as above, with bis(3,5-difluorophenyl) sulfoxide replaced with bis(3-fluoro-5-(trifluoromethyl)phenyl) sulfoxide and phenol replaced with 3-iodophenol. ESI-MS: POSITIVE m / z 717.0 ([C) ２８ H ２２ F ８ IO ３ S] ＋ )

[0399] <Synthesis Example 25: Synthesis of Tris(bis(3-fluoro-5-(trifluoromethyl)phenyl)(2-iodo-4-((1-methylcyclopentyloxycarbonyl)methyloxy)phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustophosphate (polyate (A-25))> In Synthesis Example 1, compound A1 was replaced with compound A7, potassium undecatungus silicate with potassium undecatungus phosphate, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride with bis(3-fluoro-5-(trifluoromethyl)phenyl)(2-iodo-4-((1-methylcyclopentyloxycarbonyl)methyloxy)phenyl)sulfonium bromide, and polysalt (A-25) was obtained by the same method as described above. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.04 (m, 4H), 1.39-1.86 (m, 65H), 2.12 (m, 8H), 2.40 (t, 4H), 2.81- 2.85 (m, 10H), 3.10 (m, 2H), 4.00 (t, 2H), 4.99 (s, 6H), 6.96 (d, 3H), 7.04-7.34 (m, 36H), 7.54 (dd, 8H). ２９Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -54.04 (s, 2Si). ３１ P-NMR (242.92MHz, DMSO-d6): δ (ppm) = -13.73 (s, 1P). ESI-MS: POSITIVE m / z 717.0 ([C ２８ H ２２ F ８ IO ３ S] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ PS ４ Si ２ W １１ ] ３－ )

[0400] [2. Preparation of Test Resist Materials] As test resist materials, the poly salts (A-1) to (A-25) synthesized above, an acid diffusion control agent, and an organic solvent were blended in the amounts shown in Tables 1 and 2 below (unit: parts by mass) to prepare test resist materials (R-1) to (R-45).

[0401] Furthermore, the acid diffusion control agents (B-1) to (B-9) listed below were used as (B) acid diffusion control agents as described in Table 1.

[0402] • Acid diffusion control agent (B-1): An acid diffusion control agent which is a salt of the triphenylsulfonium cation represented by the following formula (B-1) and the 2-hydroxy-5-iodobenzoate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 6.77 (d, 1H), 7.78-7.88 (m, 16H), 8.02 (s, 1H). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 262.9 ([C ７ H ４ IO ３ ] － ))

[0403] • Acid diffusion control agent (B-2): An acid diffusion control agent which is a salt of the triphenylsulfonium cation represented by the following formula (B-2) and the 2-hydroxy-3,5-diiodobenzoate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.78-7.87 (m, 15H), 8.01 (s, 1H), 8.13 (s, 1H). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 388.8 ([C ７ H ３ I ２ O ３ ] － ))

[0404] • Acid diffusion control agent (B-3): An acid diffusion control agent which is a salt of the triphenylsulfonium cation represented by the following formula (B-3) and the 2,3,5-triiodobenzene-1-carboxylate anion. (B-3) ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.78-7.87 (m, 15H), 7.95 (s, 1H), 8.07 (s, 1H). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 498.7 ([C ７ H ２ I ３ O ２ ] － ))

[0405] • Acid diffusion control agent (B-4): An acid diffusion control agent which is a salt of a triphenylsulfonium cation represented by the following formula (B-4) and a salicylate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 6.96 (d, 1H), 7.17 (m, 1H), 7.46 (m, 1H), 7.68 (d, 1H), 7.78-7.87 (m, 15H). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S]＋ ) NEGATIVE m / z 137.0 ([C ７ H ５ O ３ ] － ))

[0406] • Acid diffusion control agent (B-5): An acid diffusion control agent which is a salt of the triphenylsulfonium cation represented by the following formula (B-5) and the 2,6-dihydroxy-3,5-diiodobenzene-1-carboxylate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.78-7.87 (m, 15H), 7.96 (s, 1H). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 404.8 ([C ７ H ３ I ２ O ４ ] － ))

[0407] • Acid diffusion control agent (B-6): An acid diffusion control agent that is a salt of the (4-iodophenyl)di(2-(trifluoromethyl)phenyl)sulfonium cation represented by the following formula (B-6) and the 2-hydroxy-5-iodobenzoate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 6.77 (d, 1H), 7.10 (d, 2H), 7.23-7.47 (m, 8H), 7.77 (d, 2H), 7.88 (d, 1H), 8.02 (s, 1H). ESI-MS: POSITIVE m / z 525.0 ([C ２０ H １２ F ６ IS] ＋ ) NEGATIVE m / z 262.9 ([C ７ H ４ IO ３ ] － ))

[0408] • Acid diffusion control agent (B-7): An acid diffusion control agent which is a salt of the bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium cation represented by the following formula (B-7) and the 2-hydroxy-5-iodobenzoate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 6.75-6.81 (m, 7H), 7.10 (d, 2H), 7.77 (d, 2H), 7.88 (d, 1H), 8.01 (s, 1H). ESI-MS: POSITIVE m / z 460.9 ([C １８ H １０ F ４ IS] ＋ ) NEGATIVE m / z 262.9 ([C ７ H ４ IO ３ ] － ))

[0409] • Acid diffusion control agent (B-8): An acid diffusion control agent that is a salt of bis(3,5-difluorophenyl)(2-iodo-4-((1-methylcyclopentyloxycarbonyl)methyloxy)phenyl)sulfonium cation, represented by the following formula (B-8), and 2-hydroxy-5-iodobenzoate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.39 (s, 3H), 1.56-1.81 (m, 8H), 4.88 (s, 2H), 6.75-6.95 (m, 8H), 7.10 (d, 1H), 7.34 (s, 1H), 7.88 (d, 1H), 8.02 (s, 1H). ESI-MS: POSITIVE m / z 617.0 ([C ２６ H ２２ F ４ IO ３ S] ＋ ) NEGATIVE m / z 262.9 ([C ７ H ４ IO ３ ] － ))

[0410] • Acid diffusion control agent (B-9): An acid diffusion control agent which is a salt of the triphenylsulfonium cation represented by the following formula (B-9) and the 2-hydroxy-3,5,6-triiodobenzoate anion. ( １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.78-7.87 (m, 15H), 7.90 (s, 1H). ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 514.7 ([C ７ H ２ I ３ O ３ ] － ))

[0411]

[0412]

[0413] [3. Formation of Test LS Patterns] Each test resist material (R-1) to (R-45) was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner. A post-application bake (PAB) treatment was performed on a hot plate at 120°C for 60 seconds, followed by drying to produce a resist film with a thickness of 50 nm. The thickness of the formed resist film was measured using a film thickness measuring device (M-2000D, manufactured by J.A. Wollam). The resist film was then subjected to drawing (exposure) 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. Subsequently, a post-exposure heating (post-exposure bake (PEB)) treatment was performed at 90°C for 60 seconds. Next, development was performed at 23°C using a developer (NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) for 60 seconds, followed by rinsing with pure water for 60 seconds. As a result, a 1:1 LS pattern with a line width of 50 nm was formed, and test LS patterns (LS-1) to (LS-45) corresponding to each test resist material (R-1) to (R-45) were obtained. Note that all test LS patterns (LS-1) to (LS-45) are positive type patterns.

[0414] [4. Evaluation of Test LS Patterns] <Evaluation of Sensitivity> The optimal exposure dose Eop (μC / cm²) for forming a 1:1 LS pattern with a line width of 50 nm using the above LS pattern formation method. ２ The values ​​for each were calculated. The results are shown in Tables 3 and 4.

[0415] <Roughness Evaluation> For each test LS pattern, the line width was measured at 400 line positions along the longitudinal direction of the line using a scanning electron microscope (acceleration voltage 800V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation). The standard deviation (σ) obtained from these measurement results was then used to calculate a measure of roughness, specifically three times the standard deviation (σ) (3σ) (unit: nm). The results are shown in Tables 3 and 4. A smaller 3σ value indicates less roughness on the line sidewalls and a more uniform LS pattern.

[0416]

[0417]

[0418] The results in Table 3 show that the sensitivity of the resist materials R-1 to R-23 is good, and the roughness of LS-1 to LS-23 also yields good results.

[0419] Furthermore, in Table 3, comparing the sensitivity of resist materials (R-1) to (R-3) and (R-21) containing polyate (A-1), it can be seen that the resist materials (R-1) to (R-3) containing an acid diffusion control agent with iodine have better sensitivity than the resist material (R-21) containing an acid diffusion control agent without iodine. Comparing the roughness of LS patterns (LS-1) to (LS-3) and (LS-21), it can be seen that the LS patterns (LS-1) to (LS-3) formed using the resist material containing an acid diffusion control agent with iodine provide better roughness than the LS pattern (LS-21).

[0420] Similarly, comparing the sensitivity of the resist materials (R-16) to (R-18) and (R-22) containing polyate (A-6) in Table 3, it can be seen that the resist materials (R-16) to (R-18) containing an acid diffusion control agent with iodine have better sensitivity than the resist material (R-22) containing an acid diffusion control agent without iodine. Furthermore, it can be seen that the LS patterns (LS-16) to (LS-18) formed using the resist materials containing an acid diffusion control agent with iodine provide better roughness than the LS pattern (LS-22).

[0421] Furthermore, as shown in Table 3, a comparison of the sensitivity of the resist materials (R-10) to (R-12) and (R-23) containing polyate (A-4) reveals that the resist materials (R-10) to (R-12) containing an acid diffusion control agent with iodine have better sensitivity than the resist material (R-23) containing an acid diffusion control agent without iodine. In addition, the LS patterns (LS-10) to (LS-12) formed using the resist materials containing an iodine-containing acid diffusion control agent provide better roughness than the LS pattern (LS-23).

[0422] From the above results, it can be seen that by including an iodine-containing acid diffusion control agent in a resist material containing a heteropolyate with modified defect areas, the sensitivity of the resist material can be maintained at a good level or even improved, while simultaneously achieving good roughness in the LS pattern formed using the resist material.

[0423] From the results in Table 4, it can be seen that the resist materials (R-24) to (R-34) containing poly salts (A-9) to (A-19) that have four or more acid-dissociable polar groups in the anionic portion of the poly salt exhibit good sensitivity, and also yield good roughness results for LS-24 to LS-34.

[0424] Furthermore, the results in Table 4 show that the resist materials (R-35) to (R-45) containing poly salts (A-20) to (A-25) that include polar groups having four or more acid-dissociable groups in the anionic portion of the poly salt and fluorine or iodine in the cation portion of the poly salt exhibit good sensitivity, and also yield good roughness results for LS-35 to LS-45.

Claims

A resist material comprising (A) a heteropolyate or mixture thereof with modified defect sites, and (B) an acid diffusion control agent, The (B) acid diffusion control agent is a photodecayable base having an (B1) iodine atom. Resist material. 　 The resist material according to claim 1, wherein the (B1) photodecayable base having an iodine atom is a photodecayable base having an aromatic hydrocarbon cyclic group having an iodine atom. 　 The photo-decayable base having an aromatic hydrocarbon cyclic group containing an iodine atom is a photo-decayable base B represented by the following general formula (IX-1-1). １Ａ , photodecayable base B represented by the following general formula (IX-1-2) １Ｂ , photodecayable base B represented by the following general formula (IX-1-3) １Ｃ , or photodecayable base B represented by the following general formula (IX-1-4) １Ｄ The resist material according to claim 2. [In general formula (IX-1-1), Ar Ｂ１ａ This represents a monovalent aromatic hydrocarbon cyclic group which may have substituents, wherein at least one hydrogen atom on the aromatic hydrocarbon cyclic group is replaced by an iodine atom, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted by substituents; D ｐ＋ represents an onium cation or onium dication; p represents an integer of 1 or 2. [In general formula (IX-1-2), Ar Ｂ１ｂ This represents a monovalent aromatic hydrocarbon cyclic group which may have substituents, wherein at least one hydrogen atom on the aromatic hydrocarbon cyclic group is replaced by an iodine atom, and the remaining hydrogen atoms on the aromatic hydrocarbon cyclic group may be substituted by substituents; L Ｂ１ｂ is a C １－１８ hydrocarbylene group which may have a substituent, and any divalent carbon atom except the terminal other than the bonding part may be replaced by -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S- or -SO ２ -(provided that adjacent divalent carbon atoms are not simultaneously replaced). D ｐ＋ represents an onium cation or onium dication; p represents an integer of 1 or 2. [In general formula (IX-1-3), Ar Ｂ１ｃ １ represents a divalent aromatic hydrocarbon cyclic group which may have substituents; Ar Ｂ１ｃ ２ represents a monovalent aromatic hydrocarbon cyclic group which may have substituents; Ar Ｂ１ｃ １ or Ar Ｂ１ｃ ２ At least one hydrogen atom on the aromatic hydroxyl group is replaced by an iodine atom; L Ｂ１ｃ C may have a single bond or a substituent. １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ This represents a component that may be replaced by a hyphen (however, adjacent divalent carbon atoms cannot be replaced simultaneously); D ｐ＋ represents an onium cation or onium dication; p represents an integer of 1 or 2. [In general formula (IX-1-4), Ar Ｂ１ｄ １ represents a divalent aromatic hydrocarbon cyclic group which may have substituents; Ar Ｂ１ｄ ２ represents a monovalent aromatic hydrocarbon cyclic group which may have substituents; Ar Ｂ１ｄ １ or Ar Ｂ１ｄ ２ At least one hydrogen atom on the aromatic hydroxyl group is replaced by an iodine atom; L Ｂ１ｄ １ C may have substituents. １－１８ A hydrocarbylene group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ This represents a component that may be replaced by a hyphen (however, adjacent divalent carbon atoms cannot be replaced simultaneously); L Ｂ１ｄ ２ C may have a single bond or a substituent. １－１８ A hydrocarbylene group in which any divalent carbon atom except the ultraviolet end of the bond is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NH-, -CONH-, -NH(C=O)-, -S-, or -SO ２ This represents a component that may be replaced by a hyphen (however, adjacent divalent carbon atoms cannot be replaced simultaneously); D ｐ＋ represents an onium cation or onium dication; p represents an integer of 1 or 2. The resist material according to claim 1, wherein the anionic portion and / or cation portion of the heteropolyate modified with the (A) defect portion has one or more polar groups having an acid-dissociable group. 　 The resist material according to claim 4, wherein the resist material generates acid upon exposure and its solubility in a developer changes due to the action of the acid. 　 The resist material according to claim 4, 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. 　 The anionic portion of the heteropolyate salt modified with the (A) defect site is a heteropolyate anion having a defect site, in which the defect site is modified. The modification is performed by a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more organic groups are bonded, and by bonding some or all of the heteroatoms to the terminal oxygen atom of the heteropoly acid anion having the defect site. The resist material according to claim 1. 　 The organic group may have substituents. １－１８ It is a hydrocarbyl group, C which may have the substituent １－１８ Any divalent carbon atom other than the terminal of the hydrocarbyl group is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time). C which may have the substituent １－１８ One or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group. The resist material according to claim 7. 　 The resist material according to claim 7, wherein the organic group is represented by general formula (VII-1). (VII-1) [In general formula (VII-1), L ２Ａ１ C may have substituents. １－１２ In a hydrocarbyl group, one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are R ２Ａ１ This represents the group that has been substituted, Said L ２Ａ１ The terminal and R ２Ａ１ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ２Ａ１ Each of these independently represents a polar group having an acid-dissociable group; x represents an integer from 1 to 6; * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn. The resist material according to claim 1, wherein the (A) modified heteropolyate or mixture thereof is a heteropolyate or mixture thereof that is modified with a defect represented by general formula (I). (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In general formula (I), A ｍ＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C （ａｍ）－ This represents a heteropoly acid anion in which the missing site has been modified; A ｍ＋ and / or C （ａｍ）－ It has at least one polar group having an acid-dissociable group; m is an integer between 1 and 5, and a is a real number greater than 0. 　 The resist material according to claim 1, wherein the (A) modified heteropolyate or mixture thereof is a heteropolyate or mixture thereof that is modified with a defect represented by general formula (I'). (A’ ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C’(a’m’+bn)-) (I’) [In general formula (I'), A' ｍ’＋ Each of them independently, H ＋ , metal ions, or NH ４ ＋ It represents; B ｎ＋ Each of these independently represents an onium cation or an onium dication; C'(a'm'+bn)- represents a heteropoly acid anion in which the missing site has been modified; B ｎ＋ and / or C'(a'm'+bn)- has at least one polar group having an acid-dissociable group; m' is an integer between 1 and 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0. 　 A step of forming a resist film using a resist material according to any one of claims 1 to 11, The steps include: exposing the resist film, The process involves developing the exposed resist film using a developer solution, A pattern formation method including the following.

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