Resist material and pattern formation method

Abstract

The present invention aims to provide a novel resist material and pattern formation method that exhibit good roughness after development and provide a more uniform width LS pattern. [Solution] (A) A resist material containing at least two different poly salts (A1) and (A2) as poly salts, characterized in that the poly salts (A1) and / or (A2) contain one or more polar groups having acid-dissociable groups.

Description

[Technical Field]

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

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

[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 discloses a nanoparticle polymer resist comprising nanoparticles containing ZrO2, HfO2, TiO2, etc., as a core, and a polymer. Patent Document 2 also discloses (t-BuSn), which is an alkyltin cluster. 12 O 14 A resist based on (OH)6(HCO2)2 has been disclosed. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent No. 9696624 [Patent Document 2] WO2019 / 195522 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a novel resist material and a pattern formation method. [Means for solving the problem]

[0007] As a result of intensive studies to solve the above problems, the inventors of the present invention have found that by incorporating, as the polyacid salt, at least two different polyacid salts (A1) and (A2), wherein the polyacid salt (A1) and / or (A2) contains one or more polar groups having an acid-dissociable group, into the resist material, good roughness after development can be obtained and an LS pattern with a more uniform width can be obtained, and thus the present invention has been completed.

[0008] That is, the present invention relates to the following inventions. <1> A resist material containing, as the polyacid salt, at least two different polyacid salts (A1) and (A2), wherein the polyacid salt (A1) and / or (A2) contains one or more polar groups having an acid-dissociable group. <2> The resist material according to <1>, wherein the resist material generates an acid upon exposure and the 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, NH4 + , an onium cation, or an onium dication; C 11 (a11m11)- represents a heteropolyacid anion modified with one or more defective sites containing a polar group 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 general formula (I-1-2), A 12 m12+ Each of them independently, H + , metal ions, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; 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. <5> In the polysalt represented by the general formula (I-1-1), a 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, in which the defect site is modified 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, and by bonding to a heteropoly acid anion having the defect site via some or all of the heteroatoms. The aforementioned organic group has one or more polar groups having acid-dissociable groups. <4> The resist material described above. <6> The organic group may have substituents. 1-18 It is a hydrocarbyl group, C which may have the substituent 1-18Any divalent carbon atom of the hydrocarbyl group, excluding the terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). C which may have the substituent 1-18 One or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group. <5> The resist material described above. <7> The aforementioned polyate (A2) is a polyate represented by the following general formula (I-2): <4> The resist material described above. (A2 m2+ ) a2 (C2 (a2m2)- ) (I-2) [In general formula (I-2), A2 m2+ Each of them independently, H + , metal ions, NH4 + , represents an onium cation or onium dication; C2 (a2m2)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m2 is an integer between 1 and 5, and a2 is a real number greater than 0. <8> The mass ratio of the polyate (A1) to the polyate (A2) is 5-95:95-5. <1> The resist material described above. <9> The cation portion of the polysalt (A1) and / or (A2) comprises a sulfonium cation, a sulfonium dication, or an iodonium cation. <1> The resist material described above. <10> Furthermore, (B) contains an acid generator, <1> The resist material described above. <11> Furthermore, it contains (C) an acid diffusion control agent, The (C) acid diffusion control agent is (C1) a photodecayable base. <1> The resist material described above.

[0009] <12> The isopoly acid anion is a polyoxomolybdate anion, a polyoxotungstate anion, a polyoxoniobate anion, or a polyoxotantalate anion. <4> or <7> The resist material described above. <13> 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. <4> or <7> The resist material described above. <14> The aforementioned 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- That is, <13> The resist material described above. <15> The heteropoly acid anion having the aforementioned defect site is a deficient Keggin-type heteropoly acid anion or a deficient Dawson-type heteropoly acid anion. <5> The resist material described above. <16> The aforementioned deficient Keggin-type heteropoly acid anion is represented by the general formula (II-1), (II-2), or (II-3), <15> The resist material described above. [XM 11 O 39 ] c11- (II-1) [XM 10 O 36 ] c12- (II-2) [XM9O 34 ] c13- (II-3) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11- to c13 are natural numbers. <17> The aforementioned deficient Dawson-type heteropoly acid anion is represented by the general formula (III-1), (III-2), or (III-3), <15> The resist material described above. [X2M 17 O 61 ] c21- (III-1) [X2M 16 O 58 ] c22- (III-2) [X2M 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.

[0010] <18> The cation portion of the aforementioned polysulfate (A1) contains a sulfonium cation, a sulfonium dication, or an iodonium cation. <1> The resist material described above.

[0011] <19> The anionic portion of the polyate (A1) is a heteropoly acid anion with a modified defect, and the heteropoly acid anion with a modified defect contains one or more polar groups having an acid-dissociable group. <18> The resist material described above. <20> The aforementioned polysodium acid (A1) is a polysodium acid represented by the following general formula (I-3-1), The aforementioned polyate (A2) is a polyate represented by the following general formula (I-4-1). <19> The resist material described above. (A 31 m31+ ) a31 (B 31 n31+ ) b31 (C 31 (a31m31+b31n31)- (I-3-1) [In general formula (I-3-1), A 31 m31+is, independently, H + , a metal ion, NH4 + , an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B 31 n31+ is, independently, a sulfonium cation, a sulfonium dication, or an iodonium cation; C 31 (a31m31+b31n31)- represents a heteropolyacid anion in which at least one defective site containing a polar group 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+ is, independently, H + , a metal ion, NH4 + , an onium cation, or an onium dication;<x C 41 `[[ID=`41]] (a41m41)- represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion in which a defective site is modified; m41 is an integer of 1 to 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 at least one polar group having an acid dissociable group. <22> The polyacid salt (A1) is a polyacid salt represented by the following general formula (I-3-2),<° The polyacid salt (A2) is a polyacid salt represented by the following general formula (I-4-2), The resist material according to <21>. (A 32m32+ ) a32 (B 32 n32+ ) b32 (C 32 (a32m32+b32n32)- ) (I-3-2) [In general formula (I-3-2), A 32 m32+ each independently represents H + , a metal ion, NH4 + , an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B 32 n32+ 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 32 (a32m32+b32n32)- represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion in which the defect site is modified; 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 independently represents H + , a metal ion, NH4 + , an onium cation, or an onium dication; C 42 (a42m42)- represents an isopolyacid anion, a heteropolyacid anion, or a heteropolyacid anion in which the defect site is modified; m42 is an integer from 1 to 5, and a42 is a real number greater than 0.]

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

[0014] <24> The anionic portion of the aforementioned polyate (A2) is a heteropolyate anion with a modified defect site. The heteropoly acid anion modified at the defect site contains one or more polar groups having acid-dissociable groups. <23> The resist material described above. <25> The aforementioned polysodium acid (A1) is a polysodium acid represented by the following general formula (I-3-3), The aforementioned polysodium acid (A2) is a polysodium acid represented by the following general formula (I-4-3). <24> The resist material described above. (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, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m33 is an integer between 1 and 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, NH4 + , 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 between 1 and 5, and a43 is a real number greater than 0.

[0015] <26> The cation portion of the aforementioned polyate (A2) is a sulfonium cation, sulfonium dication, or iodonium dication containing one or more polar groups having acid-dissociable groups. <23> The resist material described above. <27> The aforementioned polyate (A1) is a polyate represented by the following general formula (I-3-4), The aforementioned polyate (A2) is a polyate represented by the following general formula (I-4-4): <26> The resist material described above. (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, NH4 + , 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)-This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m34 is an integer between 1 and 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, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; 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 aforementioned polysodium acid (A1) is a polysodium acid represented by the following general formula (I-3-5), The aforementioned polysodium acid (A2) is a polysodium acid represented by the following general formula (I-4-5). <1> The resist material described above. (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, NH4 + , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B 35 n35+ Each of these 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)- This represents a heteropoly acid anion modified by a missing site containing one or more polar groups having acid-dissociable groups; m35 is an integer between 1 and 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 of these 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)- This represents a heteropoly acid anion modified by a missing site containing one or more polar groups having acid-dissociable groups; m45 is an integer between 1 and 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> Furthermore, it contains organic solvents, <1> The resist material described above. <30> This is a resist material for electron beam or EUV applications. <1> ~ <29> A resist material as described in any of the following. <31> <1> ~ <29> A step of forming a resist film using a resist material described in any of the following: The steps include: exposing the resist film, The process involves developing the exposed resist film using a developer solution, A pattern formation method including the following. [Effects of the Invention]

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

[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 can be linear, branched, or partially or entirely cyclic. Examples of hydrocarbylene groups include alkylene groups and arylene groups. Also, "C 1-18 Any divalent carbon atom at any position in the "hydrocarbylene group" may be replaced by -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). "C 1-18 The term "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. Also, "C 1-18 Any divalent carbon atom in an alkyl group, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2-. However, adjacent divalent carbon atoms may not be replaced simultaneously. "C 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, and n-dodecyl group. "C 1-18 The alkyl group in which a divalent carbon atom at any position other than the terminal is replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- is not particularly limited, and examples include the 2-methoxyethoxymethyl group and the ethoxycarbonylmethyl group.

[0025] In this specification, "C 1-18 "Haloalkyl group" refers to "C 1-18 This refers to an alkyl group in which one or more hydrogen atoms are substituted with halogen atoms. "C 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. "C 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 This refers to an alkynyl group that has one or more triple bonds in an alkyl group. "C 2-18 The term "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, desinyl group, undecynyl group, dodecynyl group, etc.

[0028] In this specification, "C 3-18 An "alicyclic group" refers to a hydrocarbon group that has a monocyclic or polycyclic cyclic structure with 3 to 18 carbon atoms, either entirely or partially. Alicyclic groups include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, and the like. Also, "C 3-18 Any divalent carbon atom at any position in an alicyclic group, excluding the terminals, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). "C 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, etc.

[0029] In this specification, "3- to 18-membered ring non-aromatic heterocyclic group" means a 3- to 18-membered ring 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 ring, and may be saturated or partially unsaturated. The "3-18 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. "C 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". "C 7-18 The "aralkyl group" is not particularly limited and includes, for example, 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 with 1 to 18 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, and aralkyl groups. Also, "C 1-18 Any divalent carbon atom at any position in the "hydrocarbyl group" except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). This point is explained in the following "C 1-18 The term "C" is used in the explanation of the definition of "hydrocarbyl oxy group," etc. 1-18 The same applies to "hydrocarbyl groups," etc. "C 1-18 The term "hydrocarbyl group" is not particularly limited; for example, "C 1-18 "Alkyl group", "C 2-18 "Alkenyl group", "C 2-18 "Alkynyl group", "C 3-18 Alicyclic group”, “C 2-18 "Aryl group", "C 7-18 Examples include "aralkyl group," etc.

[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". "C 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-2-ethylpropyloxy group, 1-ethyl-2-methylpropyloxy group, 1,1,2-trimethylpropyloxy group, 1,2,2-trimethylpropyloxy group, 1,1-dimethylbutyloxy group, 1,2-dimethylbutyloxy group, 2,2-dimethylbutyloxy group, 2,3-dimethylbutyloxy group, 1,3-dimethylbutyloxy group, 2-ethylbutyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, etc. 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"; such as 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," etc. "C 1-18 The "hydrocarbyl oxy group" is "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 A "hydrocarbyl carbonyl group" is a "C 1-18 This refers to a group in which a carbonyl group (-C(=O)-) is bonded to a hydrocarbyl group. "C 1-18 The "hydrocarbyl carbonyl group" is not particularly limited and 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". "C 1-18 The "hydrocarbylcarbonyloxy group" is not particularly limited and includes, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, hexylcarbonyloxy group, etc. 1-18 "Alkyl carbonyloxy group"; such as cyclopropyl carbonyloxy group, cyclobutyl carbonyloxy group, cyclopentyl carbonyloxy group, cyclohexyl carbonyloxy group, etc. 3-18 "Alicyclic carbonyloxy group"; such as phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenantrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc. 6-18 Examples include "arylcarbonyloxy group," etc.

[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. "C 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 "Hydrocarbyloxycarbonyloxy group" refers to "C 1-18 This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group". "C 1-18 The term "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. 6-18Examples 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. "C 1-18 The "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"; such as 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, "DiC 1-18 A "hydrocarbylamino group" is two identical or different "C" groups. 1-18 A "hydrocarbyl group" refers to a group in which an amino group is bonded. "JiC 1-18The 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-Nn-propylamino group, N-isopropyl-N-methylamino group, and Nn-butyl-N-methylamino group. DiC groups such as N-isobutyl-N-methylamino group, Nt-butyl-N-methylamino group, N-methyl-Nn-pentylamino group, Nn-hexyl-N-methylamino group, N-ethyl-Nn-propylamino group, N-ethyl-N-isopropylamino group, Nn-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, Nt-butyl-N-ethylamino group, N-ethyl-Nn-pentylamino group, N-ethyl-Nn-hexylamino group, etc. 1-18 "Alkylamino group"; dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. 3-18 "Alicyclic amino group"; "DiC" such as diphenylamino group and phenylnaphthylamino group. 6-18 "Arylamino group"; "NC" such as N-methylcyclopentaneamino group, N-methylcyclohexylamino group, etc. 1-18 Alkyl-NC 3-18 "Cycloalkylamino group"; "NC" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. 1-18 Alkyl-NC 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". "C 1-18The term "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, "DiC 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". "JiC 1-18The 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-Nn-propylaminocarbonyl group, N-isopropyl-N-methylaminocarbonyl group, Nn-butyl-N-methyl DiC 1-18 "Alkylamino group"; such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. 3-18 "Alicyclic aminocarbonyl group"; "DiC" such as diphenylaminocarbonyl group and phenylnaphthylaminocarbonyl group. 6-18 Examples include "arylaminocarbonyl group," etc.

[0042] In this specification, "C 1-18 "Hydrocarbylcarbonylamino group" refers to "C 1-18 This refers to a group in which an amino group is bonded to a "hydrocarbyl carbonyl group". "C 1-18The "hydrocarbonylamino group" is not particularly limited and includes, for example, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, n-hexylcarbonylamino group, etc. 1-18 "Alkylcarbonylamino group"; such as cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. 3-18 "Alicyclic carbonylamino group"; such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenantrenylcarbonylamino group, anthracenylcarbonylamino group, etc. 6-18 Examples include "arylcarbonylamino group," etc.

[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". "C 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, etc. 6-18 Examples include "arylaminocarbonyloxy group".

[0044] In this specification, "DiC 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". "JiC 1-18 The term "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 The term "hydrocarbylaminocarbonyl group" refers to a group in which an amino group is bonded. "C 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, "DiC 1-18 "Hydrocarbylaminocarbonylamino group" refers to "diC 1-18 The term "hydrocarbylaminocarbonyl group" refers to a group in which an amino group is bonded. "JiC 1-18 The term "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" refers to "C 1-18 This refers to a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. "C 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". "C 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 1-18The 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. "C 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"; such as 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 This refers to a group in which a sulfonyl group (-SO2-) is bonded to a hydrocarbyl group. "C 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. 6-18 Examples 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, and that dissociates upon the action of an acid. The acid-dissociable group in the compound can be increased in polarity by the action of an acid, which dissociates the acid-dissociable group and generates the polar group. This allows for an alteration of the compound's solubility in the developer. More specifically, when a highly polar developer such as an alkaline aqueous solution is used, the solubility of the compound in the developer increases relatively, while when a less polar organic developer is used, the solubility of the compound in the developer decreases relatively. Preferred polar groups include 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). [ka] [ka] [ka] [ka]

[0053] The above-mentioned acid-dissociable group G is not particularly limited as long as it dissociates upon the action of an acid, and any known and commonly used group 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 the "allyl or benzyl acid-dissociating group G" represented by the following general formula (g-2) B ", represented by the following general formula (g-3), "acetal-type acid-dissociating group G C These are some examples. Each of these will be explained in turn below. [ka] [ka] [ka]

[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 the 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. [ka]

[0055] "R A g1 " may have substituents C 1-12 In a hydrocarbyl group, any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0056] RA g1 C may have substituents. 1-12 Alkyl alkyl group, C 3-12 Alicyclic group, C 6-12 Aryl group, or C 7-12 The aralkyl group is preferably one in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). C may have substituents 1-12 Alkyl alkyl group, or C 3-12 A more preferable alicyclic group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0057] Also, "R A g2 " and "R A g3 Each of these C atoms may independently have substituents. 1-12 A hydrocarbyl group in which any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously), or R A g2 and R A g3 These are combined and may have substituents. 3-18 The group may form an alicyclic group or a 3-18 membered non-aromatic heterocyclic group, in which divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[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 Preferably, the group forms an alicyclic group or a 3-18 membered non-aromatic heterocyclic group, and any divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). Furthermore, C which may have the above substituent 3-18 It is more preferable that the alicyclic group or the 3-18 membered non-aromatic heterocyclic group includes a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, and tricyclodecene skeleton, and that any divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0059] The tertiary carbon type acid-dissociable group G, represented by the 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] The tertiary carbon type acid-dissociable group G, represented by the general formula (g-1). A Examples of such groups include the following tertiary carbon-type acid-dissociable groups.

[0061] [ka]

[0062] <<Tertiary carbon type acid dissociable group G A1 and G A2 >> Furthermore, the "tertiary carbon-type acid-dissociating 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. 3-18 In cases where an alicyclic group or a 3-18 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 >> [ka] 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 7-12In an aralkyl group, any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0064] Also Cy A g1 This is a C that may have substituents, together with the above-mentioned tertiary carbon atom. 3-18 It forms an alicyclic group or a 3-18 membered non-aromatic heterocyclic group, and any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0065] Cy A g1 Preferably, the above tertiary carbon atoms, together with substituents, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms will not be replaced at the same time).

[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-dissociable groups.

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) A2 >> [ka] In the above general formula (g-1-2), R A g21 ~R A g23 Each of these may independently have a hydro group or a substituent. 1-12 In a hydrocarbyl group, any divalent carbon atom except at the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously), R A g21 and R A g22 , and / or, R A g22 and R A g23 These are directly linked by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via alkylene groups to form a ring.

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

[0074] Cy A g2 Preferably, the above tertiary carbon atoms, together with substituents, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms will not be replaced at the same time).

[0075] The tertiary carbon type acid-dissociable group G, represented by the general formula (g-1-2). A2 Examples of such groups include the following tertiary carbon-type acid-dissociable groups.

[0076] [ka]

[0077] [ka]

[0078] [ka]

[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. [ka]

[0080] "R B g1 " may have substituents C 1-12 In a hydrocarbyl group, any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

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

[0082] Also, "R B g2 "~"R B g4 Each of these may independently have a hydro group or a substituent. 1-12 In a hydrocarbyl group, any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0083] R B g1 and R B g2 , R B g2 and R B g3 , and / or, R B g3 and R B g4 These are directly linked by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via alkylene groups to form a ring.

[0084] Allyl or benzyl acid-dissociating 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-dissociating group G represented by general formula (g-2) B Examples include the following allyl or benzyl acid-dissociating groups.

[0086] [ka]

[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. [ka]

[0088] "R C g1 " and "R C g3 Each of these may independently have a hydro group or a substituent. 1-12In a hydrocarbyl group, any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

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

[0090] Also, "R C g2 " may have substituents C 1-12 In a hydrocarbyl group, any divalent carbon atom, excluding terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0091] R C g2 C may have substituents. 1-12 Alkyl alkyl group or C 3-12Preferably, the alicyclic group is one in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). C may have substituents 1-6 Alkyl alkyl group or C 3-8 A more preferable alicyclic group is one in which any divalent carbon atom, excluding the terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0092] Acetal-type acid-dissociating 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] The ether protecting group is not particularly limited and includes, for example, a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, a di(p-methoxyphenyl)phenylmethyl group, and the like. The silyl ether protecting group is not particularly limited and includes, for example, t-butyldimethylsilyl group (TBS), triisopropylsilyl group (TIPS), trimethylsilyl group (TMS), triethylsilyl group (TES), and t-butyldiphenylsilyl group (TBDPS). The acyl protecting group is not particularly limited and examples include acetyl, pivaloyl, and benzoyl groups. The aminocarbonyl protecting group is not particularly limited, and examples include the 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) sulfol 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 with protecting groups, (20) polar groups with acid-dissociable groups, or (21) C in which at least one part of the hydrogen atoms is substituted with the above (1) to (20). 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, C1-18 Hydrocarbylcarbonylamino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, C 1-18 Hydrocarbylthio group, C 1-18 Hydrocarbyl sulfinyl group, C 1-18 A hydrocarbyl sulfonyl group in which a divalent carbon atom at any position other than the terminal of the substituent may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0096] [1. Resist material] 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, the resist material according to this embodiment may also contain, as an optional component, polyates other than components (A1) and (A2), and may also contain (B) an acid generator, (C) an acid diffusion control agent, an organic solvent, etc.

[0097] [1-1. (A) Polysalts] (A) By providing a resist material containing at least two different polyates (A1) and (A2) as the 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 aggregation 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, among the at least two different polyate salts (A1) and (A2) contained in the resist material according to this embodiment, at least one of the polyate salts (A1) or (A2) contains a polar group having one or more acid-dissociable groups, thereby allowing the solubility in the developer to be changed by the action of acid. The number of polar groups having acid-dissociable groups contained in the above polysalt (A1) and / or (A2) is not particularly limited, but 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, and lipid solubility of the acid-dissociable groups, the range of changes in physical properties such as solubility in the developer between the exposed and unexposed areas of the active light can be adjusted.

[0100] In the resist material according to this embodiment, at least one of the two different poly salts (A1) and (A2) contained therein contains a sulfonium cation, a sulfonium dication, or an iodonium cation in its cation portion, which allows it to 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, alpha rays, beta rays, gamma rays, etc.). On the other hand, if neither of the cation portions of the above polyate 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 part of polysodium salts] As the anionic portion of the polyate according to this embodiment, an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect can be used.

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

[0105] Examples of the above isopolyoxomolybdate anion include [MoO4] 2- [Mo7O 24 ] 6- [Mo8O 26 ] 4- Examples include [W4O 13 ] 2- [W5O 16 ] 2- [W6O 19 ] 2- [W7O 22 ] 2- [W7O 24 ] 6- [H z W 12 O 40 ] -(8-z) (where z represents an integer from 1 to 4.) [W 10 O 32 ] 4- [H4W11 O 38 ] 6- [H7W 11 O 40 ] 7- [HW5O 19 ] 7- [H3W] 11 O 22 ] 5- Examples include [V4O 12 ] 4- [V 10 O 28 ] 6- Examples include [Nb6O 19 ] 8- [Nb 10 O 28 ] 6- Examples include, and the above isopolyoxotantalate anion is, for example, [Ta6O 19 ] 8- [Ta8O 21 ] 2- 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 [W4O 13 ] 2- [W5O 16 ] 2- [W6O 19 ] 2- [W7O 22 ] 2- [W7O 24 ] 6- [W 10 O 32 ] 4- [H z W 12 O 40 ] -(8-z) (However, z represents an integer from 1 to 4.) [H4W 11O 38 ] 6- [H7W 11 O 40 ] 7- [HW5O 19 ] 7- [H3W] 11 O 22 ] 5- [H4W 22 O 74 ] 12- , or [H 10 W 34 O 116 ] 18- It is preferable that [W6O 19 ] 2- [W7O 24 ] 6- [W 10 O 32 ] 4- [H z W 12 O 40 ] -(8-z) (where z represents an integer from 1 to 4.) is more preferable, [W6O 19 ] 2- [W7O 24 ] 6- [W 10 O 32 ] 4- [H2W 12 O 40 ] 6- [H3W] 12 O 40 ] 5- It is even more preferable that this be the case.

[0108] [1-1-1-2. Heteropolyate anions] Examples of heteropoly acid anions according to this embodiment include heteropolyoxomolybdate anions, heteropolyoxotungstate anions, heteropolyoxovanadate anions, heteropolyoxoniobate anions, and heteropolyoxotantalate anions. The poly atom of the above heteropoly acid 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- [BW 12 O 40 ] 5- [SW 12 O 40 ] 2- [P2W] 18 O 62 ] 6- [Si2W 18 O 62 ] 8- It is preferable that this be the case.

[0112] [1-1-1-3. Heteropolyate anions with modified defect sites] The heteropoly acid anion modified with a defect according to this embodiment can be obtained by reacting the terminal oxygen atom at the defect site of the 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 with missing sites] The heteropoly acid anion having a defect site according to this embodiment is not particularly limited, and a defect species in which a part of the basic skeleton of the heteropoly acid anion is missing can be used, and any of the 1-defect species, 2-defect species, 3-defect species, etc., may be used. Examples of the heteropoly acid anion having a defect site include a Keggin-type heteropoly acid anion and a Dawson-type heteropoly acid anion.

[0114] <Deficient Keggin-type heteropoly acid anion> 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) [XM9O 34 ] c13- (II-3) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11- to c13 are natural numbers.

[0115] In general formulas (II-1) to (II-3), the values ​​of c11 to c13 vary depending on the types of X and M. For example, in general formula (II-1), if X is P and M is Mo or W, then c11 is 7([PMo 11 O 39 ] 7- Now PW 11 O 39 ] 7- ) and if X is Si and M is Mo or W, then 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- ) Furthermore, in general formula (II-2), when X is P and M is Mo or W, c12 is 7([PMo 10 O 36 ] 7- Now PW 10 O 36 ] 7- ) and if X is Si and M is Mo or W, then c12 is 8([SiMo 10 O 36 ] 8- [SiW 10 O 36 ] 8- ) and if X is B and M is Mo or W, then c12 is 9([BMo 10 O 36 ] 9- [BW10 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, if X is P and M is Mo or W, then c13 is 9([PMo9O 34 ] 9- [PW9O 34 ] 9- ) and when X is Si and M is Mo or W, c13 is 10([SiMo9O 34 ] 10- [SiW9O 34 ] 10- ) and if X is S and M is Mo or W, then c13 is 8([SMo9O 34 ] 8- [SW9O 34 ] 8- ) and if X is Ge and M is Mo or W, then c13 is 10([GeMo9O 34 ] 10- [GeW9O 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-PW 11 O 39 ] 7- [α-PMo 11 O 39 ] 7- [β-PMo 11 O 39 ] 7- [γ-PW 11 O 39 ] 7-[α-SiW 11 O 39 ] 8- [β-SiW 11 O 39 ] 8- [γ-SiW 11 O 39 ] 8- [α-SiMo 11 O 39 ] 8- [β-SiMo 11 O 39 ] 8- [γ-SiW 11 O 39 ] 8- [α-PW 11 O 39 ] 7- [α-PMo 11 O 39 ] 7- [α-SiW 11 O 39 ] 8- [α-SiMo 11 O 39 ] 8- This is preferable. Furthermore, the isomer structure of the two-deficient keging-type heteropoly acid anion represented by the general formula (II-1) is [α-PW 10 O 36 ] 7- ..β-PW 10 O 36 ] 7- [γ-PW 10 O 36 ] 7- [α-PMo 10 O 36 ] 7- [β-PMo 10 O 36 ] 7- [γ-PW 10 O 36 ] 7- [α-SiW 10 O 36 ] 8- [β-SiW 10 O 36 ] 8- [γ-SiW 10 O 36 ] 8- [α-SiMo 10 O36 ] 8- [β-SiMo 10 O 36 ] 8- [γ-SiW 10 O 36 ] 8- [γ-PW 10 O 36 ] 7- [γ-PMo 10 O 36 ] 7- [γ-SiW 10 O 36 ] 8- [γ-SiMo 10 O 36 ] 8- This is preferable. Furthermore, the isomer structure of the 3-deficient keging-type heteropoly acid anion represented by the general formula (III-1) is [α-PW9O 34 ] 9- [β-PW9O 34 ] 9- [γ-PW9O 34 ] 9- [α-PMo9O 34 ] 9- [β-PMo9O 34 ] 9- [γ-PW9O 34 ] 9- [α-SiW9O 34 ] 10- [β-SiW9O 34 ] 10- [γ-SiW9O 34 ] 10- [α-SiMo9O 34 ] 10- [β-SiMo9O 34 ] 10- [γ-SiW9O 34 ] 10- It is preferable.

[0117] <Deficited Dawson-type heteropoly acid anion> Examples of the above-mentioned deficient Dawson heteropoly acid anions include the 1-deficient Dawson heteropoly acid anion represented by the following general formula (III-1), the 2-deficient Dawson heteropoly acid anion represented by the following general formula (III-2), and the 3-deficient Dawson heteropoly acid anion represented by the following general formula (III-3). [X2M 17 O 61 ] c21- (III-1) [X2M 16 O 58 ] c22- (III-2) [X2M 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), if X is P and M is Mo or W, then c21 is 10([P2Mo 17 O 61 ] 10- [P2W] 17 O 61 ] 10- ) and if X is S and M is W, then c21 is 8([S2W 17 O 61 ] 8- ) Furthermore, in general formula (III-2), when X is Ge and M is Mo, c22 is 12([Ge2Mo 16 O 58 ] 12- ) Furthermore, in general formula (III-3), if X is P and M is Mo or W, then c23 is 12([P2Mo 15 O 56 ] 12- [P2W] 15O 56 12- ) is obtained.

[0119] The above defective Dawson-type heteropolyacid anion preferably has an isomeric structure of α-form, β-form, or γ-form. As the isomeric structure of the defective Dawson-type heteropolyacid anion represented by General Formulas (III-1) to (III-3), [α-P2W 17 O 61 10- , [α-P2W 15 O 56 12- , [α-S2W 17 O 61 8- etc. can be preferably used.

[0120] [1-1-1-3-2. Modification of the Defective Site] The modification of the defective site of the heteropolyacid anion having the defective site according to the present embodiment is made by reacting the terminal oxygen atom at the defective site of the heteropolyacid anion having the defective site 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. By the above reaction, the terminal oxygen atom of the defective site of the heteropolyacid anion binds to a group having a heteroatom P, Si, Ge or Sn to which one or more organic groups are bonded, through a part or all of the heteroatom, thereby modifying the defective site.

[0121] <Bonding Form of the Defective Site and Its Notation> The heteropolyacid anion having the defective site modified according to the present embodiment is modified by a group having a heteroatom P, Si, Ge or Sn to which one or more organic groups are bonded, at the terminal oxygen atom of the defective site of the heteropolyacid anion having the defective site.

[0122] ​​​​The bonding form between the terminal oxygen atom at the defect site of the above heteropolyacid anion and the group having a heteroatom P, Si, Ge or Sn to which the above one or more organic groups are bonded is not particularly limited, and can be represented by, for example, the following general formulas (IV-1) to (IV-5). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [In formulas (IV-1) to (IV-5), X'represents Si or Ge; X''represents a heteroatom of Si, Ge or Sn; R 1A1 ~R 1E1 each independently represents an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, the above R 1A1 ~R 1E1 any divalent carbon atom at a position other than the terminal of may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced.), the above R 1A1 ~R 1E1The 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) sulfol 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; * indicates the bond site between the terminal oxygen atom and the missing 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 general formula (V-1) below. [X w M x O y (R 1A1 X')(R 1A2 X')O] c- (V-1) (In the formula, w, x, y, and c are all natural numbers, and 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 use R 1A It can be expressed as follows: (V-1') [X w M x O y (R 1A X')2O] c- (V-1')

[0124] A heteropoly acid anion modified by 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'Y3(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. ), alkylcarbonyloxy group (C 1-4 It is preferable that it be an alkylcarbonyloxy group. ), a 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 with )).

[0125] Similarly, in this specification, a heteropoly acid anion in which the missing 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 represented as shown in the following general formula (V-2) for convenience. [X w M x O y (R 1B1 R 1B2 X')(R 1B3 R 1B4 X')] c- (V-2) (In the formula, w, x, y, and c are all natural numbers, and 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 general formula (V-2') below. [X w M x O y (R 1B1 R 1B2 X')2] c- (V-2')

[0126] The heteropolyacid anion modified at the defect site represented by the general formula (V-2) or (V-2') is not particularly limited. For example, it can be obtained by reacting a heteropolyacid anion having a defect site with (R 1B1 )(R 1B2 )X’Y2 (Y represents a leaving group as defined above).

[0127] In this specification, for the heteropolyacid anion in which the defect site of the heteropolyacid anion is modified with a group having a heteroatom Si or Ge to which one or more organic groups represented by the general formula (IV-3) are bonded, for convenience, it may be represented as the following general formula (V-3). [X w M x O y (R 1C1 X’O)(R 1C2 X’O)(R 1C3 X’O)(R 1C4 X’O)] c- (V-3) (In the formula, w, x, y, and c are all natural numbers, and X, M, X’, R 1C1 , R 1C2 , R 1C3 and R 1C4 are the same as defined above.) Also, when R 1C1 , R 1C2 , R 1C3 and R 1C4 are the same, this can be represented as R 1C and can be represented as the following general formula (V-3’). [X w M x O y (R 1C X’O)4] c- (V-3’)

[0128] The heteropolyacid anion modified at the defect site represented by the general formula (V-3) or (V-3') is not particularly limited. For example, it can be obtained by reacting a 2-defect Keggin-type or Dawson-type heteropolyacid anion with R 1C X’Y3 (Y represents a leaving group as defined 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 general formula (V-4) below. [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, and R are all natural numbers.) 1D1 and R 1D2 (This is the same as above.) Also R 1D1 and R 1D2 If they are the same, then use R 1D It can be expressed as shown in the following general formula (V-4'). [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 It can be obtained by reacting it with P(=O)Y2 (where 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 general formula (V-5) below. [X w M x O y (R 1E1 X'')] c- (V-5) (In the formula, w, x, y, and c are all natural numbers, and X, M, X'' and R 1E1(This is the same as above.) Furthermore, the above (V-5) may sometimes be expressed as the general formula (V-5') below. 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, for example, a heteropoly acid anion having a defect site and R 1E It can be obtained by reacting it with X''Y3 (where Y represents a leaving group, as described above).

[0133] Among heteropoly acid anions modified with the deletion sites represented by general formulas (V-1) to (V-5) and (V-1') to (V-5'), heteropoly acid anions modified with the deletion 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')2O] 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')2O] c32- (VI-5) [XM10 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) [X2M 17 O 61 (R 1A X')2O] c33- (VI-9) [X2M 17 O 61 (R 1B1 R 1B2 X')2] c33- (VI-10) [X2M 17 O 61 (R 1D P=O)2] c33- (VI-11) [X2M 17 O 61 (R 1E X'')] c33- (VI-12) (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; 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. The above R 1A ~R 1EAny divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 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) sulfol 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; c31, c32, and c33 are natural numbers.

[0134] In heteropoly acid 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-deleted Keggin-type heteropoly acid 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-deleted Keggin-type heteropoly acid 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-deleted Dawson-type heteropoly acid 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 values ​​mentioned above.

[0135] <Organic group> The above R 1A , R 1B1 and R 1B2 , R1C , 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. The above R 1A ~R 1E As an organic group represented by R, 1A ~R 1E but, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 1A ~R 1E The hydrogen atoms contained in 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. C may have substituents 1-18 It is a hydrocarbyl group; the above R 1A ~R 1E Any divalent carbon atom other than the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). 1A ~R 1EThe 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. 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 other than the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). 1A ~R 1E It is even more preferable that the hydrogen atoms contained in may be replaced with (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 with acid-dissociable groups. The number of polar groups having acid-dissociable groups contained 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] <<Organic groups 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 but, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot 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 is replaced by a polar group having an acid-dissociable group. 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot 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 one hydrogen atom of is replaced by a polar group having an acid-dissociable group, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 1A ~R 1E It is even more preferable that at least one hydrogen atom of the compound is replaced by a polar group having an acid-dissociable group (t).

[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 These are some examples. 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] [ka] [* indicates a bond between a heteroatom P, Si, Ge, or Sn and an organic group containing one or more acid-dissociable polar groups.]

[0141] <<Organic groups having two or more polar groups with acid-dissociable groups>> The above R 1A ~R 1E From the viewpoint of drastically changing the solubility in the developing solution through the action of an acid, etc., it is preferable that the organic group represented by the above contains two or more polar groups having acid-dissociable groups.

[0142] 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 but, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 1A ~R 1E The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth) acryloyl groups, (m) (meth) acryloyloxy groups, (n) (meth) acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R 1A ~R 1E Preferably, at least two hydrogen atoms are replaced by polar groups having (t) acid-dissociable groups. 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 1A ~R 1EThe hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth) acryloyl groups, (m) (meth) acryloyloxy groups, (n) (meth) acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R 1A ~R 1E It is more preferable that at least two hydrogen atoms of the (t) are replaced by polar groups having acid-dissociable groups. 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot 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.

[0143] 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 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. R containing two or more polar groups having the above acid-dissociable groups 1A ~R 1EFor example, the following can be cited:

[0144] [ka] [G represents an acid-dissociable group G, and * indicates the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0145] [ka] [* is an organic group R 1A ~R 1E This refers to the bond with the heteroatom P, Si, Ge, or Sn to which it is bonded.

[0146] 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). [ka] [In formula (VII), L 2 C may have substituents. 1-12 In a hydrocarbyl group, hydrogen atoms on carbon atoms at any position including the terminals are each R 2A and R 2B This represents the group that has been substituted, Said L 2 Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). R 2A and R 2B Each of these independently represents a polar group having an acid-dissociable group. * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn.

[0147] L in an organic group represented by general formula (VII)2 As for, L 2 However, C may have substituents. 2-10 In a hydrocarbyl group, hydrogen atoms on carbon atoms at any position including the terminals are each R 2A and R 2B The group is substituted with: the above L 2 The terminal and R 2A or R 2B It is preferable that any divalent carbon atom at any position other than the carbon atom to which the compound is bonded may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). L 2 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 2A and R 2B The group is substituted with: the above L 2 The terminal and R 2A or R 2B It is 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-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). L 2 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 2A and R 2B The group is substituted with: the above L 2 The terminal and R 2A or R 2BIt 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).

[0148] R in an organic group represented by general formula (VII) 2A and R 2B As for, R 2A and R 2B Each of these is preferably an acid-dissociable hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group, R 2A and R 2B 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 2A and R 2B Each of these is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; the above acid-dissociable group is a tertiary carbon type acid-dissociable group G A It is even more preferable that this be the case.

[0149] [1-1-2. (A) Cational portion of polysalt] The cation portion of the polysalt according to this embodiment is H + , metal ions, NH4 + Onium cations or onium dications can be used.

[0150] [1-1-2-1. Metal Ions] The metal ions that can be used as the cation portion of the polysalt 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+ These are some examples. As for metal ions, + 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 this be the case. These metal ions may exist individually or in combination of two or more types.

[0151] [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 polyate according to this embodiment is not particularly limited, and known and commonly used ones can be used. Examples of the onium cation or onium dication mentioned above 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.

[0152] 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.

[0153] [1-1-2-2-1. Ammonium cation] The ammonium cation is not particularly limited, and any known and commonly used ammonium cation can be used. The above ammonium cation is not particularly limited, and for example, a primary ammonium cation (NH3(R) 3A ) + )), secondary ammonium cation (NH2(R 3A )(R 3B )) + ), tertiary ammonium cation (NH(R) 3A )(R 3B )(R 3C ) + ), quaternary ammonium cation (N(R 3A )(R 3B )(R 3C )(R 3D ) + ) are listed above. 3A ~R 3D This shall represent something equivalent to what is defined below.

[0154] 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). [ka]

[0155] In general formula (VIII-1), R 3A ~R 3DEach 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. The above R 3A ~R 3D Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 3A ~R 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 (a) to (t) 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 1-18 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 1-18Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 The substituents may be replaced by hydrocarbylthio groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). Furthermore, R 3A ~R 3D Any two of these are linked to each other directly by a single bond, 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).

[0156] 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, and trimethyl(4-(nonanoyloxy)phenyl)ammonium cation.

[0157] [1-1-2-2-2. Ammonium dication] The ammonium dication is not particularly limited, and any known and commonly used one can be used. Examples of ammonium dications include the organic quaternary ammonium dication represented by the following general formula (VIII-2). [ka]

[0158] In general formula (VIII-2), R 4A ~R 4F Each of these may independently have substituents. 1-18 This represents a hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, and a 5-18 membered aromatic heterocyclic group. The above R 4A ~R 4F Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). L 4 C may have substituents. 1-18 Represents a hydrocarbylene group, The above L 4 Any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). 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 (a) to (t) above. 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C1-18 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 substituents may be replaced by hydrocarbylthio groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). R 4A ~R 4F Any two of these are linked to each other directly by a single bond, 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).

[0159] 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)acrylamidoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium.

[0160] [1-1-2-2-3. Phosphonium cation] The phosphonium cation is not particularly limited, and known and commonly used phosphonium cations can be used. Examples of phosphonium cations include the organic quaternary phosphonium cation represented by the following general formula (VIII-3). [ka]

[0161] In general formula (VIII-3), R 5A ~R 5D 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; The above R 5A ~R 5D Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). The above R 5A ~R 5DThe 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 (a) to (t) 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 1-18 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 substituents may be replaced by hydrocarbylthio groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). Furthermore, R 5A ~R 5DAny two of these are linked to each other directly by a single bond, 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).

[0162] 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.

[0163] [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). [ka]

[0164] In general formula (VIII-4), R 6A ~R 6F 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. The above R 6A ~R 6F Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). L 6 C may have substituents. 1-18 Represents a hydrocarbylene group, The above L 6 Any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). 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 (a) to (t) above. 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18Hydrocarbylcarbonyloxy 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 substituents may be replaced by hydrocarbylthio groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). R 6A ~R 6F Any two of these are linked to each other directly by a single bond, 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 phosphorus atoms in formula (VIII-4).

[0165] 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.

[0166] [1-1-2-2-5. Sulfonium cation] The sulfonium cation is not particularly limited, and known and commonly used cations can be used. Examples of sulfonium cations include the organosulfonium cation represented by the following general formula (VIII-5). [ka]

[0167] In general formula (VIII-5), R 7A , R 7B and R 7C 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. The above R 7A , R 7B and R 7C Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). 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 (a) to (t) above. 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18Hydrocarbylcarbonyloxy 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 substituents may be replaced by hydrocarbylthio groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). Furthermore, R 7A , R 7B and R 7C 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 and form a ring together with the sulfur atoms in formula (VIII-5).

[0168] In an organic sulfonium cation represented by general formula (VIII-5), the above R 7A , R 7B and R 7C As for, R 7A , R 7B and R 7C However, each may independently have substituents. 1-18It is a hydrocarbyl group; the above R 7A , R 7B and R 7C It is preferable that any divalent carbon atoms at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). R 7A , R 7B and R 7C However, each 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 7A , R 7B and R 7C It is more preferable that any divalent carbon atom at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). R 7A , R 7B and R 7C However, each 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 (a) to (t) above. 1-18Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is preferable that these substituents may be replaced by hydrocarbylthio groups, and that the divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0169] Also R 7A , R 7B and R 7C 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 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-dithian-1-ium skeleton, 1H-thiophene-1-ium skeleton, benzo[b]thiophene-1-ium skeleton, dibenzothiophenium skeleton, 9,10-dihydrothioxanthilium skeleton, 10H-phenoxatiyne-10-ium skeleton, 5H-thiantrene-5-ium skeleton, etc., and the following are examples. Note that * indicates that it is not involved in ring formation, R 7A , R 7B or R 7C It means the connection point.

[0170] [ka]

[0171] 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 Mucation, 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.

[0172] <Organosulfonium cation containing one or more polar groups with acid-dissociable groups> From the viewpoint of providing a building block whose solubility in the developer can be changed by the action of an acid, etc., an organic sulfonium cation having one or more polar groups with acid-dissociable groups may be used as the sulfonium cation.

[0173] 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 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. The above R 7A , R 7B and R 7C Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). The above R 7A , R7B 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 (a) to (t) 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, or C 1-18 The substituents may be replaced by hydrocarbylthio groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). Also, the above R 7A One or more hydrogen atoms contained in are replaced by polar groups having (t) acid-dissociable groups, Furthermore, R 7A , R 7B and R 7C 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 and form a ring together with the sulfur atoms in formula (VIII-5).

[0174] R containing one or more polar groups having the above-mentioned acid-dissociable groups 7AC may have substituents. 1-18 It is a hydrocarbyl group; the above R 7A Any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 7A Preferably, at least one hydrogen atom is replaced by a polar group having an acid-dissociable group. 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 7A It is more preferable that at least one hydrogen atom of is replaced by a polar group having an acid-dissociable group, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 7A It is even more preferable that at least one hydrogen atom of the compound is replaced by a polar group having an acid-dissociable group (t).

[0175] 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.

[0176] R containing one or more polar groups having the above-mentioned acid-dissociable groups 7A For example, the following can be cited. Note that * represents the bond with the sulfur atom in general formula (VIII-5).

[0177] [ka]

[0178] 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above 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 (a) to (t) 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, or C 1-18 It is preferable that the substituents are replaced by hydrocarbylthio groups, and that the divalent carbon atoms at any position other than the terminals of these substituents are replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time). 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 7B and R 7C Any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above 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 (a) to (t) 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, or C 1-18 It is preferable that these substituents are replaced by hydrocarbylthio groups, and that the divalent carbon atoms at any position other than the terminals of these substituents are replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0179] Examples of sulfonium cations containing one or more polar groups having the above-mentioned 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, and (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)naphthalene-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)naphthalene-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.

[0180] Examples of organosulfonium cations containing one or more polar groups having the above-mentioned acid-dissociable groups include the following:

[0181] [ka]

[0182] [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). [ka]

[0183] In general formula (VIII-6), R 8A , R 8B , R 8C and R 8D 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. The above R 8A , R 8B , R 8C and R 8D Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). L 8 C may have substituents. 1-18 Represents a hydrocarbylene group, The above L 8 Any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). The above R 8A , R 8B , R 8C , R 8D , and L8 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 (a) to (t) 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 1-18 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 any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). R 8A , R 8Band L 8 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 with the sulfur atoms in formula (VIII-6).

[0184] <Organosulfonium dication containing one or more polar groups with acid-dissociable groups> As a sulfonium dication, an organic sulfonium dication having one or more polar groups with acid-dissociable groups may be used, from the viewpoint that its solubility in the developer can be changed by the action of an acid, etc.

[0185] 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 is replaced by a polar group having an (t) acid-dissociable group.

[0186] 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 These are some examples. R containing one or more polar groups having the above-mentioned acid-dissociable groups 8A ~R 8DFor example, R containing one or more polar groups having acid-dissociable groups. 7A Examples similar to those exemplified above can be given.

[0187] [1-1-2-2-7. Iodonium cation] The iodonium cation is not particularly limited, and any known and commonly used cation can be used. Examples of iodonium cations include the organic iodonium cation represented by the following general formula (VIII-7). [ka]

[0188] In general formula (VIII-7), R 9A and R 9B 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. The above R 9A and R 9B Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). 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 (a) to (t) above. 1-18 Hydrocarbyl group, C 1-18Hydrocarbyl 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 substituents may be replaced by hydrocarbylthio groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). Furthermore, R 9A and R 9B These are directly linked by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via alkylene groups, forming a ring together with the iodine atoms in formula (VIII-7).

[0189] In the organic iodonium cation represented by general formula (VIII-7), R 9A and R 9B As for, R 9A and R 9B However, each may independently have substituents. 1-18It is a hydrocarbyl group; the above R 9A and R 9B It is preferable that any divalent carbon atoms at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). R 9A and R 9B However, each 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 It is more preferable that any divalent carbon atom at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). R 9A and R 9B However, each 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 (a) to (t) above. 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyl oxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is preferable that these substituents may be replaced by hydrocarbylthio groups, and that the divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0190] 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- 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.

[0191] <Organiodonium cation having one or more polar groups with acid-dissociable groups> As an iodonium cation, an organic iodonium 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.

[0192] 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 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. The above R 9A and R 9B Any divalent carbon atom at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced simultaneously). 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 (a) to (t) 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, or C 1-18The substituents may be replaced by hydrocarbyloxycarbonyloxy groups, and any divalent carbon atoms at any position other than the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). Also, the above R 9A One or more hydrogen atoms contained in are replaced by polar groups having (t) acid-dissociable groups, Furthermore, R 9A and R 9B These are directly linked by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via alkylene groups, forming a ring together with the iodine atom in formula (VIII-3).

[0193] R having one or more of the above acid-dissociable groups 9A As for, C may have substituents 1-18 It is a hydrocarbyl group; the above R 9A Any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 9A Preferably, at least one hydrogen atom is replaced by a polar group having an acid-dissociable group. 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 9AAny divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 9A It is more preferable that at least one hydrogen atom of is replaced by a polar group having an acid-dissociable group, 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 may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). The above R 9A It is even more preferable that at least one hydrogen atom of the compound is replaced by a polar group having an acid-dissociable group (t).

[0194] 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 These are some examples. 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.

[0195] [1-1-3. At least two different polysalts (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 above-mentioned polyates (A1) and (A2), one or more other polyates different from these may also be included as polyates.

[0196] [1-1-3-1. When the polyate (A1) contains one or more polar groups with acid-dissociable groups] <When the anionic portion of the polysodium acid salt (A1) contains one or more polar groups having acid-dissociable groups> Examples of cases in which the anionic portion of the above-mentioned polysalt (A1) contains one or more polar groups having acid-dissociable groups include the polysalt 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, NH4 + , represents an onium cation or onium dication; C 11 (a11m11)- This represents a heteropoly acid anion modified by a missing site containing one or more polar groups having acid-dissociable groups; m11 is an integer between 1 and 5, and a11 is a real number greater than 0.

[0197] 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.

[0198] Furthermore, as a "heteropoly acid 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 may be used as appropriate 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.

[0199] 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.

[0200] <When the cation portion of the polysodium acid salt (A1) contains one or more polar groups having acid-dissociable groups> Next, as an example of a case in which the cation portion of the above-mentioned 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) is 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, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; 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.

[0201] 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 those described above as appropriate.

[0202] 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.

[0203] 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.

[0204] The ratio of a12 to b12 is A 12 m12+ B 12 n12+ , C 12 (a12m12+b12n12)- Depending on the type, etc., it is preferable that a12:b12 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. 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 it is more preferable that a12 is a real number between 0 and 4 and b12 is a real number between 2 and 8.

[0205] <Polysate (A2)> If the anionic or cation portion of the above-mentioned polysalt (A1) contains one or more polar groups having acid-dissociable groups, the cation portion and / or anionic portion of the polysalt (A2) may or may not contain polar groups having acid-dissociable groups, and the cation portion may or may not contain a sulfonium cation, a sulfonium dication, or an iodonium cation.

[0206] The above-mentioned polysulfate (A2) is not particularly limited, and examples include the polysulfate represented by the following general formula (I-2). (A2 m2+ ) a2 (C2 (a2m2)- ) (I-2) [In general formula (I-2), A2 m2+ Each of them independently, H + , metal ions, NH4 + , represents an onium cation or onium dication; C2 (a2m2)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m2 is an integer between 1 and 5, and a2 is a real number greater than 0.

[0207] 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.

[0208] In the polysalt represented by the above general formula (I-2), multiple types of A2 m2+It may include multiple types of A2 in the above case. m2+ The content ratio can be determined, for example, by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0209] [1-1-3-2. When the cation portion of the polysalt (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) polyates, 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 at least two different polyates (A1) and (A2) into the resist material, acid can be generated by exposure to active light (DUV, XUV, EUV, electron beam, etc.), and the acid-dissociable groups can be dissociated from polar groups due to the action of the acid, thereby changing the solubility in the developer and other properties.

[0210] <When the anionic portion of the polysodium acid salt (A1) contains one or more polar groups having acid-dissociable groups> An example of a case in which the anionic portion of the above-mentioned polysalt (A1) contains one or more polar groups having an acid-dissociable group is when the anionic portion of the above-mentioned polysalt (A1) is a heteropoly acid anion with a modified defect site, and the heteropoly acid anion with the modified defect site contains one or more polar groups having an acid-dissociable group.

[0211] Examples of the above-mentioned 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, NH4 + , 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)- This represents a heteropoly acid anion modified by a missing site containing one or more polar groups having acid-dissociable groups; m31 is an integer between 1 and 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, NH4 + , represents an onium cation or onium dication; C 41 (a41m41)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m41 is an integer between 1 and 5, and a41 is a real number greater than 0.

[0212] In the polysalt represented by the general formula (I-3-1) above, the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "sulfonium cation," "sulfonium dication," and "iodonium cation" can be any of those listed above as appropriate. Furthermore, as a "heteropoly acid 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 may be used as appropriate 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.

[0213] 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.

[0214] The ratio of a31 to b31 is A 31 m31+ B 31 n31+ , C 31 (a31m31+b31n31)- Depending on the type, etc., it is preferable that a31:b31 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a31m31+b31n31 is an integer between 2 and 8, and m31 and n31 are 1, it is preferable that a31 is a real number between 0 and 7 and b31 is a real number between 1 and 8, and it is more preferable that a31 is a real number between 0 and 4 and b31 is a real number between 2 and 8.

[0215] Furthermore, in the polysalt represented by the general formula (I-4-1) 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. 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.

[0216] <When the cation portion of the polysodium acid salt (A1) contains one or more polar groups having acid-dissociable groups> Examples of cases in which the cation portion of the above-mentioned polysalt (A1) contains one or more polar groups having acid-dissociable groups include cases where 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.

[0217] 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, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m32 is an integer between 1 and 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, NH4 + , represents an onium cation or onium dication; C 42 (a42m42)- This represents an isopoly acid, a heteropoly acid anion, or a heteropoly acid anion with a modified defect; m42 is an integer between 1 and 5, and a42 is a real number greater than 0.

[0218] In the polysalt represented by the general formula (I-3-2) above, 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 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.

[0219] In the polysalt represented by the above general formula (I-3-2), multiple types of A 32 m32+ and B 32 n32+ It may also include. In the above case, the values ​​of a32 and b32 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0220] The ratio of a32 to b32 is A 32 m32+ B 32 n32+ , C 32 (a32m32+b32n32)- Depending on the type, etc., it is preferable that a32:b32 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. 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 it is more preferable that a32 is a real number between 0 and 4 and b32 is a real number between 2 and 8.

[0221] Furthermore, in the polysalt represented by the general formula (I-4-2) 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. 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.

[0222] <When the anionic portion of the polysodium (A2) contains one or more polar groups with acid-dissociable groups> An example of a case in which the anionic portion of the above-mentioned polysodium acid salt (A2) contains one or more polar groups having an acid-dissociable group is when the anionic portion of the polysodium acid salt (A2) is a heteropoly acid anion with a modified defect site, and the heteropoly acid anion with the modified defect site contains one or more polar groups having an acid-dissociable group.

[0223] Examples of the above-mentioned polysulfate (A1) include the polysulfate represented by the following general formula (I-3-3), and examples of the above-mentioned polysulfate (A2) include the polysulfate 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, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m33 is an integer between 1 and 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, NH4 + , 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 between 1 and 5, and a43 is a real number greater than 0.

[0224] 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.

[0225] 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.

[0226] The ratio of a33 to b33 is A 33 m33+ B 33 n33+ , C 33 (a33m33+b33n33)- Depending on the type, etc., 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 it is more preferable that a33 is a real number between 0 and 4 and b33 is a real number between 2 and 8.

[0227] 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 "heteropoly acid 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 may be used as appropriate 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.

[0228] 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.

[0229] <When the cation portion of the polysodium acid salt (A2) contains one or more polar groups having acid-dissociable groups> Examples of cases in which the cation portion of the above-mentioned polysalt (A2) contains one or more polar groups having acid-dissociable groups include cases where 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.

[0230] 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, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; m34 is an integer between 1 and 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, NH4 + , 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)- This represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; 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.

[0231] 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.

[0232] 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.

[0233] The ratio of a34 to b34 is A 34 m34+ B 34 n34+ , C 34 (a34m34+b34n34)- Depending on the type, etc., it is preferable that a34:b34 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a34m34+b34n34 is an integer between 2 and 8, and m34 and n34 are 1, it is preferable that a34 is a real number between 0 and 7 and b34 is a real number between 1 and 8, and it is more preferable that a34 is a real number between 0 and 4 and b34 is a real number between 2 and 8.

[0234] In the polysalt represented by the general formula (I-4-4) above, the "metal ion," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," "isopolyate anion," "heteropolyate anion," and "heteropolyate anion with a modified defect site" 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 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.

[0235] 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 be included. In the above case, the values ​​of a44 and b44 can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, etc.

[0236] The ratio of a44 to b44 is A 44 m44+ B 44 n44+ , C 44 (a44m44+b44n44)- Depending on the type, etc., it is preferable that a44:b44 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a44m44+b44n44 is an integer between 2 and 8, and m44 and n44 are 1, it is preferable that a44 is a real number between 0 and 7, and b44 is a real number between 1 and 8, and it is more preferable that a44 is a real number between 0 and 4, and b44 is a real number between 2 and 8.

[0237] [1-1-3-3. When the anionic portion of the polysalts (A1) and (A2) contains one or more polar groups having acid-dissociable groups, and the cation portion of the polysalts (A1) and (A2) contains a sulfonium cation, sulfonium dication, or iodonium cation which may have a polar group having an acid-dissociable group] Another resist material according to this embodiment is characterized in that, as (A) polyate, it contains at least two different polyate salts (A1) and (A2), each of the anionic portions of the polyate salts (A1) and (A2) contains one or more polar groups having acid-dissociable groups, and the cation portions of the polyate salts (A1) and (A2) contain sulfonium cations, sulfonium dications, or iodonium cations which may have polar groups having acid-dissociable groups.

[0238] 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 by exposure to active light or the like. Furthermore, by including one or more polar groups having acid-dissociable groups in the anionic portions of the above-mentioned polyate salts (A1) and (A2), the solubility in the developer can be drastically altered by the action of acid.

[0239] 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-dissociable groups can be dissociated from polar groups having multiple acid-dissociable groups due to the action of the acid, resulting in the formation of multiple polar groups, which can drastically change the solubility in the developer.

[0240] 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, NH4 + , represents ammonium cation, ammonium dication, phosphonium cation, or phosphonium dication; B 35 n35+ Each of these 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)- This represents a heteropoly acid anion modified by a missing site containing one or more polar groups having acid-dissociable groups; m35 is an integer between 1 and 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 of these 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)-This represents a heteropoly acid anion modified by a missing site containing one or more polar groups having acid-dissociable groups; m45 is an integer between 1 and 5, n45 is an integer of 1 or 2, a45 is a real number, and b45 is a real number greater than 0.

[0241] 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.

[0242] 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 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 may be used as appropriate 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.

[0243] 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.

[0244] The ratio of a35 to b35 is A 35 m35+ B 35 n35+ , C 35 (a35m35+b35n35)- Depending on the type, etc., it is preferable that a35:b35 = 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a35m35+b35n35 is an integer between 2 and 8, and m35 and n35 are 1, it is preferable that a35 is a real number between 0 and 7 and b35 is a real number between 1 and 8, and it is more preferable that a35 is a real number between 0 and 4 and b35 is a real number between 2 and 8.

[0245] 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.

[0246] The ratio of a45 to b45 is A 45 m45+ B 45 n45+ , C 45 (a45m45+b45n45)- Depending on the type, etc., 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 it is more preferable that a45 is a real number between 0 and 4, and b45 is a real number between 2 and 8.

[0247] [1-1-4. (A) Content of components, etc.] The content of component (A) in the resist material is not particularly limited and can be appropriately set depending on the method of coating the resist material onto the substrate, the film thickness to be coated, 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.

[0248] 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.

[0249] [1-2. (B) Acid Generator] The resist material according to this embodiment may contain, in addition to component (A), an acid generator (B) as an optional component. 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. Acid generators have the function of generating acid upon exposure to active light (DUV, XUV, EUV, electron beams, etc.).

[0250] 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 an ionic acid generator as the acid generator. These may be used individually or in combination of two or more types.

[0251] [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, and the like. Furthermore, the cationic portion of the ionic acid generator is not particularly limited and may consist of, for example, an onium cation or a dication.

[0252] 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. [ka] [ka] [ka]

[0253] [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. [ka]

[0254] "R A b1 " may have substituents C1-18 A hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group, in which any divalent carbon atom except terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0255] R A b1 C may have substituents. 1-18 A hydrocarbyl group is preferred in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). C 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 is more preferably one in which any divalent carbon atom other than the terminal atoms may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). C in which 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.

[0256] 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.

[0257] 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, adamantane-1-yl group, adamantane-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-[1,2]benzenoanthracene-9-yl group, and the 9,10-dihydro-9,10-[1,2]benzenoanthracene-10-yl group.

[0258] "L A b1 " is a single bond or a C which may have a substituent 1-12In a hydrocarbylene group, any divalent carbon atom, including terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0259] L A b1 This may include a single bond or a C that may have a substituent. 1-12 A hydrocarbylene group is preferred in which any divalent carbon atom, including terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). A single bond or a C which may have substituents 1-12 Alkanediyl group, C 6-12 An arenediyl group is more preferably one in which any divalent carbon atom, including terminal atoms, may be replaced by -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously). C may have substituents 1-12 More preferably, the alkanediyl group is one in which at least one or more terminal divalent carbon atoms are replaced by -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-, CONH-, -NH(C=O)-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0260] "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.

[0261] L A b2For example, C in which at least one hydrogen atom is substituted with a halogen atom. 1-5 It is preferably a hydrocarbylene group. C in which at least one hydrogen atom is replaced by a halogen atom 1-5 It is more preferable that it be an alkanediyl group. C 1-5 A C atom that has an alkanediyl group or in which at least one hydrogen atom is substituted with a fluorine atom. 1-5 It is more preferably an alkanediyl group. C 1-5 C 1-5 C 1-5 It is even more preferable that the group be an alkanediyl group.

[0262] 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, and 2-((decahydronaphthalene-2-carbonyl)oxy)-1,1-difluoroethane -1-sulfonate anion, 2-((decahydronaphthalene-2-carbonyl)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]Heptan-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-phenoxy Tan-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, 2-((adamantane-1-carbonyl)oxy)-1,1-difluoroethane-1-sulfonate anion, 2-(((adamantane-1- (Iyl)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)-1,1,2,2-tetrafluorohexane-1-sulfonate anion, 2-(2-((adamantan-1-carbonyl)oxy)ethoxy)-1,1-difluoro-2-oxoethane- Examples include 1-sulfonate anions, 4-((adamantane-1-carbonyl)oxy)-1,1,2-trifluorobutane-1-sulfonate anions, 1,1-difluoro-2-(2-((2-methyladamantane-2-yl)oxy)-2-oxoethoxy)-2-oxoethane-1-sulfonate anions, and 2-((9,10-dihydro-9,10-ethanoanthracene-12-carbonyl)oxy)-1,1-difluoroethane-1-sulfonate anions.

[0263] [ka]

[0264] [ka]

[0265] [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. [ka]

[0266] "R B b1 " and "R B b2 Each of these may independently have a cyano group or a substituent. 1-12 A hydrocarbyl group in which any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously), or R B b1 and R B b2 However, C may be directly linked by a single bond, or by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C which may have substituents. 1-3 They may be linked via alkylene groups, forming a ring together with the nitrogen atom in formula (IX-2).

[0267] R B b1 and R B b2 Each of these may independently have a cyano group or a substituent. 1-12Preferably, the hydrocarbyl group has divalent carbon atoms at any position except the terminals that may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). C, which has a cyano group or at least one hydrogen atom substituted with a halogen atom. 1-12 Alkyl or C 6-12 More preferably, the aryl group is one in which any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). C, which has a cyano group, or at least two hydrogen atoms substituted with fluorine atoms. 1-12 Alkyl or C 6-12 An aryl group is more preferably one in which divalent carbon atoms at any position other than the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0268] Also R B b1 and R B b2 However, C may be directly linked by a single bond, or by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C which may have substituents. 1-3 Linked via an alkylene group, the nitrogen atom in formula (IX-2), R B b1 , R B b2 , L B b1In the case where a ring is formed with -S(=O)2-, it is preferable that a 5- to 7-membered ring is formed overall and one or more hydrogen atoms are substituted with halogen atoms, and it is more preferable that a 6-membered ring is formed and two or more hydrogen atoms are substituted with fluorine atoms.

[0269] "L B b1 " is a single bond or a C which may have a substituent 1-3 In a hydrocarbylene group, any divalent carbon atom, including terminal atoms, may be replaced by -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0270] L B b1 This may include a single bond or a C that may have a substituent. 1-3 A hydrocarbylene group is preferred in which any divalent carbon atom, including terminal atoms, may be replaced with -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). It is more preferable that the bond is a single bond, or -C(=O)-, -C(=O)-O-, -CONH-, or -SO2-. It is even more preferable that the bond is a single bond, or -C(=O)- or -SO2-.

[0271] 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.

[0272] [ka]

[0273] [1-2-1-3. Methido salt compound B C ] As an acid generator, "methide salt compound B" represented by the following general formula (IX-3) is used. C " and a methido anion and an onium cation or dication (D p+ ) and salt can be used. [ka]

[0274] "R C b1 "R C b2 " and "R C b3 Each of these may independently have a cyano group or a substituent. 1-12A hydrocarbyl group in which any divalent carbon atom at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously), or R C b1 , R C b2 and R C b3 Any two of these may be directly linked by a single bond, or by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C(=O)O- which may have substituents. 1-3 Linked via an alkylene group, the methide (C) in formula (IX-3) - They may form a ring together.

[0275] R C b1 , R C b2 and R C b3 Each of these may independently have a cyano group or a substituent. 1-12 Preferably, the hydrocarbyl group has divalent carbon atoms at any position except the terminals that may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). C, which has a cyano group or at least one hydrogen atom substituted with a halogen atom. 1-12 Alkyl or C 6-12 It is more preferable that the aryl group has divalent carbon atoms at any position other than the terminals replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time). C, which has a cyano group, or at least two hydrogen atoms substituted with fluorine atoms. 1-12 Alkyl or C6-12 It is even more preferable that the aryl group has divalent carbon atoms at any position other than the terminals replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0276] Also R C b1 , R C b2 and R C b3 Any two of these may be directly linked by a single bond, or by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C(=O)O- which may have substituents. 1-3 Linked via an alkylene group, the methide (C) in formula (IX-3) - When a ring is formed together with ), it is preferable that a 5-7 membered ring is formed overall and one or more hydrogen atoms are substituted with halogen atoms, and it is more preferable that a 6 membered ring is formed and two or more hydrogen atoms are substituted with fluorine atoms.

[0277] "L C b1 "L C b2 " and "L C b3 Each of these may independently have a single bond or a substituent. 1-3 In a hydrocarbylene group, any divalent carbon atom, including terminal atoms, may be replaced by -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0278] L C b1 , L C b2 and L C b3 This may include a single bond or a C that may have a substituent. 1-3A hydrocarbylene group is preferred in which any divalent carbon atom, including terminal atoms, may be replaced with -C(=O)-, -C(=O)-O-, -CONH-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced simultaneously). It is more preferable that the bond is a single bond, or -C(=O)-, -C(=O)-O-, -CONH-, or -SO2-. It is even more preferable that the bond is a single bond, or -C(=O)- or -SO2-.

[0279] The above-mentioned metanide anions are not particularly limited and include, for example, tris(methylsulfonyl)methide anion, tris((trifluoromethyl)sulfonyl)methide anion, tris((perfluoroethyl)sulfonyl)methide anion, tris(phenylsulfonyl)methide anion, dicyano((trifluoromethyl)sulfonyl)methide anion, and the like.

[0280] [ka]

[0281] [1-2-1-4. Onium cation or onium dication (D p+ )] The cation portion of the above (B) acid generator is an onium cation or a dication (D p+ ) can be used. Here, the general formula (IX-1) to (IX-3) represents "(D p+ ) 1 / p In this expression, D represents an onium cation or dication, and p represents an integer of 1 or 2.

[0282] 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.

[0283] [1-2-2. (B) Content of component] The content of the acid generator (B) 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).

[0284] [1-3. (C) Acid diffusion control agents] 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) the 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-mentioned component (C) is not particularly limited, and known and commonly used 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.

[0285] [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 control of acid diffusion. Therefore, by incorporating (C1) photodecayable bases into the resist material, properties such as increased sensitivity, reduced roughness, and suppression of coating defects can be improved.

[0286] The above-mentioned photodecayable base is not particularly limited, and known and commonly used bases can be used. Examples of photodecayable bases include "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) CExamples include carboxylic acid anions, sulfonate anions, sulfonylamide anions, onium cations, or onium dication D. p+ I will explain in that order. [ka] [ka] [ka]

[0287] [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. [ka]

[0288] "R A c1 " may have substituents C 1-18 A hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group, in which any divalent carbon atom other than the terminals other than the bond may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0289] R A c1 C may have substituents. 1-18A hydrocarbyl group is preferred in which any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). C 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 is more preferably one in which any divalent carbon atoms other than the terminals other than the bonding site may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0290] <Carboxylic acid 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. [ka]

[0291] "X A c1 " may have substituents C 1-18 Alkyl alkyl group, C 3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18 In an aralkyl group, any divalent carbon atom other than the terminals other than the bonding site may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0292] X A c1 C may have substituents.3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18 The aralkyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). C may have substituents 3-18 Alicyclic group, or C 6-18 An aryl group is more preferably one in which any divalent carbon atoms, excluding the terminals other than the bonding site, may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0293] "L A c1 " is X A c1 to-COO - A base that connects and the following general formula (L c -1)~(L c A linking group represented by -7) can be used. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [In the formula, L c1and L c2 C may have a single bond or a substituent. 1-8 *1 represents a hydrocarbylene group, and X A c1 The connection point is, *2 is -COO - This represents the connection point.

[0294] L c1 and L c2 This may include 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.

[0295] <Examples of carboxylate anions> The above carboxylate compound C A or C A1 The carboxylic acid anions are not particularly limited and include, for example, 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.

[0296] [ka]

[0297] [ka]

[0298] [ka]

[0299] [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. [ka]

[0300] "R B c1 " may have substituents C 1-18 A hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group, in which any divalent carbon atom other than the terminals other than the bond may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0301] R B c1 C may have substituents. 1-18 A hydrocarbyl group is preferred in which any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). C may have substituents 1-18 Alkyl alkyl group, C 3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18An aralkyl group is more preferably one in which any divalent carbon atoms other than the terminals other than the bonding site may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0302] <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. [ka]

[0303] "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 In an aralkyl group, any divalent carbon atom other than the terminals other than the bonding site may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0304] X B c1 C may have substituents. 3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18 The aralkyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). C may have substituents 3-18 Alicyclic group, or C6-18 An aryl group is more preferably one in which any divalent carbon atoms, excluding the terminals other than the bonding site, may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0305] "L B c1 " as X B c1 and -SO2-O - A base that connects and the above general formula (L c -1)~(L c A linking group represented by -7) can be used. In this case, the general formula (L c -1)~(L c -7) Medium, L c1 and L c2 C may have a single bond or a substituent. 1-8 *1 represents a hydrocarbylene group, and X B c1 The connection point is, *2 is -SO2-O - This represents the connection point.

[0306] L c1 and L c2 This may include 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.

[0307] <Examples of sulfonate anions> The above sulfonate compound C B or C B1The sulfonate anions are not particularly limited and include, for example, camphor sulfonate anion, (adamantan-1-yl)methanesulfonate anion, (adamantan-1-carbonyloxy)ethane-1-sulfonate anion, cyclohexanesulfonate anion, 2-(cyclohexanecarbonyloxy)ethane-1-sulfonate anion, bicyclo[2.2.1]heptane-2-sulfonate anion, benzenesulfonate anion, 4-methylbenzenesulfonate anion, and the like.

[0308] [ka]

[0309] [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. [ka]

[0310] "R C c1 " may have substituents C 1-18 A hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group, in which any divalent carbon atom other than the terminals other than the bond may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously). "R C c2 " may have substituents C 1-18In a hydrocarbyl group, any divalent carbon atom other than the terminals other than the bond may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0311] R C c1 C may have substituents. 1-18 A hydrocarbyl group is preferred in which any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). C 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 is more preferably one in which any divalent carbon atoms other than the terminals other than the bonding site may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0312] R C c2 C may have substituents. 1-18 Alkyl alkyl group, C 3-18 Preferably, the alicyclic group is one in which any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). 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.

[0313] <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. [ka]

[0314] "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 In an aralkyl group, any divalent carbon atom other than the terminals other than the bonding site may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms cannot be replaced simultaneously).

[0315] X C c1 C may have substituents. 3-18 Alicyclic group, C 6-18 Aryl group, or C 7-18 The aralkyl group is preferably one in which any divalent carbon atom other than the terminals other than the bond may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms may not be replaced at the same time). C may have substituents 3-18 Alicyclic group, or C 6-18 An aryl group is more preferably one in which any divalent carbon atoms, excluding the terminals other than the bonding site, may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced simultaneously).

[0316] "L C c1 " is X C c1 and -N - -SO2-R C c2 A base that connects and the above general formula (L c -1)~(L c A linking group represented by -7) can be used. In this case, the general formula (L c -1)~(L c -7) Medium, L c1 and L c2 C may have a single bond or a substituent. 1-8 *1 represents a hydrocarbylene group, and X C c1 The connection point is, *2 is -N - -SO2-R C c2 This represents the connection point.

[0317] L c1 and L c2 This may include 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.

[0318] <Examples of sulfonylamide anions> The above sulfonilamide 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-((adamantan-1-carbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(adamantan-1-carboxamide)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(4-((adamantan-1-carbonyl)oxy)cyclohexyl)ethyl((trifluoromethyl)sulfonyl)amide anion, and 4-((adamantan-1-carbonyl)oxy)phenyl((trifluoromethyl)sulfonyl)amide anion.

[0319] [ka]

[0320] [ka]

[0321] [ka]

[0322] [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)~(X-3) represents "(D p+ ) 1 / p In this expression, D represents an onium cation or onium dication, and p represents an integer of 1 or 2. The above-mentioned 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.

[0323] [1-3-2.(C2) Nitrogen-containing organic compound] Other (C) acid diffusion control agents may include nitrogen-containing organic compounds that do not fall under (C2)(C1). The nitrogen-containing organic compounds are not particularly limited, and for example, aliphatic amines, aromatic amines, heterocyclic amines, etc., can be used.

[0324] 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.

[0325] [1-3-3. (C) Amount of ingredient] The content of the acid diffusion control agent (C) 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).

[0326] [1-4. Organic Solvents] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and known and commonly used solvents can be used. Preferably, the organic solvent is one that can be uniformly dissolved or dispersed when prepared with (A) the polyate.

[0327] 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.

[0328] 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 solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; Ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); Nitrile-based solvents such as acetonitrile, propionitrile, and benzonitrile: Examples include aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. Other examples of 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.

[0329] 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.

[0330] The content of 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 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.

[0331] [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. The resist material according to this embodiment preferably does not contain epoxy resin. Furthermore, it is preferable that it does not contain hydrogen peroxide.

[0332] [2. Pattern Formation Method] The pattern formation 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 to light; and developing the exposed resist film.

[0333] [2-1. Coating process] The pattern formation method according to this embodiment includes a step of applying a resist material to a substrate.

[0334] <Circuit board> The substrate used in this embodiment is not particularly limited, and any known or commonly used substrate may be used. For example, a substrate for electronic components or a substrate with a predetermined wiring pattern formed on it may be used. The substrate material is not particularly limited and includes, for example, 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.

[0335] 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).

[0336] <Application 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 photoCVD; 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.

[0337] 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.

[0338] 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 baking (PAB)), a vacuum device, etc. The baking conditions are not particularly limited and can be set appropriately depending on the type and application of the resist film. 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.

[0339] 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.

[0340] [2-2. Exposure Process] The pattern formation method according to this embodiment includes a step of exposing the resist film formed by the coating step described above.

[0341] For example, an ArF exposure apparatus, electron beam lithography apparatus, or EUV exposure apparatus 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.

[0342] The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser (wavelength 193 nm), KrF excimer laser (248 nm), F2 excimer laser (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays may be used.

[0343] For the resist film, the exposure dose is 1-200 mJ / cm² when using an ArF excimer laser or KrF excimer laser. 2 Preferably, the concentration is 20-60 mJ / cm². 2 It is more preferable that this be the case. Also, in the case of extreme ultraviolet light, the exposure amount is, for example, 500 mJ / cm². 2 The following applies: 0.1 to 200 mJ / cm² 2 Preferably, the concentration is 3 to 100 mJ / cm². 2 It is more preferable that the concentration be 5-50 mJ / cm². 2 It is even more preferable that this be the case. For electron beams, 3 μC / cm at 50 kV. 2 ~2mC / cm 2 It is preferable to expose the area at a dose of 10 μC / cm². 2 ~1.5 mC / cm 2 Exposure at this dose is more preferable.

[0344] 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.

[0345] [2-3. Development process] The pattern formation method according to this embodiment includes a step of developing the exposed resist film. In the development step, a pattern can be formed by developing the exposed resist film with a developer. 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 treatment may be performed further.

[0346] 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.

[0347] <Alkaline Development Process> Conventional metal oxide resist materials have presented challenges in achieving high-resolution positive patterns through alkaline development processes. In contrast, the resist material according to this embodiment can be patterned with good resolution using a developer containing water.

[0348] 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.

[0349] 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).

[0350] Furthermore, pure water can be used as the rinsing solution in the alkaline development process.

[0351] <Organic Solvent Developing Process> Examples of developers used in the organic solvent development process include those containing one or more polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0352] Examples of organic solvents include, for instance, 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-based 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); Nitrile-based solvents such as acetonitrile, propionitrile, and benzonitrile: Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; Ether-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; Hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene; These are some examples. These can be used individually or in combination of two or more.

[0353] Among these, the organic solvent used in the developing solution is preferably a polar solvent, and more preferably contains amide solvents, alcohol solvents, ester solvents, or 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. Furthermore, 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. Furthermore, the alcohol-based 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.

[0354] 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.

[0355] 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).

[0356] 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.

[0357] 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.

[0358] 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 alcohol include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. These organic solvents may be used individually or in combination of two or more.

[0359] 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).

[0360] [3. Patterned Structures] The patterned structure according to this embodiment is obtained by forming a pattern on a substrate using the pattern formation method described above.

[0361] 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.

[0362] 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 forming a pattern using the pattern formation method described above, the resist material according to this embodiment can be patterned to produce parts of the patterned structure with pitches of 50 nm, 20 nm, and 15 nm.

[0363] [4. Resist materials for electron beam or EUV applications] The resist material according to this embodiment contains at least two different polyate salts (A1) and (A2) as (A) polyate salts. Each polyate salt (A1) and / or (A2) contains 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 an acid or the like.

[0364] 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.

[0365] Therefore, the resist material according to this embodiment is a resist material that generates acid upon exposure such as electron beam or EUV, and whose solubility in a developer solution changes due to the action of the acid, and can be suitably used as a resist material for electron beam or EUV exposure. [Examples]

[0366] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0367] [1. Synthesis of Polyate] <Manufacturing Example 1: Potassium Undecatungus Silicate (α-K8[SiW 11 O 39 Manufacturing of ]) SiW tungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.): H4[SiW 12 O 40 63 g of (xH2O) 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, filtered by suction filtration, and vacuum dried to obtain 34 g of the target compound. 29 Si-NMR(119.22MHz,D2O):δ(ppm)=-84.6(s,1Si). 183 W-NMR (20.84MHz, D2O): 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).

[0368] <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))> [ka] 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-K8[SiW) synthesized above. 11 O 399.8g of ]) was added. The pH was adjusted to 1.8 with 1M hydrochloric acid, and after stirring for 2 hours, the filtrate after filtration was concentrated to approximately 200g. 5.7g of triphenylsulfonium chloride and 40g of pure water were added to this concentrate to precipitate the powder. The precipitated powder was filtered off, washed three times with 180mL of pure water, and filtered off again. Further thorough vacuum drying yielded 10.7g 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 S2Si3W 11 ] 4- )

[0369] <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))> [ka] 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). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-53.02(s,2Si),-85.04(s,1Si). ESI-MS:POSITIVE m / z 399.1([C 20 H 13 F6S] + ) NEGATIVE m / z 801.1 (median) ([C 24 H 42 O 44 S2Si3W 11 ] 4- )

[0370] <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))> [ka] Polyate (A-3) was obtained by the same method as described above, except that 3-(2-((1-phenylcyclopentyl)oxycarbonyl)ethylthio)propyltrimethoxysilane was used as the starting compound in Synthesis Example 1, 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 S2Si3W 11 ] 4- )

[0371] <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))> [ka] Polyate (A-4) was obtained by the same method as described above, except that (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide was used as the starting compound in Synthesis Example 1, instead of triphenylsulfonium chloride. ESI-MS:POSITIVE m / z 461.2([C 29 H 33 O3S] + ) NEGATIVE m / z 801.1 (median) ([C 24 H 42 O 44 S2Si3W 11 ] 4- )

[0372] <Synthesis Example 5: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium) keitangstate(polyate (A-5))> [ka] 35.47 g of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium chloride is dissolved in 50 g of cyclohexanone, and silactungstic acid (H4[SiW 12 O 40 41.06 g of 26H2O 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). 183W-NMR (20.84MHz, DMSO-D6): δ(ppm)=-92.7(s, 12W). ESI-MS:NEGATIVE m / z 718.5 (median) ([SiW 12 O 40 ] 4- ) XPS analysis S:W (molar ratio of S to W) = 4:12

[0373] <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))> [ka] 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 (119.22MHz, DMSO-d6): δ(ppm)=-53.04(s,2Si),-85.01(s,1Si). ESI-MS:POSITIVE m / z 399.1([C 20 H 13 F6S] + ) NEGATIVE m / z 926.2 (median) ([C 58 H 70 O 48 S2Si3W 11 ] 4- )

[0374] <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))> [ka] 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(119.22MHz,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 S2Si3W 11 ] 4- )

[0375] [2. Preparation of resist material] As resist materials, the poly salts (A-1) to (A-7) synthesized above, 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.

[0376] The following polysodium compounds (A-8) to (A-10) listed in Table 5 were used. All of the following polysodium compounds (A-8) to (A-10) were manufactured by Nippon Inorganic Chemical Industry Co., Ltd. • Polyate (A-8): Ammonium metatungstate [ka] • Polyate (A-9): Silicate tungstic acid [ka] • Polyate (A-10): Phosphate tungstic acid [ka]

[0377] Furthermore, as the acid diffusion control agent (C-1) described in Tables 1-5, an acid diffusion control agent consisting of a salt of a triphenylsulfonium cation represented by the following formula (C-1) and a salicylate anion was used. [ka]

[0378] [Table 1]

[0379] [Table 2]

[0380] [Table 3]

[0381] [Table 4]

[0382] [Table 5]

[0383] [3. Formation of the resist pattern] On an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS), the resist materials from Examples 1-1 to 5-4 and Comparative Examples 1-1 to 5-5 were applied using a spinner. A post-application bake (PAB) treatment was then 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 (JAWoollam's "M-2000D"). The above resist film was subjected to lithography (exposure) using an electron beam lithography system F7000S-VD2 (manufactured by Advantest Corporation) at an acceleration voltage of 50kV, creating a 1:1 line-and-space pattern (hereinafter also referred to as "LS pattern") with a target size of 50nm line width. Subsequently, a post-exposure baking (PEB) treatment was performed at 90°C for 60 seconds. Next, at 23°C, development was performed for 60 seconds using developer (NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.)), followed by rinsing with pure water for 60 seconds. Based on the above, a 1:1 LS pattern with a line width of 50 nm was formed, and LS patterns corresponding to each resist material were obtained. Note that all of the above LS patterns are positive-type patterns.

[0384] [4. Evaluation of LS pattern shape] <Roughness Assessment> The shape of the LS patterns in Examples 1-1 to 5-4 and Comparative Examples 1-1 to 5-5 was measured 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 roughness was calculated as three times the standard deviation (σ) obtained from these measurement results (3σ) (unit: nm). Here, a smaller value of 3σ means that the roughness of the line sidewalls is smaller, and a more uniform LS pattern width is obtained. Tables 1 to 5 show the above roughness (3σ) values ​​for the LS patterns of Examples 1-1 to 5-4 and Comparative Examples 1-1 to 5-5.

[0385] The results in Table 1 show 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 5-95:95-5, show a significantly reduced 3σ value compared to the resist materials of Comparative Examples 1-1 and 1-2.

[0386] 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 LS pattern with better roughness 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 5-95:95-5, show a significantly reduced 3σ value compared to the resist materials of Comparative Examples 2-1 and 2-2.

[0387] 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 5-95:95-5, show a significantly reduced 3σ value compared to the resist materials of Comparative Examples 3-1 and 3-2.

[0388] 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 better 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.

[0389] 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 better 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. Furthermore, the resist films prepared using Comparative Examples 5-2 to 5-5, each containing one of the polyate salts (A-7) to (A-10), did not resolve.

[0390] 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 an acid-dissociable polar 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) A resist material containing at least two different polyates (A1) and (A2) as polyates, wherein the polyates (A1) and / or (A2) contain one or more polar groups having acid-dissociable groups. Resist material.

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 aforementioned polyate (A1) is a polyate represented by the following general formula (I-1-1) or (I-1-2). The resist material according to claim 1. (A １１ ｍ１１＋ ) ａ１１ (C １１ （ａ１１ｍ１１）－ ) (I-1-1) [In general formula (I-1-1), A １１ ｍ１１＋ is, independently of each other, H ＋ , a metal ion, NH ４ ＋ , an onium cation, or an onium dication; C １１ （ａ１１ｍ１１）－ This represents a heteropoly acid anion modified by a defect site containing one or more polar groups having acid-dissociable groups; m11 is an integer between 1 and 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 general formula (I-1-2), A １２ ｍ１２＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents 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）－ represents an isopolyate anion, a heteropolyate anion, or a heteropolyate anion with a modified defect; 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.

5. In the polysalt represented by the general formula (I-1-1), a 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, and the heteropoly acid anion modified with the defect site is 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, and by bonding to a heteropoly acid anion having the defect site via some or all of the heteroatoms. The aforementioned organic group has one or more polar groups having acid-dissociable groups. The resist material according to claim 4.

6. The organic group may have substituents. １－１８ It is a hydrocarbyl group, C which may have the substituent １－１８ Any divalent carbon atom other than the terminal of the hydrocarbyl group is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time). C which may have the substituent １－１８ One or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group. The resist material according to claim 5.

7. The aforementioned polyate (A2) is a polyate represented by the following general formula (I-2). The resist material according to claim 4. (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 defect; 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) and 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. Furthermore, (B) contains an acid generator, The resist material according to claim 1.

11. Furthermore, it contains (C) an acid diffusion control agent, The (C) acid diffusion control agent is a (C1) photodecayable base. The resist material according to claim 1.

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