Resist material, pattern formation method, and patterned structure

Abstract

The present invention aims to provide a novel resist material, a pattern forming method, and a patterned structure, wherein the heteropolyphosphate or mixture thereof has a defect site (A) modified by general formula (I), and wherein a sulfonium cationic acid, sulfonium dication, or iodonium cationic acid has one or more polar groups having acid dissociable groups introduced into the cationic portion of the heteropolyphosphate or mixture thereof having the defect site modified. (Am+)a(Bn+)b(C(am+bn)-) (I)

Description

Technology Field

[0001] The present invention relates to a resist material, a pattern forming method, and a patterned structure. Background Technology

[0002] Polyacids have the general formula [M x O y ] n- It is an anionic metal oxide cluster represented by (where x, y, and n are all natural numbers). The metal atom M constituting the polyacid is called a poly atom, and examples include Mo (6-valent or 5-valent), W (6-valent or 5-valent), V (5-valent), Nb (5-valent), Ta (5-valent), etc. Polyacids include isopolyacids composed of the above polyatom M and an oxyacid, and heteroatoms X of a different type other than oxygen and the above polyatom M (for example, P as the heteroatom X). 5＋ , Si 4＋ , Ge 4＋ , B 3＋ Heteropoly acids ([X w M x O y ] n- (In the expression, w, x, y, and n are all natural numbers.)) It can be broadly distinguished as.

[0003] Polyacids can change their physicochemical properties, such as oxidation-reduction ability, active light reactivity, and acidic properties, depending on the combination of their constituent elements, structure, and the type of countercation.

[0004] In addition, it is known that polyacids contain multiple defective species in which a portion of the basic framework is missing. The terminal oxygen atoms at the defective sites where a portion of the basic framework of the polyacid is missing possess a certain degree of negative charge density on said oxygen atom and exhibit nucleophilicity due to their high reactivity. For this reason, by reacting the said terminal oxygen atoms with electrophilic atoms or molecules, various functional polyacid complexes or organic / inorganic hybrid structures can be formed.

[0005] Patent Document 1 discloses a polyoxometallate compound having a metal-substituted polyoxometallate, wherein the polyoxometallate has a vacancy site, a substituted metal atom (divalent platinum or palladium) introduced into the vacancy site, and an organic ligand. Prior art literature

[0006] U.S. Patent No. 11420871 Specification The problem to be solved

[0007] The present invention aims to provide a novel resist material, a pattern forming method, and a patterned structure. means of solving the problem

[0008] The inventors, as a result of careful consideration to solve the above problem, discovered that by using a sulfonium cation, sulfonium dication, or iodonium cation having one or more polar groups having acid dissociable groups as a counter cation of a heteropolyacid anion with a modified defect site, an acid can be generated by exposure to DUV, XUV, EUV, electron beams, etc., and the solubility in a developer can be changed by the action of said acid, thereby completing the present invention.

[0009] That is, the present invention relates to each of the following inventions.

[0010] <1> A resist material containing a heteropolyphosphate or a mixture thereof in which the (A) defect site represented by general formula (I) is modified.

[0011] (A m＋ ) a (B n＋ ) b (C (am＋bn)- ) (I)

[0012] [In the (I) formula,

[0013] A m＋ is, each independently H ＋ , representing a metal ion, ammonium cation, ammonium dicathione, phosphonium cation, or phosphonium dicathione;

[0014] B n＋ represents a sulfonium cation, sulfonium dication, or iodonium cation having one or more polar groups having acid-dissociable groups, each independently;

[0015] C (am＋bn)- ... represents a heteropolyacid anion having a defect site, wherein the defect site is modified;

[0016] m is an integer from 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

[0017] <2> A resist material described in <1>, wherein the sulfonium cationic, sulfonium dication, or iodonium cationic having one or more polar groups having acid dissociable groups is an organic sulfonium cationic, organic sulfonium dication, or organic iodonium cationic having one or more polar groups having acid dissociable groups.

[0018] <3> A resist material described in <1>, wherein the above acid dissociable group is a tertiary carbon-type acid dissociable group, an allyl-type or benzyl-type acid dissociable group, an acetal-type acid dissociable group, or an aminocarbonyl-type acid dissociable group.

[0019] <4> A resist material described in <1>, wherein the poly atoms of the above heteropolyacid anion are Mo, W, V, Nb or Ta, and the hetero atoms are P, Si, B, S or Ge.

[0020] <5> A resist material described in <1>, wherein the heteropolyacid anion having the above-mentioned defect is a defective Kegyn-type heteropolyacid anion or a defective Dawson-type heteropolyacid anion.

[0021] <6> A resist material described in <1>, wherein the above formula is formed by a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more organic groups are bonded, bonding to a heteropolyacid anion having the above defect site by interposing part or all of the said heteroatoms.

[0022] <7> Additionally, (B) a resist material described in <1> containing an acid diffusion control agent.

[0023] <8> A resist material described in <7>, wherein the above (B) acid diffusion control agent is (B1) a photodisintegrating base.

[0024] <9> A resist material described in <1> that additionally contains an organic solvent.

[0025] <10> Resist material for electron beams or EUV, as described in <1> to <9>.

[0026] A process of forming a resist film using a resist material described in any one of <11>, <1> to <9>, and

[0027] A process for exposing the above resist film, and

[0028] A process of developing the above-mentioned exposed resist film using a developer.

[0029] A pattern forming method including

[0030] <12> A pattern forming method described in <11>, wherein the process of exposing the resist film comprises exposing the resist film to an electron beam with a dose of 2 mC / ㎠ or less or an extreme ultraviolet beam with a dose of 200 mJ / ㎠ or less.

[0031] A patterned structure obtained by patterning a resist material described in any one of <13>, <1>, to <9>.

[0032] <14> A resist material described in <5> in which the above-mentioned defective Kegyn-type heteropolyacid anion is represented by general formula (II-1), (II-2) or (II-3).

[0033] [XM 11 O 39 ] c11- (II-1)

[0034] [XM 10 O 36 ] c12- (II-2)

[0035] [XM9O 34 ] c13- (II-3)

[0036] (during the meal,

[0037] X represents a heteroatom of P, Si, B, S, or Ge;

[0038] M represents a polyatom of Mo, W, V, Nb, or Ta;

[0039] c11- ~ c13- represent negative charge numbers, and c11 ~ c13 are natural numbers.

[0040] <15> A resist material described in <5>, wherein the above-mentioned defective Dawson-type heteropolyacid anion is represented by general formula (III-1), (III-2) or (III-3).

[0041] [X2M 17 O 61 ] c21- (III-1)

[0042] [X2M 16 O 58] c22- (III-2)

[0043] [X2M 15 O 56 ] c23- (III-3)

[0044] (during the meal,

[0045] X represents a heteroatom of P, Si, B, S, or Ge;

[0046] M represents a polyatom of Mo, W, V, Nb, or Ta;

[0047] c21- ~ c23- represent negative charge numbers, and c21 ~ c23 are natural numbers.

[0048] <16> A resist material described in <1>, wherein the heteropolyacid anion with the above-mentioned defect site modified is a heteropolyacid anion with the defect site modified by general formulas (VI-1) to (VI-12).

[0049] [XM 11 O 39 (R 1A X')2O] c31- (VI-1)

[0050] [XM 11 O 39 (R 1B1 R 1B2 X')2] c31- (VI-2)

[0051] [XM 11 O 39 (R 1D P=O)2] c31- (VI-3)

[0052] [XM 11 O 39 (R 1E X'')] c31- (VI-4)

[0053] [XM 10 O 36 (R 1A X')2O] c32- (VI-5)

[0054] [XM 10 O36 (R 1B1 R 1B2 X')2] c32- (VI-6)

[0055] [XM 10 O 36 (R 1C X'O)4] c32- (VI-7)

[0056] [XM 10 O 36 (R 1D P=O)2] c32- (VI-8)

[0057] [X2M 17 O 61 (R 1A X')2O] c33- (VI-9)

[0058] [X2M 17 O 61 (R 1B1 R 1B2 X')2] c33- (VI-10)

[0059] [X2M 17 O 61 (R 1D P=O)2] c33- (VI-11)

[0060] [X2M 17 O 61 (R 1E X'')] c33- (VI-12)

[0061] (during the meal,

[0062] X represents a heteroatom of P, Si, B, S, or Ge;

[0063] M represents a polyatom of Mo, W, V, Nb, or Ta;

[0064] X' represents a heteroatom of Si or Ge;

[0065] X'' represents a heteroatom of Si, Ge, or Sn;

[0066] R 1A ~ R 1EC, which may each independently have a hydride group or a substituent 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0067] The above R 1A ~ R 1E Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted),

[0068] The above R 1A ~ R 1E The hydrogen atoms included in are, for example, (a) halogen atoms, (b) C 1-3 (c) hydroxyl group, (d) thiol group, (e) nitro group, (f) cyano group, (g) carboxyl group, (h) amino group, (i) sulfo group, (j) vinyl group, (k) allyl group, (l) (meth)acryloyl group, (m) (meth)acryloyloxy group, (n) (meth)acrylamide group, (o) styryl group, (p) epoxy group, (q) glycidyl group, (r) amide group, (s) hydroxyl or carboxyl group having a protecting group, or (t) may be substituted with a polar group having an acid-dissociable group;

[0069] c31, c32, and c33 are natural numbers. Effects of the invention

[0070] According to the present invention, it is possible to provide a novel resist material, a pattern forming method, and a patterned structure. The resist material related to the present invention includes a heteropolyphosphate or a mixture thereof in which a defect site is modified, and furthermore, in the cation portion of the heteropolyphosphate or mixture thereof in which the defect site is modified, a sulfonium cation, a sulfonium dicathion, or an iodonium cation having one or more polar groups having acid dissociable groups is introduced. Accordingly, by exposing the resist material related to the present invention to DUV, XUV, EUV, electron beams, etc., acid is generated, and the solubility of the resist material in a developer is changed by the action of said acid, thereby making it possible to form a pattern with good resolution. Specific details for implementing the invention

[0071] Preferred embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0072] In this specification, the term “(meth)acryloyl group” is used to include both acrylyl and methacryloyl groups.

[0073] In this specification, "halogen atom" means fluorine atom, chlorine atom, bromine atom, and iodine atom.

[0074] In this specification, for example, "C 1-6 Terms such as 」 refer to the number of carbon atoms of the base group.

[0075] In this specification, "C 1-18 "Hydrocarbylene group" refers to a divalent hydrocarbon group formed by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be in a straight-chain or branched-chain form, and may be partially or wholly cyclic. Hydrocarbylene groups include alkylene groups, arylene groups, etc.

[0076] Also, "C 1-18Any divalent carbon atom at any position of the “hydrocarbylene group” may be substituted with -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0077] 「C 1-18 The "hydrocarbylene group" is not particularly limited and, for example, includes "C" such as a 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. 1-18 "Alkylene group" ; "C" of 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, anthracendiyl group, phenanthrendiyl group, naphthacendiyl group, pyrendiyl group, perylendiyl group, chrysendiyl group, etc. 6-18 Examples include the arylengi.

[0078] In this specification, "C 1-18 "Alkyl group" means a straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms.

[0079] Also, "C 1-18 Any divalent carbon atom at any position other than the terminal included in the alkyl group may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2-. However, adjacent divalent carbon atoms are not substituted simultaneously.

[0080] 「C 1-18The "alkyl group" is not particularly limited and, 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, 1,1-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, Examples include 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc.

[0081] 「C 1-18 The divalent carbon atom at any position other than the terminal included in the alkyl group is not particularly limited to being substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2-, and examples include 2-methoxyethoxymethyl group, ethoxycarbonylmethyl group, etc.

[0082] In this specification, "C 1-18 "Haloalkyl group" refers to "C 1-18 It means a group in which one or more hydrogen atoms of an alkyl group are substituted with halogen atoms.

[0083] 「C 1-18 The "haloalkyl group" is not particularly limited and examples include dichloromethyl group, trifluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, etc.

[0084] In this specification, "C 2-18 An "alkenyl group" refers to a "C" having 2 or more carbon atoms. 1-18"Alkyl group" refers to an alkenyl group having one or more double bonds, and includes alkadienyl groups, alkatrienyl groups, etc.

[0085] 「C 2-18 The "alkenyl group" is not particularly limited and examples include 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.

[0086] In this specification, "C 2-18 An "alkynyl group" refers to a "C" having 2 or more carbon atoms. 1-18 It means an alkynyl group having one or more triple bonds among the alkyl groups.

[0087] 「C 2-18 The "alkynyl group" is not particularly limited and examples include the ethinyl group, 1-propynyl group, 2-propynyl group, fentinyl group, hexinyl group, heptynyl group, octinyl group, noninyl group, decinyl group, undecinyl group, dodecinyl group, etc.

[0088] In this specification, "C 3-18 The term "alicyclic group" means a hydrocarbon group having a ring-shaped structure of a single ring or a polycyclic ring having 3 to 18 carbon atoms, wholly or partially. Alicyclic groups include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc.

[0089] Also, "C 3-18 Any divalent carbon atom at any position, excluding the terminal included in the “aliphatic group,” may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0090] 「C 3-18The "cycloalkyl group" is not particularly limited and, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-i-propylcyclopentane-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, norbornyl group, phenyl 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, Examples include the cycloheptenyl group.

[0091] In this specification, the term “3 to 18-membered non-aromatic complex cyclic group” means a 3 to 18-membered non-aromatic complex cyclic group comprising one or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and may be a monocyclic, polycyclic, or condensed ring, and may be saturated or partially unsaturated.

[0092] The “3 to 18-membered non-aromatic heterocyclic group” is not particularly limited and examples include 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.

[0093] In this specification, "C 2-18"Aryl group" means an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms or an aromatic complex cyclic group having 2 to 10 carbon atoms. In the case of an aromatic complex cyclic group, it forms a ring with one or more heteroatoms selected from the group consisting of carbon atoms having 2 to 10 carbon atoms and nitrogen atoms, oxygen atoms, and sulfur atoms, and each may be a monocyclic, polycyclic, or condensed ring.

[0094] 「C 2-18 The aryl group is not particularly limited and examples include the phenyl group, 1-naphthyl group, 2-naphthyl group, azulenyl group, pentalenyl group, heptalenyl group, indacenyl group, acenaphthyl group, phenanthrenyl group, anthracenyl group, etc.

[0095] In this specification, "C 7-18 "Aralkyl group" refers to "C 1-12 In the alkyl group, the substitutable portion is the above "C 2-12 It refers to a group substituted with "aryl group".

[0096] 「C 7-18 The aralkyl group is not particularly limited and examples include the benzyl group, phenethyl group, 3-phenylpropyl group, 4-phenylbutyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, etc.

[0097] In this specification, "C 1-18 "Hydrocarbyl group" refers to a group formed by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, aralkyl groups, etc.

[0098] Also, "C 1-18Any divalent carbon atom at any position, excluding the terminal included in the "hydrocarbyl group," may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously). This point is [defined in the following] "C 1-18 "C" used in the explanation of definitions such as "hydrocarbyloxygen" 1-18 The same shall apply to hydrocarbyl groups, etc.

[0099] 「C 1-18 As for the "hydrocarbyl group," it is not particularly limited, for example, "C 1-18 alkyl group」, 「C 2-18 "Alkenyl group", "C 2-18 alkynyl group」, 「C 3-18 Circular tableware”, “C 2-18 Arilgi」, 「C 7-18 Examples include aralkyl groups.

[0100] In this specification, "C 1-18 "Hydrocarbyloxygen" refers to "C 1-18 It refers to a group in which an oxygen atom (-O-) is bonded to a hydrocarbyl group.

[0101] 「C 1-18The "hydrocarbyloxy group" is not particularly limited and, 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, "C" of 2-ethylbutyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, etc. 1-18 "Alkoxy group" ; "C" of cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-methylcyclopentyloxycarbonylmethoxy group, 1-ethylcyclohexyloxycarbonylmethoxy group, 1-methyladamanthyloxycarbonylmethoxy group, etc. 3-18 "Alicyclic oxy groups" ; "C" of phenyloxy groups, 1-naphthyloxy groups, 2-naphthyloxy groups, azulenyloxy groups, pentalenyloxy groups, heptalenyloxy groups, indacenyloxy groups, acenaphthyloxy groups, phenanthrenyloxy groups, anthracenyloxy groups, etc. 6-18 Examples include aryloxy groups.

[0102] 「C 1-18 As for the "hydrocarbyloxygen," "C 1-18 It is preferable that a divalent carbon atom at any position in the “hydrocarbyl group,” excluding the terminal, is substituted with -O-, -C(=O)-, and / or -C(=O)O-, and “C 1-18A “hydrocarbyloxycarbonylalkyloxy group” is more preferable, and from the perspective of solubility, it is even more preferable that the carbon bonded to the oxygen atom of the hydrocarbyloxy is a tertiary carbon. Specific examples of the hydrocarbyloxy that may be substituted include ethylcyclopentyloxy, methyladamanthyloxy, ethyladamanthyloxy, t-butyloxy, etc.

[0103] In this specification, "C 1-18 "Hydrocarbylcarbonyl group" refers to "C 1-18 It refers to a group in which a carbonyl group (-C(=O)-) is bonded to a hydrocarbyl group.

[0104] 「C 1-18 The "hydrocarbylcarbonyl group" is not particularly limited and, for example, includes "C" such as an acetyl group, propionyl group, isopropionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pentanoyl group, 3-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, etc. 1-18 "Alkyl carbonyl group" ; "C" of 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" of benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. 6-18 Examples include the aryl carbonyl group.

[0105] In this specification, "C 1-18 "Hydrocarbylcarbonyloxygen" refers to "C 1-18 It refers to a group in which an oxygen atom (-O-) is bonded to a hydrocarbylcarbonyl group.

[0106] 「C 1-18"Hydrocarbylcarbonyloxy group" is not particularly limited and, for example, "C" such as 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" ; "C" of cyclopropyl carbonyloxy group, cyclobutyl carbonyloxy group, cyclopentyl carbonyloxy group, cyclohexyl carbonyloxy group, etc. 3-18 "Alicyclic carbonyloxy group" ; "C" of phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenanthrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc. 6-18 Examples include the arylcarbonyloxygen.

[0107] In this specification, "C 1-18 "Hydrocarbyloxycarbonyl group" refers to "C 1-18 It refers to a group in which a carbonyl group (-C(=O)-) is bonded to a hydrocarbyloxy group.

[0108] 「C 1-18 The "hydrocarbyloxycarbonyl group" is not particularly limited and, for example, includes "C" such as a 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" ; "C" of 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" ; "C" of phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenanthrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc.6-18 Examples include the aryloxycarbonyl group.

[0109] In this specification, "C 1-18 "Hydrocarbyloxycarbonyloxygen" refers to "C 1-18 It refers to a group in which an oxygen atom (-O-) is bonded to a hydrocarbyloxycarbonyl group.

[0110] 「C 1-18 "Hydrocarbyloxycarbonyloxy group" is not particularly limited and, for example, "C" such as 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" ; "C" of cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. 3-18 "Alicyclic oxycarbonyloxy group" ; "C" of phenoxycarbonyloxy group, naphthoxycarbonyloxy group, acenaphthyloxycarbonyloxy group, phenanthrenyloxycarbonyloxy group, anthracenyloxycarbonyloxy group, etc. 6-18 Examples include the aryloxycarbonyloxy group.

[0111] In this specification, "C 1-18 A "hydrocarbylamino group" refers to one "C 1-18 It refers to a group in which a hydrocarbyl group is bonded to an amino group.

[0112] 「C 1-18 The "hydrocarbylamino group" is not particularly limited and, for example, includes "C" such as a 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" ; "C" of 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"; "C" of phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. 6-18 Examples include arylamino groups.

[0113] In this specification, "D C" 1-18 "Hydrocarbylamino group" refers to two identical or different "C 1-18 It refers to a group in which a hydrocarbyl group is bonded to an amino group.

[0114] "D C 1-18 The "hydrocarbylamino group" is not particularly limited and, for example, includes a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, an N-ethyl-N-methylamino group, a N-methyl-Nn-propylamino group, an N-isopropyl-N-methylamino group, an Nn-butyl-N-methylamino group, an N-isobutyl-N-methylamino group, an Nt-butyl-N-methylamino group, an N-methyl-Nn-pentylamino group, an Nn-hexyl-N-methylamino group, an N-ethyl-Nn-propylamino group, an N-ethyl-N-isopropylamino group, an Nn-butyl-N-ethylamino group, an N-ethyl-N-isobutylamino group, an Nt-butyl-N-ethylamino group, N-ethyl-Nn-pentylamino group, N-ethylNn-hexylamino group, etc. "D C 1-18 "alkylamino group"; "di C" of dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. 3-18 "Alicyclic amino group"; "Di C" of diphenylamino group, phenylnaphthylamino group, etc. 6-18 "Aryl amino group"; "NC" of N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. 1-18Alkyl-NC 3-18 "Cycloalkylamino group"; "NC" of N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. 1-18 Alkyl-NC 6-18 Examples include the arylamino group.

[0115] In this specification, "C 1-18 "Hydrocarbylaminocarbonyl group" refers to "C 1-18 It refers to a group in which a carbonyl group (-C(=O)-) is bonded to a hydrocarbylamino group.

[0116] 「C 1-18 The "hydrocarbylaminocarbonyl group" is not particularly limited and, for example, includes "C" such as a 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" ; "C" of 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"; "C" of phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc. 6-18 An example is the arylaminocarbonyl group.

[0117] In this specification, "D C" 1-18 "Hydrocarbylaminocarbonyl group" refers to "D C 1-18 It refers to a group in which a carbonyl group (-C(=O)-) is bonded to a hydrocarbylamino group.

[0118] "D C1-18 The "hydrocarbylaminocarbonyl group" is not particularly limited and, for example, includes a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a diisopropylaminocarbonyl group, a di-n-butylaminocarbonyl group, a diisobutylaminocarbonyl group, a di-t-butylaminocarbonyl group, a di-n-pentylaminocarbonyl group, a di-n-hexylaminocarbonyl group, an N-ethyl-N-methylaminocarbonyl group, an N-methyl-Nn-propylaminocarbonyl group, an N-isopropyl-N-methylaminocarbonyl group, an Nn-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an Nt-butyl-N-methylaminocarbonyl group, an N-methyl-Nn-pentylaminocarbonyl group, and a Nn-hexyl-N-methylaminocarbonyl group. N-ethyl-Nn-propylaminocarbonyl group, N-ethyl-N-isopropylaminocarbonyl group, Nn-butyl-N-ethylaminocarbonyl group, N-ethyl-N-isobutylaminocarbonyl group, Nt-butyl-N-ethylaminocarbonyl group, N-ethyl-Nn-pentylaminocarbonyl group, N-ethyl-Nn-hexylaminocarbonyl group, etc. "D C 1-18 "alkylamino group"; "di C" of dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. 3-18 "Alicyclic aminocarbonyl group"; "Di C" of diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group, etc. 6-18 Examples include the arylaminocarbonyl group.

[0119] In this specification, "C 1-18 "Hydrocarbylcarbonylamino group" refers to "C 1-18 It refers to a group in which an amino group is attached to a hydrocarbylcarbonyl group.

[0120] 「C 1-18The "hydrocarbylcarbonylamino group" is not particularly limited and, for example, "C" such as a 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 "Alkyl carbonylamino group"; "C" of cyclopropyl carbonylamino group, cyclobutyl carbonylamino group, cyclopentyl carbonylamino group, cyclohexyl carbonylamino group, etc. 3-18 "Alicyclic carbonylamino group" ; "C" of phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenanthrenylcarbonylamino group, anthracenylcarbonylamino group, etc. 6-18 Examples include the arylcarbonylamino group.

[0121] In this specification, "C 1-18 "Hydrocarbylaminocarbonyloxygen" refers to "C 1-18 It refers to a group in which an oxygen atom (-O-) is bonded to a hydrocarbylaminocarbonyl group.

[0122] 「C 1-18 "Hydrocarbylaminocarbonyloxy group" is not particularly limited and, for example, "C" such as methylaminocarbonyloxy group, ethylaminocarbonyloxy group, n-propylaminocarbonyloxy group, etc. 1-18 "alkylaminocarbonyloxy group"; "C" of cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. 3-18 "Alicyclic aminocarbonyloxy group"; "C" of phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc. 6-18 Examples include the arylaminocarbonyloxy group.

[0123] In this specification, "D C" 1-18 "Hydrocarbylaminocarbonyloxygen" refers to "D C 1-18It refers to a group in which an oxygen atom (-O-) is bonded to a hydrocarbylaminocarbonyl group.

[0124] "D C 1-18 As for the "hydrocarbylaminocarbonyloxy group," it is not particularly limited, and, for example, "di C" such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, di-n-propylaminocarbonyloxy group, etc. 1-18 Examples include alkylaminocarbonyloxy groups.

[0125] In this specification, "C 1-18 "Hydrocarbylaminocarbonylamino group" refers to "C 1-18 It refers to a group in which a “hydrocarbylaminocarbonyl group” is bonded to an amino group.

[0126] 「C 1-18 The "hydrocarbylaminocarbonylamino group" is not particularly limited and, for example, includes "C" such as a methylaminocarbonylamino group, an ethylaminocarbonyloxy group, an n-propylaminocarbonylamino group, etc. 1-18 "alkylaminocarbonylamino group"; "C" of cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. 3-18 "Alicyclic aminocarbonylamino group"; "C" of phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. 6-18 Examples include the arylaminocarbonylamino group.

[0127] In this specification, "D C" 1-18 "Hydrocarbylaminocarbonylamino group" refers to "D C 1-18 It refers to a group in which a “hydrocarbylaminocarbonyl group” is bonded to an amino group.

[0128] "D C 1-18 The "hydrocarbylaminocarbonylamino group" is not particularly limited and, for example, includes "di C" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, di-n-propylaminocarbonylamino group, etc. 1-18 Examples include alkylaminocarbonylamino groups.

[0129] In this specification, "C 1-18 "Hydrocarbyloxycarbonylamino group" refers to "C 1-18 It refers to a group in which a “hydrocarbyloxycarbonyl group” is bonded to an amino group.

[0130] 「C 1-18 The "hydrocarbyloxycarbonylamino group" is not particularly limited and, for example, includes "C" such as a methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc. 1-18 "Alkoxycarbonylamino group"; "C" of cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. 3-18 "Alicyclic oxycarbonylamino group"; "C" of phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. 6-18 Examples include the aryloxycarbonylamino group.

[0131] In this specification, "C 1-18 "Hydrocarbylthio group" refers to "C 1-18 It refers to a group in which a sulfur atom (-S-) is bonded to a hydrocarbyl group.

[0132] 「C 1-18 The "hydrocarbylthio group" is not particularly limited and, for example, includes "C" such as 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 "Alkyl thio group" ; "C" of cyclopropyl thio group, cyclobutyl thio group, cyclopentyl thio group, cyclohexyl thio group, 2-methylcyclopentyl thio group, 3-methylcyclopentyl thio group, 2-methylcyclohexyl thio group, 3-methylcyclohexyl thio group, 4-methylcyclohexyl thio group, etc. 3-18 "Alicyclic thio group" ; "C" of phenylthio group, 1-naphthylthio group, 2-naphthylthio group, acenaphthylthio group, phenanthrenylthio group, anthracenylthio group, etc. 6-18 Examples include "Ariltiogi".

[0133] In this specification, "C 1-18 "Hydrocarbylsulfinyl group" refers to "C 1-18 It refers to a group in which a sulfinyl group (-S(=O)-) is bonded to a hydrocarbyl group.

[0134] 「C 1-18 The "hydrocarbylsulfinyl group" is not particularly limited and, for example, includes "C" such as a methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, hexylsulfinyl group, etc. 1-18 "Alkylsulfinyl group"; "C" of cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-methylcyclohexylsulfinyl group, 3-methylcyclohexylsulfinyl group, 4-methylcyclohexylsulfinyl group, etc. 3-18 "Alicyclic sulfinyl group"; "C" of phenylsulfinyl group, naphthylsulfinyl group, acenaphthylsulfinyl group, phenanthrenylsulfinyl group, anthracenylsulfinyl group, etc. 6-18 Examples include the arylsulfinyl group.

[0135] In this specification, "C 1-18 "Hydrocarbylsulfonyl group" refers to "C 1-18 It refers to a group in which a sulfonyl group (-SO2-) is bonded to a hydrocarbyl group.

[0136] 「C 1-18 The "hydrocarbylsulfonyl group" is not particularly limited and, for example, includes "C" such as a methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, t-butylsulfonyl group, pentylsulfonyl group, etc. 1-18 "Alkyl sulfonyl group" ; "C" of cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, 4-methylcyclohexyl group, etc. 3-18"Alicyclic sulfonyl group" ; "C" of phenylsulfonyl group, naphthylsulfonyl group, acenaphthylsulfonyl group, phenanthrenylsulfonyl group, anthracenylsulfonyl group, etc. 6-18 Examples include the arylsulfonyl group.

[0137] In this specification, "acid dissociable group" means a polar group that substitutes for a hydrogen atom, such as a hydroxyl group (including phenolic hydroxyl groups, etc.), a carboxyl group, an amino group, a sulfonate group, etc., and is dissociated by the action of an acid.

[0138] A compound having a polar group having an acid-dissociable group can increase its polarity by causing the acid-dissociable group to dissociate upon the action of an acid, thereby generating the polar group. Accordingly, the solubility of the compound in a developer can be altered. More specifically, when a highly polar developer, such as an alkaline aqueous solution, is used as the developer, the solubility of the compound in the developer relatively increases; on the other hand, when a low-polarity organic developer is used as the developer, the solubility of the compound in the developer relatively decreases.

[0139] As the polar group above, a hydroxyl group (including phenolic hydroxyl groups, etc.) and a carboxyl group are preferred.

[0140] The above acid dissociable group is not particularly limited, and any known and commonly used acid dissociable group applicable to chemically amplified resists may be used. As an example of an acid dissociable group, an acid dissociable group G for a polar group having an acid dissociable group represented by the following general formulas (G-1) to (G-4) may be used.

[0141] [Chemical Formula 1]

[0142]

[0143] [Chemical Formula 2]

[0144]

[0145] [Chemical Formula 3]

[0146]

[0147] [Chemical Formula 4]

[0148]

[0149] As for the above acid dissociable group G, it is not particularly limited as long as it dissociates by the action of an acid, and known and conventional ones may be used. As for the acid dissociable group G, for example, the "tertiary carbon-type acid dissociable group G" represented by the following general formula (g-1). A 」, the “allyl or benzyl acid-dissociable group G represented by the following general formula (g-2) B ”, the “acetal-type acid-dissociable group G represented by the following general formula (g-3) C 」, the "aminocarbonyl acid dissociable group G represented by the following general formula (g-4) D Examples include 」 etc. Each of these will be explained sequentially below.

[0150] [Chemical Formula 5]

[0151]

[0152] [Chemical Formula 6]

[0153]

[0154] [Chemical Formula 7]

[0155]

[0156] [Chemical Formula 8]

[0157]

[0158] <Third carbon-type acid dissociative group G A >

[0159] As the above acid dissociable group G, the "tertiary carbon-type acid dissociable group G" represented by the following general formula (g-1) A As in 」, it is a carbon that directly bonds to a polar group, and also, R A g1 ~ R A g3The carbon bonded to this can use an acid-dissociable group that is a tertiary carbon atom.

[0160] [Chemical Formula 9]

[0161]

[0162] "R A g1 」 is C that may have substituents 1-12 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0163] R A g1 As for, C which may have substituents 1-12 Alkyl group, C 3-12 Circular tableware, C 6-12 aryl group, or C 7-12 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted), and

[0164] C that can have substituents 1-12 alkyl group or C 3-12 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0165] Also, "R A g2 」 and 「R A g3」 is C which may each have a substituent independently 1-12 As a hydrocarbyl group, a divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted), or R A g2 and R A g3 This combination allows C to have substituents. 3-18 It may form a dicyclic group or a 3 to 18-membered non-aromatic complex ring, and any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0166] R A g2 and R A g3 As for, R A g2 and R A g3 This combination allows C to have substituents. 3-18 It is preferable that the divalent carbon atoms at any position excluding the terminals form an alicyclic group or a 3 to 18-membered non-aromatic complex cyclic group, and that the divalent carbon atoms are substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0167] Also, C which may have the above substituent 3-18It is more preferable that the alicyclic group, or the 3 to 18-membered non-aromatic heterocyclic group, comprises a cyclopentane backbone, a cyclohexane backbone, a cycloheptane backbone, a cyclooctane backbone, a cyclononane backbone, a cyclodecane backbone, a cyclododecane backbone, a cyclopentene backbone, a cyclohexene backbone, a cycloheptene backbone, a cyclooctane backbone, a cyclodecene backbone, a norbornane backbone, an adamantane backbone, a tricyclodecane backbone, a tetracyclododecane backbone, a norbornene backbone, and that any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0168] Tertiary carbon-type acid dissociable group G represented by the general formula (g-1). A Examples include, for instance, 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-methylpropane-2-yl)cyclopentyl group, 1-(1-ethoxy-2-methylpropane-2-yl)cyclopentyl group, etc.

[0169] << Tertiary carbon-type acid dissociative group G A1 and G A2 >>

[0170] Also, the “tertiary carbon-type acid dissociable group G” represented by the general formula (g-1). A In 」, R A g2 and R A g3 This combination allows C to have substituents. 3-18A case in which a 3 to 18-membered ring non-aromatic complex cyclic 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 acid dissociable group G represented by (g-1-2). A2 You can lift the back.

[0171] << Tertiary carbon-type acid dissociable group G represented by the general formula (g-1-1) A1 >>

[0172] [Chemical Formula 10]

[0173]

[0174] The tertiary carbon-type acid dissociable group G represented by the above general formula (g-1-1). A1 In this regard, R A g11 C that can have substituents 1-12 Alkyl group, C 3-12 Circular tableware, C 6-12 aryl group, or C 7-12 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0175] Also Cy A g1 C, which may have a substituent together with the above-mentioned tertiary carbon atom. 3-18 It forms a dicyclic group or a 3 to 18-membered non-aromatic complex ring, and any divalent carbon atom may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0176] CyA g1 It is preferable that, together with the above-mentioned tertiary carbon atom, the cyclopentane backbone, cyclohexane backbone, cycloheptane backbone, cyclooctane backbone, cyclononane backbone, cyclodecane backbone, cyclododecane backbone, cyclopentene backbone, cyclohexene backbone, cycloheptene backbone, cyclooctane backbone, cyclodecene backbone, norbornane backbone, adamantan backbone, tricyclodecane backbone, tetracyclododecane backbone, norbornene backbone, and the divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0177] The tertiary carbon-type acid dissociable group G represented by the general formula (g-1-1). A1 For example, the following tertiary carbon-type acid dissociable group can be exemplified.

[0178] [Chemical Formula 11]

[0179]

[0180] [Chemical Formula 12]

[0181]

[0182] [Chemical Formula 13]

[0183]

[0184] << Tertiary carbon-type acid dissociable group G represented by the general formula (g-1-2) A2 >>

[0185] [Chemical Formula 14]

[0186]

[0187] In the above general formula (g-1-2), R A g21 ~ R Ag23 C, which may each independently have a hydride group or a substituent 1-12 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted), R A g21 and R A g22 , and / or R A g22 and R A g23 These are directly connected to each other by single bonds, or by divalent linkers -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group to form a ring.

[0188] R A g21 and R A g22 , and / or R A g22 and R A g23 There are cases where a ring is formed together with the carbon atom included in this ethylenically unsaturated double bond, such as cases where a cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexylideneethenyl group, etc., which may have a substituent, are formed.

[0189] Also Cy A g2 C, which may have a substituent together with the above-mentioned tertiary carbon atom. 3-18It forms a dicyclic group or a 3 to 18-membered non-aromatic complex ring, and any divalent carbon atom may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0190] Cy A g2 It is preferable that, together with the above-mentioned tertiary carbon atom, the cyclopentane backbone, cyclohexane backbone, cycloheptane backbone, cyclooctane backbone, cyclononane backbone, cyclodecane backbone, cyclododecane backbone, cyclopentene backbone, cyclohexene backbone, cycloheptene backbone, cyclooctane backbone, cyclodecene backbone, norbornane backbone, adamantan backbone, tricyclodecane backbone, tetracyclododecane backbone, norbornene backbone, and the divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0191] The tertiary carbon-type acid dissociable group G represented by the general formula (g-1-2). A2 For example, the following tertiary carbon-type acid dissociable group can be exemplified.

[0192] [Chemical Formula 15]

[0193]

[0194] <allyl or benzyl acid dissociative group G B >

[0195] As the above acid dissociable group G, the "allyl or benzyl acid dissociable group G" represented by the following general formula (g-2) BAs shown in 」, the carbon directly bonded to the polar group may use an acid-dissociable group corresponding to the allyl or benzyl position.

[0196] [Chemical Formula 16]

[0197]

[0198] "R B g1 」 is C that may have substituents 1-12 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0199] R B g1 As for, C which may have substituents 1-12 Alkyl group, C 3-12 Circular tableware, C 6-12 aryl group, or C 7-12 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted), and

[0200] C that can have substituents 1-12 alkyl group or C 3-12 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0201] Also, "R B g2 」∼ 「RB g4 " is C which may each independently have a hydride group or a substituent 1-12 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0202] R B g1 and R B g2 , R B g2 and R B g3 , and / or R B g3 and R B g4 a and b directly bond to each other, or are linked by two valence linkers -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group to form a ring.

[0203] The allyl or benzyl acid-dissociable group G represented by the general formula (g-2). B In this regard, R B g1 and R B g2 , R B g2 and R B g3 , and / or R B g3 and R B g4 There are cases where a ring is formed together with a carbon atom included in an ethylenically unsaturated double bond, such as cases where a cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexylideneethenyl group, benzyl group, or 2,3-dihydro-1H-indanyl group is formed, which may have a substituent.

[0204] The allyl or benzyl acid-dissociable group G represented by the general formula (g-2). B For example, the following allyl or benzyl acid dissociable groups can be exemplified.

[0205] [Chemical Formula 17]

[0206]

[0207] <Acetal-type acid-dissociative G C >

[0208] As the above acid dissociable group G, the "acetal-type acid dissociable group G" represented by the following general formula (g-3) C As shown in 」, an acid dissociable group in which an oxygen atom is bonded to a carbon atom that is directly bonded to a polar group can be used.

[0209] [Chemical Formula 18]

[0210]

[0211] "R C g1 」 and 「R C g3 " is C which may each independently have a hydride group or a substituent 1-12 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0212] R C g1 and R C g3 As for, C which may have a hydride group or a substituent 1-12 alkyl group or C 3-12As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0213] C that may have a hydride or a substituent 1-6 alkyl group or C 3-8 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0214] Also, "R C g2 」 is C that may have substituents 1-12 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0215] R C g2 As for, C which may have substituents 1-12 alkyl group or C 3-12 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0216] C that can have substituents 1-6 alkyl group or C3-8 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0217] Acetal-type acid-dissociable group G represented by the general formula (g-3). C Examples include, for instance, methoxymethoxy groups, ethoxymethoxy groups, n-propoxymethoxy groups, n-butoxymethoxy groups, 2,2-dimethylpropoxymethoxy groups, 2,2-dimethylbutoxymethoxy groups, cyclohexyloxymethoxy groups, 1-ethoxyethoxy groups, 1-n-butoxyethoxy groups, 1-cyclohexyloxyethoxy groups, etc.

[0218] <Aminocarbonyl acid dissociable group G D >

[0219] As the above acid dissociable group G, the "aminocarbonyl type acid dissociable group G" represented by the following general formula (g-4) D As in 」, an acid-dissociable group in which an aminocarbonyl group is attached to a polar group can be used.

[0220] [Chemical Formula 19]

[0221]

[0222] "R D g1 」 and 「R D g2 " is C which may each independently have a hydride group or a substituent 1-12 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0223] R Dg1 and R D g2 As for, C which may have a hydride group or a substituent 1-12 alkyl group or C 3-12 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0224] C that may have a hydride or a substituent 1-6 alkyl group or C 3-8 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0225] The aminocarbonyl acid dissociable group G represented by the general formula (g-4). D Examples include dimethylaminocarbonyl groups, diethylaminocarbonyl groups, diisopropylaminocarbonyl groups, N-phenyl-N-methyl-aminocarbonyl groups, etc.

[0226] [Chemical Formula 20]

[0227]

[0228] In this specification, "hydroxyl group or carboxyl group having a protecting group" means a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group that is protected by an ether-based protecting group, a silyl ether-based protecting group, an acyl-based protecting group, etc.

[0229] Ether-based protecting groups are not particularly limited and examples include methyl groups, benzyl groups, p-methoxybenzyl groups, t-butyl groups, triphenylmethyl groups, p-methoxyphenyldiphenylmethyl groups, di(p-methoxyphenyl)phenylmethyl groups, etc.

[0230] Silyl ether-based protecting groups are not particularly limited, and examples include t-butyldimethylsilyl groups (TBS), triisopropylsilyl groups (TIPS), trimethylsilyl groups (TMS), triethylsilyl groups (TES), t-butyldiphenylsilyl groups (TBDPS), etc.

[0231] Acyl protecting groups are not particularly limited and, for example, acetyl groups, pivaloyl groups, benzoyl groups, etc.

[0232] In this specification, the phrase “may have a substituent” is not particularly limited, as long as it is chemically permissible and has the effects of the present invention.

[0233] As a “substituent,” for example, (1) a halogen atom, (2) a haloalkyl group, (3) a hydroxyl group, (4) a thiol group, (5) a nitro group, (6) a cyano group, (7) a carboxyl group, (8) an amino group, (9) a sulfo group, (10) a vinyl group, (11) an allyl group, (12) a (meth)acryloyl group, (13) a (meth)acryloyloxy group, (14) a (meth)acrylamide group, (15) a styryl group, (16) an epoxy group, (17) a glycidyl group, (18) an amide group, (19) a hydroxyl or carboxyl group having a protecting group, (20) a polar group having an acid-dissociable group, or (21) at least some of the hydrogen atoms may be substituted with (1) to (20). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxygen, C 1-18Hydrocarbylamino group, D C 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbylaminocarbonyl group, D C 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbylcarbonylamino group, C 1-18 Hydrocarbylaminocarbonyloxygen, D C 1-18 Hydrocarbylaminocarbonyloxygen, C 1-18 Hydrocarbylaminocarbonylamino group, D C 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, C 1-18 Hydrocarbilthio group, C 1-18 Hydrocarbylsulfinyl group, C 1-18 Examples of hydrocarbylsulfonyl groups include those in which a divalent carbon atom at any position other than the terminal of the substituent may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0234] [1. Resist Material]

[0235] The resist material related to the present embodiment contains (A) a heteropolyphosphate or a mixture thereof in which the defect site is modified.

[0236] (A m＋ ) a (B n＋ ) b (C (am＋bn)- ) (I)

[0237] [During the meal,

[0238] A m＋ is, each independently H ＋ , representing a metal ion, ammonium cation, ammonium dicathione, phosphonium cation, or phosphonium dicathione;

[0239] Bn＋ represents a sulfonium cation, sulfonium dication, or iodonium cation having one or more polar groups having acid-dissociable groups, each independently;

[0240] C (am＋bn)- ... represents a heteropolyacid anion having a defect site, wherein the defect site is modified;

[0241] m is an integer from 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

[0242] In addition, the resist material related to the present embodiment may contain (B) an acid diffusion control agent as an optional component.

[0243] [1-1. (A) Heteropolysate or mixture thereof with the defect site modified]

[0244] (A) As a heteropolyphosphate or a mixture thereof with a missing site modified, a heteropolyphosphate or a mixture thereof with a missing site modified by the above general formula (I) may be used. The anion portion of the heteropolyphosphate or mixture thereof with a missing site modified is composed of the heteropolyphosphate anion with a missing site modified therein. In addition, the cation portion of the heteropolyphosphate or mixture thereof with a missing site modified is composed of a sulfonium cation, a sulfonium dicathione, or an iodonium cation having one or more polar groups having acid dissociable groups.

[0245] [1-1-1. Anionic portion of heteropolyphosphate or mixture thereof with a modified defect site]

[0246] The anion portion of the heteropoly acid salt or mixture thereof having a defective portion modified in relation to the present embodiment is composed of the heteropoly acid anion having a defective portion, wherein the defective portion is modified in the heteropoly acid anion.

[0247] [1-1-1-1. Heteropolyacid anion with modified defect site]

[0248] As for the heteropolyacid anion having a defect site, the heteropolyacid anion having a defect site modified may be the heteropolyacid anion having a defect site obtained by reacting the terminal oxygen atom of the defect site of the heteropolyacid anion having a defect site with a compound of P, Si, Ge, or Sn having one or more hydroxyl or organic groups and two or more degreasing groups.

[0249] [1-1-1-1-1. Heteropolyacid anion having a defect site]

[0250] The heteropolyacid anion having a defect site related to the present embodiment is not particularly limited, and a defect type in which a part of the basic framework of the heteropolyacid anion is missing may be used, and any of a 1-defect type, 2-defect type, 3-defect type, etc. may be used. Examples of the heteropolyacid anion having a defect site include a defect Kegine-type heteropolyacid anion, a defect Dawson-type heteropolyacid anion, etc.

[0251] [1-1-1-1-1-1. Defective Keggin-type heteropolisan anion]

[0252] Examples of the above-mentioned defective Kegyn-type heteropolyacid anions include, for instance, a defective Kegyn-type heteropolyacid anion represented by the following general formula (II-1), a defective Kegyn-type heteropolyacid anion represented by the following general formula (II-2), and a defective Kegyn-type heteropolyacid anion represented by the following general formula (II-3).

[0253] [XM 11 O 39 ] c11- (II-1)

[0254] [XM 10 O 36 ] c12- (II-2)

[0255] [XM9O34 ] c13- (II-3)

[0256] (during the meal,

[0257] X represents a heteroatom of P, Si, B, S, or Ge;

[0258] M represents a polyatom of Mo, W, V, Nb, or Ta;

[0259] c11- ~ c13- represent negative charge numbers, and c11 ~ c13 are natural numbers.

[0260] In general formulas (II-1) to (II-3), the values ​​of c11 to c13 vary depending on the types of X and M.

[0261] For example, in general formula (II-1), if X is P and M is Mo or W, c11 is 7([PMo 11 O 39 ] 7- , [PW 11 O 39 ] 7- ) becomes, and if X is Si and M is Mo or W, c11 is 8([SiMo 11 O 39 ] 8- , [SiW 11 O 39 ] 8- ) and if X is S and M is Mo or W, then c11 is 6([SMo 11 O 39 ] 6- , [SW 11 O 39 ] 6- ) and if X is B and M is Mo or W, then c11 is 9([BMo 11 O 39 ] 9- , [BW 11 O 39 ] 9- ) becomes, and if X is Ge and M is Mo or W, then c11 is 8([GeMo 11 O39 ] 8- , [GeW 11 O 39 ] 8- It becomes.

[0262] Also, in general formula (II-2), if X is P and M is Mo or W, c12 is 7([PMo 10 O 36 ] 7- , [PW 10 O 36 ] 7- ) becomes, 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- , [BW 10 O 36 ] 9- ) becomes, 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- It becomes.

[0263] Also, in general formula (II-3), for example, if X is P and M is Mo or W, c13 is 9([PMo9O 34 ] 9- , [PW9O 34 ] 9- ) becomes, and if 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- It becomes.

[0264] The above-mentioned defective Kegyn-type heteropolyacid anion preferably has an isomer structure of an α-body, a β-body, or a γ-body.

[0265] As the isomer structure of the 1-deleted Kegyn-type heteropolyacid anion represented by general formula (II-1), [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- is desirable, and [α-PW 11 O 39 ] 7- , [α-PMo 11 O 39] 7- , [α-SiW 11 O 39 ] 8- , [α-SiMo 11 O 39 ] 8- It is more desirable.

[0266] In addition, as an isomer structure of the 2-deleted Kegyn-type heteropolyacid anion represented by general formula (II-1), [α-PW 10 O 36 ] 7- , [β-PW 10 O 36 ] 7- , [γ-PW 10 O 36 ] 7- , [α-PMo 10 O 36 ] 7- , [β-PMo 10 O 36 ] 7- , [γ-PW 10 O 36 ] 7- , [α-SiW 10 O 36 ] 8- , [β-SiW 10 O 36 ] 8- , [γ-SiW 10 O 36 ] 8- , [α-SiMo 10 O 36 ] 8- , [β-SiMo 10 O 36 ] 8- , [γ-SiW 10 O 36 ] 8- is desirable, and [γ-PW 10 O 36 ] 7- , [γ-PMo 10 O 36 ] 7- , [γ-SiW 10 O 36 ] 8- , [γ-SiMo 10 O 36 ] 8- It is more desirable.

[0267] In addition, as an isomer structure of the 3-deleted Kegyn-type heteropolyacid anion represented by general formula (III-1), [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 desirable.

[0268] [1-1-1-1-1-2. Defective Dawson-type heteropolisan anion]

[0269] Examples of the above-mentioned vacancy-type Dawson heteropolyacid anions include, for instance, a 1-vacancy-type Dawson heteropolyacid anion represented by the following general formula (III-1), a 2-vacancy-type Dawson heteropolyacid anion represented by the following general formula (III-2), and a 3-vacancy-type Dawson heteropolyacid anion represented by the following general formula (III-3).

[0270] [X2M 17 O 61 ] c21- (III-1)

[0271] [X2M 16 O 58 ] c22- (III-2)

[0272] [X2M 15 O 56 ]c23- (III-3)

[0273] (during the meal,

[0274] X represents a heteroatom of P, Si, B, S, or Ge;

[0275] M represents a polyatom of Mo, W, V, Nb, or Ta;

[0276] c21- ~ c23- represent negative charge numbers, and c21 ~ c23 are natural numbers.

[0277] In general formulas (III-1) to (III-3), the values ​​of c21 to c23 vary depending on the types of X and M.

[0278] For example, in general formula (III-1), if X is P and M is Mo or W, 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- It becomes.

[0279] Also, in general formula (III-2), when X is Ge and M is Mo, c22 is 12([Ge2Mo 16 O 58 ] 12- It becomes.

[0280] Also, in general formula (III-3), if X is P and M is Mo or W, c23 is 12([P2Mo 15 O 56 ] 12- , [P2W 15 O 56 ] 12- It becomes.

[0281] The above-mentioned defective Dawson-type heteropolyacid anion preferably has an isomer structure of an α-body, a β-body, or a γ-body.

[0282] As isomer structures of the duplicating 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- The back can be used in a desirable way.

[0283] [1-1-1-1-2. Formula for Defective Areas]

[0284] The modification of the defect site of the heteropolyacid anion having the defect site related to the present embodiment is achieved by reacting the terminal oxygen atom at the defect site with a compound of P, Si, Ge, or Sn having one or more hydroxyl or organic groups and two or more degreasing groups to modify the defect site. Through the above reaction, the defect site is modified by the terminal oxygen atom at the defect site of the heteropolyacid anion being bonded to a group having a heteroatom P, Si, Ge, or Sn that is bonded to one or more hydroxyl or organic groups, through part or all of the said heteroatom.

[0285] [1-1-1-1-2-1. Connection Type of Defective Sites and Notation]

[0286] The heteropolyacid anion with a modified defect site related to the present embodiment is such that the terminal oxygen atom of the defect site of the heteropolyacid anion having the defect site is modified by a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more hydroxyl or organic groups are bonded.

[0287] The bonding form of the group having one or more heteroatoms P, Si, Ge, or Sn, which is bonded to the terminal oxygen atom of the vacancy site of the above heteropolyacid anion and one or more hydroxyl or organic groups, is not particularly limited and can be represented, for example, by the following general formulas (IV-1) to (IV-5).

[0288] [Chemical Formula 21]

[0289]

[0290] [Chemical Formula 22]

[0291]

[0292] [Chemical Formula 23]

[0293]

[0294] [Chemical Formula 24]

[0295]

[0296] [Chemical Formula 25]

[0297]

[0298] [Among Equations (IV-1) to (IV-5),

[0299] X' represents Si or Ge;

[0300] X'' represents a heteroatom of Si, Ge, or Sn;

[0301] R 1A1 ~ R 1E1 C, which may each independently have a hydride group or a substituent 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0302] The above R 1A1 ~ R 1E1Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted),

[0303] The above R 1A1 ~ R 1E1 The hydrogen atom included in may be substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, or (t) a polar group having an acid-dissociable group;

[0304] * indicates the terminal oxygen atom at the defect site.

[0305] In this specification, for a heteropolyacid anion modified by a group having a heteroatom Si or Ge bonded to one or more hydroxyl or organic groups represented by general formula (IV-1), the vacancy site may be indicated as the following general formula (V-1) for convenience.

[0306] [X w M x O y (R 1A1 X')(R 1A2 X')O] c- (V-1)

[0307] (In the expression, w, x, y, and c are all natural numbers, and X, M, X', R 1A1 and R 1A2 is the same as above.)

[0308] Also R 1A1and R 1A2 If they are the same, this is R 1A By doing so, it can be expressed as the following general formula (V-1').

[0309] [X w M x O y (R 1A X')2O] c- (V-1')

[0310] Heteropolyacid anions modified by a vacancy site represented by general formula (V-1) or (V-1') are not particularly limited, and, for example, a heteropolyacid anion having a vacancy site and (R 1A )X'Y3(Y represents a deglue, e.g., a halogen atom, hydroxyl group, alkoxy group (C 1-4 It is desirable that it be an alkoxy group, and C 1-2 An alkoxy group is more preferable), an alkyl carbonyloxy group (C 1-4 It is preferable that it be an alkyl carbonyloxy group), a hydrocarbylsulfonyloxy group (C 1-6 alkyl or C 7-10 It is preferable that it be an aralkylsulfonyloxy group. Examples include methanesulfonyloxy groups, p-toluenesulfonyloxy groups, etc.)) It can be obtained by reacting with.

[0311] Likewise, in this specification, for a heteropolyacid anion in which the defect site is modified by a group having one or more heteroatoms Si or Ge bonded to one or more hydro or organic groups represented by general formula (IV-2), for convenience, it may be indicated as the following general formula (V-2).

[0312] [X w M x O y (R 1B1 R 1B2 X')(R 1B3 R 1B4 Si)] c- (V-2)

[0313] (In the expression, w, x, y, and c are all natural numbers, and X, M, X', R 1B1 , R 1B2 , R 1B3 and R 1B4 is the same as above.)

[0314] Also R 1B1 R 1B2 and R 1B3 R 1B4 If the values ​​are the same, they can be expressed as the following general formula (V-2').

[0315] [X w M x O y (R 1B1 R 1B2 X')2] c- (V-2')

[0316] Heteropolyacid anions modified by a vacancy site represented by general formula (V-2) or (V-2') are not particularly limited, and, for example, a heteropolyacid anion having a vacancy site and (R 1B1 )(R 1B2 It can be obtained by reacting with )X'Y2 (Y represents degreasing in the same way as above).

[0317] In this specification, for a heteropolyacid anion modified by a group having a heteroatom Si or Ge bonded to one or more hydroxyl or organic groups represented by general formula (IV-3), the vacancy site may be indicated as the following general formula (V-3) for convenience.

[0318] [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)

[0319] (In the expression, w, x, y, and c are all natural numbers, and X, M, X', R 1C1 , R 1C2 , R1C3 and R 1C4 is the same as above.)

[0320] Also R 1C1 , R 1C2 , R 1C3 and R 1C4 If they are the same, this is R 1C By doing so, it can be expressed as the following general formula (V-3').

[0321] [X w M x O y (R 1C X'O)4] c- (V-3')

[0322] Heteropolyacid anions modified by a vacancy site represented by general formula (V-3) or (V-3') are not particularly limited, and, for example, two-vacancy Kegyn or Dawson type heteropolyacid anions and R 1C It can be obtained by reacting with X'Y3 (Y represents degreasing as above).

[0323] In this specification, for a heteropolyacid anion modified by a group having a heteroatom P to which one or more hydroxyl or organic groups represented by general formula (IV-4) are bonded, the vacancy site may be indicated as the following general formula (V-4) for convenience.

[0324] [X w M x O y (R 1D1 P=O)(R 1D2 P=O)] c- (V-4)

[0325] (In the expression, w, x, y, and c are all natural numbers, and X, M, R 1D1 and R 1D2 is the same as above.)

[0326] Also R 1D1 and R 1D2 If they are the same, this is R 1D By doing so, it can be expressed as the following general formula (V-4').

[0327] [X w M x O y (R 1D P=O)2] c- (V-4')

[0328] Heteropolyacid anions modified by a vacancy site represented by general formula (V-4) or (V-4') are not particularly limited, and, for example, a heteropolyacid anion having a vacancy site and R 1D It can be obtained by reacting with P(=O)Y2 (Y represents degreasing as above).

[0329] In this specification, for a heteropolyacid anion modified by a group having one or more heteroatoms Si, Ge, or Sn to which one or more hydroxyl or organic groups represented by general formula (IV-5) are bonded, the vacancy site may be indicated as the following general formula (V-5) for convenience.

[0330] [X w M x O y (R 1E1 X'')] c- (V-5)

[0331] (In the expression, w, x, y, and c are all natural numbers, and X, M, X'' and R 1E1 is the same as above.)

[0332] In addition, regarding the above (V-5), in some cases, it may be expressed as the following general formula (V-5'). Also, R 1E is R 1E1 The same definition as is used.

[0333] [X w M x O y (R 1E X'')] c- (V-5')

[0334] Heteropolyacid anions modified by a vacancy site represented by general formula (V-5) or (V-5') are not particularly limited, and, for example, a heteropolyacid anion having a vacancy site and R 1E It can be obtained by reacting with X''Y3 (Y represents degreasing in the same way as above).

[0335] Among heteropolyacid anions modified by the vacancy sites represented by general formulas (V-1) to (V-5) and (V-1') to (V-5'), heteropolyacid anions modified by the vacancy sites represented by the following general formulas (VI-1) to (VI-12) are particularly preferred in terms of being relatively stable and capable of controlling reactivity.

[0336] [XM 11 O 39 (R 1A X')2O] c31- (VI-1)

[0337] [XM 11 O 39 (R 1B1 R 1B2 X')2] c31- (VI-2)

[0338] [XM 11 O 39 (R 1D P=O)2] c31- (VI-3)

[0339] [XM 11 O 39 (R 1E X'')] c31- (VI-4)

[0340] [XM 10 O 36 (R 1A X')2O] c32- (VI-5)

[0341] [XM 10 O 36 (R 1B1 R 1B2 X')2] c32- (VI-6)

[0342] [XM 10 O36 (R 1C X'O)4] c32- (VI-7)

[0343] [XM 10 O 36 (R 1D P=O)2] c32- (VI-8)

[0344] [X2M 17 O 61 (R 1A X')2O] c33- (VI-9)

[0345] [X2M 17 O 61 (R 1B1 R 1B2 X')2] c33- (VI-10)

[0346] [X2M 17 O 61 (R 1D P=O)2] c33- (VI-11)

[0347] [X2M 17 O 61 (R 1E X'')] c33- (VI-12)

[0348] (during the meal,

[0349] X represents a heteroatom of P, Si, B, S, or Ge;

[0350] M represents a polyatom of Mo, W, V, Nb, or Ta;

[0351] X' represents a heteroatom of Si or Ge;

[0352] X'' represents a heteroatom of Si, Ge, or Sn;

[0353] R 1A ~ R 1E C, which may each independently have a hydride group or a substituent 1-18Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0354] The above R 1A ~ R 1E Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted),

[0355] The above R 1A ~ R 1E The hydrogen atoms included in are, for example, (a) halogen atoms, (b) C 1-3 (c) hydroxyl group, (d) thiol group, (e) nitro group, (f) cyano group, (g) carboxyl group, (h) amino group, (i) sulfo group, (j) vinyl group, (k) allyl group, (l) (meth)acryloyl group, (m) (meth)acryloyloxy group, (n) (meth)acrylamide group, (o) styryl group, (p) epoxy group, (q) glycidyl group, (r) amide group, (s) hydroxyl or carboxyl group having a protecting group, or (t) may be substituted with a polar group having an acid-dissociable group;

[0356] c31, c32, and c33 are natural numbers.

[0357] In a heteropolyacid anion with a modified vacancy site, since four terminal oxygen atoms of the vacancy site are modified, typically the value of c31 becomes c11-4, the value of c32 becomes c12-4, and the value of c33 becomes c21-4.

[0358] On the other hand, for example, in cases where the organic group contains an amino group and is protonated to become an ammonium cation, or where the organic group contains a carboxyl group and is formed to become a carboxyanion, the values ​​of c31 to c33 will differ from the above values.

[0359] [1-1-2. Cationic portion of heteropolysate or mixture thereof with a modified defect site]

[0360] In the cation portion of the heteropolysodium salt or mixture thereof in which the defect portion related to the present embodiment is modified, a sulfonium cation, sulfonium dication, or iodondium cation (B) having one or more polar groups having acid-dissociable groups. n＋ ) may be used. It is preferable that the sulfonium cationic, sulfonium dication, or iodonium cationic having one or more polar groups having acid-dissociable groups exhibit both the function of a photocatalytic agent and the function of changing solubility in the developer solution by the action of acid. In addition, in the cationic portion of the heteropolyphosphate or mixture thereof in which the above-mentioned defect site is modified, other counter-categories (A m＋ It is acceptable to include ).

[0361] [1-1-2-1. A sulfonium cation or sulfonium dication or iodonium cation having one or more polar groups having acid-dissociable groups (B n＋ )]

[0362] As a sulfonium cationic, sulfonium dication, or iodonium cationic having one or more polar groups having acid dissociable groups related to the present embodiment, an organic sulfonium cationic, organic sulfonium dication, or organic iodonium cationic having one or more polar groups having acid dissociable groups may be used.

[0363] [1-1-2-1-1. Organic sulfonium cation having one or more polar groups having acid-dissociable groups]

[0364] As for the organic sulfonium cation having one or more polar groups having acid dissociable groups, there are no particular limitations, and known and commonly used ones may be used. Examples of organic sulfonium cations having one or more polar groups having acid dissociable groups include, for instance, the organic sulfonium cation represented by the following general formula (VII-1).

[0365] [Chemical Formula 26]

[0366]

[0367] In general formula (VII-1), R 2A , R 2B and R 2C C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0368] The above R 2A , R 2B and R 2C Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0369] The above R 2A , R 2B and R 2CThe hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It may be substituted with a hydrocarbylthio group, and any divalent carbon atom at any position excluding the terminals of these substituents may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0370] Also, the above R 2A One or more hydrogen atoms included in are substituted with (t) a polar group having an acid dissociable group, and

[0371] Also R 2A , R 2B and R 2C Any two of them are directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3It may be connected via an alkylene group and form a ring together with the sulfur atom in formula (VII-1).

[0372] R having one or more polar groups having the above acid-dissociable groups 2A As for, C which may have substituents 1-18 It is a hydrocarbyl group; and the above R 2A Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 2A It is preferable that at least one hydrogen atom (t) is substituted with a polar group having an acid dissociable group, and

[0373] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 It is an aralkyl group; and the above R 2A Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 2A It is more preferable that at least one hydrogen atom (t) is substituted with a polar group having an acid dissociable group, and

[0374] C that can have substituents 6-18 aryl group or C 7-18 It is an aralkyl group; and the above R 2AAny divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 2A It is more preferable that at least one hydrogen atom (t) is substituted with a polar group having an acid dissociable group.

[0375] The above R 2A It is characterized by having one or more polar groups having acid-dissociable groups, and for example, polar groups such as hydroxyl groups, carboxyl groups, amino groups, or sulfonate groups having acid-dissociable groups are introduced. As the acid-dissociable groups, for example, a tertiary carbon-type acid-dissociable group G A , allyl or benzyl acid-dissociating group G B , acetal-type acid-dissociative group G C , aminocarbonyl acid dissociable group G D You can lift the back.

[0376] R having one or more polar groups having the above acid-dissociable groups 2A As such, for example, the following can be exemplified. Also, * represents a bond with a sulfur atom of general formula (VII-1).

[0377] [Chemical Formula 27]

[0378]

[0379] R 2B and R 2C As for, C which may each have independent substituents 1-18 It is a hydrocarbyl group; and the above R 2B and R 2CAny divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 2B and R 2C The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is preferable that the divalent carbon atoms at any position excluding the terminals of these substituents may be substituted with hydrocarbylthio groups, and that the divalent carbon atoms at any position may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0380] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18aryl group, or C 7-18 It is an aralkyl group; and the above R 2B and R 2C Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 2B and R 2C The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It may be substituted with a hydrocarbylthio group, and it is more preferable that any divalent carbon atom at any position excluding the terminal of these substituents be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0381] Also R2A , R 2B and R 2C Any two of them are directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 Cases in which a ring is formed together with the sulfur atom in Formula (VII) by being connected via an alkylene group include, for example, those having a thian-1-ium backbone, a thiophene-1-ium backbone, a 1,4-oxathian-4-ium backbone, a 1,4-dithian-1-ium backbone, a 1H-thiophene-1-ium backbone, a benzo[b]thiophene-1-ium backbone, a dibenzothiophenium backbone, a 9,10-dihydrothioxantylium backbone, a 10H-phenoxathine-10-ium backbone, a 5H-thianthrene-5-ium backbone, and the following examples. Also, * is R that does not participate in the formation of the ring. 2A , R 2B or R 2C It refers to the connection part with.

[0382] [Chemical Formula 28]

[0383]

[0384] As an organic sulfonium cationic group having one or more polar groups having the above acid-dissociable groups, for example, (3,5-dimethyl-4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl)diphenylsulfonium cationic group, (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cationic group, (3,5-dimethyl-4-(2-((1-methylcyclopentyl)oxy)-2-oxoethoxy)phenyl)diphenylsulfonium cationic group, 5-(2-(t-butoxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cationic group, (3,5-dimethyl-4-(2-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)-2-oxoethoxy)phenyl)diphenylsulfonium cationic, 5-(3,5-dimethyl-4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl)-5H-dibenzo[b,d]thiophene-5-ium cationic, (4-(2-((1-ethylcyclohexyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cationic, 1-(4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)naphthalene-1-yl)tetrahydro-1H-thiophene-1-ium cationic, Examples include (4-(t-butoxy)-3,5-dimethylphenyl)diphenylsulfonium cationic acid, (4-((diisopropylcarbamoyl)oxy)phenyl)dimethylsulfonium cationic acid, 1-(4-methoxymethoxy)naphthalene-1-yl)tetrahydro-1H-thiophene-1-ium cationic acid, 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)tetrahydro-1H-thiophene-1-ium cationic acid, 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)hexahydrothiopyrillium cationic acid.

[0385] As an organic sulfonium cationic group having one or more polar groups having the above acid dissociable groups, examples include the following.

[0386] [Chemical Formula 29]

[0387]

[0388] [1-1-2-1-2. Organic sulfonium dicathione having one or more polar groups having acid-dissociable groups]

[0389] As for the organic sulfonium dicathion having one or more polar groups having acid dissociable groups, there are no particular limitations, and known and commonly used ones may be used. Examples of organic sulfonium dicathions having one or more polar groups having acid dissociable groups include, for instance, the organic sulfonium dicathion represented by the following general formula (VII-2).

[0390] [Chemical Formula 30]

[0391]

[0392] In general formula (VII-2), R 3A , R 3B , R 3C and R 3D C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0393] The above R 3A , R 3B , R 3C and R 3D Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0394] K 3A , K 3B and L 3 C, which may each have independent substituents 1-18 Representing a hydrocarbylene group,

[0395] The above K 3A , K 3BThe divalent carbon atom at any position in and L may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0396] The above R 3A , R 3B , R 3C , R 3D , K 3A , K 3B and L 3 The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It may be substituted with a hydrocarbylthio group, and any divalent carbon atom at any position excluding the terminals of these substituents may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0397] Also, the above R 3A , R 3B , R 3C , R 3D , K 3A , K 3B and L 3 At least one hydrogen atom included in is substituted with a polar group having an acid-dissociable group;

[0398] R 3A , R 3B and K 3A Any two of, and / or, R 3C , R 3D and K 3B Any two of these, directly connected to each other by a single bond, or, being two linkers -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group to form a ring together with the sulfur atom in formula (VII-2).

[0399] The above R 3A ~ R 3D As for, C which may each have independent substituents 1-18 It is a hydrocarbyl group; and the above R 3A ~ R 3D Divalent carbon atoms at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously); above R 3A ~ R 3DThe hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is preferable that the divalent carbon atoms at any position excluding the terminals of these substituents may be substituted with hydrocarbylthio groups, and that the divalent carbon atoms at any position may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0400] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 It is an aralkyl group; and the above R 3A ~ R 3DAny divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 3A ~ R 3D The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It may be substituted with a hydrocarbylthio group, and it is more preferable that any divalent carbon atom at any position excluding the terminal of these substituents be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0401] The above K 3A , K 3B and L 3As for, C which may each have independent substituents 1-18 alkylene group or C 1-18 Representing an arylene group; the above K 3A , K 3B and L 3 A divalent carbon atom at any position of may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above K 3A , K 3B and L 3 It is preferable that the hydrogen atoms included in the above be substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl group or a carboxyl group having a protecting group, or (t) a polar group having an acid-dissociable group.

[0402] R having one or more polar groups having acid-dissociable groups 3A , R 3B , R 3C , R 3D , K 3A , K 3B and / or L 3 Examples include the introduction of a polar group having an acid-dissociable group, such as a hydroxyl group, a carboxyl group, an amino group, or a sulfonate group. As for the acid-dissociable group, for example, a tertiary carbon-type acid-dissociable group G A , allyl or benzyl acid-dissociating group G B , acetal-type acid-dissociative group G C , aminocarbonyl acid dissociable group GD You can lift the back.

[0403] R having one or more polar groups having the above acid-dissociable groups 3A ~ R 3D As such, R having one or more polar groups having acid-dissociable groups as described above 2A It is possible to exemplify the same thing as exemplified as.

[0404] [1-1-2-1-3. Organic iodine cation having one or more polar groups having acid-dissociable groups]

[0405] As for the organic iodium cation having one or more polar groups having acid dissociable groups, there are no particular limitations, and known and commonly used ones may be used. Examples of organic iodium cations having one or more polar groups having acid dissociable groups include the organic iodium cation represented by the following general formula (VII-3).

[0406] [Chemical Formula 31]

[0407]

[0408] In general formula (VII-3), R 4A and R 4B C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0409] The above R 4A and R 4B Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0410] The above R 4A and R 4BThe hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, or C 1-18 It may be substituted with a hydrocarbyloxycarbonyloxy group, and any divalent carbon atom at any position excluding the terminals of these substituents may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0411] Also, the above R 4A One or more hydrogen atoms included in are substituted with a polar group having an acid-dissociable group (t), and

[0412] Also R 4A and R 4B are directly connected to each other by single bonds, or by divalent linkers -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group and form a ring together with the iodine atom in formula (VII-3).

[0413] R having one or more polar groups having the above acid-dissociable groups 4A As,

[0414] C that can have substituents 1-18 It is a hydrocarbyl group; and the above R 4A Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 4A It is preferable that at least one hydrogen atom (t) is substituted with a polar group having an acid dissociable group, and

[0415] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 It is an aralkyl group; and the above R 4A Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 4A It is more preferable that at least one hydrogen atom (t) is substituted with a polar group having an acid dissociable group, and

[0416] C that can have substituents 6-18 aryl group or C 7-18 It is an aralkyl group; and the above R 4AAny divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 4A It is more preferable that at least one hydrogen atom (t) is substituted with a polar group having an acid dissociable group.

[0417] The above R 4A It is characterized by having one or more polar groups having acid-dissociable groups, and for example, polar groups such as hydroxyl groups, carboxyl groups, amino groups, or sulfonate groups having acid-dissociable groups are introduced. As the acid-dissociable groups, for example, a tertiary carbon-type acid-dissociable group G A , allyl or benzyl acid-dissociating group G B , acetal-type acid-dissociative group G C , aminocarbonyl acid dissociable group G D You can lift the back.

[0418] R having one or more polar groups having the above acid-dissociable groups 4A As such, R having one or more polar groups having acid-dissociable groups as described above 2A It is possible to exemplify the same thing as exemplified as.

[0419] R 4B As for, C which may have substituents 1-18 It is a hydrocarbyl group; and the above R 4B Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 4BThe hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is preferable that the divalent carbon atoms at any position excluding the terminals of these substituents may be substituted with hydrocarbylthio groups, and that the divalent carbon atoms at any position may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0420] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 It is an aralkyl group; and the above R 4BAny divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted); the above R 4B The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It may be substituted with a hydrocarbylthio group, and it is more preferable that any divalent carbon atom at any position excluding the terminal of these substituents be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0421] [1-1-2-2. Other countercations (A m＋ )]

[0422] Other counter cations related to this embodiment (A m＋ ) is, H ＋ , represents a metal ion, ammonium cation, ammonium dicathione, phosphonium cation, or phosphonium dicathione.

[0423] <Metal Ions>

[0424] "A m＋ The metal ions that can be used as 」 are not particularly limited, for example, Li ＋ , Na ＋ , K ＋ , Rb ＋ , Cs ＋ , Be 2＋ , Mg 2＋ , Ca 2＋ , Sr 2＋ , Ba 2＋ , Al 3＋ , Co 3＋ , Bi 3＋ , Zr 4＋ , Hf 4＋ , Bi 5＋ Examples include the following. These metal ions may consist of a single type or a combination of two or more types.

[0425] As for metal ions, Li ＋ , Na ＋ , K ＋ , Rb ＋ , Cs ＋ , Mg 2＋ , Ca 2＋ , Sr 2＋ , Ba 2＋ , Al 3＋ , Co 3＋ is desirable, and Na ＋ , K ＋ , Rb ＋ , Cs ＋ , Ca 2＋ , Al 3＋ , Co 3＋ It is more desirable.

[0426] <Ammonium Cationic>

[0427] The ammonium cation is not particularly limited and known and commonly used ones may be used. The above ammonium cation is not particularly limited and, for example, ammonium ion (NH4) ＋ ), primary ammonium cation (NH3(R 5A ) ＋ )), secondary ammonium cation (NH2(R 5A )(R 5B )) ＋ ), tertiary ammonium cation (NH(R 5A )(R 5B )(R 5C ) ＋ ), quaternary ammonium cation (N(R 5A )(R 5B )(R 5C )(R 5D ) ＋ ...can be cited. Also, the above R 5A ~ R 5D ...is to be indicated as the same as defined below.

[0428] As for ammonium cations, ammonium ions (NH4) ＋ ), preferably a quaternary ammonium cation, and in particular, ammonium ion (NH4 ＋ ), an organic quaternary ammonium cation represented by the following general formula (VIII-1) is more preferred.

[0429] [Chemical Formula 32]

[0430]

[0431] In general formula (VIII-1), R 5A ~ R 5D C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0432] The above R 5A ~ R 5DAny divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted),

[0433] The above R 5A ~ R 5D The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxygen, C 1-18 Hydrocarbylamino group, D C 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbylaminocarbonyl group, D C 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbylcarbonylamino group, C 1-18 Hydrocarbylaminocarbonyloxygen, D C 1-18 Hydrocarbylaminocarbonyloxygen, C 1-18 Hydrocarbylaminocarbonylamino group, D C 1-18 Hydrocarbylaminocarbonylamino group, C1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be substituted with a hydrocarbylthio group, and any divalent carbon atom at any position excluding the terminals of these substituents may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0434] Also R 5A ~ R 5D Any two of them are directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group and form a ring together with the nitrogen atom in formula (VIII-1).

[0435] In general formula (VIII-1), R 5A ~ R 5D As for, C which may each have independent substituents 1-18 It is preferable that it be a hydrocarbyl group, and C 1-12 Alkyl group, C 1-12 alkenyl group, C 1-12 alkynyl group, C 1-12 It is more desirable to have a circular table.

[0436] 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, etc.

[0437] <Ammonium Decathione>

[0438] Ammonium dicathions are not particularly limited and known and commonly used ones may be used. Examples of ammonium dicathions include organic quaternary ammonium dicathions represented by the following general formula (VIII-2).

[0439] [Chemical Formula 33]

[0440]

[0441] Among general formulas (VIII-2),

[0442] R 6A ~ R 6F C, which may each have independent substituents 1-18 It represents a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, and a 5–18 member aromatic complex cyclic group, and

[0443] The above R 6A ~ R 6F Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0444] L 6 C that may have substituents 1-18 Representing a hydrocarbylene group,

[0445] The above L 6 Any divalent carbon atom at any position may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0446] The above R 6A ~ R 6F and L 6The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxygen, C 1-18 Hydrocarbylamino group, D C 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbylaminocarbonyl group, D C 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbylcarbonylamino group, C 1-18 Hydrocarbylaminocarbonyloxygen, D C 1-18 Hydrocarbylaminocarbonyloxygen, C 1-18 Hydrocarbylaminocarbonylamino group, D C 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18It may be substituted with a hydrocarbylthio group, and any divalent carbon atom at any position excluding the terminals of these substituents may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0447] R 6A ~ R 6F Any two of them are directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group and form a ring together with the nitrogen atom in formula (VIII-2).

[0448] The organic quaternary ammonium dicathion represented by the above general formula (VIII-2) is not particularly limited, and examples include 1,4-diallyl-1,4-diazabicyclo[2.2.2]octan-1,4-diium, 1,4-di(2-(meth)acryloyloxyethyl)-1,4-diazabicyclo[2.2.2]octan-1,4-diium, 1,4-bis(2-(meth)acrylamideethyl)-1,4-diazabicyclo[2.2.2]octan-1,4-diium.

[0449] <Phosphonium Cationic>

[0450] Phosphonium cations are not particularly limited and known and commonly used ones may be used. Examples of phosphonium cations include organic quaternary phosphonium cations represented by the following general formula (VIII-3).

[0451] [Chemical Formula 34]

[0452]

[0453] In general formula (VIII-3), R 7A ~ R 7DC, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group;

[0454] The above R 7A ~ R 7D Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0455] The above R 7A ~ R 7D The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxygen, C 1-18 Hydrocarbylamino group, D C 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbylaminocarbonyl group, D C 1-18 Hydrocarbylaminocarbonyl group, C1-18 Hydrocarbylcarbonylamino group, C 1-18 Hydrocarbylaminocarbonyloxygen, D C 1-18 Hydrocarbylaminocarbonyloxygen, C 1-18 Hydrocarbylaminocarbonylamino group, D C 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be substituted with a hydrocarbylthio group, and any divalent carbon atom at any position excluding the terminals of these substituents may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0456] Also R 7A ~ R 7D Any two of them are directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group and form a ring together with the phosphorus atom in formula (VIII-3).

[0457] R in Equation (VIII-3) 7A , R 7B , R 7C and R 7D As for, C which may each have independent substituents 1-18 It is preferable that it be a hydrocarbyl group, and C 1-12 Alkyl group, C 1-12 alkenyl group, C 1-12 alkynyl group, C 1-12 It is more desirable to have a circular table.

[0458] Specific examples of the above organic phosphonium cations include (methoxymethyl)triphenylphosphonium cation, tetrabutylphosphonium cation, tetraethylphosphonium cation, amyltriphenylphosphonium cation, acetonyltriphenylphosphonium cation, benzyltriphenylphosphonium cation, ethyltriphenylphosphonium cation, butyltriphenylphosphonium cation, hexyltriphenylphosphonium cation, (1-naphthylmethyl)triphenylphosphonium cation, (4-nitrobenzyl)triphenylphosphonium cation, (2-hydroxybenzyl)triphenylphosphonium cation, tetraphenylphosphonium cation, triphenyltetradecylphosphonium cation, cyclopropylphenylphosphonium cation, ethoxycarbonylmethyl(triphenyl)phosphonium cation, phenacyltriphenylphosphonium cation, etc.

[0459] <Phosphonium Decathione>

[0460] Phosphonium dications are not particularly limited and known and commonly used ones may be used. Examples of phosphonium dications include organic quaternary phosphonium dications represented by the following general formula (VIII-4).

[0461] [Chemical Formula 35]

[0462]

[0463] In general formula (VIII-4), R 8A ~ R 8F C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0464] The above R 8A ~ R 8FAny divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted),

[0465] L 8 is, C that may have substituents 1-18 Representing a hydrocarbylene group,

[0466] The above L 8 Any divalent carbon atom at any position may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0467] The above R 8A ~ R 8F and L 8 The hydrogen atoms included in [the formula] are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxyl group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxyl group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxyl or carboxyl group having a protecting group, (t) a polar group having an acid-dissociable group, or (u) C such that at least some of the hydrogen atoms may be substituted with (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxygen, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxygen, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxygen, C1-18 Hydrocarbylamino group, D C 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbylaminocarbonyl group, D C 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbylcarbonylamino group, C 1-18 Hydrocarbylaminocarbonyloxygen, D C 1-18 Hydrocarbylaminocarbonyloxygen, C 1-18 Hydrocarbylaminocarbonylamino group, D C 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 It may be substituted with a hydrocarbylthio group, and any divalent carbon atom at any position excluding the terminals of these substituents may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0468] R 8A ~ R 8F Any two of them are directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group to form a ring together with the phosphorus atom in formula (VIII-4).

[0469] 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)dicathione, ethylenebis(triphenylphosphonium)dicathione, pentamethylenebis(triphenylphosphonium)dicathione, etc.

[0470] [1-1-2-3. A m＋ and B n＋ [Ratio of]

[0471] In general formula (I), m is an integer from 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

[0472] (A m＋ ) a (B n＋ ) b (C (am＋bn)- ) (I)

[0473] In addition, in the mixture of heteropolyphosphates in which the defect site is modified, A m＋ and B n＋ A heteropolyphosphate modified with multiple defect sites having different ratios may be included. In this case, the values ​​of a and b can be obtained by, for example, by performing analysis by NMR, XRF analysis, XPS analysis, etc.

[0474] As for the ratio of a to b, the heteropolyacid anion with the vacancy site modified, A m＋ , B n＋ Although it varies depending on the type, it is preferable that a : b = 0 ~ 8 : 1 ~ 12, more preferable that 0 ~ 4 : 2 ~ 8, and even more preferable that 0 ~ 2 : 1 ~ 4.

[0475] In particular, when the value of am+bn is an integer from 2 to 8 and m and n are 1, it is preferable that a is a real number from 0 to 7 and b is a real number from 1 to 8, and more preferable that a is a real number from 0 to 4 and b is a real number from 2 to 8.

[0476] [1-1-3. (A) Content of Ingredient]

[0477] The content of component (A) in the resist material is not particularly limited and can be appropriately set according to the method of applying the resist material to a substrate, etc., the thickness of the applied film, etc. As for the content of component (A) in the resist material, when the resist material is 100 mass%, it is preferable that it is 0.01 to 20 mass%, more preferable that it is 0.1 to 15 mass%, and even more preferable that it is 0.2 to 10 mass%.

[0478] [1-2. (B) Acid Diffusion Control Agents]

[0479] The resist material according to the present embodiment may contain, in addition to (A) a heteropolyphosphate or a mixture thereof in which the defect site is modified, (B) an acid diffusion control agent as an optional component that traps acid generated by exposure.

[0480] The above acid diffusion control agent is not particularly limited and any known or commonly used one may be used. Examples of acid diffusion control agents include (B1) a photodegradable base that decomposes upon exposure to light and loses its acid diffusion control ability, (B2) a nitrogen-containing organic compound that does not correspond to the component of (B1), and one of these may be used alone or two or more may be used in combination.

[0481] [1-2-1. (B1) Photodecomposition bases]

[0482] (B1) The photodisintegrating base loses its ability to control acid diffusion by decomposing upon exposure, while acting as a quencher in the unexposed area to control acid diffusion. For this reason, by incorporating (B1) the photodisintegrating base into the resist material, characteristics such as increased sensitivity, reduced roughness, and suppression of coating defects can be improved.

[0483] The above photodisintegrating base is not particularly limited and known and commonly used ones may be used. As a photodisintegrating base, for example, "carboxylate compound B" represented by the following general formula (IX-1) A 」, “sulfonate compound B” represented by the following general formula (IX-2). B 」, “sulfonilamide salt compound B” represented by the following general formula (IX-3). C Examples include 」 etc. In the following, carboxylic acid anions, sulfonic acid anions, sulfonylamide anions, onium cations, or dications (D) included in the following general formulas (IX-1) to (IX-3). p＋ Explain each of the following.

[0484] [Chemical Formula 36]

[0485]

[0486] [Chemical Formula 37]

[0487]

[0488] [Chemical Formula 38]

[0489]

[0490] [1-2-1-1. Carboxylate Compound B A ]

[0491] As the above (B1) photodecaying base, the “carboxylate compound B” represented by the following general formula (IX-1) is used. A As with 」, carboxylic acid anions and onium cations or dications (D p＋ Salts of ) can be used.

[0492] [Chemical Formula 39]

[0493]

[0494] "R A b1 」 is C that may have substituents 1-18As a hydrocarbyl group, a 3- to 18-membered non-aromatic complex cyclic group, or a 5- to 18-membered aromatic complex cyclic group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0495] R A b1 As for, C which may have substituents 1-18 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0496] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0497] <Carboxylate compound B A1 >

[0498] Carboxylate compound B represented by the above general formula (IX-1). A is a carboxylate compound B represented by the following general formula (IX-1-1). A1 It is okay to continue.

[0499] [Chemical Formula 40]

[0500]

[0501] "X A 」 is C that may have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0502] X A As for, C which may have substituents 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted), and

[0503] C that can have substituents 3-18 Circular table or C 6-18 As an aryl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0504] "L A 」 is, X A Wow -COO - As a device connecting, the following general formula (L A -1) ∼ (L A You can use a connector represented by -7).

[0505] [Chemical Formula 41]

[0506]

[0507] [Chemical Formula 42]

[0508]

[0509] [Chemical Formula 43]

[0510]

[0511] [Chemical Formula 44]

[0512]

[0513] [Chemical Formula 45]

[0514]

[0515] [Chemical Formula 46]

[0516]

[0517] [Chemical Formula 47]

[0518]

[0519] [During the meal, L A b1 and L A b2 C, which may have single bonds or substituents 1-8 Represents a hydrocarbylene group, and *1 is X A The connection with, *2 is -COO - Indicates the connection with.

[0520] L A b1 and L A b2 As for, C which may have a single bond or a substituent 1-8 alkylene group or C 6-8 It is preferable that it be an arylene group, and C may have a single bond or a substituent. 1-8 It is more preferable that it be an alkylene group.

[0521] <Examples of Carboxylic Acid Anions>

[0522] The above carboxylate compound B Aor B A1 The carboxylic acid anions are not particularly limited and examples include trifluoroacetic acid anion, pentafluoropropionic acid anion, 2-methoxyacetic acid anion, 2-methoxy-2-methylpropionic acid anion, 2-hydroxyacetic acid anion, 2-hydroxy-2-methylpropionic acid anion, 2-acetoxyacetic acid anion, adamantan-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, benzoic acid anion, salicylic acid anion, 3-hydroxybenzoic acid anion, 3-trifluoromethylbenzoic acid anion, etc.

[0523] [Chemical Formula 48]

[0524]

[0525] [Chemical Formula 49]

[0526]

[0527] [Chemical Formula 50]

[0528]

[0529] [1-2-1-2. Sulfonate Compound B B ]

[0530] As the above (B1) photodecaying base, the “sulfonate compound B” represented by the following general formula (IX-2) is used. B As with 」, sulfonic acid anions and onium cationic or dicationic (D p＋ Salts of ) can be used.

[0531] [Chemical Formula 51]

[0532]

[0533] "R B b1 」 is C that may have substituents 1-18As a hydrocarbyl group, a 3- to 18-membered non-aromatic complex cyclic group, or a 5- to 18-membered aromatic complex cyclic group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0534] R B b1 As for, C which may have substituents 1-18 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0535] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0536] <Sulfonate compound B B1 >

[0537] Sulfonate compound B represented by the above general formula (IX-2). B a. Sulfonate compound B represented by the following general formula (IX-2-1). B1 It is okay to continue.

[0538] [Chemical Formula 52]

[0539]

[0540] "X B 」 is C that may have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0541] X B As for, C which may have substituents 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted), and

[0542] C that can have substituents 3-18 Circular table or C 6-18 As an aryl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0543] "L B 」 is, X B and -SO2-O - As a device connecting, the following general formula (L B -1) ∼ (L B You can use a connector represented by -7).

[0544] [Chemical Formula 53]

[0545]

[0546] [Chemical Formula 54]

[0547]

[0548] [Chemical Formula 55]

[0549]

[0550] [Chemical Formula 56]

[0551]

[0552] [Chemical Formula 57]

[0553]

[0554] [Chemical Formula 58]

[0555]

[0556] [Chemical Formula 59]

[0557]

[0558] [During the meal, L B b1 and L B b2 C, which may have single bonds or substituents 1-8 Representing a hydrocarbylene group, *1 is X B The connection with, *2 is -SO2-O - Indicates the connection with.

[0559] L B b1 and L B b2 As for, C which may have a single bond or a substituent 1-8 alkylene group or C 6-8 It is preferable that it be an arylene group, and C may have a single bond or a substituent. 1-8 It is more preferable that it be an alkylene group.

[0560] <Example of Sulfonate Anion>

[0561] The above sulfonate compound BB or B B1 Sulfonate anions are not particularly limited and examples include camphorsulfonic acid anion, (adamantan-1-yl)methanesulfonic acid anion, (adamantan-1-carbonyloxy)ethane-1-sulfonic acid anion, cyclohexanesulfonic acid anion, 2-(cyclohexanecarbonyloxy)ethane-1-sulfonic acid anion, bicyclo[2.2.1]heptane-2-sulfonic acid anion, benzenesulfonic acid anion, 4-methylbenzenesulfonic acid anion, etc.

[0562] [Chemical Formula 60]

[0563]

[0564] [1-2-1-3. Sulfonilamide Compound B C ]

[0565] As the above (B1) photodisintegrable base, the “sulfonylamide salt compound B” represented by the following general formula (IX-3) is used. C As with 」, sulfonylamide anions and onium cationic or dicationic (D p＋ Salts of ) can be used.

[0566] [Chemical Formula 61]

[0567]

[0568] "R C b1 」 is C that may have substituents 1-18 As a hydrocarbyl group, a 3- to 18-membered non-aromatic complex cyclic group, or a 5- to 18-membered aromatic complex cyclic group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0569] "R C b2 」 is C that may have substituents 1-18As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0570] R C b1 As for, C which may have substituents 1-18 As a hydrocarbyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0571] C that can have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0572] R C b2 As for, C which may have substituents 1-18 alkyl group or C 3-18 As a divalent group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0573] C 1-12It is more preferable that it be a haloalkyl group, and C 1-5 It is more preferable that it be a fluorinated alkyl group.

[0574] <Sulfonilamide compound B C1 >

[0575] Sulfonylamide salt compound B represented by the above general formula (IX-3). C a. Sulfonilamide salt compound B represented by the following general formula (IX-3-1). C1 It is okay to continue.

[0576] [Chemical Formula 62]

[0577]

[0578] "X C 」 is C that may have substituents 1-18 Alkyl group, C 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0579] X C As for, C which may have substituents 3-18 Circular tableware, C 6-18 aryl group, or C 7-18 As an aralkyl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted), and

[0580] C that can have substituents 3-18 Circular table or C 6-18As an aryl group, any divalent carbon atom excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not substituted simultaneously).

[0581] "L C 」 is, X C wa -N - -SO2-R C b2 As a device connecting, the following general formula (L C -1) ∼ (L C You can use a connector represented by -7).

[0582] [Chemical Formula 63]

[0583]

[0584] [Chemical Formula 64]

[0585]

[0586] [Chemical Formula 65]

[0587]

[0588] [Chemical Formula 66]

[0589]

[0590] [Chemical Formula 67]

[0591]

[0592] [Chemical Formula 68]

[0593]

[0594] [Chemical Formula 69]

[0595]

[0596] [During the meal, L C b1 and L C b2 C, which may have single bonds or substituents 1-12Represents a hydrocarbylene group, and *1 is X C The connection with, *2 is -N - -SO2-R C b2 Indicates the connection with.

[0597] L C b1 and L C b2 As for, C which may have a single bond or a substituent 1-12 Alkylene group, C 1-12 Cycloalkylene group or C 6-12 It is preferable that it be an arylene group, and C may have a single bond or a substituent. 1-8 alkylene group or C 1-8 It is more preferable that it be a cycloalkylene group.

[0598] <Examples of Sulfonylamide Anions>

[0599] The above sulfonylamide salt compound B C or B C1The sulfonylamide anions are not particularly limited and include, 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-((cyclohexanecarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1]heptane-2-ylmethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1]heptane-7-ylmethyl((trifluoromethyl)sulfonyl)amide anion, Examples include 2-((adamantan-1-carbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anone, 2-(adamantan-1-carboxamide)ethyl((trifluoromethyl)sulfonyl)amide anone, 2-(4-((adamantan-1-carbonyl)oxy)cyclohexyl)ethyl((trifluoromethyl)sulfonyl)amide anone, 4-((adamantan-1-carbonyl)oxy)phenyl((trifluoromethyl)sulfonyl)amide anone, etc.

[0600] [Chemical Formula 70]

[0601]

[0602] [Chemical Formula 71]

[0603]

[0604] [Chemical Formula 72]

[0605]

[0606] [1-2-1-4. Onium cation or dicathione (D p＋ )]

[0607] As the cation portion of the above (B1) photodecayable base, onium cation or dication D p＋ ...can be used. Here, "(D p＋ ) 1 / pIn 」, (D p＋ ) represents an onium cation or decathion, and p represents an integer of 1 or 2.

[0608] The above onium cation or dication is not particularly limited, and organic sulfonium cation, organic sulfonium dication, organic iodonium cation, organic quaternary ammonium cation, organic quaternary ammonium dication, organic phosphonium cation, organic phosphonium dication, etc. may be used.

[0609] The above onium cation or dicathion (D p＋ As for ), for example, an organic sulfonium cation represented by the following general formula (X-1) can be used.

[0610] [Chemical Formula 73]

[0611]

[0612] In the general formula (X-1), R D 1A , R D 1B and R D 1C C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0613] The above R D 1A , R D 1B and R D 1C Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0614] R D 1A , RD 1B and R D 1C Any two of them are directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group and form a ring together with the sulfur atom in formula (X-1).

[0615] Also, the above onium cation or dicathion (D p＋ As for ), for example, an organic sulfonium dicathione represented by the following general formula (X-2) can be used.

[0616] [Chemical Formula 74]

[0617]

[0618] In the general formula (X-2), R D 2A , R D 2B , R D 2C and R D 2D C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0619] The above R D 2A , R D 2B , R D 2C and R D 2D Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0620] KD 2A , K D 2B and L D 2 C, which may each have independent substituents 1-18 Representing a hydrocarbylene group,

[0621] The above K D 2A , K D 2B and L D 2 Any divalent carbon atom at any position may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0622] R D 2A , R D 2B and K D 2A Any 2 of, and / or R D 2C , R D 2D and K D 2B Any two of these, directly connected to each other by a single bond, or by a divalent linker such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group to form a ring together with the sulfur atom in formula (X-2).

[0623] The above onium cation or dicathion (D p＋ As for ), for example, an organic iodine cation represented by the following general formula (X-3) can be used.

[0624] [Chemical Formula 75]

[0625]

[0626] In the general formula (X-3), RD 3A and R D 3B C, which may each have independent substituents 1-18 Representing a hydrocarbyl group, a 3–18 member non-aromatic complex cyclic group, or a 5–18 member aromatic complex cyclic group, and

[0627] The above R D 3A and R D 3B Any divalent carbon atom at any position excluding the terminal may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0628] R D 3A and R D 3B are directly connected to each other by single bonds, or by divalent linkers -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may be connected via an alkylene group and form a ring together with the iodine atom in formula (X-3).

[0629] [1-2-2. (B2) Nitrogen-containing organic compounds]

[0630] In addition (B) as an acid diffusion control agent, (B2) a nitrogen-containing organic compound that does not correspond to (B1) may be included. The nitrogen-containing organic compound is not particularly limited and, for example, aliphatic amines, aromatic amines, heterocyclic amines, etc. may be used.

[0631] Examples of nitrogen-containing organic compounds include, for instance, 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.

[0632] These nitrogen-containing organic compounds may be used as a single type or in combination of two or more types.

[0633] [1-2-3. (B) Content of Ingredient]

[0634] The content of the acid diffusion control agent (B) included in the resist material related to the present embodiment is not particularly limited and can be appropriately selected depending on the content and type of component (A). As for the content of component (B) in the resist material, it is preferable to have 0.1 to 30 parts by mass per 100 parts by mass of component (A), more preferable to have 0.2 to 25 parts by mass, and even more preferable to have 0.5 to 20 parts by mass.

[0635] [1-3. Organic Solvents]

[0636] The resist material related to the present embodiment may additionally contain an organic solvent. The organic solvent is not particularly limited and any known or commonly used one may be used. As for the organic solvent, it is preferable that it be an organic solvent capable of uniformly dissolving or dispersing when prepared with (A) a heteropolyphosphate or a mixture thereof in which the defective site is modified.

[0637] 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 types.

[0638] Specific examples of the above polar solvent include, for example,

[0639] 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, propylene glycol monomethyl ether (PGME);

[0640] Ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.;

[0641] Ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methylisopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, furfural, etc.;

[0642] Amid-based solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, 1-butyl-2-pyrrolidone;

[0643] Ester-based solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, propylene glycol monomethyl ether acetate (PGMEA);

[0644] Nitrile-based solvents such as acetonitrile, propionitrile, and benzonitrile:

[0645] Examples include non-proton polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea.

[0646] In addition, non-polar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene.

[0647] The above organic solvent may be used as a single type or in combination of two or more types.

[0648] As for the organic solvent to be included in the resist material related to the present embodiment, a polar solvent is preferred in terms of coating properties, and it is more preferable to include an amide-based solvent, an ester-based solvent, an alcohol-based solvent, or a ketone-based solvent in terms of solubility. As for the amide-based solvent, it is preferable to have at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. Furthermore, as for the ester-based solvent or alcohol-based solvent, it is preferable to have an ester bond and / or a hydroxyl group in terms of solubility, and among those mentioned above, it is preferable to have 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.

[0649] The content of the organic solvent in the resist material is not particularly limited and can be appropriately set depending on the method of applying the resist material to a substrate, the thickness of the applied film, etc. As for the content of the organic solvent in the resist material, it is preferable that the solid content concentration of the resist material be 0.01 to 20 mass%, more preferable that it be 0.1 to 15 mass%, and even more preferable that it be in the range of 0.2 to 10 mass%.

[0650] [1-4. Others]

[0651] The resist material related to the present embodiment may additionally contain, as 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.

[0652] In the resist material related to the present embodiment, it is preferable not to include epoxy resin. In addition, it is preferable not to include hydrogen peroxide.

[0653] [2. Pattern Formation Method]

[0654] A pattern forming method related to the present embodiment comprises a process of applying a resist material to a substrate, a process of exposing a resist film formed by the application process, and a process of developing the exposed resist film.

[0655] [2-1. Coating Process]

[0656] The pattern forming method related to the present embodiment has a process of applying a resist material to a substrate.

[0657] <Circuit Board>

[0658] The substrate used in this embodiment is not particularly limited and may use a known or conventional one. As a substrate, for example, a substrate for electronic components or a substrate having a predetermined wiring pattern formed thereon may be used.

[0659] The material of the substrate is not particularly limited, and examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and substrates made of inorganic materials such as glass, titanium oxide, and silicon dioxide.

[0660] The size and shape of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, have irregularities, or be in the form of a thin sheet.

[0661] Surface treatment may be performed on the surface of the substrate as needed. In the case of a substrate having hydroxyl groups on its surface layer, surface treatment of the substrate using a silane-based coupling agent capable of reacting with hydroxyl groups can change the surface layer of the substrate from hydrophilic to hydrophobic, thereby increasing the adhesion between the substrate and the metal compound-containing film. Examples of the above-mentioned silane-based coupling agents include hexamethyldisilazane (HMDS).

[0662] <Application Method>

[0663] The method of applying the resist material onto the substrate is not particularly limited, and known and conventional methods may be used. As for the application method, dry methods may include, for example, CVD methods (chemical vapor deposition) such as thermal CVD, plasma CVD, and photo-CVD; PVD methods (physical vapor deposition) such as vacuum deposition, plasma-induced deposition, sputtering, and ion plating. Additionally, wet methods may include, for example, spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, screen printing, etc.

[0664] Regarding the method of applying the resist material related to the present embodiment onto a substrate, it is preferable to use a wet method such as a spin coating method or screen printing, and it is more preferable to use a spin coating method, from the perspective of forming a uniform film thickness. After forming the coating film, backside rinsing and edge bead removal steps may be performed to remove edge beads.

[0665] The method for drying the resist film formed by applying a resist material onto a substrate is not particularly limited, and, for example, can be carried out using a heating device such as a hot plate (post-applied bake (PAB)), a pressure reducing device, etc.

[0666] The baking conditions are not particularly limited and can be appropriately set depending on the type and application of the resist film. As for the baking temperature, it is preferable to have a temperature of 80 to 300°C, more preferable to have a temperature of 80 to 200°C, and even more preferable to have a temperature of 80 to 130°C. In addition, as for the baking time, it is preferable to have a baking time of 10 seconds to 300 seconds, more preferable to have a baking time of 20 seconds to 180 seconds, and even more preferable to have a baking time of 30 seconds to 120 seconds.

[0667] 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.

[0668] [2-2. Photolithography Process]

[0669] The pattern forming method related to the present embodiment has a process of exposing a resist film formed by the coating process to light.

[0670] As an exposure device for the exposure process of a resist film, for example, an ArF exposure device, an electron beam lithography device, an EUV exposure device, etc. may be used. In addition, in the exposure process, exposure may be performed through a mask (mask pattern) having a predetermined pattern formed thereon, or selective exposure may be performed by lithography by direct irradiation of an electron beam without passing through a mask pattern.

[0671] 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-ray, and soft X-ray may be used.

[0672] As for the exposure amount onto the resist film, in the case of an ArF excimer laser or a KrF excimer laser, it is preferable to be 1 to 200 mJ / ㎠, and more preferable to be 20 to 60 mJ / ㎠. In addition, in the case of extreme ultraviolet light, the exposure amount is, for example, 500 mJ / ㎠ or less, preferably 0.1 to 200 mJ / ㎠, more preferable to be 3 to 100 mJ / ㎠, and even more preferable to be 5 to 50 mJ / ㎠.

[0673] In the case of electron beams, it is preferable to expose at a dose of 3 μC / ㎠ to 2 mC / ㎠ at 50 kV, and more preferable to expose at a dose of 10 μC / ㎠ to 1.5 mC / ㎠.

[0674] After exposing the resist film to light, a bake (post-exposure bake (PEB)) treatment may or may not be performed. The bake conditions are not particularly limited and can be appropriately set according to the type and application of the resist film. As for the bake temperature, using a heating device such as a hot plate, it is preferable to have a temperature of 80 to 300°C, more preferable to have a temperature of 80 to 200°C, and even more preferable to have a temperature of 80 to 130°C. In addition, as for the bake time, it is preferable to have a temperature of 10 to 300 seconds, more preferable to have a temperature of 20 to 180 seconds, and even more preferable to have a temperature of 30 to 120 seconds.

[0675] [2-3. Development Process]

[0676] The pattern formation method related to the present embodiment includes a process of developing the exposed resist film. In the development process, a pattern can be formed by developing the exposed resist film with a developer. A case where the exposed area remains as a pattern after development is a negative-type pattern formation process, and a case where the exposed area is removed after development is a positive-type pattern formation process. Whether a positive or negative pattern is formed can be appropriately selected based on the resist material or the developer. Furthermore, after development, the film may be washed with a rinse solution and then dried, or, in some cases, additionally baked.

[0677] As for the developer used in this embodiment, an alkaline developer may be used as a developer for an alkaline development process, or a developer containing an organic solvent (an organic developer) may be used as a developer for an organic solvent development process.

[0678] <Alkaline Phenomenon Process>

[0679] The alkaline developer used in the alkaline development process is not particularly limited and any known or commonly used one may be used. Examples of the 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 dimethyl ethanolamine and triethanolamine.

[0680] In addition, pure water can be used as the rinsing solution in the alkaline development process.

[0681] <Organic Solvent Development Process>

[0682] Examples of developers used in organic solvent development processes include developers containing one or more organic solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, polar solvents such as amide-based solvents and ether-based solvents, and hydrocarbon-based solvents.

[0683] Specific examples of organic solvents include, for example,

[0684] Ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methylisopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, furfural, etc.;

[0685] Ester-based solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, propylene glycol monomethyl ether acetate (PGMEA);

[0686] 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, propylene glycol monomethyl ether (PGME);

[0687] Nitrile-based solvents such as acetonitrile, propionitrile, and benzonitrile:

[0688] Amid-based solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, 1-butyl-2-pyrrolidone;

[0689] Ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.;

[0690] Hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene;

[0691] Examples include the following. These may be used as a single type or in combination of two or more types.

[0692] Among these, as an organic solvent used in the developer, it is preferable that it be a polar solvent, and it is preferable that it include an amide solvent, an alcohol solvent, or an ester solvent, and it is more preferable that it includes an amide solvent or an ester solvent and an alcohol solvent.

[0693] As for the amide solvent, it is preferable to use at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone.

[0694] In addition, as an ester solvent, it is preferable to use one or more selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate.

[0695] And as an alcohol-based solvent, it is preferable to use at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol.

[0696] When the developing solution contains both an amide-based solvent or an ester-based solvent and an alcohol-based solvent, the mixing ratio (weight ratio) of the amide-based solvent or ester-based solvent and the alcohol-based solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0697] After developing with the above-mentioned developer, a process of washing with a rinsing solution may be included. The rinsing solution is not particularly limited and any known conventional one may be used. As for the rinsing solution, among the water or organic solvents included in the above-mentioned developer, one that is difficult to dissolve the resist pattern may be appropriately selected and used.

[0698] As for the rinsing solution, it 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 may be used. Among these, as the rinsing solution, 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, more preferable to use at least one selected from the group consisting of alcohol solvents and ester solvents, and even more preferable to use at least one alcohol solvent.

[0699] As an alcohol-based solvent used in the rinse solution, a monohydric alcohol having 2 to 8 carbon atoms is preferred, and the monohydric alcohol may be of any straight-chain, branched, or cyclic type. Specific examples of the monohydric alcohol include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, etc.

[0700] These organic solvents may be used as a single type or in combination of two or more types.

[0701] <Development method using developer solution, and cleaning method using rinse solution>

[0702] The method of developing the exposed resist film using the above developer is not particularly limited, and known and conventional methods may be used. Examples of methods for developing using the above developer include, for instance, a method of immersing a substrate having a resist film after exposure in the above developer for a certain period of time (dip method), a method of spraying the above developer onto the surface of the resist film after exposure (spray method), and a method of dispensing the above developer at a certain speed from a discharge nozzle toward the surface of the resist film after exposure on a substrate rotating at a certain speed (dynamic dispensing method).

[0703] The method of cleaning the resist pattern with the above-mentioned rinse solution is not particularly limited, and known and conventional methods may be used. Examples of cleaning methods using the above-mentioned rinse solution include, for instance, a method of immersing the resist pattern in the above-mentioned rinse solution for a certain period of time (dip method), a method of spraying the above-mentioned rinse solution onto the surface of the resist pattern (spray method), and a method of dispensing the above-mentioned rinse solution at a certain speed from a discharge nozzle toward the surface of the resist pattern rotating at a certain speed (dynamic dispensing method).

[0704] [3. Patterned Structure]

[0705] The patterned structure related to the present embodiment is obtained by forming a pattern on a substrate using the pattern forming method.

[0706] The average thickness of part or all of the patterned structure related to the present embodiment is not particularly limited and can be appropriately set according to the purpose of use, etc. In the patterned structure, it is preferable to have a portion with an average thickness of 1 to 100 nm, more preferable to have a portion with an average thickness of 5 to 75 nm, and even more preferable to have a portion with an average thickness of 10 to 60 nm.

[0707] In addition, the pitch of some or all of the patterned structure related to the present embodiment is not particularly limited and can be appropriately set according to the purpose of use, etc. In the patterned structure, it is preferable to have a portion with a pitch of 100 nm or less, more preferable to have a portion with a pitch of 50 nm or less, and even more preferable to have a portion with a pitch of 20 nm or less.

[0708] By patterning the resist material related to the present embodiment using the pattern forming method, it becomes possible to manufacture parts with a pitch of 50 nm, 20 nm, and 15 nm on part or all of the patterned structure.

[0709] [4. Resist materials for electron beams or EUV]

[0710] The resist material related to the present embodiment contains a heteropolyphosphate or a mixture thereof with a modified defect site, and a sulfonium cationic acid, sulfonium dication, or iodonium cationic acid having one or more polar groups having acid-dissociable groups in the cation portion of the heteropolyphosphate or mixture thereof with the modified defect site is used. Accordingly, the heteropolyphosphate or mixture thereof with the modified defect site can exhibit both the function of a photocatalytic agent and the function of changing solubility in a developer solution through the action of an acid. For this reason, the resist material related to the present embodiment has good sensitivity to electron beam and EUV light sources and can be preferably used as a resist material corresponding to these exposure light sources.

[0711] Examples

[0712] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0713] [1. Synthesis of Heteropolysates (Polysates) with Modified Defect Sites]

[0714] Polyphosphates (A-1) to (A-7) were each synthesized by the following methods.

[0715] <Preparation Example: Potassium undecatungstosilicate (α-K8[SiW 11 O 39 ])>

[0716] Silicate hydrate (Manufactured by Japan Inorganic Chemical Industry Co., Ltd.: H4[SiW 12 O 40 380 g of 1 M acetic acid was added to 63 g of ]·xH2O, and the reaction mixture was heated to 45 ℃. Potassium bicarbonate was added (52 g) to make the pH 6.0. Afterwards, the reaction mixture was cooled to room temperature, and 56 g of crude material was obtained by filtration separation by suction filtration. 216 g of pure water was added to the obtained crude material and redissolved by heating to 73 ℃. The solution was recrystallized by cooling at 4 ℃ for 16 hours, and 34 g of the target compound was obtained by filtration separation by suction filtration and vacuum drying.

[0717]

[0718] <Synthetic Example 1: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-diphenyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polysate (A-1))>

[0719] [Chemical Formula 76]

[0720]

[0721] 2.0 mL (10.9 mmol) of phenyltrimethoxysilane (PhSi(OCH3)3) was added to a mixed solvent of 402 g of acetonitrile and 184 g of pure water, and the 1-deleted Keggin-type potassium undecatungsilicate (α-K8[SiW3]) synthesized above was added. 11 O 3910.9 g (3.6 mmol) of ]) was added. The pH was adjusted to 1.8 using 1 M hydrochloric acid. After stirring for 2 hours, the unreacted powder was separated by suction filtration, and the filtrate was concentrated to about 200 g using a rotary evaporator. To this concentrate, a solution of 9.9 g (18.2 mmol) of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide dissolved in 40 g of methanol was added to precipitate the powder. The precipitated powder was separated by suction filtration and washed three times each with 180 mL of pure water, 180 mL of methanol, and 180 mL of methyl-t-butyl ether. Afterwards, the obtained powder was dispersed and washed with 160 g of methanol for 3 hours, separated by filtration by suction filtration, and washed three times with 160 g of methanol. Additionally, by sufficiently vacuum drying, 15.1 g of the target compound, polyphosphate (A-1), was obtained as a white powder.

[0722]

[0723] <Synthetic Example 2: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-di(2-carboxyethyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polysate (A-2))>

[0724] [Chemical Formula 77]

[0725]

[0726] In Synthesis Example 1, the target compound, polyphosphate (A-2), was obtained by the same method as above, except that 2-carboxyethyltrihydroxysilane was used instead of phenyltrimethoxysilane (PhSi(OCH3)3) as the raw material compound.

[0727]

[0728] <Synthetic Example 3 : Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-di(3,3,3-trifluoropropyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polysate (A-3))>

[0729] [Chemical Formula 78]

[0730]

[0731] In Synthesis Example 1, the target compound, polyphosphate (A-3), was obtained by the same method as above, except that 3,3,3-trifluoropropyltrimethoxysilane was used instead of phenyltrimethoxysilane (PhSi(OCH3)3) as the raw material compound.

[0732]

[0733] <Synthetic Example 4: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-di(4-hydroxyphenyl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polysate (A-4))>

[0734] [Chemical Formula 79]

[0735]

[0736] In Synthesis Example 1, the target compound, polyphosphate (A-4), was obtained by the same method as above, except that 4-hydroxyphenyltrimethoxysilane was used instead of phenyltrimethoxysilane (PhSi(OCH3)3) as the raw material compound.

[0737]

[0738] <Synthetic Example 5 : Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-dimethyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polysate (A-5))>

[0739] [Chemical Formula 80]

[0740]

[0741] In Synthesis Example 1, the target compound, polyphosphate (A-5), was obtained by the same method as above, except that methyltrimethoxysilane was used instead of phenyltrimethoxysilane (PhSi(OCH3)3) as the raw material compound.

[0742]

[0743] <Synthetic Example 6 : Tetrakis((4-(2-((2-methyl-2-adamanthyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-diphenyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polysate (A-6))>

[0744] [Chemical Formula 81]

[0745]

[0746] In Synthesis Example 1, the target compound polyphosphate (A-6) was obtained by the same method as above, except that (4-(2-((2-methyl-2-adamanthyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium chloride was used instead of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide as the raw material compound.

[0747]

[0748] <Synthesizing Example 7: Tetrakis(triphenylsulfonium)sutungstate (polysate (A-7))>

[0749] [Chemical Formula 82]

[0750]

[0751] Dissolve 25.6 g of triphenylsulfonium chloride in 50 g of cyclohexanone, and tungstic acid (H4[SiW 12 O 4041.06 g of ]·26H2O was added, and the reaction mixture was stirred at room temperature for 2 hours. The powder obtained by filtering the reaction mixture was dried under reduced pressure at room temperature for 18 hours. The powder after drying was crystallized at room temperature using dichloromethane and acetonitrile to obtain the target compound, polyphosphate (A-7).

[0752]

[0753] [2. Preparation of Test Resist Material]

[0754] As test resist materials, the polyphosphates (A-1) to (A-7) synthesized above, an acid diffusion control agent, and an organic solvent were mixed in the amounts shown in Table 1 below (unit: parts by mass) to prepare test resist materials (R-1) to (R-11).

[0755] In addition, as the acid diffusion control agent (B) listed in Table 1, the acid diffusion control agents (B-1) to (B-3) listed below were used.

[0756] · Acid diffusion control agent (B-1): An acid diffusion control agent which is a salt of a triphenylsulfonium cation and a salicylic acid anion represented by the following formula (B-1).

[0757] [Chemical Formula 83]

[0758]

[0759] · Acid diffusion control agent (B-2): An acid diffusion control agent which is a salt of (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation and salicylic acid anion represented by the following formula (B-2).

[0760] [Chemical Formula 84]

[0761]

[0762] · Acid diffusion control agent (B-3): An acid diffusion control agent which is a salt of a triphenylsulfonium cation and a heptafluorobutyric acid anion represented by the following formula (B-3).

[0763] [Chemical Formula 85]

[0764]

[0765]

[0766] [3. Formation of LS Pattern]

[0767] A resist material (R-1) to (R-11) was applied using a spinner onto an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS), and a post-applied bake (PAB) treatment was performed on a hot plate at a temperature of 120°C for 60 seconds, followed by drying to produce a resist film with a thickness of 50 nm. In addition, the thickness of the formed film was measured using a film thickness measuring device ("M-2000D" manufactured by JA Woollam).

[0768] For the above resist film, an electron beam lithography device F7000S-VD2 (manufactured by Advantest Co., Ltd.) was used to perform lithography (exposure) at an acceleration voltage of 50 kV with a target size of 1:1 line and space pattern with a line width of 50 nm (hereinafter also referred to as the "LS pattern"). After that, a post-exposure bake (PEB) treatment was performed after exposure at 90°C for 60 seconds.

[0769] Next, at 23°C, development was performed for 60 seconds using a developer (NMD-W (manufactured by Tokyo Ohka Industrial Co., Ltd.)), and rinsing was performed for 15 seconds using pure water.

[0770] From the above, a 1:1 LS pattern with a line width of 50 nm is formed, and LS patterns (LS-1) to (LS-11) corresponding to test resist materials (R-1) to (R-11) are obtained. Also, LS patterns (LS-1) to (LS-11) are all positive type patterns.

[0771] [4. Evaluation of LS Pattern Shape]

[0772] The shapes of the above LS patterns (LS-1) to (LS-11) were observed using a field scanning electron microscope (scanning electron microscope, acceleration voltage 10 kV, product name: SU-5000, manufactured by Hitachi High Technology Corporation), and the shapes were evaluated according to the following criteria. The results are shown in Table 2.

[0773] A: The resolution is excellent as almost no footing is observed in the LS pattern of the SEM image.

[0774] B: Slight footing is observed in part of the LS pattern of the SEM image.

[0775] C: No LS pattern is formed across the entire SEM image (not resolved).

[0776]

[0777] From the results of Table 2 above, it can be seen that by using resist materials (R-1) to (R-9) containing polyphosphates (A-1) to (A-6) having polar groups having acid dissociable groups in the cation portion, an LS pattern with a line width of 50 nm with almost no footing and good resolution is obtained ((LS-1) to (LS-9)).

[0778] In addition, when comparing the pattern resolution of (LS-1) and (LS-2), it can be seen that compared to the case where a resist material (R-1) containing a polyphosphate (A-1) having a polar group having an acid dissociable group in the cation portion is used, an LS pattern with even better resolution is obtained by using a resist material (R-2) containing an additional acid diffusion control agent (B-1).

Claims

Claim 1 A resist material containing a heteropolyphosphate or a mixture thereof in which the (A) defect site represented by general formula (I) is modified. (A m＋ ) a (B n＋ ) b (C (am＋bn)- ) (I)[Equation (I) of,A m＋ is, each independently H ＋ , representing a metal ion, ammonium cation, ammonium dicathione, phosphonium cation, or phosphonium dicathione ;B n＋ represents a sulfonium cation, sulfonium dication, or iodonium cation having one or more polar groups having acid-dissociable groups, each independently; C (am＋bn)- [ represents a heteropolyacid anion having a vacancy site, wherein the vacancy site is modified in the heteropolyacid anion; m is an integer from 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.] Claim 2 A resist material according to claim 1, wherein the sulfonium cationic, sulfonium dication, or iodonium dication having one or more polar groups having acid dissociable groups is an organic sulfonium cationic, organic sulfonium dication, or organic iodonium cationic having one or more polar groups having acid dissociable groups. Claim 3 A 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, an acetal-type acid dissociable group, or an aminocarbonyl-type acid dissociable group. Claim 4 A resist material according to claim 1, wherein the poly atoms of the heteropolyacid anion are Mo, W, V, Nb, or Ta, and the hetero atoms are P, Si, B, S, or Ge. Claim 5 A resist material according to claim 1, wherein the heteropolyacid anion having the defect site is a defect Kegyn-type heteropolyacid anion or a defect Dawson-type heteropolyacid anion. Claim 6 A resist material according to claim 1, wherein the formula is formed by a group having one or more heteroatoms P, Si, Ge, or Sn bonded to one or more organic groups bonding to a heteropolyacid anion having the defect site by interposing part or all of the said heteroatoms. Claim 7 In claim 1, a resist material additionally containing (B) an acid diffusion control agent. Claim 8 In claim 7, the above (B) acid diffusion control agent is (B1) a photodisintegrating base, a resist material. Claim 9 A resist material according to claim 1, additionally containing an organic solvent. Claim 10 A resist material that is a resist material for electron beams or EUV in any one of claims 1 to 9. Claim 11 A pattern forming method comprising: a process of forming a resist film using a resist material described in any one of claims 1 to 9; a process of exposing the resist film to light; and a process of developing the exposed resist film using a developer. Claim 12 A pattern forming method according to claim 11, wherein the process of exposing the resist film comprises exposing the resist film to an electron beam with a dose of 2 mC / ㎠ or less or an extreme ultraviolet beam with a dose of 200 mJ / ㎠ or less. Claim 13 A patterned structure obtained by patterning a resist material described in any one of claims 1 to 9.

Images