Resist material and pattern formation method

Abstract

The present invention provides a resist material that contains at least two different polyacid salts (A1) and (A2) as (A) a polyacid salt. The resist material is characterized in that at least one of the polyacid salts (A1) and (A2) includes at least one polar group that has an acid-dissociable group.

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 resist materials containing metal compounds, organometallic compounds, metal nanoparticles, metal clusters, etc., have been proposed as new resist materials.

[0004] For example, Patent Document 1 describes a core made of ZrO ２ , HfO ２ , TiO ２ A nanoparticle polymer resist is disclosed, comprising nanoparticles containing the above and a polymer. Furthermore, Patent Document 2 discloses (t-BuSn), which is an alkyltin cluster. １２ O １４ (OH) ６ (HCO ２ ) ２ A resist based on this has been disclosed.

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

[0006] The present invention aims to provide a novel resist material and a pattern formation method.

[0007] As a result of diligent research to solve the above problems, the present inventors have found that by including at least two different poly salts (A1) and (A2) as (A) poly salts, wherein the poly salts (A1) and / or (A2) contain one or more polar groups having acid-dissociable groups, the roughness after development is good and an LS pattern of more uniform width can be obtained, thus completing the present invention.

[0008] That is, the present invention relates to the following inventions. <1> A resist material containing at least two different polyacid salts (A1) and (A2) as polyacid salts, wherein the polyacid salt (A1) and / or (A2) contains one or more polar groups having an acid dissociable group, characterized by a resist material. <2> The resist material according to <1>, which is a resist material that generates an acid upon exposure and whose solubility in a developer changes by the action of the acid. <3> The resist material according to <1>, wherein the acid dissociable group is a tertiary carbon type acid dissociable group, an allyl type or benzyl type acid dissociable group, or an acetal type acid dissociable group. <4> The resist material according to <1>, wherein the polyacid salt (A1) is a polyacid salt represented by the following general formula (I-1-1) or (I-1-2). (A １１ ｍ１１＋ ) ａ１１ (C １１ （ａ１１ｍ１１）－ ) (I-1-1) [In the general formula (I-1-1), A １１ ｍ１１＋ each independently represents H ＋ , a metal ion, NH ４ ＋ , an onium cation, or an onium dication; C １１ （ａ１１ｍ１１）－ represents a heteropolyacid anion modified with one or more polar groups having an acid dissociable group; m11 is an integer of 1 to 5, and a11 is a real number greater than 0.] (A １２ ｍ１２＋ ) ａ１２ (B １２ ｎ１２＋ ) ｂ１２ (C １２ (a12m12 + b12n12)-) (I-1-2) [In the general formula (I-1-2), A １２ ｍ１２＋ each independently represents H ＋ , a metal ion, NH ４ ＋ , an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B １２ ｎ１２＋Each of these independently represents a sulfonium cation, sulfonium dication, or iodonium cation containing one or more polar groups having acid-dissociable groups; C １２ (a12m12+b12n12)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m12 is an integer from 1 to 5, n12 is an integer of 1 or 2, a12 is a real number, and b12 is a real number greater than 0. ] <5> The resist material according to <4>, wherein the polyate represented by the general formula (I-1-1) is a heteropolyate anion with a modified defect containing one or more polar groups having an acid-dissociable group, 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 heteroatom of the heteropolyate anion having the defect via some or all of the heteroatoms, and the organic group has one or more polar groups having an acid-dissociable group. <6> 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 <5>, wherein one or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group. <7> The resist material according to <4>, wherein the polyate (A2) is a polyate represented by the following general formula (I-2). (A ２ ｍ２＋ ) ａ２ (C ２ （ａ２ｍ２）－ ) (I-2) [In general formula (I-2), A ２ ｍ２＋ Each of them independently, H＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C ２ （ａ２ｍ２）－ is an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m2 is an integer from 1 to 5, and a2 is a real number greater than 0. ] <8> The resist material according to <1>, wherein the mass ratio of the polyate (A1) to the polyate (A2) is 5 to 95:95 to 5. <9> The resist material according to <1>, wherein the cation portion of the polyate (A1) and / or (A2) contains a sulfonium cation, a sulfonium dication, or an iodonium cation. <10> The resist material according to <1>, further containing (B) an acid generator. <11> The resist material according to <1>, further containing (C) an acid diffusion control agent, wherein the (C) acid diffusion control agent is (C1) a photodecayable base.

[0009] <12> The resist material according to <4> or <7>, wherein the isopoly acid anion is a polyoxomolybdate anion, a polyoxotungstate anion, a polyoxoniobate anion, or a polyoxotantalate anion. <13> The resist material according to <4> or <7>, wherein the poly atom of the heteropoly acid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge. <14> The heteropoly acid anion is [PW １２ O ４０ ] ３－ [SiW １２ O ４０ ] ４－ [BW １２ O ４０ ] ５－ or [SW １２ O ４０ ] ２－The resist material according to <13>. <15> The resist material according to <5>, wherein the heteropoly acid anion having the defect is a defective Keggin-type heteropoly acid anion or a defective Dawson-type heteropoly acid anion. <16> The resist material according to <15>, 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) (wherein X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.) <17> The resist material according to <15>, wherein the defective Dawson-type heteropoly acid anion is represented by the general formula (III-1), (III-2), or (III-3). [X ２ M １７ O ６１ ] ｃ２１－ (III-1) [X ２ M １６ O ５８ ] ｃ２２－ (III-2) [X ２ M １５ O ５６ ] ｃ２３－ (III-3) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the negative charge number, and c21- to c23 are natural numbers.)

[0010] <18> The resist material according to <1>, wherein the cation portion of the polyate (A1) comprises a sulfonium cation, a sulfonium dication, or an iodonium cation.

[0011] <19> The anion part of the polyacid salt (A1) is a heteropolyacid anion in which the defect site is modified, and the heteropolyacid anion in which the defect site is modified contains one or more polar groups having an acid dissociable group. The resist material according to <18>. <20> The polyacid salt (A1) is a polyacid salt represented by the following general formula (I-3-1), and the polyacid salt (A2) is a polyacid salt represented by the following general formula (I-4-1). The resist material according to <19>. (A ３１ ｍ３１＋ ) ａ３１ (B ３１ ｎ３１＋ ) ｂ３１ (C ３１ (a31m31 + b31n31)-) (I-3-1) [In the general formula (I-3-1), A ３１ ｍ３１＋ are each independently H ＋ , a metal ion, NH ４ ＋ , an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B ３１ ｎ３１＋ are each independently a sulfonium cation, a sulfonium dication, or an iodonium cation; C ３１ (a31m31 + b31n31)- represents a heteropolyacid anion in which a defect site containing one or more polar groups having an acid dissociable group is modified; m31 is an integer of 1 to 5, n31 is an integer of 1 or 2, a31 is a real number, and b31 is a real number greater than 0. ] (A ４１ ｍ４１＋ ) ａ４１ (C ４１ （ａ４１ｍ４１）－ ) (I-4-1) [In the general formula (I-4-1), A ４１ ｍ４１＋ are each independently H ＋ , a metal ion, NH ４ ＋ , an onium cation, or an onium dication; C ４１ （ａ４１ｍ４１）－represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deficiency; m41 is an integer between 1 and 5, and a41 is a real number greater than 0.

[0012] <21> The resist material according to <18>, wherein the sulfonium cation, sulfonium dication, or iodonium cation contains one or more polar groups having acid-dissociable groups. <22> The resist material according to <21>, wherein the polyate (A1) is a polyate represented by the following general formula (I-3-2), and the polyate (A2) is a polyate represented by the following general formula (I-4-2). (A ３２ ｍ３２＋ ) ａ３２ (B ３２ ｎ３２＋ ) ｂ３２ (C ３２ (a32m32+b32n32)-) (I-3-2) [In general formula (I-3-2), A ３２ ｍ３２＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３２ ｎ３２＋ Each of these independently represents a sulfonium cation, sulfonium dication, or iodonium cation containing one or more polar groups having acid-dissociable groups; C ３２ (a32m32+b32n32)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m32 is an integer from 1 to 5, n32 is an integer of 1 or 2, a32 is a real number, and b32 is a real number greater than 0. ] (A ４２ ｍ４２＋ ) ａ４２ (C ４２ （ａ４２ｍ４２）－ ) (I-4-2) [In general formula (I-4-2), A ４２ ｍ４２＋ Each of them independently, H ＋ , metal ions, NH ４ ＋, represents an onium cation or onium dication; C ４２ （ａ４２ｍ４２）－ represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m42 is an integer between 1 and 5, and a42 is a real number greater than 0.

[0013] <23> The resist material according to <18>, wherein the cation portion or anion portion of the polyate (A2) contains one or more polar groups having acid-dissociable groups.

[0014] <24> The resist material according to <23>, wherein the anionic portion of the polyate (A2) is a heteropolyate anion with a modified defect, and the heteropolyate anion with a modified defect contains one or more polar groups having an acid-dissociable group. <25> The resist material according to <24>, wherein the polyate (A1) is a polyate represented by the following general formula (I-3-3), and the polyate (A2) is a polyate represented by the following general formula (I-4-3). (A ３３ ｍ３３＋ ) ａ３３ (B ３３ ｎ３３＋ ) ｂ３３ (C ３３ (a33m33+b33n33)-) (I-3-3) [In general formula (I-3-3), A ３３ ｍ３３＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３３ ｎ３３＋ Each of these independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C ３３ (a33m33+b33n33)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m33 is an integer from 1 to 5, n33 is an integer of 1 or 2, a33 is a real number, and b33 is a real number greater than 0. ] (A ４３ ｍ４３＋ )ａ４３ (C ４３ （ａ４３ｍ４３）－ ) (I-4-3) [In general formula (I-4-3), A ４３ ｍ４３＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C ４３ （ａ４３ｍ４３）－ This represents a heteropoly acid anion modified by a defect site having one or more polar groups with acid-dissociable groups; m43 is an integer from 1 to 5, and a43 is a real number greater than 0.

[0015] <26> The resist material according to <23>, wherein the cation portion of the polyate (A2) is a sulfonium cation, sulfonium dication, or iodonium dication containing one or more polar groups having an acid-dissociable group. <27> The resist material according to <26>, wherein the polyate (A1) is a polyate represented by the following general formula (I-3-4), and the polyate (A2) is a polyate represented by the following general formula (I-4-4). (A ３４ ｍ３４＋ ) ａ３４ (B ３４ ｎ３４＋ ) ｂ３４ (C ３４ (a34m34+b34n34)-) (I-3-4) [In general formula (I-3-4), A ３４ ｍ３４＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３４ ｎ３４＋ Each of these independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C ３４(a34m34+b34n34)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m34 is an integer from 1 to 5, n34 is an integer of 1 or 2, a34 is a real number, and b34 is a real number greater than 0. ] (A ４４ ｍ４４＋ ) ａ４４ (B ４４ ｎ４４＋ ) ｂ４４ (C ４４ (a44m44+b44n44)-) (I-4-4) [In general formula (I-4-4), A ４４ ｍ４４＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ４４ ｎ４４＋ Each of these independently represents a sulfonium cation, sulfonium dication, or iodonium cation having one or more polar groups with acid-dissociable groups; C ４４ (a44m44+b44n44)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m44 is an integer between 1 and 5, n44 is an integer of 1 or 2, a44 is a real number, and b44 is a real number greater than 0.

[0016] <28> The resist material according to <1>, wherein the polyate (A1) is a polyate represented by the following general formula (I-3-5), and the polyate (A2) is a polyate represented by the following general formula (I-4-5). (A ３５ ｍ３５＋ ) ａ３５ (B ３５ ｎ３５＋ ) ｂ３５ (C ３５ (a35m35+b35n35)-) (I-3-5) [In general formula (I-3-5), A ３５ ｍ３５＋ Each of them independently, H ＋ , metal ions, NH ４＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３５ ｎ３５＋ Each independently represents a sulfonium cation, sulfonium dication, or iodonium cation which may have a polar group having an acid-dissociable group; C ３５ (a35m35+b35n35)- represents a heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups; m35 is an integer from 1 to 5, n35 is an integer of 1 or 2, a35 is a real number, and b35 is a real number greater than 0. ] (A ４５ ｍ４５＋ ) ａ４５ (B ４５ ｎ４５＋ ) ｂ４５ (C ４５ (a45m45+b45n45)-) (I-4-5) [In general formula (I-4-5), A ４５ ｍ４５＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ４５ ｎ４５＋ Each independently represents a sulfonium cation, sulfonium dication, or iodonium cation which may have a polar group having an acid-dissociable group; C ４５ (a45m45+b45n45)- represents a heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups; m45 is an integer from 1 to 5, n45 is an integer of 1 or 2, a45 is a real number, and b45 is a real number greater than 0.

[0017] <29> The resist material according to <1>, further containing an organic solvent. <30> The resist material according to any one of <1> to <29>, which is an electron beam or EUV resist material. <31> A pattern forming method comprising the steps of: forming a resist film using the resist material according to any one of <1> to <29>; exposing the resist film; and developing the exposed resist film using a developer.

[0018] According to the present invention, a novel resist material and a pattern formation method can be provided.

[0019] Preferred embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0020] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0021] In this specification, "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0022] In this specification, for example, "C １－６ Terms such as "[...]" refer to the number of carbon atoms in the core group.

[0023] In this specification, "C １－１８ A "hydrocarbylene group" refers to a divalent hydrocarbon group produced by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbylene groups may be linear, branched, or partially or entirely cyclic. Hydrocarbylene groups include alkylene groups and arylene groups. １－１８ The divalent carbon atoms at any position in the "hydrocarbylene group" are -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time). １－１８The "hydrocarbylene group" is not particularly limited and includes, for example, methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadiyl group, cyclohexanediyl group, oxyethane-1,1-diyl group, oxyethane-1,2-diyl group, oxypropane-1,3-diyl group, oxypropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, oxyethyleneoxyethane-1,1-diyl group, etc. 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, phenanthrendiyl group, naphthacenediyl group, pyrenediyl group, perylenediyl group, chrysendiyl group, etc. ６－１８ Examples include the "arylene group."

[0024] In this specification, "C １－１８ "Alkyl alkyl group" refers to a linear or branched alkyl group having 1 to 18 carbon atoms. １－１８ Any divalent carbon atom in an alkyl group, excluding the terminals, 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. １－１８The "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.

[0025] 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.

[0026] In this specification, "C ２－１８ An "alkenyl group" is a group with two or more carbon atoms. １－１８"Alkyl group" refers to an alkenyl group having one or more double bonds, and includes alkadinyl groups, alkatrienyl groups, etc. ２－１８ The "alkenyl group" is not particularly limited and includes, for example, vinyl group (ethenyl group), allyl group (2-propenyl group), 1-propenyl group, isopropenyl group (1-methylvinyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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 The divalent carbon atoms at any position in the "hydrocarbyl group" excluding the terminals 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). 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."

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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".

[0038] 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.

[0039] 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.

[0040] 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."

[0041] 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. DiC １－１８ "Alkylamino group"; 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.

[0042] 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"; "C" 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.

[0043] 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".

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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 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. Preferred polar groups are hydroxyl groups (including phenolic hydroxyl groups, etc.) and carboxyl groups.

[0052] 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).

[0053] 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.

[0054] <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.

[0055] "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).

[0056] R Ａ ｇ１ C may have substituents. １－１２ Alkyl 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).

[0057] 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).

[0058] 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).

[0059] 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.

[0060] 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.

[0061]

[0062] <<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.

[0063] <<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 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).

[0064] 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).

[0065] 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).

[0066] 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.

[0067]

[0068]

[0069]

[0070]

[0071] <<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.

[0072] 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.

[0073] 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).

[0074] 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).

[0075] 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.

[0076]

[0077]

[0078]

[0079] <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.

[0080] "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).

[0081] R Ｂ ｇ１ C may have substituents. １－１２ Alkyl 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).

[0082] 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).

[0083] 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.

[0084] 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.

[0085] Allyl or benzyl acid-dissociable group G represented by general formula (g-2) Ｂ Examples include the following allyl or benzyl acid-dissociating groups.

[0086]

[0087] <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.

[0088] "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).

[0089] 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 carbon atoms may be replaced by a ⁻ (however, adjacent divalent carbon atoms may not be replaced simultaneously), and that the carbon atoms may have a hydro group or substituents. 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).

[0090] 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).

[0091] 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).

[0092] 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.

[0093] 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.

[0094] 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.

[0095] In this specification, "may have substituents" is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of substituents include: (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, C １－１８ Hydrocarbylamino group, diC １－１８Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C １－１８ Hydrocarbylthio group, C １－１８ 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).

[0096] [1. Resist Material] The resist material according to this embodiment contains at least two different poly salts (A1) and (A2) as (A) poly salts, and is characterized in that the poly salts (A1) and / or (A2) contain one or more polar groups having acid-dissociable groups. The resist material according to this embodiment may also contain poly salts other than components (A1) and (A2) as optional components, and may also contain (B) an acid generator, (C) an acid diffusion control agent, an organic solvent, etc.

[0097] [1-1. (A) Polyate] By providing a resist material containing at least two different polyates (A1) and (A2) as (A) polyate, it is possible to provide a resist material that exhibits good roughness after development and gives an LS pattern of a more uniform width.

[0098] Although the exact mechanism is unclear, it is thought that by incorporating two or more polyate salts into the resist material, the crystallinity and cohesiveness of each polyate salt are suppressed, thereby improving the solubility and dispersibility of these polyate salts in organic solvents. Furthermore, by improving the dispersibility of (A) polyate salt and other optional components in the resist material, it is thought that the roughness after development is improved, resulting in a more uniform LS pattern width.

[0099] Furthermore, in the resist material according to this embodiment, at least one polar group having an acid-dissociable group is included in at least one of the two different poly salts (A1) and (A2), so that the solubility in the developer can be changed by the action of acid. The number of polar groups having an acid-dissociable group included in the poly salt (A1) and / or (A2) is not particularly limited, for example, it is preferably 1 to 12, more preferably 2 to 10, and even more preferably 4 to 8. Furthermore, by adjusting the bulkiness, hydrophobicity, lipophilicity, etc. of the acid-dissociable group, the range of change in physical properties such as solubility in the developer between the exposed and unexposed portions of the active light can be adjusted.

[0100] In the resist material according to this embodiment, if at least one of the two different poly salts (A1) and (A2) contains a sulfonium cation, sulfonium dication, or iodonium cation in its cation portion, it can function as a photoacid generator that generates acid upon exposure to active light (including visible light, ultraviolet light, DUV, XUV, EUV, X-rays, electron beams, α-rays, β-rays, γ-rays, etc.). On the other hand, if neither of the cation portions of the poly salts (A1) and (A2) contains a sulfonium cation, sulfonium dication, or iodonium cation, a known and conventional (B) acid generator, as described later, may be added to the resist material.

[0101] Therefore, the resist material according to this embodiment can be suitably used as a resist material that generates acid upon exposure and whose solubility in a developer solution changes due to the action of the acid.

[0102] In the following, the anionic portion and the cation portion of the (A) polysalt according to this embodiment will be described separately.

[0103] [1-1-1. (A) Anionic portion of the polyate] As the anionic portion of the polyate according to this embodiment, an isopolyate anion, a heteropolyate anion, or a heteropolyate anion modified with a defect site can be used.

[0104] [1-1-1-1. Isopolyate Anion] The isopolyate anion according to this embodiment is not particularly limited, and isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, isopolyoxotantalate anion, etc. can be used.

[0105] Examples of the above isopolyoxomolybdate anion include [MoO ４ ] ２－ [Mo ７ O ２４ ] ６－ [Mo ８ O ２６ ] ４－ Examples include the above isopolyoxotungstate anion, for example, [W ４ O １３ ] ２－ [W ５ O １６ ] ２－ [W ６ O １９ ] ２－ [W ７ O ２２ ] ２－ [W ７ O ２４ ] ６－ [H ｚ W １２ O ４０ ] －（８－ｚ） (However, z represents an integer from 1 to 4.) [W １０ O３２ ] ４－ [H ４ W １１ O ３８ ] ６－ [H ７ W １１ O ４０ ] ７－ [HW ５ O １９ ] ７－ [H ３ W １１ O ２２ ] ５－ Examples include the above isopolyoxovanadate anion, for example, [V ４ O １２ ] ４－ 'yV' １０ O ２８ ] ６－ Examples include [Nb ６ O １９ ] ８－ [Nb １０ O ２８ ] ６－ Examples include [Ta ６ O １９ ] ８－ ᘐTa ８ O ２１ ] ２－ These are some examples.

[0106] The above-mentioned isopolyoxomolybdate anions, isopolyoxotungstate anions, isopolyoxovanadate anions, isopolyoxoniobate anions, and isopolyoxotantalate anions shall include various isomers, etc.

[0107] The above isopolyoxotungstate anion is [W ４ O １３ ] ２－ [W ５ O １６ ] ２－ [W ６ O １９ ] ２－ [W ７ O ２２ ] ２－ [W ７O ２４ ] ６－ [W １０ O ３２ ] ４－ [H ｚ W １２ O ４０ ] －（８－ｚ） (However, z represents an integer from 1 to 4.) [H ４ W １１ O ３８ ] ６－ [H ７ W １１ O ４０ ] ７－ [HW ５ O １９ ] ７－ [H ３ W １１ O ２２ ] ５－ [H ４ W ２２ O ７４ ] １２－ , or [H １０ W ３４ O １１６ ] １８－ It is preferable that [W ６ O １９ ] ２－ [W ７ O ２４ ] ６－ [W １０ O ３２ ] ４－ [H ｚ W １２ O ４０ ] －（８－ｚ） (where z represents an integer from 1 to 4.) It is more preferable that [W ６ O １９ ] ２－ [W ７ O ２４ ] ６－ [W １０ O ３２ ] ４－ [H ２ W １２ O ４０ ] ６－ [H ３ W １２ O ４０ ] ５－ It is even more preferable that this be the case.

[0108] [1-1-1-2. Heteropolyacid anions] Examples of heteropolyacid anions according to this embodiment include heteropolyoxomolybdate anion, heteropolyoxotungstate anion, heteropolyoxovanadate anion, heteropolyoxoniobate anion, heteropolyoxotantalate anion, and the like. The poly atom of the above heteropolyacid anion is preferably Mo, W, V, Nb, or Ta, and more preferably Mo or W.

[0109] Examples of heteropolyoxomolybdate anions include phosphomolybdate anion, silicamolybdate anion, bonymolybdate anion, sulfurmolybdate anion, phosphotungstomolybdate anion, cobaltmolybdate anion, arsenicmolybdate anion, germaniummolybdate anion, etc. Examples of heteropolyoxotungstate anions include phosphotungstate anion, silicatungstate anion, bonytungstate anion, sulfurtungstate anion, cobalttungstate anion, arsenictungstate anion, germaniumtungstate anion, etc. Examples of heteropolyoxovanadate anions include phosphomolybdovanadate anion, bonybdovanadate anion, bonybdotungstovanadate anion, etc. The heteroatom of the above heteropoly acid anion is preferably P, Si, Ge, B, S, Co, or As, and more preferably P, Si, B, S, or Ge.

[0110] The above-mentioned heteropolyoxomolybdate anions, heteropolyoxotungstate anions, heteropolyoxovanadate anions, etc., include the Keggin type, Dawson type, Anderson type, and their isomers.

[0111] The above heteropolyoxotungstate anion is [PW １２ O ４０ ] ３－ [SiW １２ O ４０ ] ４－ [BW１２ O ４０ ] ５－ [SW １２ O ４０ ] ２－ [P ２ W １８ O ６２ ] ６－ [Si ２ W １８ O ６２ ] ８－ It is preferable that this be the case.

[0112] [1-1-1-3. Heteropoly acid anions with modified defect sites] The heteropoly acid anions with modified defect sites according to this embodiment are obtained by reacting the terminal oxygen atom at the defect site of a heteropoly acid anion having a defect site with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups.

[0113] [1-1-1-3-1. Heteropoly acid anions having a defect] The heteropoly acid anion having a defect according to this embodiment is not particularly limited, and a defect species in which a part of the basic skeleton of the above heteropoly acid anion is missing can be used, and any of the above-mentioned 1-defect species, 2-defect species, 3-defect species, etc., may be used. Examples of the above-mentioned heteropoly acid anion having a defect include a Keggin-type heteropoly acid anion with a defect, a Dawson-type heteropoly acid anion with a defect, and the like.

[0114] <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.)

[0115] 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－ [SiW１０ 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－ )

[0116] 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-PW１１ O ３９ ７－ , [α-PMo １１ O ３９ ７－ , [β-PMo １１ O ３９ ７－ , [γ-PW １１ O ３９ ７－ , [α-SiW １１ O ３９ ８－ , [β-SiW １１ O ３９ ８－ , [γ-SiW １１ O ３９ ８－ , [α-SiMo １１ O ３９ ８－ , [β-SiMo １１ O ３９ ８－ , [γ-SiW １１ O ３９ ８－ is preferred, and [α-PW １１ O ３９ ７－ , [α-PMo １１ O ３９ ７－ , [α-SiW １１ O ３９ ８－ , [α-SiMo １１ O ３９ ８－ is more preferred. Also, as the isomeric structures of the 2-defect Keggin-type heteropolyacid anions represented by the general formula (II-1), [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－ ８－ , [β-SiW １０ O ３６ ８－ ８－ , [γ-SiW １０ O ３６ ８－ ８－ , [α-SiMo １０ O ３６ ８－ ８－ , [β-SiMo １０ O ３６ ８－ ８－ , [γ-SiW １０ O ３６ ８－ ８－ are preferred, and [γ-PW １０ O ３６ ７－ ７－ , [γ-PMo １０ O ３６ ７－ ７－ , [γ-SiW １０ O ３６ ８－ ８－ , [γ-SiMo １０ O ３６ ８－ ８－ are more preferred. Further, as the isomeric structures of the tridefect Keggin-type heteropolyacid anions represented by the general formula (III-1), [α-PW ９ O ３４ ９－ ９－ , [β-PW ９ O ３４ ９－ ９－ , [γ-PW ９ O ３４ ９－ ９－ , [α-PMo ９ O ３４ ９－ ９－ , [β-PMo ９ O ３４ ９－ ９－ , [γ-PW ９ O ３４ ９－ ９－ , [α-SiW ９ O ３４ １０－ １０－ , [β-SiW ９ O ３４ １０－ １０－ , [γ-SiW ９ O ３４ １０－ １０－ , [α-SiMo ９O ３４ １０－ 、 [β-SiMo ９ O ３４ １０－ 、 [γ-SiW ９ O ３４ １０－ is preferred.

[0117] <Defective Dawson type heteropolyacid anion> As the defective Dawson type heteropolyacid anion, for example, a 1-defective Dawson type heteropolyacid anion represented by the following general formula (III-1), a 2-defective Dawson type heteropolyacid anion represented by the following general formula (III-2), a 3-defective Dawson type heteropolyacid anion represented by the following general formula (III-3), etc. may be mentioned. [X ２ M １７ O ６１ ｃ２１－ (III-1) [X ２ M １６ O ５８ ｃ２２－ (III-2) [X ２ M １５ O ５６ ｃ２３－ (III-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.)

[0118] In general formulas (III-1) to (III-3), the values of c21 to c23 vary depending on the types of X and M. For example, in general formula (III-1), when X is P and M is Mo or W, c21 is 10 ([P ２ Mo １７ O ６１ [[ID=5))] １０－ , [P ２ W １７ O ６１ １０－ ), and when X is S and M is W, c21 is 8 ([S ２ W １７ O ６１ ８－ ). Also, 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－ )

[0119] 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 W １５ O ５６ ] １２－ [α-S ２ W １７ O ６１ ] ８－ These can be suitably used.

[0120] [1-1-1-3-2. 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 oxygen atom at 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 part or all of the heteroatom, thereby modifying the defective site.

[0121] <Bonding format and notation of the defective site> 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.

[0122] The bonding configuration between the terminal oxygen atom of the vacant site of the heteropoly acid anion and the group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded is not particularly limited and can be represented, for example, by the following general formulas (IV-1) to (IV-5). [In formulas (IV-1) to (IV-5), X' represents Si or Ge; X'' represents a heteroatom of Si, Ge, or Sn; R １Ａ１ ~R １Ｅ１ Each 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 １Ｅ１ 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), 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 site with the terminal oxygen atom of the deficiency site of the heteropoly acid anion.

[0123] 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')

[0124] 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 ().

[0125] 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')

[0126] 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).

[0127] 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) (R１Ｃ４ 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')

[0128] 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).

[0129] 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')

[0130] 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).

[0131] 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 １Ｅ１ The 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')

[0132] 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).

[0133] 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 R １Ｂ２ X') ２ ] ｃ３２－ (VI-6) [XM １０ O ３６ (R １Ｃ X'O) ４ ] ｃ３２－ (VI-7) [XM １０ O ３６ (R １Ｄ P = O) ２ ] ｃ３２－ (VI-8) [X ２ M １７ O ６１ (R １Ａ X') ２ O] ｃ３３－ (VI-9) [X ２ M １７ O ６１ (R １Ｂ１ R１Ｂ２ 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 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 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), 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.

[0134] 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.

[0135] <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 group 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 １ＥThe 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 １Ｅ The 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 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.

[0136] Also, the above R １Ａ ~R １Ｅ From 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.

[0137] <<An 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.

[0138] 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 １ＥAny 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 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 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 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 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 one hydrogen atom is replaced by a polar group having a (t) acid-dissociable group.

[0139] The above R １Ａ ~R １Ｅ It is characterized by containing one or more polar groups having acid-dissociable groups, for example, polar groups such as hydroxyl groups, carboxyl groups, amino groups, or sulfo groups 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 containing one or more polar groups having the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, the following can be cited:

[0140] [* indicates a bond between a heteroatom P, Si, Ge, or Sn to an organic group containing one or more acid-dissociable polar groups.]

[0141] 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).

[0142] [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 ends 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.

[0143] 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 ２Ａ１ The group substituted for: the above L ２Ａ１ The ends 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 ２It 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 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 ends 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 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 R ２Ａ１ The group substituted for: the above L ２Ａ１ The ends 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).

[0144] 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 ＡAllyl 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 phenolic hydroxyl groups) or a carboxyl group having an acid-dissociating group; and the above acid-dissociating group is a tertiary carbon type acid-dissociating group G Ａ It is even more preferable that this be the case.

[0145] 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.

[0146] <<Organic group having two or more polar groups with acid-dissociable groups>> 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.

[0147] R is an organic group containing two or more polar groups having the above-mentioned acid-dissociable group. 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 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 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 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 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 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. １－１８Alkyl 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.

[0148] The above R １Ａ ~R １Ｅ It is characterized by containing 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 containing two or more polar groups having the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, the following can be cited:

[0149] [G represents an acid-dissociable group G, and * indicates the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0150] [* 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.

[0151] The organic group containing two 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-2). [In formula (VII-2), L ２Ａ２C 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.

[0152] 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 ２Ａ２ and R ２Ｂ２ The group substituted for: the above L ２Ａ２ The ends 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 will not be replaced at the same time), L ２Ａ２ However, C may have substituents. ２－１０ Alkyl 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 ends and R ２Ａ２ or R２Ｂ２ 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 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 ２Ａ２ The ends 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).

[0153] R in an organic group represented by general formula (VII-2) ２Ａ２ and R ２Ｂ２ For example, R ２Ａ２ and R ２Ｂ２ 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 ＡIt is even more preferable that this be the case.

[0154] [1-1-2. (A) Cation part of the polyate] The cation part of the polyate according to this embodiment is H ＋ , metal ions, NH ４ ＋ Onium cations or onium dications can be used.

[0155] [1-1-2-1. Metal Ions] The metal ions that can be used as the cation portion of the polyate according to this embodiment 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 ＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ Al ３＋ Co ３＋ Na is preferred. ＋ _K ＋ , Rb ＋ , Cs ＋ Ca ２＋ Al ３＋ Co ３＋ More preferably, Na ＋ _K ＋ , Rb ＋ , Cs ＋ Ca ２＋ It is even more preferable that these metal ions are present individually or in combination of two or more.

[0156] [1-1-2-2. Onium Cation or Onium Dication] The onium cation or onium dication that can be used as the cation portion of the polysalt according to this embodiment is not particularly limited, and known and commonly used ones can be used. Examples of the above onium cation or onium dication include ammonium cation, ammonium dication, phosphonium cation, phosphonium dication, sulfonium cation, sulfonium dication, or iodonium cation. These onium cations or onium dications may be used individually or in combination of two or more.

[0157] From the viewpoint of providing a building block that generates acid when exposed to DUV, XUV, EUV, electron beam, etc., the above onium cation or onium dication is preferably a sulfonium cation, sulfonium dication, or iodonium cation.

[0158] [1-1-2-2-1. Ammonium Cation] The ammonium cation is not particularly limited, and known and commonly used ones can be used. The above ammonium cation is not particularly limited, for example, primary ammonium cation (NH ３ (R ３Ａ ) ＋ )), secondary ammonium cation (NH ２ (R ３Ａ ) (Caution ３Ｂ )) ＋ ), tertiary ammonium cation (NH(R ３Ａ ) (Caution ３Ｂ ) (Caution ３Ｃ ) ＋ ), quaternary ammonium cation (N(R ３Ａ ) (Caution ３Ｂ ) (Caution ３Ｃ ) (Caution ３Ｄ ) ＋ ) are listed above. ３Ａ ~R ３Ｄ This shall represent something equivalent to what is defined below.

[0159] The ammonium cation is preferably a quaternary ammonium cation, and more preferably an organic quaternary ammonium cation represented by the following general formula (VIII-1).

[0160] In general formula (VIII-1), R ３Ａ ~R ３Ｄ 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 ３Ｄ 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), and the above R ３Ａ ~R ３Ｄ 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, diC１－１８ 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 ３Ａ ~R ３Ｄ Any two of these are linked to each other by a single bond, directly, or by the 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 nitrogen atom in formula (VIII-1).

[0161] Specific examples of the above organic quaternary ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, tetraheptylammonium cation, trimethylethylammonium cation, dimethyldiethylammonium cation, dimethylethylpropylammonium cation, methylethylpropylbutylammonium cation, trimethylphenylammonium cation, triethylhexylammonium cation, triethylcyclohexylammonium cation, dodecyltrimethylammonium cation, diallyldimethylammonium cation, (3-acrylamidopropyl)trimethylammonium cation, trimethyl-2-methacroyloxyethylammonium cation, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium Examples include ammonium cations, trimethylvinylammonium cation, N-4-vinylbenzyltriallylammonium cation, 3-hydroxypropyltriallylammonium cation, 2-trifluoromethylbenzyltriallylammonium cation, di-2-(N-methylacrylamide)ethyldimethylammonium cation, allyltrimethylammonium cation, butyl(2-methacryloyloxyethyl)dimethylammonium cation, ethoxycarbonylmethyltriethylammonium cation, 2-hydroxyethyltrimethylammonium cation, 2-acetylethyltrimethylammonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)trimethylammonium cation, (4-(methacryloyloxy)phenyl)trimethylammonium cation, trimethyl(4-(nonanoyloxy)phenyl)ammonium cation, etc.

[0162] [1-1-2-2-2. Ammonium Dication] The ammonium dication is not particularly limited, and known and commonly used ones can be used. Examples of ammonium dications include the organic quaternary ammonium dication represented by the following general formula (VIII-2).

[0163] In general formula (VIII-2), R ４Ａ ~R ４Ｆ Each of these may independently have substituents. １－１８ The above R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ４Ａ ~R ４Ｆ Any divalent carbon atom at any position except the terminals 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 ４Ｆ and L ４ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８Hydrocarbyloxycarbonyloxy 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 ４Ｆ Any two of these are linked to each other by a single bond, directly, or by the 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 nitrogen atom in formula (VIII-2).

[0164] The organic quaternary ammonium dication represented by the above general formula (VIII-2) is not particularly limited, and examples include 1,4-diallyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1,4-di(2-(meth)acryloyloxyethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-bis(2-(meth)acrylamideethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium.

[0165] [1-1-2-2-3. Phosphonium Cations] Phosphonium cations are not particularly limited and known and commonly used ones can be used. Examples of phosphonium cations include the organic quaternary phosphonium cation represented by the following general formula (VIII-3).

[0166] In general formula (VIII-3), R ５Ａ ~R ５Ｄ Each of these may independently have substituents. １－１８ Represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; the above R ５Ａ ~R ５Ｄ 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 ~R ５Ｄ 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 １－１８Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, 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 ~R ５Ｄ Any two of these are linked to each other by a single bond, directly, or by the 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 phosphorus atom in formula (VIII-3).

[0167] The organic quaternary phosphonium cation represented by the above general formula (VIII-3) is not particularly limited, and includes, for example, tributylcyanomethylphosphonium cation, methyltriphenylphosphonium cation, ethyltriphenylphosphonium cation, cyanomethyltriphenylphosphonium cation, formylmethyltriphenylphosphonium cation, methoxymethyltriphenylphosphonium cation, chloromethyltriphenylphosphonium cation, acetonyltriphenylphosphonium cation, tributyl-1,3-dioxan-2-ylmethylphosphonium cation, triphenylpropargylphosphonium cation, allyltriphenyl Examples include triphosphonium cations, cyclopropyltriphenylphosphonium cations, benzyltriphenylphosphonium cations, tetrakis(hydroxymethyl)phosphonium cations, 2-carboxyethyltriphenylphosphonium cations, methoxycarbonylmethyltriphenylphosphonium cations, t-butoxycarbonylmethyltriphenylphosphonium cations, (4-((diisopropylcarbamoyl)oxy)phenyl)triphenylphosphonium cations, (4-(methacryloyloxy)phenyl)triphenylphosphonium cations, and triphenyl(4-(nonanoyloxy)phenyl)phosphonium cations.

[0168] [1-1-2-2-4. Phosphonium Dication] The phosphonium dication is not particularly limited, and known and commonly used ones can be used. Examples of phosphonium dications include the organic quaternary phosphonium dication represented by the following general formula (VIII-4).

[0169] In general formula (VIII-4), R ６Ａ ~R ６Ｆ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ６Ａ ~R ６ＦAny 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 ６ C may have substituents. １－１８ Represents a hydrocarbylene group, and the above L ６ 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 ６Ａ ~R ６Ｆ and L ６ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C１－１８ 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 ６Ａ ~R ６Ｆ Any two of these are linked to each other by a single bond, directly, or by the 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 together with the phosphorus atom in formula (VIII-4).

[0170] The organic quaternary phosphonium dication represented by the above general formula (VIII-4) is not particularly limited, and examples include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylenebis(triphenylphosphonium) dication, pentamethylenebis(triphenylphosphonium) dication, and the like.

[0171] [1-1-2-2-5. Sulfonium Cations] The sulfonium cation is not particularly limited, and known and commonly used ones can be used. Examples of sulfonium cations include the organic sulfonium cation represented by the following general formula (VIII-5).

[0172] In general formula (VIII-5), R ７Ａ , R ７Ｂ and R ７Ｃ Each of these may independently have substituents. １－１８R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ７Ａ , R ７Ｂ and R ７Ｃ 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 ７Ａ , R ７Ｂ and R ７Ｃ 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 １－１８Hydrocarbylaminocarbonylamino 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 ７Ａ , R ７Ｂ and R ７Ｃ 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-5).

[0173] In an organic sulfonium cation represented by the general formula (VIII-5), the above R ７Ａ , R ７Ｂ and R ７Ｃ For example, R ７Ａ , R ７Ｂ and R ７Ｃ However, each C may independently have substituents. １－１８ It is a hydrocarbyl group; the above R ７Ａ , R ７Ｂ and R ７Ｃ 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 ７Ａ , R ７Ｂ and R ７Ｃ However, each C may independently have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８It is an aralkyl group; the above R ７Ａ , R ７Ｂ and R ７Ｃ 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 ７Ａ , R ７Ｂ and R ７Ｃ However, each C may independently have substituents. ６－１８ It is an aryl group; the above R ７Ａ , R ７Ｂ and R ７Ｃ 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 ２It is even more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0174] Also R ７Ａ , R ７Ｂ and R ７Ｃ 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. ７Ａ , R ７Ｂ or R ７Ｃ It means the connection point.

[0175]

[0176] 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.

[0177] <Organosulfonium cation containing one or more polar groups having acid-dissociable groups> As a sulfonium cation, an organic sulfonium cation having one or more polar groups having acid-dissociable groups may be used, from the viewpoint of providing a building block whose solubility in the developer can be changed by the action of an acid, etc.

[0178] As an organosulfonium cation having one or more polar groups with acid-dissociable groups, in general formula (VIII-5), R ７Ａ , R ７Ｂ and R ７Ｃ 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. ７Ａ , R ７Ｂ and R ７Ｃ 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 ７Ａ , R ７Ｂ and R ７ＣThe 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 ７Ａ One or more hydrogen atoms contained in are replaced by polar groups having (t) acid-dissociable groups, and further R ７Ａ , R ７Ｂ and R ７Ｃ 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-5).

[0179] R containing one or more polar groups having the above-mentioned acid-dissociable groups ７Ａ C may have substituents. １－１８It is a hydrocarbyl group; the above R ７Ａ 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 ７Ａ 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 alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ７Ａ 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 ７Ａ 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 ７Ａ 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 ７Ａ It is even more preferable that at least one hydrogen atom is replaced by a polar group having a (t) acid-dissociable group.

[0180] The above R ７ＡIt is characterized by containing one or more polar groups having acid-dissociable groups, for example, polar groups such as hydroxyl groups, carboxyl groups, amino groups, or sulfo groups 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.

[0181] R containing one or more polar groups having the above-mentioned acid-dissociable groups ７Ａ For example, the following can be cited. Note that * indicates the bond with the sulfur atom in general formula (VII-5).

[0182]

[0183] R ７Ｂ and R ７Ｃ Each of these may independently have substituents. １－１８ It is a hydrocarbyl group; the above R ７Ｂ and R ７Ｃ 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 ７Ｂ and R ７Ｃ 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 alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ７Ｂ and R ７Ｃ 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 ７Ｂ and R ７Ｃ 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).

[0184] Examples of sulfonium cations containing 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.

[0185] Examples of organosulfonium cations containing one or more polar groups having the above-mentioned acid-dissociable groups include the following:

[0186]

[0187] [1-1-2-2-6. 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-6).

[0188] In general formula (VIII-6), R ８Ａ , R ８Ｂ , R ８Ｃ and R ８Ｄ 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. ８Ａ , R ８Ｂ , R ８Ｃ and R ８Ｄ 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 ８ C may have substituents. １－１８ Represents a hydrocarbylene group, and the above L ８ 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 ８Ａ , R ８Ｂ , R ８Ｃ , R ８Ｄ , and L ８The 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 ８Ａ , R ８Ｂ and L８ Any two of the following, and / or R ８Ｃ , R ８Ｄ and L ８ 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 together with the sulfur atoms in formula (VIII-6).

[0189] <Organosulfonium dication containing one or more polar groups having acid-dissociable groups> As a sulfonium dication, an organic sulfonium dication having one or more polar groups having 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.

[0190] As an organosulfonium dication having one or more polar groups with acid-dissociable groups, in general formula (VIII-6), R ８Ａ , R ８Ｂ , R ８Ｃ , R ８Ｄ , and L ８ Examples include those in which at least one hydrogen atom contained therein is replaced by a polar group having a (t) acid-dissociable group.

[0191] R containing one or more polar groups having acid-dissociable groups ８Ａ , R ８Ｂ , R ８Ｃ , R ８Ｄ , and / or, L ８ 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 containing one or more polar groups having the above-mentioned acid-dissociable groups. ８Ａ ~R ８Ｄ For example, R containing one or more polar groups having acid-dissociable groups. ７ＡExamples similar to those exemplified above can be given.

[0192] [1-1-2-2-7. Iodonium Cations] The iodonium cation is not particularly limited, and known and commonly used ones can be used. Examples of iodonium cations include the organic iodonium cation represented by the following general formula (VIII-7).

[0193] In general formula (VIII-7), R ９Ａ and R ９Ｂ 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. ９Ａ and R ９Ｂ 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 ９Ａ and R ９Ｂ 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 １－１８Hydrocarbyloxycarbonyloxy 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 (however, adjacent divalent carbon atoms cannot be replaced at the same time); further R ９Ａ and R ９Ｂ 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-7).

[0194] In the organic iodonium cation represented by the general formula (VIII-7), R ９Ａ and R ９Ｂ For example, R ９Ａ and R ９Ｂ However, each C may independently have substituents. １－１８ It is a hydrocarbyl group; the above R ９Ａ and R ９Ｂ 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 -SO２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), R ９Ａ and R ９Ｂ However, each C may independently have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ９Ａ and R ９Ｂ 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 ９Ａ and R ９Ｂ However, each C may independently have substituents. ６－１８ It is an aryl group; the above R ９Ａ and R ９Ｂ 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).

[0195] 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.

[0196] <Organiodonium cation having one or more polar groups with acid-dissociable groups> As an iodonium cation, an organiciodonium 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.

[0197] As an organiodonium cation having one or more polar groups with acid-dissociable groups, in general formula (VIII-7), R ９Ａ and R ９Ｂ 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. ９Ａ and R ９Ｂ 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 ９Ａ and R ９Ｂ 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 ９Ａ One or more hydrogen atoms contained in are replaced by polar groups having (t) acid-dissociable groups, and further R ９Ａ and R ９Ｂ 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).

[0198] R having one or more of the above acid-dissociable groups ９Ａ For example, C which may have substituents. １－１８ It is a hydrocarbyl group; the above R ９Ａ 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 ９Ａ 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 alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ９Ａ 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 ９Ａ 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 ９Ａ 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 ９Ａ It is even more preferable that at least one hydrogen atom is replaced by a polar group having a (t) acid-dissociable group.

[0199] The above R ９Ａ It is characterized by containing one or more polar groups having acid-dissociable groups, for example, polar groups such as hydroxyl groups, carboxyl groups, amino groups, or sulfo groups 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 containing one or more polar groups having the above-mentioned acid-dissociable groups. ９Ａ As an example, R containing one or more polar groups having acid-dissociable groups as described above. ７Ａ Examples similar to those given as examples can be provided.

[0200] [1-1-3. At least two different polyate salts (A1) and (A2)] The resist material according to this embodiment contains at least two different polyate salts (A1) and (A2) as (A) polyate salts, and is characterized in that the polyate salts (A1) and / or (A2) contain one or more polar groups having acid-dissociable groups. Furthermore, in addition to the polyate salts (A1) and (A2) above, one or more different polyate salts may be included as polyate salts.

[0201] [1-1-3-1. When the polyate (A1) contains one or more polar groups having acid-dissociable groups] <When the anionic portion of the polyate (A1) contains one or more polar groups having acid-dissociable groups> An example of a case in which the anionic portion of the above polyate (A1) contains one or more polar groups having acid-dissociable groups is the polyate represented by the following general formula (I-1-1). (A １１ ｍ１１＋ ) ａ１１ (C １１ （ａ１１ｍ１１）－ ) (I-1-1) [In general formula (I-1-1), A １１ ｍ１１＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C １１ （ａ１１ｍ１１）－ This represents a heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups; m11 is an integer from 1 to 5, and a11 is a real number greater than 0.

[0202] In the polysalt represented by the above general formula (I-1-1), the "metal ion," "onium cation," and "onium dication" can be those described above as appropriate.

[0203] Furthermore, as a "heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups," a group having heteroatoms P, Si, Ge, or Sn to which an "organic group containing one or more polar groups having acid-dissociable groups" or an "organic group containing two or more polar groups having acid-dissociable groups" is bonded, can be appropriately used by bonding to the terminal oxygen atom of the defect site of the heteropoly acid anion having the defect site via some or all of the heteroatoms.

[0204] In the polysalt represented by the above general formula (I-1-1), multiple types of A １１ ｍ１１＋ It may include multiple types of A. １１ ｍ１１＋The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0205] <When the cation portion of the polyate (A1) contains one or more polar groups having acid-dissociable groups> Next, as an example of the case in which the cation portion of the above polyate (A1) contains one or more polar groups having acid-dissociable groups, an example of a polyate represented by the following general formula (I-1-2) can be given. (A １２ ｍ１２＋ ) ａ１２ (B １２ ｎ１２＋ ) ｂ１２ (C １２ (a12m12+b12n12)-) (I-1-2) [In general formula (I-1-2), A １２ ｍ１２＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B １２ ｎ１２＋ Each of these independently represents a sulfonium cation, sulfonium dication, or iodonium cation containing one or more polar groups having acid-dissociable groups; C １２ (a12m12 + b12n12)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m12 is an integer between 1 and 5, n12 is an integer of 1 or 2, a12 is a real number, and b12 is a real number greater than 0.

[0206] In the polysalt represented by the general formula (I-1-2) above, the "metal ion," "onium cation," "onium dication," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with modified defect sites" can be any of the above as appropriate.

[0207] Furthermore, as the "sulfonium cation, sulfonium dication, or iodonium cation containing one or more polar groups having acid-dissociable groups," the above-mentioned "organosulfonium cation containing one or more polar groups having acid-dissociable groups," "organosulfonium dication containing one or more polar groups having acid-dissociable groups," or "organiodonium cation containing one or more polar groups having acid-dissociable groups" can be used as appropriate.

[0208] In the polysalt represented by the above general formula (I-1-2), multiple types of A １２ ｍ１２＋ and B １２ ｎ１２＋ It may also include. In the above case, the values ​​of a12 and b12 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0209] The ratio of a12 to b12 is A １２ ｍ１２＋ , B １２ ｎ１２＋ , C １２ Depending on the type of (a12m12 + b12n12), it is preferable that a12:b12 = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of a12m12 + b12n12 is an integer between 2 and 8, and m12 and n12 are 1, it is preferable that a12 is a real number between 0 and 7, and b12 is a real number between 1 and 8, and more preferably a12 is a real number between 0 and 4, and b12 is a real number between 2 and 8.

[0210] <Polysate (A2)> If the anionic or cation portion of the above polysate (A1) contains one or more polar groups having acid-dissociable groups, the cation portion and / or anionic portion of the polysate (A2) may or may not contain polar groups having acid-dissociable groups, and the cation portion may or may not contain a sulfonium cation, sulfonium dication, or iodonium cation.

[0211] The above-mentioned polysalt (A2) is not particularly limited, and examples include polysalts represented by the following general formula (I-2). (A ２ ｍ２＋ ) ａ２ (C ２ （ａ２ｍ２）－ ) (I-2) [In general formula (I-2), A ２ ｍ２＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C ２ （ａ２ｍ２）－ represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m² is an integer between 1 and 5, and a² is a real number greater than 0.

[0212] In the polysalt represented by the general formula (I-2) above, the "metal ion," "onium cation," "onium dication," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with modified defect sites" can be any of the above as appropriate.

[0213] In the polysalt represented by the above general formula (I-2), multiple types of A ２ ｍ２＋ It may include multiple types of A. ２ ｍ２＋ The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0214] [1-1-3-2. When the cation portion of the polyate (A1) contains a sulfonium cation, sulfonium dication, or iodonium cation] Another resist material according to this embodiment contains at least two different polyates (A1) and (A2) as (A) polyate, wherein the polyates (A1) and / or (A2) contain one or more polar groups having acid-dissociable groups, and the cation portion of the polyate (A1) contains a sulfonium cation, a sulfonium dication, or an iodonium cation. By incorporating the above two different polyates (A1) and (A2) into the resist material, acid is generated by exposure to active light (DUV, XUV, EUV, electron beam, etc.), and the acid-dissociable groups dissociate from the polar groups having acid-dissociable groups due to the action of the acid, thereby changing the solubility in the developer, etc.

[0215] <When the anionic portion of the polyate (A1) contains one or more polar groups having an acid-dissociable group> An example of a case in which the anionic portion of the polyate (A1) contains one or more polar groups having an acid-dissociable group is when the anionic portion of the polyate (A1) is a heteropolyate anion with a modified defect site, and the heteropolyate anion with the modified defect site contains one or more polar groups having an acid-dissociable group.

[0216] Examples of the above polysulfate (A1) include the polysulfate represented by the following general formula (I-3-1), and examples of the polysulfate (A2) include the polysulfate represented by the following general formula (I-4-1). (A ３１ ｍ３１＋ ) ａ３１ (B ３１ ｎ３１＋ ) ｂ３１ (C ３１ (a31m31+b31n31)-) (I-3-1) [In general formula (I-3-1), A ３１ ｍ３１＋ Each of them independently, H ＋ , metal ions, NH ４ ＋, represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３１ ｎ３１＋ Each of these independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C ３１ (a31m31+b31n31)- represents a heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups; m31 is an integer from 1 to 5, n31 is an integer of 1 or 2, a31 is a real number, and b31 is a real number greater than 0. ] (A ４１ ｍ４１＋ ) ａ４１ (C ４１ （ａ４１ｍ４１）－ ) (I-4-1) [In general formula (I-4-1), A ４１ ｍ４１＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C ４１ （ａ４１ｍ４１）－ represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deficiency; m41 is an integer between 1 and 5, and a41 is a real number greater than 0.

[0217] In the polysalt represented by the above general formula (I-3-1), the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "sulfonium cation," "sulfonium dication," and "iodonium cation" can be any of those described above as appropriate. Furthermore, as a "heteropolyaltate anion modified with a defect site containing one or more polar groups having acid-dissociable groups," a group having a heteroatom P, Si, Ge, or Sn to which an "organic group containing one or more polar groups having acid-dissociable groups" or an "organic group containing two or more polar groups having acid-dissociable groups" is bonded to a part or all of the heteroatom, thereby modifying the defect site of the heteropolyaltate anion having the defect site, and a heteropolyaltate anion modified with the defect site can be any of those described above.

[0218] In the polysalt represented by the above general formula (I-3-1), multiple types of A ３１ ｍ３１＋ and B ３１ ｎ３１＋ It may also include. In the above case, the values ​​of a31 and b31 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0219] The ratio of a31 to b31 is A ３１ ｍ３１＋ , B ３１ ｎ３１＋ , C ３１ Depending on the type of (a31m31 + b31n31), it is preferable that a31:b31 = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of a31m31 + b31n31 is an integer from 2 to 8, and m31 and n31 are 1, it is preferable that a31 is a real number from 0 to 7 and b31 is a real number from 1 to 8, and more preferably a31 is a real number from 0 to 4 and b31 is a real number from 2 to 8.

[0220] Furthermore, in the polysalt represented by the above general formula (I-4-1), the "metal ion," "onium cation," "onium dication," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with modified defect sites" can be appropriately replaced with those described above. In the polysalt represented by the above general formula (I-4-1), multiple types of A ４１ ｍ４１＋ It may include multiple types of A. ４１ ｍ４１＋ The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0221] <When the cation portion of the polysalt (A1) contains one or more polar groups having acid-dissociable groups> An example of a case in which the cation portion of the polysalt (A1) contains one or more polar groups having acid-dissociable groups is when the sulfonium cation, sulfonium dication, or iodonium cation of the cation portion of the polysalt (A1) contains one or more polar groups having acid-dissociable groups.

[0222] Examples of the above-mentioned polysulfate (A1) include the polysulfate represented by the following general formula (I-3-2), and examples of the above-mentioned polysulfate (A2) include the polysulfate represented by the following general formula (I-4-2). (A ３２ ｍ３２＋ ) ａ３２ (B ３２ ｎ３２＋ ) ｂ３２ (C ３２ (a32m32+b32n32)-) (I-3-2) [In general formula (I-3-2), A ３２ ｍ３２＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３２ ｎ３２＋ Each of these independently represents a sulfonium cation, sulfonium dication, or iodonium cation containing one or more polar groups having acid-dissociable groups; C ３２ (a32m32+b32n32)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m32 is an integer from 1 to 5, n32 is an integer of 1 or 2, a32 is a real number, and b32 is a real number greater than 0. ] (A ４２ ｍ４２＋ ) ａ４２ (C ４２ （ａ４２ｍ４２）－ ) (I-4-2) [In general formula (I-4-2), A ４２ ｍ４２＋ Each of them independently, H ＋ , metal ions, NH ４＋ , represents an onium cation or onium dication; C ４２ （ａ４２ｍ４２）－ represents an isopolyacid, a heteropolyacid anion, or a heteropolyacid anion with a modified deletion site; m42 is an integer between 1 and 5, and a42 is a real number greater than 0.

[0223] In the polysodium salt represented by the above general formula (I-3-2), the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with modified defect sites" can be any of the above as appropriate. Furthermore, as the "sulfonium cation, sulfonium dication, or iodonium cation containing one or more polar groups having acid-dissociable groups," the "organosulfonium cation containing one or more polar groups having acid-dissociable groups," "organosulfonium dication containing one or more polar groups having acid-dissociable groups," or "organiodonium cation containing one or more polar groups having acid-dissociable groups" can be any of the above as appropriate.

[0224] In the polysalt represented by the above general formula (I-3-2), multiple types of A ３２ ｍ３２＋ and B ３２ ｎ３２＋ It may include the following. In the above case, the values ​​of a32 and b32 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0225] The ratio of a32 to b32 is A ３２ ｍ３２＋ , B ３２ ｎ３２＋ , C ３２Depending on the type of (a32m32 + b32n32), it is preferable that a32:b32 = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of a32m32 + b32n32 is an integer between 2 and 8, and m32 and n32 are 1, it is preferable that a32 is a real number between 0 and 7, and b32 is a real number between 1 and 8, and more preferably a32 is a real number between 0 and 4, and b32 is a real number between 2 and 8.

[0226] Furthermore, in the polysalt represented by the above general formula (I-4-2), the "metal ion," "onium cation," "onium dication," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with modified defect sites" can be appropriately replaced with those described above. In the polysalt represented by the above general formula (I-4-2), multiple types of A ４２ ｍ４２＋ It may include multiple types of A. ４２ ｍ４２＋ The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0227] <When the anionic portion of the polyate (A2) contains one or more polar groups having an acid-dissociable group> An example of a case in which the anionic portion of the polyate (A2) contains one or more polar groups having an acid-dissociable group is when the anionic portion of the polyate (A2) is a heteropolyate anion with a modified defect site, and the heteropolyate anion with the modified defect site contains one or more polar groups having an acid-dissociable group.

[0228] Examples of the above poly acid salt (A1) include the poly acid salt represented by the following general formula (I-3-3), and examples of the above poly acid salt (A2) include the poly acid salt represented by the following general formula (I-4-3). (A ３３ ｍ３３＋ ) ａ３３ (B ３３ ｎ３３＋ ) ｂ３３ (C ３３(a33m33+b33n33)-) (I-3-3) [In general formula (I-3-3), A ３３ ｍ３３＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３３ ｎ３３＋ Each of these independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C ３３ (a33m33+b33n33)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m33 is an integer from 1 to 5, n33 is an integer of 1 or 2, a33 is a real number, and b33 is a real number greater than 0. ] (A ４３ ｍ４３＋ ) ａ４３ (C ４３ （ａ４３ｍ４３）－ ) (I-4-3) [In general formula (I-4-3), A ４３ ｍ４３＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C ４３ （ａ４３ｍ４３）－ This represents a heteropoly acid anion modified by a defect site having one or more polar groups with acid-dissociable groups; m43 is an integer from 1 to 5, and a43 is a real number greater than 0.

[0229] In the polysalt represented by the general formula (I-3-3) above, the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "sulfonium cation," "sulfonium dication," "iodonium cation," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with modified defect sites" can be any of the above as appropriate.

[0230] In the polysalt represented by the above general formula (I-3-3), multiple types of A ３３ ｍ３３＋ and B ３３ ｎ３３＋ It may also include. In the above case, the values ​​of a33 and b33 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0231] The ratio of a33 to b33 is A ３３ ｍ３３＋ , B ３３ ｎ３３＋ , C ３３ Depending on the type of (a33m33 + b33n33), it is preferable that a33:b33 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a33m33 + b33n33 is an integer between 2 and 8, and m33 and n33 are 1, it is preferable that a33 is a real number between 0 and 7, and b33 is a real number between 1 and 8, and more preferably a33 is a real number between 0 and 4, and b33 is a real number between 2 and 8.

[0232] In the polysalt represented by the general formula (I-4-3) above, the "metal ion," "onium cation," and "onium dication" can be those described above as appropriate. Furthermore, as a "heteropolyate anion modified with a defect site containing one or more polar groups having acid-dissociable groups," a group having heteroatoms P, Si, Ge, or Sn to which an "organic group containing one or more polar groups having acid-dissociable groups" or an "organic group containing two or more polar groups having acid-dissociable groups" is bonded can be appropriately used by bonding to the terminal oxygen atom of the defect site of the heteropolyate anion having the defect site via some or all of the heteroatoms.

[0233] In the polysalt represented by the above general formula (I-4-3), multiple types of A ４３ ｍ４３＋ It may include multiple types of A. ４３ ｍ４３＋The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0234] <When the cation portion of the polysalt (A2) contains one or more polar groups having acid-dissociable groups> An example of a case in which the cation portion of the polysalt (A2) contains one or more polar groups having acid-dissociable groups is when the sulfonium cation, sulfonium dication, or iodonium cation of the cation portion of the polysalt (A2) contains one or more polar groups having acid-dissociable groups.

[0235] Examples of the above-mentioned polysulfate (A1) include the polysulfate represented by the following general formula (I-3-4), and examples of the above-mentioned polysulfate (A2) include the polysulfate represented by the following general formula (I-4-4). (A ３４ ｍ３４＋ ) ａ３４ (B ３４ ｎ３４＋ ) ｂ３４ (C ３４ (a34m34+b34n34)-) (I-3-4) [In general formula (I-3-4), A ３４ ｍ３４＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３４ ｎ３４＋ Each of these independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation; C ３４ (a34m34+b34n34)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m34 is an integer from 1 to 5, n34 is an integer of 1 or 2, a34 is a real number, and b34 is a real number greater than 0. ] (A ４４ ｍ４４＋ ) ａ４４ (B ４４ ｎ４４＋ ) ｂ４４ (C ４４(a44m44+b44n44)-) (I-4-4) [In general formula (I-4-4), A ４４ ｍ４４＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ４４ ｎ４４＋ Each of these independently represents a sulfonium cation, sulfonium dication, or iodonium cation having one or more polar groups with acid-dissociable groups; C ４４ (a44m44+b44n44)- represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m44 is an integer between 1 and 5, n44 is an integer of 1 or 2, a44 is a real number, and b44 is a real number greater than 0.

[0236] In the polysalt represented by the general formula (I-3-4) above, the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "sulfonium cation," "sulfonium dication," "iodonium cation," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion modified with a missing site" can be any of the above as appropriate.

[0237] In the polysalt represented by the above general formula (I-3-4), multiple types of A ３４ ｍ３４＋ and B ３４ ｎ３４＋ It may also include. In the above case, the values ​​of a34 and b34 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0238] The ratio of a34 to b34 is A ３４ ｍ３４＋ , B ３４ ｎ３４＋ , C ３４Depending on the type of (a34m34 + b34n34), it is preferable that a34:b34 = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of a34m34 + b34n34 is an integer from 2 to 8, and m34 and n34 are 1, it is preferable that a34 is a real number from 0 to 7 and b34 is a real number from 1 to 8, and more preferably a34 is a real number from 0 to 4 and b34 is a real number from 2 to 8.

[0239] In the polysodium salt represented by the above general formula (I-4-4), the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with modified defect sites" can be any of the above as appropriate. Furthermore, as the "sulfonium cation, sulfonium dication, or iodonium cation containing one or more polar groups having acid-dissociable groups," the "organosulfonium cation containing one or more polar groups having acid-dissociable groups," "organosulfonium dication containing one or more polar groups having acid-dissociable groups," or "organiodonium cation containing one or more polar groups having acid-dissociable groups" can be any of the above as appropriate.

[0240] In the polysalt represented by the above general formula (I-4-4), multiple types of A ４４ ｍ４４＋ and B ４４ ｎ４４＋ It may also include. In the above case, the values ​​of a44 and b44 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0241] The ratio of a44 to b44 is A ４４ ｍ４４＋ , B ４４ ｎ４４＋ , C ４４Depending on the type of (a44m44 + b44n44), it is preferable that a44:b44 = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of a44m44 + b44n44 is an integer from 2 to 8, and m44 and n44 are 1, it is preferable that a44 is a real number from 0 to 7 and b44 is a real number from 1 to 8, and more preferably a44 is a real number from 0 to 4 and b44 is a real number from 2 to 8.

[0242] [1-1-3-3. Cases where the anionic portions of the polysalts (A1) and (A2) contain one or more polar groups having acid-dissociable groups, and the cation portions of the polysalts (A1) and (A2) contain sulfonium cations, sulfonium dications, or iodonium cations which may have polar groups having acid-dissociable groups] Another resist material according to this embodiment contains at least two different polysalts (A1) and (A2) as (A) polysalts, each of the anionic portions of the polysalts (A1) and (A2) contains one or more polar groups having acid-dissociable groups, and the cation portions of the polysalts (A1) and (A2) contain sulfonium cations, sulfonium dications, or iodonium cations which may have polar groups having acid-dissociable groups.

[0243] The cation portions of at least two different polysalts (A1) and (A2) described above each contain a sulfonium cation, sulfonium dication, or iodonium cation, which may each have a polar group having an acid-dissociable group, thereby enabling the generation of acid upon exposure to active light or the like. Furthermore, the anionic portions of the polysalts (A1) and (A2) each contain one or more polar groups having an acid-dissociable group, thereby drastically changing the solubility in the developer through the action of the acid.

[0244] Therefore, by incorporating at least two different polyates (A1) and (A2) into the resist material, acid can be generated by exposure to active light, and the acid can cause multiple polar groups to dissociate from polar groups having multiple acid-dissociable groups due to the action of the acid, thereby creating multiple polar groups and drastically changing the solubility in the developer.

[0245] Examples of the above-mentioned polysulfate (A1) include the polysulfate represented by the following general formula (I-3-5), and examples of the above-mentioned polysulfate (A2) include the polysulfate represented by the following general formula (I-4-5). (A ３５ ｍ３５＋ ) ａ３５ (B ３５ ｎ３５＋ ) ｂ３５ (C ３５ (a35m35+b35n35)-) (I-3-5) [In general formula (I-3-5), A ３５ ｍ３５＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ３５ ｎ３５＋ Each independently represents a sulfonium cation, sulfonium dication, or iodonium cation which may have a polar group having an acid-dissociable group; C ３５ (a35m35+b35n35)- represents a heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups; m35 is an integer from 1 to 5, n35 is an integer of 1 or 2, a35 is a real number, and b35 is a real number greater than 0. ] (A ４５ ｍ４５＋ ) ａ４５ (B ４５ ｎ４５＋ ) ｂ４５ (C ４５ (a45m45+b45n45)-) (I-4-5) [In general formula (I-4-5), A ４５ ｍ４５＋ Each of them independently, H ＋ , metal ions, NH４ ＋ , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B ４５ ｎ４５＋ Each independently represents a sulfonium cation, sulfonium dication, or iodonium cation which may have a polar group having an acid-dissociable group; C ４５ (a45m45+b45n45)- represents a heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups; m45 is an integer from 1 to 5, n45 is an integer of 1 or 2, a45 is a real number, and b45 is a real number greater than 0.

[0246] In the polysalts represented by the above general formulas (I-3-5) and (I-4-5), the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," and "sulfonium cation" can be any of those described above as appropriate.

[0247] In the polysodium salts represented by the above general formulas (1-3-5) and (I-4-5), the "sulfonium cation, sulfonium dication, or iodonium cation which may have a polar group having an acid-dissociable group" can be any of the above-mentioned "sulfonium cation," "organosulfonium cation containing one or more polar groups having an acid-dissociable group," "sulfonium dication," "organosulfonium dication containing one or more polar groups having an acid-dissociable group," "iodonium cation," or "organiodonium cation containing one or more polar groups having an acid-dissociable group." Furthermore, as a "heteropoly acid anion modified with a defect site containing one or more polar groups having acid-dissociable groups," a group having heteroatoms P, Si, Ge, or Sn to which an "organic group containing one or more polar groups having acid-dissociable groups" or an "organic group containing two or more polar groups having acid-dissociable groups" is bonded, can be appropriately used by bonding to the terminal oxygen atom of the defect site of the heteropoly acid anion having the defect site via some or all of the heteroatoms.

[0248] In the polysalt represented by the above general formula (I-3-5), multiple types of A ３５ ｍ３５＋ and B ３５ ｎ３５＋ It may also include. In the above case, the values ​​of a35 and b35 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0249] The ratio of a35 to b35 is A ３５ ｍ３５＋ , B ３５ ｎ３５＋ , C ３５ Depending on the type of (a35m35 + b35n35), it is preferable that a35:b35 = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of a35m35 + b35n35 is an integer from 2 to 8, and m35 and n35 are 1, it is preferable that a35 is a real number from 0 to 7 and b35 is a real number from 1 to 8, and more preferably a35 is a real number from 0 to 4 and b35 is a real number from 2 to 8.

[0250] Similarly, in the polysalt represented by the above general formula (I-4-5), multiple types of A ４５ ｍ４５＋ and B ４５ ｎ４５＋ It may also include. In the above case, the values ​​of a45 and b45 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0251] The ratio of a45 to b45 is A ４５ ｍ４５＋ , B ４５ ｎ４５＋ , C ４５Depending on the type of (a45m45 + b45n45), it is preferable that a45:b45 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a45m45 + b45n45 is an integer between 2 and 8, and m45 and n45 are 1, it is preferable that a45 is a real number between 0 and 7, and b45 is a real number between 1 and 8, and more preferably a45 is a real number between 0 and 4, and b45 is a real number between 2 and 8.

[0252] [1-1-4. Content of Component (A), etc.] 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.

[0253] Furthermore, the mass ratio of the polyate (A1) to the polyate (A2) in the resist material is not particularly limited and can be set appropriately depending on the types of component (A1) and component (A2). The mass ratio of component (A1) to component (A2) in the resist material is preferably 0.01 to 99.9:99.9 to 0.01, more preferably 1 to 99:99 to 1, even more preferably 5 to 95:95 to 5, even more preferably 10 to 90:90 to 10, and may also be 20 to 80:80 to 20.

[0254] [1-2. (B) Acid Generator] The resist material according to this embodiment may contain (B) an acid generator as an optional component in addition to component (A). The acid generator is not particularly limited, and any known and commonly used acid generator in the field of chemically amplified resist materials can be used. The acid generator has the function of generating acid upon exposure to active light (DUV, XUV, EUV, electron beam, etc.).

[0255] Examples of acid generators include ionic acid generators such as sulfonium salts, iodonium salts, ammonium salts, and other onium salts; and nonionic acid generators such as imidosulfonates, oximesulfonates, and sulfonyldiazomethanes. From the viewpoint of resolution and sensitivity, it is preferable to use ionic acid generators. These may be used individually or in combination of two or more.

[0256] [1-2-1. Ionic Acid Generator] The anion portion of the ionic acid generator is not particularly limited and may consist of, for example, a sulfonate anion, a sulfonamide anion, a sulfonimide anion, a methide anion, etc. The cation portion of the ionic acid generator is not particularly limited and may consist of, for example, an onium cation or a dication.

[0257] Examples of acid generators include "sulfonate compound B" represented by the following general formula (IX-1). Ａ ", and "sulfonamide or sulfonimide salt compound B" represented by the following general formula (IX-2) Ｂ ", and "methide salt compound B" represented by the following general formula (IX-3) Ｃ Examples include the following: sulfonate anion, sulfonylamide anion, sulfonimide anion, methido anion, onium cation or onium dication (D ｐ＋ ) will be explained in detail.

[0258] [1-2-1-1. Sulfonate Compound B] Ａ As an acid generator, "sulfonate compound B" is represented by the following general formula (IX-1). Ａ " and sulfonate anion and onium cation or dication (D ｐ＋ ) and salt can be used.

[0259] "R Ａ ｂ１ " may have substituents C １－１８A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom excluding 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 cannot be replaced at the same time).

[0260] R Ａ ｂ１ 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 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 more preferable that C is replaced by a ⁻ (however, adjacent divalent carbon atoms are not replaced at the same time), and one or more hydrogen atoms are substituted with halogen atoms. １－１２ C, which may have an alkyl group or substituent. ３－１８ Alicyclic group, or C ６－１８ It is even more preferable that the group be an aryl group.

[0261] C may have substituents. ３－１８ Alicyclic group, or C ６－１８ The aryl group is not particularly limited and can be, for example, a C having a benzene skeleton, naphthalene skeleton, anthracene skeleton, phenanthrene skeleton, or biphenyl skeleton. ６－１８C having an aryl group; cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, tricyclodecene skeleton, bicyclo[2.2.1]heptane skeleton, bicyclo[2.2.2]octane skeleton, 9,10-dihydro-9,10-ethanoanthracene skeleton, 9,10-dihydro-9,10-[1,2]benzenoanthracene skeleton ３－１８ Examples include alicyclic groups.

[0262] R Ａ ｂ１ Specific examples include, for instance, trifluoromethyl group, perfluoroethyl group, perfluorobutyl group, perfluoropentyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, azlenyl group, acenaphthyl group, phenantrenyl group, anthracenyl group, cyclopentyl group, cyclopenta-1-en-1-yl group, 2-methylcyclopenta-1-en-1-yl group, cyclohexa-1-en-1-yl group, adamantan-1-yl group, adamantan-2-yl group, bicyclo[2.2.1]heptanyl group, bicyclo[2.2.2]octanyl group, Examples include the bicyclo[2.2.1]heptenyl group, the bicyclo[2.2.2]octenyl group, the 9,10-dihydro-9,10-ethanoanthracene-11-yl group, the 9,10-dihydro-9,10-ethanoanthracene-12-yl group, the 9,10-dihydro-9,10-ethanoanthracene-9-yl group, the 9,10-dihydro-9,10-ethanoanthracene-10-yl group, the 9,10-dihydro-9,10-[1,2]benzenoanthracene-9-yl group, and the 9,10-dihydro-9,10-[1,2]benzenoanthracene-10-yl group.

[0263] "L Ａ ｂ１ " is a single bond or a C which may have a substituent １－１２A hydrocarbylene group in which any divalent carbon atom, including terminals, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0264] L Ａ ｂ１ This may consist of a single bond or a C that may have a substituent. １－１２ A hydrocarbylene group in which any divalent carbon atom, including terminals, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a single bond or a substituent. (However, adjacent divalent carbon atoms may not be replaced simultaneously.) １－１２ Alkanediyl group, C ６－１２ An arenediyl group in which any divalent carbon atom, including terminals, is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO ２ It is more preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), and the carbon atoms may have substituents. １－１２ An alkanediyl group in which any divalent carbon atom including at least one terminal is -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, CONH-, -NH(C=O)-, -S-, or -SO ２ A more preferable option is one in which a ∫ is replaced by a ∫ (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0265] "L Ａ ｂ２ " is a C in which at least one hydrogen atom is replaced by a halogen atom. １－５ This represents a hydrocarbylene group.

[0266] L Ａ ｂ２For example, C in which at least one hydrogen atom is substituted with a halogen atom. １－５ Preferably a hydrocarbylene group, and at least one hydrogen atom is substituted with a halogen atom. １－５ It is more preferable that the group is an alkanediyl group, and that at least one hydrogen atom of the carbon atom at the α position relative to the sulfonic acid group is substituted with a halogen atom. １－５ C is either an alkanediyl group or one or more hydrogen atoms are substituted with fluorine atoms. １－５ It is even more preferable that the group is an alkanediyl group, and that at least one hydrogen atom of the carbon atom at the α position relative to the sulfonic acid group is substituted with a fluorine atom. １－５ C １－５ C is a carbon atom in which two or more hydrogen atoms of the carbon atom at the γ position relative to the alkanediyl group or sulfonic acid group are substituted with fluorine atoms. １－５ It is even more preferable that the group be an alkanediyl group.

[0267] The above sulfonic acid anions are not particularly limited and include, for example, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid anion, 2-((cyclohexanecarbonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonic acid anion, 2-((cyclohexanecarbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion, 2-((decahydronaphthalene-2-carbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion, 2-((decahydronaphthalene-2-carbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion, 2-((decahydronaphthalene-2-carbonyl)oxy) Bonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate anion, 2-((bicyclo[2.2.1]heptane-2-carbonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate anion, 2-((bicyclo[2.2.1]heptane-2-carbonyl)oxy)-1,1-difluoroethane-1-sulfonate anion, 2-(bicyclo[2.2.1]heptane-2-yl)-1,1,2,2-tetrafluoroethane-1-sulfonate anion, 2-(benzoyloxy)-1,1,3,3 ,3-pentafluoropropane-1-sulfonate anion, 2-(benzoyloxy)-1,1-difluoroethane-1-sulfonate anion, 2-(benzoyloxy)-3,3,3-trifluoro-2-(trifluoromethyl)propane-1-sulfonate anion, 1,1-difluoro-2-oxo-2-phenoxyethane-1-sulfonate anion, 1,1-difluoro-2-phenoxyethane-1-sulfonate anion, 2-((adamantane-1-carbonyl)oxy)-1,1,3,3,3-pentafluoropropane-1-sulfonate anion Honate anion, 2-((adamantan-1-carbonyl)oxy)-1,1-difluoroethane-1-sulfonate anion, 2-(adamantan-1-yl)-1,1-difluoroethane-1-sulfonate anion, 2-(((adamantan-1-yl)oxy)carbonyl)-1,1,1,3,3,3-hexafluoropropane-2-sulfonate anion, 2-((adamantan-1-yl)oxy)-1,1-difluoro-2-oxoethane-1-sulfonate anion, 6-((adamantan-1-carbonyl)oxy)-1,1,2,Examples include 2-tetrafluorohexane-1-sulfonic acid anion, 2-(2-((adamantane-1-carbonyl)oxy)ethoxy)-1,1-difluoro-2-oxoethane-1-sulfonic acid anion, 4-((adamantane-1-carbonyl)oxy)-1,1,2-trifluorobutane-1-sulfonic acid anion, 1,1-difluoro-2-(2-((2-methyladamantane-2-yl)oxy)-2-oxoethoxy)-2-oxoethane-1-sulfonic acid anion, and 2-((9,10-dihydro-9,10-ethanoanthracene-12-carbonyl)oxy)-1,1-difluoroethane-1-sulfonic acid anion.

[0268]

[0269]

[0270] [1-2-1-2. Sulfonamide or sulfonimide salt compound B] Ｂ As an acid generator, "sulfonamide or sulfonimide salt compound B" represented by the following general formula (IX-2) is used. Ｂ " and a sulfonamide anion or sulfonimide anion and an onium cation or dication (D ｐ＋ ) and salt can be used.

[0271] "R Ｂ ｂ１ " and "R Ｂ ｂ２ Each of these may independently have a cyano group or a substituent. １－１２ In a hydrocarbyl group, 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 Ｂ ｂ１ and R Ｂ ｂ２ However, they are directly linked by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２-, -C(=O)O-, or C which may have a substituent. １－３ They may be linked via alkylene groups and form a ring together with the nitrogen atom in formula (IX-2).

[0272] R Ｂ ｂ１ and R Ｂ ｂ２ Each of these may independently have a cyano group or a substituent. １－１２ In a hydrocarbyl group, 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 preferable that the carbon atoms may be replaced by a cyano group, or that at least one hydrogen atom is substituted with a halogen atom. １－１２ Alkyl or C ６－１２ An aryl 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 It is preferable that the cyano group or C in which at least two hydrogen atoms are substituted with fluorine atoms may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and that C １－１２ Alkyl or C ６－１２ An aryl 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 It is even more preferable that the atoms may be replaced by (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0273] Also R Ｂ ｂ１ and R Ｂ ｂ２ However, they are directly linked by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C which may have a substituent.１－３ Linked via an alkylene group, the nitrogen atom in formula (IX-2), R Ｂ ｂ１ , R Ｂ ｂ２ , L Ｂ ｂ１ , and -S (=O) ２ - When a ring is formed, it is preferable that the ring has 5 to 7 members in total and one or more hydrogen atoms are substituted with halogen atoms, and it is more preferable that the ring has 6 members and two or more hydrogen atoms are substituted with fluorine atoms.

[0274] "L Ｂ ｂ１ " is a single bond or a C which may have a substituent １－３ A hydrocarbylene group in which any divalent carbon atom, including terminals, is -C(=O)-, -C(=O)-O-, -CONH-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0275] L Ｂ ｂ１ This may consist of a single bond or a C that may have a substituent. １－３ A hydrocarbylene group in which any divalent carbon atom, including terminals, is -C(=O)-, -C(=O)-O-, -CONH-, or -SO ２ It is preferable that the bonds are replaced by - (however, adjacent divalent carbon atoms are not replaced at the same time), and the bonds are single bonds, or -C(=O)-, -C(=O)-O-, -CONH-, or -SO ２ It is more preferable that the bond is a single bond, or -C(=O)- or -SO ２ - is even more preferable.

[0276] The above-mentioned sulfonamide anions or sulfonimide anions are not particularly limited and include, for example, (4,4,5,5,6,6-hexafluoro-1,3,2-dithiadinane-2-oid 1,1,3,3-tetraoxide) anions, (4,4,5,5,6,6-hexafluoro-3-oxo-1,2-thiadinane-2-oid 1,1-dioxide) anions, and (3,3,4,4,5,5,6,6-octafluoro-1,2-thiadinane-2-oid Examples include 1,1-dioxide anions, bis((trifluoromethyl)sulfonyl)amide anions, (phenylsulfonyl)((trifluoromethyl)sulfonyl)amide anions, ((perfluoroethyl)sulfonyl)(phenylsulfonyl)amide anions, ((perfluorobutyl)sulfonyl)((trifluoromethyl)sulfonyl)amide anions, and bis((perfluorobutyl)sulfonyl)amide anions.

[0277]

[0278] [1-2-1-3. Methido salt compound B] Ｃ As an acid generator, the following general formula (IX-3) represents "methide salt compound B" Ｃ " and a methido anion and an onium cation or dication (D ｐ＋ ) and salt can be used.

[0279] "R Ｃ ｂ１ "R" Ｃ ｂ２ " and "R Ｃ ｂ３ Each of these may independently have a cyano group or a substituent. １－１２ In a hydrocarbyl group, 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 Ｃ ｂ１ , R Ｃ ｂ２ and RＣ ｂ３ 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 which may have a substituent. １－３ Linked via an alkylene group, the methide (C) in formula (IX-3) － They may form a ring together.

[0280] R Ｃ ｂ１ , R Ｃ ｂ２ and R Ｃ ｂ３ Each of these may independently have a cyano group or a substituent. １－１２ In a hydrocarbyl group, 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 preferable that the carbon atoms may be replaced by a cyano group, or that at least one hydrogen atom is substituted with a halogen atom. １－１２ Alkyl or C ６－１２ In an aryl group, 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 preferable that the cyano group or C in which at least two hydrogen atoms are substituted with fluorine atoms may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and that C １－１２ Alkyl or C ６－１２ In an aryl group, 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 even more preferable that the atoms may be replaced by (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0281] Also RＣ ｂ１ , R Ｃ ｂ２ and R Ｃ ｂ３ 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 which may have a substituent. １－３ Linked via an alkylene group, the methide (C) in formula (IX-3) － When a ring is formed together with the other elements, it is preferable that the ring forms a total of 5 to 7 members and one or more hydrogen atoms are substituted with halogen atoms, and it is more preferable that the ring forms a 6-membered ring and two or more hydrogen atoms are substituted with fluorine atoms.

[0282] "L Ｃ ｂ１ "L Ｃ ｂ２ " and "L Ｃ ｂ３ Each of these may independently have a single bond or a substituent. １－３ A hydrocarbylene group in which any divalent carbon atom, including terminals, is -C(=O)-, -C(=O)-O-, -CONH-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0283] L Ｃ ｂ１ , L Ｃ ｂ２ and L Ｃ ｂ３ This may consist of a single bond or a C that may have a substituent. １－３ A hydrocarbylene group in which any divalent carbon atom, including terminals, is -C(=O)-, -C(=O)-O-, -CONH-, or -SO ２ It is preferable that the bonds are replaced by - (however, adjacent divalent carbon atoms are not replaced at the same time), and the bonds are single bonds, or -C(=O)-, -C(=O)-O-, -CONH-, or -SO ２It is more preferable that the bond is a single bond, or -C(=O)- or -SO ２ - is even more preferable.

[0284] The above-mentioned metanide anions are not particularly limited and include, for example, tris(methylsulfonyl)methionine, tris((trifluoromethyl)sulfonyl)methionine, tris((perfluoroethyl)sulfonyl)methionine, tris(phenylsulfonyl)methionine, dicyano((trifluoromethyl)sulfonyl)methionine, and the like.

[0285]

[0286] [1-2-1-4. Onium cation or onium dication (D ｐ＋ )] The cation portion of the above (B) acid generator may be an onium cation or a dication (D ｐ+ ) can be used. Here, the general formula (IX-1) to (IX-3) can be used to express "(D ｐ+ ) １／ｐ In this expression, D represents an onium cation or dication, and p represents an integer of 1 or 2.

[0287] The above-mentioned onium cation or dication is not particularly limited, and the above-mentioned organic sulfonium cation, organic sulfonium dication, organic iodonium cation, etc., can be used.

[0288] [1-2-2. Content of Component (B)] The content of the acid generator (B) contained in the resist material according to this embodiment is not particularly limited and can be appropriately selected depending on the content and type of component (A). The content of component (B) in the resist material is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass, and even more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A).

[0289] [1-3. (C) Acid Diffusion Control Agent] The resist material according to this embodiment may contain (C) an acid diffusion control agent as an optional component in addition to component (A). By including (C) an acid diffusion control agent in the resist material, the acid generated by exposure can be trapped and the diffusion of the acid can be controlled. The above (C) component is not particularly limited, and known and conventional components can be used. Examples of acid diffusion control agents include (C1) a photodegradable base that decomposes upon exposure and loses its acid diffusion control properties, and (C2) a nitrogen-containing organic compound that does not fall under component (C1). These may be used individually or in combination of two or more.

[0290] [1-3-1. (C1) Photodecayable Bases] (C1) photodecayable bases lose their ability to control acid diffusion when decomposed by exposure to active light, etc., but in unexposed areas they act as acid quenchers, allowing for the control of acid diffusion. For this reason, by incorporating (C1) photodecayable bases into the resist material, properties such as increased sensitivity, reduced roughness, and suppression of coating defects can be improved.

[0291] The above-mentioned photodecayable base is not particularly limited, and known and commonly used bases can be used. For example, a photodecayable base is a carboxylate compound C represented by the following general formula (X-1). Ａ ", and "sulfonate compound C" represented by the following general formula (X-2) Ｂ ", and "sulfonylamide salt compound C" represented by the following general formula (X-3) Ｃ Examples include the following: carboxylate anions, sulfonate anions, sulfonylamide anions, onium cations, or onium dication D. ｐ＋ I will explain in that order.

[0292] [1-3-1-1. Carboxylate Compound C] Ａ The above (C1) photodecayable base is a "carboxylate compound C" represented by the following general formula (X-1). Ａ " and onium cation or dication (D ｐ＋ ) and salt can be used.

[0293] "R Ａ ｃ１ " may have substituents C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom other than the terminals other than the bond 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).

[0294] R Ａ ｃ１ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond 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 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 terminals other than the bond 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).

[0295] <Carboxylate compound C Ａ１ > Carboxylate compound B represented by the above general formula (X-1) Ａ This is a carboxylate compound C represented by the following general formula (X-1-1). Ａ１ That's fine.

[0296] "X Ａ ｃ１ " may have substituents C１－１８ Alkyl 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 terminals other than the bond 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).

[0297] X Ａ ｃ１ 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 terminals other than the bond 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 In an aryl group, any divalent carbon atom other than the terminals other than the bond 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).

[0298] "L Ａ ｃ１ " is X Ａ ｃ１ to-COO － A base that connects and the following general formula (L ｃ -1) to (L ｃ A linking group represented by -7) can be used. [In the formula, L ｃ１and L ｃ２ C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ａ ｃ１ The connection part is, *2 is -COO － This represents the connection point.

[0299] L ｃ１ and L ｃ２ 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.

[0300] <Example of carboxylate anion> The above carboxylate salt compound C Ａ or C Ａ１ 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.

[0301]

[0302]

[0303]

[0304] [1-3-1-2. Sulfonate Compound C] Ｂ The above (C1) photodecayable base is "sulfonate compound C" represented by the following general formula (X-2). Ｂ " and sulfonate anion and onium cation or dication (D ｐ＋) and salt can be used.

[0305] "R Ｂ ｃ１ " may have substituents C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom other than the terminals other than the bond 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).

[0306] R Ｂ ｃ１ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond 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 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 terminals other than the bond 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).

[0307] <Sulfonate compound C Ｂ１ > Sulfonate compound C represented by the above general formula (X-2) Ｂ However, sulfonate compound C, represented by the following general formula (X-2-1), Ｂ１ That's fine.

[0308] "X Ｂ ｃ１" may have substituents C １－１８ Alkyl 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 terminals other than the bond 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).

[0309] X Ｂ ｃ１ 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 terminals other than the bond 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 In an aryl group, any divalent carbon atom other than the terminals other than the bond 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).

[0310] "L Ｂ ｃ１ " is X Ｂ ｃ１ to-SO ２ -O － A base that connects and the above general formula (L ｃ -1) to (L ｃ A linking group represented by -7) can be used. In this case, the general formula (L ｃ -1) to (L ｃ -7) Medium, L ｃ１ and L ｃ２C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ｂ ｃ１ The connection point is, *2 is -SO ２ -O － This represents the connection point.

[0311] L ｃ１ and L ｃ２ 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.

[0312] <Example of sulfonate anion> The above sulfonate compound C Ｂ or C Ｂ１ The sulfonate anions are not particularly limited, and examples include 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.

[0313]

[0314] [1-3-1-3. Sulfonylamide salt compound C] Ｃ The above (C1) photodecayable base is a "sulfonylamide salt compound C" represented by the following general formula (X-3). Ｃ " and a sulfonylamide anion and an onium cation or dication (D ｐ＋ ) and salt can be used.

[0315] "R Ｃ ｃ１ " may have substituents C １－１８A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom other than the terminals other than the bond 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). Ｃ ｃ２ " may have substituents C １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond 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).

[0316] R Ｃ ｃ１ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond 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 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 terminals other than the bond 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).

[0317] R Ｃ ｃ２ C may have substituents. １－１８ Alkyl alkyl group, C ３－１８In an alicyclic group, any divalent carbon atom other than the terminals other than the bond 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.

[0318] <Sulfonylamide salt compound C Ｃ１ > Sulfonylamide salt compound C represented by the above general formula (X-3) Ｃ However, sulfonylamide salt compound C, represented by the following general formula (X-3-1) Ｃ１ That's fine.

[0319] "X Ｃ ｃ１ " may have substituents C １－１８ Alkyl 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 terminals other than the bond 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).

[0320] X Ｃ ｃ１ 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 terminals other than the bond 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. ３－１８Alicyclic group, or C ６－１８ In an aryl group, any divalent carbon atom other than the terminals other than the bond 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).

[0321] "L Ｃ ｃ１ " is X Ｃ ｃ１ to-N － -SO ２ -R Ｃ ｃ２ A base that connects and the above general formula (L ｃ -1) to (L ｃ A linking group represented by -7) can be used. In this case, the general formula (L ｃ -1) to (L ｃ -7) Medium, L ｃ１ and L ｃ２ C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ｃ ｃ１ The connection point is, *2 is -N － -SO ２ -R Ｃ ｃ２ This represents the connection point.

[0322] L ｃ１ and L ｃ２ 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.

[0323] <Example of sulfonylamide anion> The above sulfonylamide salt compound C Ｃ or C 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.

[0324]

[0325]

[0326]

[0327] [1-3-1-4. Onium cation or onium dication (D ｐ＋ )] The cation portion of the above (C1) photodecayable base is an onium cation or an onium dication (D ｐ＋ ) can be used. Here, the general formula (X-1) to (X-3) can be used to express "(D ｐ+ ) １／ｐIn this expression, D represents an onium cation or onium dication, and p represents an integer of 1 or 2. The onium cation or onium dication is not particularly limited, and the above-mentioned organic sulfonium cation, organic sulfonium dication, organic iodonium cation, etc., can be used.

[0328] [1-3-2. (C2) Nitrogen-containing organic compounds] Other (C) acid diffusion control agents may include nitrogen-containing organic compounds that do not fall under (C2) or (C1). The nitrogen-containing organic compounds are not particularly limited, and for example, aliphatic amines, aromatic amines, heterocyclic amines, etc., can be used.

[0329] Examples of nitrogen-containing organic compounds include aliphatic amines such as n-hexylamine, n-heptylamine, diethylamine, di-n-propylamine, di-n-butylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n-octylamine; aromatic amines such as aniline, N-methylaniline, N-ethylamine, N,N-dimethylaniline, 4-methylaniline, and pyrrole; and heterocyclic amines such as pyridine, imidazole, benzimidazole, piperidine, piperazine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane. These nitrogen-containing organic compounds may be used individually or in combination of two or more.

[0330] [1-3-3. Amount of Component (C)] The amount of the acid diffusion control agent (C) contained in the resist material according to this embodiment is not particularly limited and can be appropriately selected depending on the content and type of component (A). The content of component (C) in the resist material is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass, and even more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A).

[0331] [1-4. Organic Solvents] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and known and commonly used ones can be used. The organic solvent is preferably an organic solvent that can be uniformly dissolved or dispersed when prepared with (A) a polyate.

[0332] 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.

[0333] 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.

[0334] 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.

[0335] 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.

[0336] [1-5. Others] The resist material according to this embodiment may further contain, if desired, miscible additives such as additional resins to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.

[0337] [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.

[0338] [2-1. Coating Process] The pattern formation method according to this embodiment includes a step of coating a resist material onto a substrate.

[0339] <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.

[0340] 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).

[0341] <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.

[0342] 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.

[0343] 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.

[0344] 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.

[0345] [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.

[0346] 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.

[0347] 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.

[0348] 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.

[0349] 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.

[0350] [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.

[0351] 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.

[0352] <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.

[0353] 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.

[0354] 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).

[0355] Furthermore, pure water can be used as the rinsing solution in the alkaline development process.

[0356] <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.

[0357] 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.

[0358] 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.

[0359] 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.

[0360] 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).

[0361] 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.

[0362] 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.

[0363] 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.

[0364] 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).

[0365] [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.

[0366] 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.

[0367] 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.

[0368] [4. Resist material for electron beam or EUV] The resist material according to this embodiment contains at least two different poly salts (A1) and (A2) as (A) poly salt. The poly salts (A1) and / or (A2) each contain one or more polar groups having acid-dissociable groups. Therefore, the resist material has the function of having its solubility in a developer solution change significantly due to the action of acid, etc.

[0369] Furthermore, by introducing sulfonium cations, sulfonium dications, or iodonium cations into the cation portion of the polyate (A1) contained in the resist material according to this embodiment, or by including (B) an acid generator in the resist material, it is possible to provide a function that generates acid by exposure such as electron beam or EUV.

[0370] Therefore, the resist material according to this embodiment is a resist material that generates acid upon exposure with an electron beam, EUV, etc., and whose solubility in a developer changes due to the action of the acid, and can be suitably used as a resist material for electron beam or EUV exposure.

[0371] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0372] [1. Synthesis of Polyates] <Production 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 ２ O) 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).

[0373] <Synthesis Example 1: Tetrakis(triphenylsulfonium)(1,3-bis(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-1))> To a mixed solvent of 402 g of acetonitrile and 184 g of pure water, 5.5 g of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane was added to produce the monodeficient keging-type potassium undecatungus silicate (α-K) synthesized above. ８ [SiW １１ O ３９ 9.8 g of [C] 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. 5.7 g of triphenylsulfonium chloride and 40 g of pure water were added to this concentrate 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 10.7 g of polysulfate (A-1). 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－ )

[0374] <Synthesis Example 2: Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-di(3-(2-((1-methylcyclopentyl)oxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-2))> In Synthesis Example 1, polysulfate (A-2) was obtained by the same method as described above, except that bis(2-trifluoromethylphenyl)phenylsulfonium chloride was used as the starting compound instead of triphenylsulfonium chloride. 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). ２９Si-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－ )

[0375] <Synthesis Example 3: Tetrakis(triphenylsulfonium)(1,3-di(3-(2-((1-phenylcyclopentyl)oxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-3))> In Synthesis Example 1, polysodium chloride (A-3) was obtained by the same method as above, except that 3-(2-((1-phenylcyclopentyl)oxycarbonyl)ethylthio)propyltrimethoxysilane was used as the starting compound instead of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane. ESI-MS: POSITIVE m / z 263.1 ([C １８ H １５ S] ＋ ) NEGATIVE m / z 832.1 (median) ([C ３４ H ４６ O ４４ S ２ Si ３ W １１ ] ４－ )

[0376] <Synthesis Example 4: 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-4))> In Synthesis Example 1, polysulfonium bromide was used instead of triphenylsulfonium chloride as the starting compound, except that polysulfonium bromide (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide was used in the same manner as above to obtain polysulfonium bromide (A-4). 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－ )

[0377] <Synthesis Example 5: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium) keitangstate(polyate (A-5))> 35.47 g of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium chloride is dissolved in 50 g of cyclohexanone, and carboxytungstic acid (H ４ [SiW １２ O ４０ ]・26H ２ O) 41.06 g was added, and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered, and the resulting powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized at room temperature using dichloromethane and acetonitrile to obtain the polyate (A-5). １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.76-7.82 (m, 40H), 7.59 (s, 8H), 4.55 (s, 8 H), 2.29 (m, 24H), 1.90-1.93 (m, 16H), 1.48-1.75 (m, 24H), 0.77-0.81 (t, 12H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２O ４０ ] ４－ XPS analysis S:W (molar ratio of S to W) = 4:12

[0378] <Synthesis Example 6: 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-6))> In Synthesis Example 1, polysodium chloride (A-6) was obtained by the same method as described above, except that di(1-phenylcyclopentyl)2-(3-(trimethoxysilyl)propylthio)butanediate was used instead of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane as the starting compound, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was used instead of triphenylsulfonium chloride. 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－ )

[0379] <Synthesis Example 7: Tetrakis(benzyltriethylammonium)(1,3-di(3-(2-((1-methylcyclopentyl)oxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-7))> In Synthesis Example 1, polysulfate (A-7) was obtained by the same method as described above, except that an aqueous solution of benzyltriethylammonium chloride was used as the starting compound instead of triphenylsulfonium chloride. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.34 (t, 36H), 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), 3.20 (q, 24H), 4.49 (s, 8H), 7.52 (m, 20H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 192.2 ([C １３ H ２２ N] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0380] [2. Preparation of Resist Materials] As resist materials, the poly salts (A-1) to (A-7) synthesized above and the poly salts (A-8) to (A-10) shown below, an acid diffusion control agent (C-1), and an organic solvent (cyclopentanone) were blended in the amounts shown in Tables 1 to 5 below (unit: parts by mass) to prepare the resist materials for Examples 1-1 to 5-4 and Comparative Examples 1-1 to 5-5.

[0381] The following polysalts (A-8) to (A-10) listed in Table 5 were used. All of the following polysalts (A-8) to (A-10) were manufactured by Nippon Inorganic Chemical Industry Co., Ltd. • Polysalt (A-8): Ammonium metatungstate • Polyate (A-9): Silicate tungstic acid • Polyate (A-10): Phosphate tungstic acid

[0382] Furthermore, as the acid diffusion control agent (C-1) described in Tables 1 to 5, an acid diffusion control agent that is a salt of a triphenylsulfonium cation represented by the following formula (C-1) and a salicylate anion was used.

[0383]

[0384]

[0385]

[0386]

[0387]

[0388] [3. Formation of Resist Patterns] The resist materials from Examples 1-1 to 5-4 and Comparative Examples 1-1 to 5-5 were 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 LS patterns corresponding to each resist material were obtained. All of the above LS patterns are positive type patterns.

[0389] [4. Evaluation of LS Pattern Shape] <Evaluation of Roughness> The shape of the LS patterns of Examples 1-1 to 5-4 and Comparative Examples 1-1 to 5-5 was evaluated using a scanning electron microscope (acceleration voltage 800V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation). The line width was measured at 400 line positions along the longitudinal direction of the line, and the value of three times the standard deviation (σ) obtained from the measurement results (3σ) (unit: nm) was calculated as a measure of roughness. Here, the smaller the value of 3σ, the smaller the roughness of the line sidewalls, and the more uniform the width of the LS pattern obtained. The values ​​of the above roughness (3σ) for the LS patterns of Examples 1-1 to 5-4 and Comparative Examples 1-1 to 5-5 are shown in Tables 1 to 5.

[0390] From the results in Table 1, it can be seen that the resist materials of Examples 1-1 to 1-9, which contain both polyate (A-1) and polyate (A-2), provide a better LS pattern with better roughness compared to the resist materials of Comparative Examples 1-1 and 1-2, which contain either polyate (A-1) or polyate (A-2) alone. In particular, the resist materials of Examples 1-2 to 1-8, in which the mass ratio of polyate (A-1) to polyate (A-2) is 5 to 95:95 to 5, show a significantly reduced 3σ value compared to the resist materials of Comparative Examples 1-1 and 1-2.

[0391] Furthermore, the results in Table 2 show that the resist materials of Examples 2-1 to 2-9, which contain both polyate (A-1) and polyate (A-3), provide a better roughness LS pattern compared to the resist materials of Comparative Examples 2-1 and 2-2, which contain either polyate (A-1) or polyate (A-3) alone. In particular, the resist materials of Examples 2-2 to 2-8, in which the mass ratio of polyate (A-1) to polyate (A-3) is 5 to 95:95 to 5, show a significantly reduced 3σ value compared to the resist materials of Comparative Examples 2-1 and 2-2.

[0392] Furthermore, the results in Table 3 show that the resist materials of Examples 3-1 to 3-9, which contain both polyate (A-2) and polyate (A-3), provide a better LS pattern with better roughness compared to the resist materials of Comparative Examples 3-1 and 3-2, which contain either polyate (A-2) or polyate (A-3) alone. In particular, the resist materials of Examples 3-2 to 3-8, in which the mass ratio of polyate (A-2) to polyate (A-3) is 5 to 95:95 to 5, show a significantly reduced 3σ value compared to the resist materials of Comparative Examples 3-1 and 3-2.

[0393] From the results in Table 4, it can be seen that the resist materials of Examples 4-1 to 4-5, which contain two types of polyate salts such as polyate salts (A-1) and (A-4), polyate salts (A-1) and (A-5), polyate salts (A-1) and (A-6), polyate salts (A-2) and (A-6), and polyate salts (A-3) and (A-6), provide a better LS pattern with roughness compared to the resist materials of Comparative Examples 4-1 to 4-6, which each contain polyate salts (A-1) to (A-6) individually.

[0394] Furthermore, the results in Table 5 show that the resist materials of Examples 5-1 to 5-4, which contain two types of polyate salts such as polyate salts (A-1) and (A-7), polyate salts (A-1) and (A-8), polyate salts (A-1) and (A-9), and polyate salts (A-1) and (A-10), provide a better LS pattern with roughness compared to the resist materials of Comparative Examples 5-1 to 5-5, which contain polyate salts (A-1) and (A-7) to (A-10) individually. Note that the resist films prepared using Comparative Examples 5-2 to 5-5, which contain polyate salts (A-7) to (A-10) individually, all failed to resolve.

[0395] Even more interestingly, the results from Examples 5-2 to 5-4 in Table 5 show that even when only one of the polyate salts has a polar group with an acid-dissociable group, and only one of the polyate salts has a sulfonium cation, such as polyate salts (A-1) and (A-8), polyate salts (A-1) and (A-9), and polyate salts (A-1) and (A-10), including two types of polyate salts, as in the resist materials of Examples 5-2 to 5-4, yields a resist film with very good roughness after development.

Claims

1. A resist material comprising (A) at least two different poly salts (A1) and (A2) as poly salts, wherein the poly salts (A1) and / or (A2) each contain one or more polar groups having acid-dissociable groups.

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

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

4. The resist material according to claim 1, wherein the polyacid salt (A1) is a polyacid salt represented by the following general formula (I-1-1) or (I-1-2). (A １１ ｍ１１＋ ) ａ１１ (C １１ （ａ１１ｍ１１）－ )(I-1-1) [In general formula (I-1-1), A １１ ｍ１１＋ each independently represents H ＋ , a metal ion, NH ４ ＋ , an onium cation, or an onium dication; C １１ （ａ１１ｍ１１）－ represents a heteropolyacid anion in which one or more defective sites having an acid dissociable group are modified; m11 is an integer of 1 to 5, and a11 is a real number greater than 0.](A １２ ｍ１２＋ ) ａ１２ (B １２ ｎ１２＋ )(B ｂ１２ (C １２ (a12m12 + b12n12)-)(I-1-2) [In general formula (I-1-2), A １２ ｍ１２＋ each independently represents H ＋ , a metal ion, NH ４ ＋ , an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B １２ ｎ１２＋ each independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation containing one or more polar groups having an acid dissociable group; C １２ （ａ１２ｍ１２）－ represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion in which a defective site is modified; m12 is an integer of 1 to 5, n12 is an integer of 1 or 2, a12 is a real number, and b12 is a real number greater than 0.] 5. The resist material according to claim 4, wherein the polysalt represented by the general formula (I-1-1), the heteropoly acid anion modified with a defect site containing one or more polar groups having an acid-dissociable group, is a heteropoly acid anion having a defect site, wherein the modification is made by a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more organic groups are bonded, bonding to the heteropoly acid anion having the defect site via some or all of the heteroatoms, and the organic group has one or more polar groups having an acid-dissociable group.

6. 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 claim 5, wherein one or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group.

7. The resist material according to claim 4, wherein the polyate (A2) is a polyate represented by the following general formula (I-2). (A ２ ｍ２＋ ) ａ２ (C ２ （ａ２ｍ２）－ ) (I-2) [In general formula (I-2), A ２ ｍ２＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; C ２ （ａ２ｍ２）－ represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified deletion site; m² is an integer between 1 and 5, and a² is a real number greater than 0.

8. The resist material according to claim 1, wherein the mass ratio of the polyate (A1) to the polyate (A2) is 5 to 95:95 to 5.

9. The resist material according to claim 1, wherein the cation portion of the polyate (A1) and / or (A2) comprises a sulfonium cation, a sulfonium dication, or an iodonium cation.

10. The resist material according to claim 1, further comprising (B) an acid generator.

11. The resist material according to claim 1, further comprising (C) an acid diffusion control agent, wherein the (C) acid diffusion control agent is (C1) a photodecayable base.

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