Resist material, pattern formation method, and patterned structure

Abstract

To provide a novel resist material, a pattern formation method and a patterned structure.SOLUTION: Provided is a resist material which contains (A) a heteropoly acid salt having a modified defect site, represented by general formula (I), or a mixture thereof. The heteropoly acid salt having a modified defect site or a mixture thereof includes a cation moiety into which a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups has been introduced. (Am+)a(Bn+)b(C(am+bn)-) (I)SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Polyacids are anionic metal oxide clusters represented by the general formula [M x O y n- (where x, y, and n are all natural numbers). The metal atom M that constitutes the polyacid is called a polyatom, and examples thereof include Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), Ta (pentavalent), etc. Polyacids include isopolyacids composed of the above polyatom M and oxygen acids, and different types of heteroatoms X in addition to the above polyatom M and oxygen (for example, as heteroatom X, P 5+ , Si 4+ , Ge 4+ , B 3+ , etc. can be mentioned.).) and heteropolyacids containing ([X w M x O y n- (where w, x, y, and n are all natural numbers).)) and can be roughly classified into two categories.

[0003] Polyacids can change their physicochemical properties such as redox ability, actinic ray reactivity, and acidic properties depending on the combination of their constituent elements, structure, type of counter cation, etc.

[0004] It is also known that there are a plurality of defective species in which a part of the basic skeleton of the polyacid is missing. The terminal oxygen atom at the defective site where a part of the basic skeleton of the polyacid is missing has a certain degree of negative charge density on the oxygen atom, and is highly reactive and nucleophilic. Therefore, by reacting the terminal oxygen atom with an atom or molecule having electrophilicity, various polyacid complexes and organic / inorganic hybrid structures having functionality can be formed.

[0005] ​​Patent Document 1 discloses a polyoxometalate compound having a metal-substituted polyoxometalate, which comprises a polyoxometalate having a defect site, a substituted metal atom (divalent platinum or palladium) introduced into the defect site, and an organic ligand. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 11420871 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] An object of the present invention is to provide a novel resist material, a patterning method, and a patterned structure. [Means for Solving the Problems]

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that by using a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups as a counter cation of a heteropolyacid anion having a modified defect site, an acid can be generated by exposure to DUV, XUV, EUV, an electron beam, etc., and the solubility in a developer can be changed by the action of the acid, thereby completing the present invention by providing a novel resist material, a patterning method, and a patterned structure.

[0009] That is, the present invention relates to the following inventions. <1> A resist material containing (A) a heteropolyacid salt represented by the general formula (I) in which a defect site is modified or a mixture thereof. (A m+ ) a (B n+ ) b (C (am+bn)- ) (I) [In formula (I), A m+ each independently represents H + , a metal ion, an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B n+ each independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups; C (am+bn)- represents a heteropolyacid anion in which the defect site in the heteropolyacid anion having a defect site is modified; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.] <2> The resist material according to <1>, wherein the sulfonium cation, sulfonium dication, or iodonium cation having one or more acid dissociable groups is an organic sulfonium cation, organic sulfonium dication, or organic iodonium cation having one or more acid dissociable groups. <3> The resist material according to <1>, wherein the acid dissociable group is a tertiary carbon type acid dissociable group, an allyl type or benzyl type acid dissociable group, an acetal type acid dissociable group, or an aminocarbonyl type acid dissociable group. <4> The resist material according to <1>, wherein the poly atom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the hetero atom is P, Si, B, S, or Ge. <5> The resist material according to <1>, wherein the heteropolyacid anion having a defect site is a defective Keggin type heteropolyacid anion or a defective Dawson type heteropolyacid anion. <6> The resist material according to <1>, wherein the modification is made by a group having one or more hetero atoms P, Si, Ge, or Sn to which one or more organic groups are bonded, bonding to the heteropolyacid anion having the defect site through part or all of the hetero atoms. <7> The resist material according to <1>, further containing (B) an acid diffusion control agent. <8> The resist material according to <7>, wherein the (B) acid diffusion controller is a (B1) photo-disintegrating base. <9> The resist material according to <1>, further containing an organic solvent. <10> The resist material according to <1> to <9>, which is an electron beam resist material or an EUV resist material. <11> A step of forming a resist film using the resist material according to any one of <1> to <9>, a step of exposing the resist film, a step of developing the exposed resist film with a developer, and a pattern forming method including the above steps. <12> The pattern forming method according to <11>, wherein the step of exposing the resist film includes exposing the resist film with an electron beam having a dose of 2 mC / cm or less 2 or an extreme ultraviolet ray having a dose of 200 mJ / cm or less. 2 <13> A patterned structure obtained by patterning the resist material according to any one of <1> to <9>.

[0010] <14> The resist material according to <5>, wherein the defective Keggin-type heteropolyacid anion is represented by the general formula (II-1), (II-2) or (II-3). [XM 11 O 39 c11- (II-1) [XM 10 O 36 c12- (II-2) [XM9O 34 c13- (II-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.) ​​​<15> The resist material according to <5>, wherein the defective Dawson-type heteropolyacid anion is represented by the general formula (III-1), (III-2) or (III-3). [X2M 17 O 61 c21- (III-1) [X2M 16 O 58 c22- (III-2) [X2M 15 O 56 c23- (III-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; c21-~c23- represents the number of negative charges, and c21~c23 are natural numbers.)

[0011] <16> The resist material according to <1>, wherein the heteropolyacid anion with the modified defect site is a heteropolyacid anion with the modified defect site represented by the general formula (VI-1) to (VI-12). [XM 11 O 39 (R 1A X’)2O] c31- (VI-1) [XM 11 O 39 (R 1B1 R 1B2 X’)2] c31- (VI-2) [XM 11 O 39 (R 1D P=O)2] c31- (VI-3) [XM 11 O 39 (R 1E X’’)] c31- (VI-4) [XM 10 O 36 (R 1A X’)2O] c32- (VI-5) [XM 10 O​​​36 (R 1B1 R 1B2 X’)2] c32- (VI-6) [XM 10 O 36 (R 1C X’O)4] c32- (VI-7) [XM 10 O 36 (R 1D P=O)2] c32- (VI-8) [X2M 17 O 61 (R 1A X’)2O] c33- (VI-9) [X2M 17 O 61 (R 1B1 R 1B2 X’)2] c33- (VI-10) [X2M 17 O 61 (R 1D P=O)2] c33- (VI-11) [X2M 17 O 61 (R 1E X’’)] c33- (VI-12) (wherein, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; X’ represents a heteroatom of Si or Ge; X’’ represents a heteroatom of Si, Ge or Sn; R 1A ~R 1E each independently represents a hydro group, or a C 1-18 hydrocarbyl group which may have a substituent, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, the above R 1A ~R 1EThe divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). The above R 1A ~R 1E The hydrogen atoms contained in 1-3 ~R c31, c32 and c33 are natural numbers.) [Effect of the Invention]

[0012] According to the present invention, it is possible to provide a novel resist material, a pattern formation method, and a patterned structure. The resist material according to the present invention contains a heteropolyacid salt or a mixture thereof in which a defective site is modified, and a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups is introduced into the cation part of the heteropolyacid salt or the mixture in which the defective site is modified. Therefore, by exposing the resist material according to the present invention with DUV, XUV, EUV, an electron beam, etc., an acid is generated, and the solubility of the resist material in a developer is changed by the action of the acid, making it possible to form a pattern with good resolution. [Embodiments for Carrying Out the Invention]

[0013] Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0014] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0015] In this specification, the term "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0016] In this specification, for example, terms such as "C 1-6 " mean the number of carbon atoms in the group that forms the parent nucleus.

[0017] In this specification, "C 1-18 hydrocarbylene group" means a divalent hydrocarbon group formed by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear, branched, or partially or wholly cyclic. The hydrocarbylene group includes an alkylene group, an arylene group, and the like. Also, the divalent carbon atom at any position of the "C 1-18 hydrocarbylene group" may be replaced by -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced). The "C 1-18 hydrocarbylene group" is not particularly limited. For example, it includes a methylene group, an ethylene group, an n-propylene group, an i-propylene group, a cyclopentadienyl group, a cyclohexanediyl group, an oxyethane-1,1-diyl group, an oxyethane-1,2-diyl group, an oxypropane-1,3-diyl group, an oxypropane-1,2-diyl group, a 2-methylpropane-1,3-diyl group, an oxyethyleneoxyethane-1,1-diyl group, etc. of "C 1-18"alkylene group"; 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 4,4'-biphenylene group, anthracenediyl group, phenanthrenediyl group, naphthacenediyl group, pyrenediyl group, perylenediyl group, chrysenediyl group, etc. of "C" 6-18 Examples thereof include "arylene groups" and the like.

[0018] In this specification, "C" 1-18 "alkyl group" means a linear or branched alkyl group having 1 to 18 carbon atoms. Also, "C" 1-18 Any divalent carbon atom at an arbitrary position except the terminal included in the "alkyl group" may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2-. However, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced. "C" 1-18 The "alkyl group" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an i-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 2,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1,1,2-trimethylpropyl group, a 1,2,2-trimethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1-ethyl-2-methylpropyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, etc. "C" 1-18The divalent carbon atoms at any position excluding the terminal contained in the "alkyl group" are not particularly limited as long as they are replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2-. Examples thereof include a 2-methoxyethoxymethyl group and an ethoxycarbonylmethyl group.

[0019] In this specification, "C" 1-18 The "haloalkyl group" means a group in which one or more hydrogen atoms of the "C" 1-18 "alkyl group" are replaced by halogen atoms. "C" 1-18 The "haloalkyl group" is not particularly limited. Examples thereof include a dichloromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 3,3,3-trifluoropropyl group.

[0020] In this specification, "C" 2-18 The "alkenyl group" means an alkenyl group having one or more double bonds in the "C" 1-18 "alkyl group" having 2 or more carbon atoms, and includes an alkadienyl group, an alkatrienyl group, etc. "C" 2-18 The "alkenyl group" is not particularly limited. Examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a 1-propenyl group, an isopropenyl group (1-methylvinyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group.

[0021] In this specification, "C" 2-18 The "alkynyl group" means an alkynyl group having one or more triple bonds in the "C" 1-18 "alkyl group" having 2 or more carbon atoms. "C" 2-18The "alkynyl group" is not particularly limited, and examples thereof include an ethynyl group, 1-propynyl group, 2-propynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, dodecynyl group, and the like.

[0022] In this specification, "C" 3-18 The "alicyclic group" means a hydrocarbon group having a monocyclic or polycyclic cyclic structure with 3 to 18 carbon atoms in whole or in part. The alicyclic group includes a cycloalkyl group, cycloalkenyl group, cycloalkynyl group, monocycloalkyl group, polycycloalkyl group, and the like. Also, any divalent carbon atom at a position other than the terminal included in the "C" 3-18 alicyclic group may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). "C" 3-18 The "cycloalkyl group" is not particularly limited, and examples thereof include a cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-i-propylcyclopentan-1-yl group, cyclohexyl group, t-butylcyclohexyl group, tricyclodecanyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, 2-methyladamantan-2-yl group, 2-i-propyladamantan-2-yl group, bornyl group, norbornyl group, fenchyl group, pinanyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, bornylmethyl group, norbornylmethyl group, adamantylmethyl group, 1-methylcyclopentyloxycarbonylmethyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, and the like.

[0023] As used herein, the term "3- to 18-membered non-aromatic heterocyclic group" means a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, which may be a monocyclic, polycyclic or condensed ring, and may be saturated or partially unsaturated. The "3- to 18-membered non-aromatic heterocyclic group" is not particularly limited, and examples thereof include an aziridinyl group, an azetidyl group, a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a thiomorpholinyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an oxetanyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an imidazolinyl group, an oxazolinyl group, a 2,5-diazabicyclo[2.2.1]heptyl group, a 2,5-diazabicyclo[2.2.2]octyl group, a 3,8-diazabicyclo[3.2.1]octyl group, a 1,4-diazabicyclo[4.3.0]nonyl group, a 1-azaadamantyl group, a 2-azaadamantyl group, and the like.

[0024] As used herein, "C 2-18 aryl group" means an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 2 to 10 carbon atoms. In the case of an aromatic heterocyclic group, a ring is formed by 2 to 10 carbon atoms and one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and each may be a monocyclic, polycyclic or condensed ring. "C 2-18 aryl group" is not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an azulenyl group, a pentalenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a phenanthrenyl group, an anthracenyl group, and the like.

[0025] As used herein, "C 7-18 aralkyl group" means a group in which a substitutable part in the "C 1-12 alkyl group" is substituted with the above-mentioned "C 2-12 aryl group". "C 7-18The "aralkyl group" is not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and the like.

[0026] In this specification, "C" 1-18 The "hydrocarbyl group" means a monovalent group formed by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbyl group includes an alkyl group, an alkenyl group, an alkynyl group, an alicyclic group, an aryl group, an aralkyl group, and the like. Also, "C" 1-18 Any divalent carbon atom at a position other than the terminal contained in the "hydrocarbyl group" may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that two adjacent divalent carbon atoms are not simultaneously replaced). This point shall apply equally to the "C" 1-18 used in the description of the definition of "hydrocarbyloxy group" and the like, such as "C" 1-18 in "hydrocarbyl group" and the like. "C" 1-18 The "hydrocarbyl group" is not particularly limited, and examples thereof include, for example, "C" 1-18 alkyl group", "C" 2-18 alkenyl group", "C" 2-18 alkynyl group", "C" 3-18 alicyclic group", "C" 2-18 aryl group", "C" 7-18 aralkyl group", and the like.

[0027] In this specification, "C" 1-18 The "hydrocarbyloxy group" means a group in which an oxygen atom (-O-) is bonded to a "C" 1-18 hydrocarbyl group". "C" 1-18The "hydrocarbyloxy group" is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, an i-pentyloxy group, a sec-pentyloxy group, an n-hexyloxy group, an i-hexyloxy group, a 1,1-dimethylpropyloxy group, a 1,2-dimethylpropyloxy group, a 2,2-dimethylpropyloxy group, a 1-methyl-2-ethylpropyloxy group, a 1-ethyl-2-methylpropyloxy group, a 1,1,2-trimethylpropyloxy group, a 1,2,2-trimethylpropyloxy group, a 1,1-dimethylbutyloxy group, a 1,2-dimethylbutyloxy group, a 2,2-dimethylbutyloxy group, a 2,3-dimethylbutyloxy group, a 1,3-dimethylbutyloxy group, a 2-ethylbutyloxy group, a 2-methylpentyloxy group, a 3-methylpentyloxy group, etc. of "C 1-18 alkoxy group"; a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a 1-methylcyclopentyloxycarbonylmethoxy group, a 1-ethylcyclohexyloxycarbonylmethoxy group, a 1-methyladamantyloxycarbonylmethoxy group, etc. of "C 3-18 alicyclic oxy group"; a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, an azulenyloxy group, a pentalenyloxy group, a heptalenyloxy group, an indenylenyloxy group, an acenaphthyloxy group, a phenanthrenyloxy group, an anthracenyloxy group, etc. of "C 6-18 aryloxy group", and the like. The "C 1-18 hydrocarbyloxy group" preferably has a divalent carbon atom at any position except the terminal contained in the "C 1-18 hydrocarbyl group" replaced by -O-, -C(=O)-, and / or -C(=O)O-, and "C 1-18The "hydrocarbyloxycarbonylalkyl oxy group" is more preferred, and from the viewpoint of solubility, it is further preferred that the carbon bonded to the oxygen atom of the hydrocarbyloxy is a tertiary carbon. Specific examples of the hydrocarbyloxy include optionally substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, and the like.

[0028] In this specification, "C 1-18 The "hydrocarbylcarbonyl group" means a group in which a carbonyl group (-C(=O)-) is bonded to a "C 1-18 hydrocarbyl group". "C 1-18 The "hydrocarbylcarbonyl group" is not particularly limited. For example, "C 1-18 alkylcarbonyl groups" such as 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; "C 3-18 alicyclic carbonyl groups" such as cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, 2-methylcyclopentylcarbonyl group, 3-methylcyclopentylcarbonyl group, cyclohexylcarbonyl group, 2-methylcyclohexylcarbonyl group, 3-methylcyclohexylcarbonyl group, 4-methylcyclohexylcarbonyl group, adamantylcarbonyl group; "C 6-18 arylcarbonyl groups" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. can be mentioned.

[0029] In this specification, "C 1-18 The "hydrocarbylcarbonyloxy group" means a group in which an oxygen atom (-O-) is bonded to a "C 1-18 hydrocarbylcarbonyl group". "C 1-18The "hydrocarbylcarbonyloxy group" is not particularly limited, and examples thereof include "C 1-18 alkylcarbonyloxy groups" 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; "C 3-18 alicycliccarbonyloxy groups" such as cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group; "C 6-18 arylcarbonyloxy groups" such as phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenanthrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc.

[0030] In this specification, "C 1-18 hydrocarbyloxycarbonyl group" means a group in which a carbonyl group (-C(=O)-) is bonded to a "C 1-18 hydrocarbyloxy group". "C 1-18 hydrocarbyloxycarbonyl group" is not particularly limited, and examples thereof include "C 1-18 alkoxycarbonyl groups" such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group; "C 3-18"alicyclic oxycarbonyl group"; "C" such as phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenanthrenyloxycarbonyl group, anthracenyloxycarbonyl group 6-18 "aryloxycarbonyl group" and the like can be mentioned.

[0031] In this specification, "C" 1-18 "hydrocarbyloxycarbonyloxy group" means a group in which an oxygen atom (-O-) is bonded to a "C" 1-18 "hydrocarbyloxycarbonyl group". "C" 1-18 The "hydrocarbyloxycarbonyloxy group" is not particularly limited. 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 1-18 "alkoxycarbonyloxy group"; "C" such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group 3-18 "alicyclic oxycarbonyloxy group"; "C" such as phenoxycarbonyloxy group, naphthoxycarbonyloxy group, acenaphthyloxycarbonyloxy group, phenanthrenyloxycarbonyloxy group, anthracenyloxycarbonyloxy group 6-18 "aryloxycarbonyloxy group" and the like can be mentioned.

[0032] In this specification, "C" 1-18 "hydrocarbylamino group" means a group in which one "C" 1-18 "hydrocarbyl group" is bonded to an amino group. "C" 1-18The "hydrocarbylamino group" is not particularly limited. For example, "C 1-18 alkylamino groups" such as 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.; "C 3-18 alicyclic amino groups" such as cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, 2-methylcyclopentylamino group, 3-methylcyclopentylamino group, cyclohexylamino group, 2-methylcyclohexylamino group, 3-methylcyclohexylamino group, 4-methylcyclohexylamino group, etc.; "C 6-18 aryl amino groups" such as phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. can be mentioned.

[0033] In this specification, "diC 1-18 hydrocarbylamino group" means a group in which two identical or different "C 1-18 hydrocarbyl groups" are bonded to an amino group. "DiC 1-18 hydrocarbylamino group" is not particularly limited. For example, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-t-butylamino group, di-n-pentylamino group, di-n-hexylamino group, N-ethyl-N-methylamino group, N-methyl-N-n-propylamino group, N-isopropyl-N-methylamino group, N-n-butyl-N-methylamino group, N-isobutyl-N-methylamino group, N-t-butyl-N-methylamino group, N-methyl-N-n-pentylamino group, N-n-hexyl-N-methylamino group, N-ethyl-N-n-propylamino group, N-ethyl-N-isopropylamino group, N-n-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, N-t-butyl-N-ethylamino group, N-ethyl-N-n-pentylamino group, N-ethyl-N-n-hexylamino group, etc. of "diC 1-18"alkylamino group"; "diC" such as dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. 3-18 "alicyclic amino group"; "diC" such as diphenylamino group, phenylnaphthylamino group, etc. 6-18 "aryl amino group"; "N-C" such as N-methylcyclopentanamine group, N-methylcyclohexylamine group, etc. 1-18 alkyl-N-C 3-18 "cycloalkylamino group"; "N-C" such as N-methyl-2-phenylethylamine group, N-ethyl-N-(4-methylphenyl)amine group, etc. 1-18 alkyl-N-C 6-18 "aryl amino group", etc. can be mentioned.

[0034] In this specification, "C" 1-18 "hydrocarbylaminocarbonyl group" means a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group". 1-18 "C" 1-18 The "hydrocarbylaminocarbonyl group" is not particularly limited, and for example, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, t-butylaminocarbonyl group, n-pentylaminocarbonyl group, 2-pentylaminocarbonyl group, neopentylaminocarbonyl group, 4-methyl-2-pentylaminocarbonyl group, n-hexylaminocarbonyl group, 3-methyl-n-pentylaminocarbonyl group, etc. of "C" 1-18 "alkylaminocarbonyl group"; cyclopropylaminocarbonyl group, cyclobutylaminocarbonyl group, cyclopentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-methylcyclopentylaminocarbonyl group, 3-methylcyclopentylaminocarbonyl group, 2-methylcyclohexylaminocarbonyl group, 3-methylcyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group, etc. of "C" 3-18"alicyclic aminocarbonyl group"; "C such as phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group" 6-18 "aryl aminocarbonyl group" can be mentioned.

[0035] In this specification, "diC" 1-18 "hydrocarbylaminocarbonyl group" means a group in which a carbonyl group (-C(=O)-) is bonded to a "diC" 1-18 "hydrocarbylamino group". "diC" 1-18 "hydrocarbylaminocarbonyl group" is not particularly limited. For example, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, diisopropylaminocarbonyl group, di-n-butylaminocarbonyl group, diisobutylaminocarbonyl group, di-t-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, N-ethyl-N-methylaminocarbonyl group, N-methyl-N-n-propylaminocarbonyl group, N-isopropyl-N-methylaminocarbonyl group, N-n-butyl-N-methylaminocarbonyl group, N-isobutyl-N-methylaminocarbonyl group, N-t-butyl-N-methylaminocarbonyl group, N-methyl-N-n-pentylaminocarbonyl group, N-n-hexyl-N-methylaminocarbonyl group, N-ethyl-N-n-propylaminocarbonyl group, N-ethyl-N-isopropylaminocarbonyl group, N-n-butyl-N-ethylaminocarbonyl group, N-ethyl-N-isobutylaminocarbonyl group, N-t-butyl-N-ethylaminocarbonyl group, N-ethyl-N-n-pentylaminocarbonyl group, N-ethyl-N-n-hexylaminocarbonyl group, etc. of "diC" 1-18 "alkylamino group"; "diC" such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group 3-18 "alicyclic aminocarbonyl group"; "diC" such as diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group 6-18 "aryl aminocarbonyl group", etc. can be mentioned.

[0036] In this specification, "C 1-18 hydrocarbylcarbonylamino group" means a group in which an amino group is bonded to a "C 1-18 hydrocarbylcarbonyl group". "C 1-18 hydrocarbylcarbonylamino group" is not particularly limited, and examples thereof include "C 1-18 alkylcarbonylamino groups" such as methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, n-hexylcarbonylamino group; "C 3-18 alicyclic carbonylamino groups" such as cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group; "C 6-18 arylcarbonylamino groups" such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenanthrenylcarbonylamino group, anthracenylcarbonylamino group, etc.

[0037] In this specification, "C 1-18 hydrocarbylaminocarbonyloxy group" means a group in which an oxygen atom (-O-) is bonded to a "C 1-18 hydrocarbylaminocarbonyl group". "C 1-18 hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "C 1-18 alkylaminocarbonyloxy groups" such as methylaminocarbonyloxy group, ethylaminocarbonyloxy group, n-propylaminocarbonyloxy group; "C 3-18"alicyclic aminocarbonyloxy group"; "C 6-18 such as "aryl aminocarbonyloxy group" including phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc.

[0038] In this specification, "diC 1-18 "hydrocarbylaminocarbonyloxy group" means a group in which an oxygen atom (-O-) is bonded to a "diC 1-18 hydrocarbylaminocarbonyl group". "diC 1-18 "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "diC 1-18 such as alkylaminocarbonyloxy group including dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, di-n-propylaminocarbonyloxy group, etc.

[0039] In this specification, "C 1-18 "hydrocarbylaminocarbonylamino group" means a group in which a "C 1-18 hydrocarbylaminocarbonyl group" is bonded to an amino group. "C 1-18 "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "C 1-18 such as alkylaminocarbonylamino group including methylaminocarbonylamino group, ethylaminocarbonyloxy group, n-propylaminocarbonylamino group, etc.; "C 3-18 such as alicyclic aminocarbonylamino group including cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc.; "C 6-18 such as arylaminocarbonylamino group including phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc.

[0040] In this specification, "diC 1-18 "hydrocarbylaminocarbonylamino group" means a group in which a "diC 1-18 hydrocarbylaminocarbonyl group" is bonded to an amino group. "diC 1-18The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "diC 1-18 alkylaminocarbonylamino groups" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, di-n-propylaminocarbonylamino group, etc.

[0041] In this specification, the "C 1-18 hydrocarbyloxycarbonylamino group" means a group in which a "C 1-18 hydrocarbyloxycarbonyl group" is bonded to an amino group. The "C 1-18 hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C 1-18 alkoxycarbonylamino groups" such as methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc.; "C 3-18 alicyclic oxycarbonylamino groups" such as cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc.; "C 6-18 aryloxycarbonylamino groups" such as phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc.

[0042] In this specification, the "C 1-18 hydrocarbylthio group" means a group in which a sulfur atom (-S-) is bonded to a "C 1-18 hydrocarbyl group". The "C 1-18 hydrocarbylthio group" is not particularly limited, and examples thereof include "C 1-18"alkylthio group"; "C" such as cyclopropylthio group, cyclobutylthio group, cyclopentylthio group, cyclohexylthio group, 2-methylcyclopentylthio group, 3-methylcyclopentylthio group, 2-methylcyclohexylthio group, 3-methylcyclohexylthio group, 4-methylcyclohexylthio group, etc. 3-18 "alicyclic thio group"; "C" such as phenylthio group, 1-naphthylthio group, 2-naphthylthio group, acenaphthylthio group, phenanthrenylthio group, anthracenylthio group, etc. 6-18 "arylthio group" and the like can be mentioned.

[0043] In this specification, "C" 1-18 "hydrocarbyl sulfinyl group" means a group in which a sulfinyl group (-S(=O)-) is bonded to a "C" 1-18 "hydrocarbyl group". "C" 1-18 The "hydrocarbyl sulfinyl group" is not particularly limited. For example, "C" such as methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, hexylsulfinyl group, etc. 1-18 "alkyl sulfinyl group"; "C" such as cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-methylcyclohexylsulfinyl group, 3-methylcyclohexylsulfinyl group, 4-methylcyclohexylsulfinyl group, etc. 3-18 "alicyclic sulfinyl group"; "C" such as phenylsulfinyl group, naphthylsulfinyl group, acenaphthylsulfinyl group, phenanthrenylsulfinyl group, anthracenylsulfinyl group, etc. 6-18 "aryl sulfinyl group" and the like can be mentioned.

[0044] In this specification, "C" 1-18 "hydrocarbyl sulfonyl group" means a group in which a sulfonyl group (-SO2-) is bonded to a "C" 1-18 "hydrocarbyl group". "C 1-18 The "hydrocarbyl sulfonyl group" is not particularly limited. For example, "C 1-18 alkyl sulfonyl groups" such as methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, t-butylsulfonyl group, pentylsulfonyl group, etc.; "C 3-18 alicyclic sulfonyl groups" such as cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, 4-methylcyclohexyl group, etc.; "C 6-18 aryl sulfonyl groups" such as phenylsulfonyl group, naphthylsulfonyl group, acenaphthylsulfonyl group, phenanthrenylsulfonyl group, anthracenylsulfonyl group, etc. can be mentioned.

[0045] In this specification, the "acid-dissociable group" is a group that substitutes a hydrogen atom of a polar group such as a hydroxy group (including phenolic hydroxy groups, etc.), a carboxy group, an amino group, a sulfo group, etc., and means a group that dissociates by the action of an acid. The compound having the above acid-dissociable group can increase the polarity of the compound by the dissociation of the acid-dissociable group by the action of an acid and the generation of the above polar group. Thereby, the solubility of the compound in the developer can be changed. More specifically, when a highly polar developer such as an alkaline aqueous solution is used as the developer, the solubility of the compound in the developer relatively increases, while when a low-polarity organic developer is used as the developer, the solubility of the compound in the developer relatively decreases. As the above polar group, a hydroxy group (including phenolic hydroxy groups, etc.) and a carboxy group are preferable.

[0046] The acid dissociable group is not particularly limited, and known and commonly used acid dissociable groups that can be used in chemically amplified resists can be employed. Examples of the acid dissociable group include an acid dissociable group G for a polar group represented by the following general formulas (G-1) to (G-4).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0047] The acid dissociable group G is not particularly limited as long as it dissociates by the action of an acid, and known and commonly used ones can be used. Examples of the acid dissociable group G include a "tertiary carbon type acid dissociable group G" represented by the following general formula (g-1), A a "allyl type or benzyl type acid dissociable group G" represented by the following general formula (g-2), B an "acetal type acid dissociable group G" represented by the following general formula (g-3), C an "aminocarbonyl type acid dissociable group G" represented by the following general formula (g-4), D and the like. Each of these will be sequentially described below.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0048] <Tertiary carbon type acid dissociable group G A > As the acid dissociable group G, a "tertiary carbon type acid dissociable group G" represented by the following general formula (g-1), A i.e., a carbon directly bonded to a polar group and having R A g1 ~R A g3 bonded carbon being a tertiary carbon atom, can be used as the acid dissociable group. [Chemical formula]

[0049] "R A g1 " is an optionally substituted C 1-12 hydrocarbyl group, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0050] R A g1 is preferably an optionally substituted C 1-12 alkyl group, C 3-12 alicyclic group, C 6-12 aryl group, or C 7-12 aralkyl group, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), more preferably an optionally substituted C 1-12 alkyl group or C 3-12 alicyclic group, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0051] Also, "RA g2 」 and 「R A g3 」 each independently may have a substituent and is a C 1-12 hydrocarbyl group, wherein the divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). Or, R A g2 and R A g3 combine to form an optionally substituted C 3-18 alicyclic group, or a 3- to 18-membered non-aromatic heterocyclic group, and the divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0052] R A g2 and R A g3 As R A g2 and R A g3 combine to form an optionally substituted C 3-18 alicyclic group, or a 3- to 18-membered non-aromatic heterocyclic group, and the divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), which is preferred, and further may have the above-mentioned substituent and is a C 3-18An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group contains a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). It is more preferable that it is such a group.

[0053] The tertiary carbon type acid dissociable group G represented by the general formula (g-1) A Examples thereof include a t-butyl group, a t-amyl group, a 1,1-dimethylpropyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, a 1-methyl-1-cyclohexyl group, a 1-ethyl-1-cyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group, and the like.

[0054] <<The tertiary carbon type acid dissociable group G A1 and G A2 >> In addition, in the "tertiary carbon type acid dissociable group G A " represented by the general formula (g-1), R A g2 and R A g3 are combined to form an alicyclic group which may have a substituent, or a 3- to 18-membered non-aromatic heterocyclic group. For example, the tertiary carbon type acid dissociable group G 3-18 represented by the following general formula (g-1-1), and the tertiary carbon type oxygen dissociable group G A1 represented by (g-1-2) A2 and the like can be mentioned.

[0055] <<The tertiary carbon type acid dissociable group G represented by the general formula (g-1-1) A1 >>

Chemical formula

[0056] Also Cy A g1 forms an optionally substituted C 3-18 alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group together with the above tertiary carbon atom, and any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced).

[0057] Cy A g1As for the above tertiary carbon atom, together with it, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton which may have a substituent is formed, and a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (however, it is assumed that two adjacent divalent carbon atoms are not simultaneously replaced).

[0058] The tertiary carbon type acid dissociable group G represented by the general formula (g-1-1) A1 As for it, for example, the following tertiary carbon type acid dissociable groups can be exemplified.

[0059]

Chemical formula

[0060]

Chemical formula

[0061]

Chemical formula

[0062] <<The tertiary carbon type acid dissociable group G represented by the general formula (g-1-2) A2 >>

Chemical formula

[0063] R A g21 and R A g22 and / or R A g22 and R A g23 When R and R and / or R and R form a ring together with the carbon atom contained in the ethylenically unsaturated double bond, for example, a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, etc., which may have substituents, may be formed.

[0064] Also, Cy A g2 forms a C 3-18 alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, which may have substituents, together with the above tertiary carbon atom, and any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced).

[0065] Cy A g2Examples thereof include a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, and a tricyclodecene skeleton, which may have a substituent together with the above tertiary carbon atom, and the divalent carbon atoms at any positions except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (however, it is assumed that two adjacent divalent carbon atoms are not simultaneously replaced).

[0066] The tertiary carbon type acid dissociable group G represented by the general formula (g-1-2) A2 Examples thereof include the following tertiary carbon type acid dissociable groups.

[0067]

Chemical formula

[0068] <An allyl type or benzyl type acid dissociable group G B > As the acid dissociable group G, an acid dissociable group in which the carbon directly bonded to the polar group is in the allyl position or the benzyl position, such as the "allyl type or benzyl type acid dissociable group G B " represented by the following general formula (g-2) can be used.

Chemical formula

[0069] "R B g1 " may be a C which may have a substituent 1-12A hydrocarbyl group, wherein any divalent carbon atom except the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced).

[0070] R B g1 Examples of R include an optionally substituted C 1-12 alkyl group, a C 3-12 cycloaliphatic group, a C 6-12 aryl group, or a C 7-12 aralkyl group, wherein any divalent carbon atom except the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced), and preferably an optionally substituted C 1-12 alkyl group, or a C 3-12 cycloaliphatic group, wherein any divalent carbon atom except the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced), and more preferably

[0071] Also, each of "R B g2 " to "R B g4 " is independently a hydrogen group or an optionally substituted C 1-12 hydrocarbyl group, wherein any divalent carbon atom except the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced).

[0072] R B g1 and R B g2 、RB g2 and R B g3 , and / or, R B g3 and R B g4 are directly bonded to each other by a single bond, or are a divalent linkage of -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 may be linked via an alkylene group to form a ring.

[0073] The allyl-type or benzyl-type acid-dissociable group G represented by the general formula (g-2) B In, R B g1 and R B g2 , R B g2 and R B g3 , and / or, R B g3 and R B g4 When they form a ring together with the carbon atom contained in the ethylenically unsaturated double bond, for example, a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, a benzyl group, a 2,3-dihydro-1H-indenyl group which may have a substituent, etc. are exemplified.

[0074] The allyl-type or benzyl-type acid-dissociable group G represented by the general formula (g-2) B As, for example, the following allyl-type or benzyl-type acid-dissociable groups can be exemplified.

[0075] [Chemical formula]

[0076] <Acetal-type acid-dissociable group G C > As the above acid-dissociable group G, the "acetal-type acid-dissociable group G" represented by the following general formula (g-3) CAs in 「」, an acid dissociable group in which an oxygen atom is bonded to a carbon atom directly bonded to a polar group can be used.

Chemical formula

[0077] 「R C g1 」and「R C g3 」are each independently a hydrogen group or a C 1-12 hydrocarbyl group which may have a substituent, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0078] R C g1 and R C g3 are preferably a hydrogen group or a C 1-12 alkyl group or a C 3-12 alicyclic group which may have a substituent, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), more preferably a hydrogen group or a C 1-6 alkyl group or a C 3-8 alicyclic group which may have a substituent, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0079] Also,「R C g2 」is a C 1-12A hydrocarbyl group, wherein any divalent carbon atom except the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0080] R C g2 Examples of R include an optionally substituted C 1-12 alkyl group or a C 3-12 alicyclic group, wherein any divalent carbon atom except the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), and such groups are preferred. Examples of R include an optionally substituted C 1-6 alkyl group or a C 3-8 alicyclic group, wherein any divalent carbon atom except the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), and such groups are more preferred.

[0081] The acetal-type acid-dissociable group G represented by the general formula (g-3) C Examples thereof include a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, an n-butoxymethoxy group, a 2,2-dimethylpropoxymethoxy group, a 2,2-dimethylbutoxymethoxy group, a cyclohexyloxymethoxy group, a 1-ethoxyethoxy group, a 1-n-butoxyethoxy group, a 1-cyclohexyloxyethoxy group, and the like.

[0082] <An aminocarbonyl-type acid-dissociable group G D > As the acid-dissociable group G, an acid-dissociable group in which an aminocarbonyl group is bonded to a polar group, such as the "aminocarbonyl-type acid-dissociable group G D " represented by the following general formula (g-4), can be used. [Chemical formula]

[0083] 「R D g1 」 and 「R D g2 」 are each independently a hydrogen group or a C 1-12 hydrocarbyl group which may have a substituent, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0084] R D g1 and R D g2 are preferably a hydrogen group or a C 1-12 alkyl group or a C 3-12 alicyclic group which may have a substituent, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). A hydrogen group or a C 1-6 alkyl group or a C 3-8 alicyclic group which may have a substituent, and any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced) is more preferred.

[0085] The aminocarbonyl type acid dissociable group G represented by the general formula (g-4) DExamples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, an N-phenyl-N-methyl-aminocarbonyl group, and the like.

[0086]

Chemical formula

[0087] In the present specification, the "hydroxy group or carboxy group having a protecting group" means a hydroxy group (including a phenolic hydroxy group) or a carboxy group that is protected by an ether-based protecting group, a silyl ether-based protecting group, an acyl-based protecting group, or the like.

[0088] The ether-based protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, a di(p-methoxyphenyl)phenylmethyl group, and the like. The silyl ether-based protecting group is not particularly limited, and examples thereof include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), a t-butyldiphenylsilyl group (TBDPS), and the like. The acyl-based protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, a benzoyl group, and the like.

[0089] In the present specification, "optionally having a substituent" is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of the "substituent" include, for example, (1) a halogen atom, (2) a haloalkyl group, (3) a hydroxy group, (4) a thiol group, (5) a nitro group, (6) a cyano group, (7) a carboxy group, (8) an amino group, (9) a sulfo group, (10) a vinyl group, (11) an allyl group, (12) a (meth)acryloyl group, (13) a (meth)acryloyloxy group, (14) a (meth)acrylamide group, (15) a styryl group, (16) an epoxy group, (17) a glycidyl group, (18) an amide group, (19) a hydroxy group or a carboxy group having a protecting group, (20) a polar group having an acid dissociable group, or (21) a C 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, C 1-18 hydrocarbyloxycarbonyloxy group, C 1-18 hydrocarbylamino group, diC 1-18 hydrocarbylamino group, C 1-18 hydrocarbylaminocarbonyl group, diC 1-18 hydrocarbylaminocarbonyl group, C 1-18 hydrocarbylcarbonylamino group, C 1-18 hydrocarbylaminocarbonyloxy group, diC 1-18 hydrocarbylaminocarbonyloxy group, C 1-18 hydrocarbylaminocarbonylamino group, diC 1-18 hydrocarbylaminocarbonylamino group, C 1-18 hydrocarbyloxycarbonylamino group, C 1-18 hydrocarbylthio group, C 1-18 hydrocarbylsulfinyl group, C 1-18A hydrocarbylsulfonyl group, wherein the divalent carbon atoms at any position except the terminal of the above substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). etc. are mentioned.

[0090] [1. Resist material] The resist material according to this embodiment contains (A) a heteropolyacid salt in which a defect site is modified or a mixture thereof. (A m+ ) a (B n+ ) b (C (am+bn)- ) (I) [Wherein, A m+ each independently represents H + , a metal ion, an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B n+ each independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups; C (am+bn)- represents a heteropolyacid anion in which the defect site is modified in the heteropolyacid anion having the defect site; 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.] Further, the resist material according to this embodiment may contain (B) an acid diffusion control agent as an optional component.

[0091] [1-1. (A) Heteropolyacid salt in which a defect site is modified or a mixture thereof] (A) As the heteropolyacid salt or a mixture thereof in which the defective site is modified, the heteropolyacid salt or a mixture thereof in which the defective site is modified represented by the above general formula (I) can be used. The anion part of the heteropolyacid salt or a mixture thereof in which the defective site is modified is composed of a heteropolyacid anion in which the defective site is modified in the heteropolyacid anion having the defective site. Further, the cation part of the heteropolyacid salt or a mixture thereof in which the defective site is modified is composed of a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups.

[0092] [1-1-1. Anion part of the heteropolyacid salt or a mixture thereof in which the defective site is modified] The anion part of the heteropolyacid salt or a mixture thereof in which the defective site is modified according to the present embodiment is composed of a heteropolyacid anion in which the defective site is modified in the heteropolyacid anion having the defective site.

[0093] [1-1-1-1. Heteropolyacid anion in which the defective site is modified] As the heteropolyacid anion in which the defective site is modified in the heteropolyacid anion having the defective site, a heteropolyacid anion in which the defective site is modified can be obtained by reacting the terminal oxygen atom of the defective site of the heteropolyacid anion having the defective site with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups.

[0094] [1-1-1-1-1. Heteropolyacid anion having a defective site] The heteropolyacid anion having a defective site according to the present embodiment is not particularly limited, and a defective species in which a part of the basic skeleton of the heteropolyacid anion is defective can be used, and any of one defective species, two defective species, three defective species, etc. may be used. Examples of the heteropolyacid anion having the defective site include a defective Keggin type heteropolyacid anion and a defective Dawson type heteropolyacid anion.

[0095] [1-1-1-1-1-1. Defective Keggin-type heteropolyacid anion] Examples of the defective Keggin-type heteropolyacid anion include, for example, a 1-defective Keggin-type heteropolyacid anion represented by the following general formula (II-1), a 2-defective Keggin-type heteropolyacid anion represented by the following general formula (II-2), a 3-defective Keggin-type heteropolyacid anion represented by the following general formula (II-3), and the like. [XM 11 O 39 c11- (II-1) [XM 10 O 36 c12- (II-2) [XM9O 34 c13- (II-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; c11-~c13- represents the number of negative charges, and c11~c13 are natural numbers.)

[0096] In general formulas (II-1) to (II-3), the values of c11~c13 vary depending on the types of X and M. For example, in general formula (II-1), when X is P and M is Mo or W, c11 is 7 ([PMo 11 O 39 7- , [PW 11 O 39 7- ), and when X is Si and M is Mo or W, c11 is 8 ([SiMo 11 O 39 8- , [SiW 11 O 39 8- ), and when X is S and M is Mo or W, c11 is 6 ([SMo 11 O 39 6- , [SW 11 O 39 6- ), and when X is B and M is Mo or W, c11 is 9 ([BMo 11 ​​​​​​​​​O 39 9- 、[BW 11 O 39 9- ) becomes, when X is Ge and M is Mo or W, c11 is 8([GeMo 11 O 39 8- 、[GeW 11 O 39 8- ) becomes. Also, in general formula (II-2), when X is P and M is Mo or W, c12 is 7([PMo 10 O 36 7- 、[PW 10 O 36 7- ) becomes, when X is Si and M is Mo or W, c12 is 8([SiMo 10 O 36 8- 、[SiW 10 O 36 8- ) becomes, when X is B and M is Mo or W, c12 is 9([BMo 10 O 36 9- 、[BW 10 O 36 9- ) becomes, when X is Ge and M is Mo or W, c12 is 8([GeMo 10 O 36 8- 、[GeW 10 O 36 8- ) becomes. Furthermore, in general formula (II-3), for example, when X is P and M is Mo or W, c13 is 9([PMo9O 34 9- 、[PW9O 34 9- ) becomes, when X is Si and M is Mo or W, c13 is 10([SiMo9O 34 10- 、[SiW9O 34 10- ) becomes, when X is S and M is Mo or W, c13 is 8([SMo9O 34 8- 、[SW9O 34 ​​​​​​​​​​​​​​​​​​8- ) and when X is Ge and M is Mo or W, c13 is 10([GeMo9O 34 10- , [GeW9O 34 10- ).

[0097] It is preferable that the isomer structure of the defective Keggin type heteropolyacid anion is the α-form, β-form, or γ-form. As the isomer structure of the 1-defective Keggin type heteropolyacid anion represented by the 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- are preferable, and [α-PW 11 O 39 7- , [α-PMo 11 O 39 7- , [α-SiW 11 O 39 8- , [α-SiMo 11 O​​​​​​​​​​​​​​​​​39 8- is more preferable. In addition, as the isomeric structures of the 2-deficient Keggin-type heteropolyacid anions represented by the general formula (II-1), [α-PW 10 O 36 7- , [β-PW 10 O 36 7- , [γ-PW 10 O 36 7- , [α-PMo 10 O 36 7- , [β-PMo 10 O 36 7- , [γ-PW 10 O 36 7- , [α-SiW 10 O 36 8- , [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- are preferable, 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- are more preferable. Furthermore, as the isomeric structures of the 3-deficient Keggin-type heteropolyacid anions represented by the 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- is preferred.

[0098] [1-1-1-1-1-2. Defective Dawson-type heteropolyacid anion] Examples of the defective Dawson-type heteropolyacid anion include a 1-defective Dawson-type heteropolyacid anion represented by the following general formula (III-1), a 2-defective Dawson-type heteropolyacid anion represented by the following general formula (III-2), a 3-defective Dawson-type heteropolyacid anion represented by the following general formula (III-3), and the like. [X2M 17 O 61 c21- (III-1) [X2M 16 O 58 c22- (III-2) [X2M 15 O 56 c23- (III-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; c21-~c23- represents the number of negative charges, and c21~c23 are natural numbers.)

[0099] ​​​​​​​​​​​​​In general formulas (III-1) to (III-3), the values of c21 to c23 vary depending on the types of X and M. For example, in general formula (III-1), when X is P and M is Mo or W, c21 is 10 ([P2Mo 17 O 61 10- 、[P2W 17 O 61 10- ) and when X is S and M is W, c21 is 8 ([S2W 17 O 61 8- ). Also, in general formula (III-2), when X is Ge and M is Mo, c22 is 12 ([Ge2Mo 16 O 58 12- ). Furthermore, in general formula (III-3), when X is P and M is Mo or W, c23 is 12 ([P2Mo 15 O 56 12- 、[P2W 15 O 56 12- ).

[0100] The above defective Dawson-type heteropolyacid anion preferably has an isomer structure of an α-form, a β-form, or a γ-form. As the isomer structure of the defective Dawson-type heteropolyacid anion represented by general formulas (III-1) to (III-3), [α-P2W 17 O 61 10- 、[α-P2W 15 O 56 12- 、[α-S2W 17 O 61 8- etc. can be preferably used.

[0101] [1-1-1-1-2. Modification of the Defective Site] ​​​​​​​​​The modification of the defective site of the heteropolyacid anion having the defective site according to the present embodiment is performed by reacting the terminal oxygen atom at the defective site with a P, Si, Ge, or Sn compound having one or more hydro groups or organic groups and two or more leaving groups to modify the defective site. By the above reaction, the terminal oxygen atom of the defective site of the heteropolyacid anion is bonded via a group having a heteroatom P, Si, Ge, or Sn to which one or more hydro groups or organic groups are bonded, and a part or all of the heteroatom, thereby modifying the defective site.

[0102] [1-1-1-1-2-1. Bonding form of defective site and its notation] The heteropolyacid anion having the defective site modified according to the present embodiment is modified by a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more hydro groups or organic groups are bonded, at the terminal oxygen atom of the defective site of the heteropolyacid anion having the defective site.

[0103] The bonding form between the terminal oxygen atom of the defective site of the heteropolyacid anion and the group having one or more heteroatoms P, Si, Ge, or Sn to which one or more hydro groups or organic groups are bonded is not particularly limited, and can be represented by, for example, the following general formulas (IV-1) to (IV-5).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0104] In this specification, for a heteropolyacid anion modified with a group having a heteroatom Si or Ge to which one or more hydrogen groups or organic groups represented by the general formula (IV-1) are bonded at the defect site, for convenience, it can be represented as the following general formula (V-1). [X w M x O y (R 1A1 X’)(R 1A2 X’)O] c- (V-1) (wherein w, x, y, and c are all natural numbers, and X, M, X’, R 1A1 and R 1A2 are the same as above.) Also, R 1A1 and R 1A2When they are the same, this is represented as R 1A and can be expressed as in the following general formula (V-1’). [X w M x O y (R 1A X’)2O] c- (V-1’)

[0105] The heteropolyacid anion modified at the defective site represented by the general formula (V-1) or (V-1’) is not particularly limited. For example, it can be obtained by reacting a heteropolyacid anion having a defective site with (R 1A )X’Y3 (Y represents a leaving group, for example, a halogen atom, a hydroxy group, an alkoxy group (C 1-4 preferably an alkoxy group, more preferably a C 1-2 alkoxy group.), an alkylcarbonyloxy group (C 1-4 preferably an alkylcarbonyloxy group.), a hydrocarbylsulfonyloxy group (C 1-6 alkyl or C 7-10 preferably an aralkylsulfonyloxy group. For example, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, etc. may be mentioned.)).

[0106] Similarly, in this specification, for a heteropolyacid anion in which the defective site is modified with a group having one or more heteroatoms Si or Ge to which one or more hydro groups or organic groups represented by the general formula (IV-2) are bonded, for convenience, it can be represented as in the following general formula (V-2). [X w M x O y (R 1B1 R 1B2 X’)(R 1B3 R 1B4 Si)] c- (V-2) (In the formula, w, x, y, and c are all natural numbers, and X, M, X’, R 1B1 , R 1B2 , R 1B3 and R 1B4 are the same as above.) Also R 1B1 R 1B2 and R 1B3 R 1B4 are the same, it can be expressed as the following general formula (V-2’). [X w M x O y (R 1B1 R 1B2 X’)2] c- (V-2’)

[0107] The heteropolyacid anion modified at the defective site represented by the general formula (V-2) or (V-2’) is not particularly limited. For example, it can be obtained by reacting a heteropolyacid anion having a defective site with (R 1B1 )(R 1B2 )X’Y2 (Y represents a leaving group as defined above).

[0108] In this specification, for the heteropolyacid anion in which the defective site is modified by a group having a heteroatom Si or Ge to which one or more hydro groups or organic groups represented by the general formula (IV-3) are bonded, for convenience, it can be expressed as the following general formula (V-3). [X w M x O y (R 1C1 X’O)(R 1C2 X’O)(R 1C3 X’O)(R 1C4 X’O)] c- (V-3) (In the formula, w, x, y, and c are all natural numbers, and X, M, X’, R 1C1 , R 1C2 , R 1C3 and R 1C4 are the same as above.) Also when R 1C1 , R 1C2 , R 1C3 and R 1C4 are the same, this can be designated as R 1C and can be expressed as the following general formula (V-3’). [X w M x O y (R1C X’O)4] c- (V-3’)

[0109] The heteropolyacid anion modified at the defect site represented by the general formula (V-3) or (V-3’) is not particularly limited. For example, it can be obtained by reacting a 2-deficient Keggin-type or Dawson-type heteropolyacid anion with R 1C X’Y3 (Y represents a leaving group as defined above)

[0110] In this specification, for the heteropolyacid anion modified at the defect site with a group having a heteroatom P to which one or more hydro groups or organic groups represented by the general formula (IV-4) are bonded, for convenience, it can be expressed as the following general formula (V-4). [X w M x O y (R 1D1 P=O)(R 1D2 P=O)] c- (V-4) (In the formula, w, x, y, and c are all natural numbers, and X, M, R 1D1 and R 1D2 are the same as defined above.) Also, when R 1D1 and R 1D2 are the same, this can be represented as R 1D and can be expressed as the following general formula (V-4’). [X w M x O y (R 1D P=O)2)] c- (V-4’)

[0111] The heteropolyacid anion modified at the defect site represented by the general formula (V-4) or (V-4’) is not particularly limited. For example, it can be obtained by reacting a heteropolyacid anion having a defect site with R 1D P(=O)Y2 (Y represents a leaving group as defined above).

[0112] In this specification, for the heteropolyacid anion modified at the defect site with a group having one or more heteroatoms Si, Ge, or Sn to which one or more hydro groups or organic groups represented by the general formula (IV-5) are bonded, for convenience, it can be expressed as the following general formula (V-5). [X w M x O y (R 1E1 X’’)] c- (V-5) (In the formula, w, x, y, and c are all natural numbers, and X, M, X’’, and R 1E1 are the same as above.) Regarding the above (V-5), in some cases, it may be expressed as the following general formula (V-5’). Note that R 1E has the same definition as R 1E1 . [X w M x O y (R 1E X’’)] c- (V-5’)

[0113] The heteropolyacid anion modified at the defect site represented by the general formula (V-5) or (V-5’) is not particularly limited. For example, it can be obtained by reacting a heteropolyacid anion having a defect site with R 1E X’’Y3 (Y represents a leaving group as defined above).

[0114] Among the heteropolyacid anions modified at the defect site represented by the general formulas (V-1) to (V-5) and (V-1’) to (V-5’), from the viewpoint of being particularly stable and having controllable reactivity, the heteropolyacid anions modified at the defect site represented by the following general formulas (VI-1) to (VI-12) are preferred. [XM 11 O 39 (R 1A X’)2O] c31- (VI-1) [XM 11 O 39 (R 1B1 R 1B2 X’)2] c31-(VI-2) [XM 11 O 39 (R 1D P=O)2] c31- (VI-3) [XM 11 O 39 (R 1E X’’)] c31- (VI-4) [XM 10 O 36 (R 1A X’)2O] c32- (VI-5) [XM 10 O 36 (R 1B1 R 1B2 X’)2] c32- (VI-6) [XM 10 O 36 (R 1C X’O)4] c32- (VI-7) [XM 10 O 36 (R 1D P=O)2] c32- (VI-8) [X2M 17 O 61 (R 1A X’)2O] c33- (VI-9) [X2M 17 O 61 (R 1B1 R 1B2 X’)2] c33- (VI-10) [X2M 17 O 61 (R 1D P=O)2] c33- (VI-11) [X2M 17 O 61 (R 1E X’’)] c33- (VI-12) (wherein, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb or Ta; X’ represents a heteroatom of Si or Ge; X’’ represents a heteroatom of Si, Ge, or Sn; R 1A ~R 1E each independently represents a hydrogen group, or a C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group which may have a substituent; For the above R 1A ~R 1E any divalent carbon atom at a position other than the terminal of may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). For the above R 1A ~R 1E the hydrogen atoms contained in may be replaced by, for example, (a) a halogen atom, (b) a C 1-3 haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid dissociable group; c31, c32, and c33 are natural numbers.

[0115] In the heteropolyacid anion in which the defect site is modified, since four terminal oxygen atoms of the defect site are modified, usually, the value of c31 becomes c11 - 4, the value of c32 becomes c12 - 4, and the value of c33 becomes c21 - 4. On the other hand, for example, when an amino group is contained in an organic group and this is protonated to form an ammonium cation, or when a carboxy group is contained in an organic group and this becomes a carboxy anion, etc., the values of c31 to c33 are different from the above values.

[0116] [1-1-2. Cation part of heteropolyacid salt or its mixture in which the defective part is modified] In the cation part of the heteropolyacid salt or its mixture in which the defective part according to this embodiment is modified, a sulfonium cation, a sulfonium dication, or an iodonium cation (B n+ ) having one or more acid-dissociable groups can be used. The sulfonium cation, sulfonium dication, or iodonium cation having one or more acid-dissociable groups preferably exhibits both the function as a photoacid generator and the function of changing solubility in a developer due to the action of an acid. Further, the cation part of the heteropolyacid salt or its mixture in which the defective part is modified may contain other counter cations (A m+ ).

[0117] [1-1-2-1. Sulfonium cation or sulfonium dication having one or more acid-dissociable groups, or iodonium cation (B n+ )] As the sulfonium cation, sulfonium dication, or iodonium cation having one or more acid-dissociable groups according to this embodiment, an organic sulfonium cation, an organic sulfonium dication, or an organic iodonium cation having one or more acid-dissociable groups can be used.

[0118] [1-1-2-1-1. Organic sulfonium cation having one or more acid-dissociable groups] The organic sulfonium cation having one or more acid-dissociable groups is not particularly limited, and known and commonly used ones can be used. Examples of the organic sulfonium cation having one or more acid-dissociable groups include, for example, an organic sulfonium cation represented by the following general formula (VII-1). [Chemical formula]

[0119] In general formula (VII-1), R 2A , R 2B and R 2Ceach independently represents an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, any divalent carbon atom at any position except the termini of the above R 2A , R 2B and R 2C may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced); any hydrogen atom contained in the above R 2A , R 2B and R 2C is (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyloxy group, or a C 1-18 hydrocarbylthio group, and any divalent carbon atom at any position except the termini of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced); also the above R 2AOne or more hydrogen atoms contained therein are replaced with a polar group having a (t) acid dissociable group, Further, R 2A and R 2B and R 2C Any two of them may be directly connected to each other by a single bond or a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or a C 1-3 alkylene group to form a ring together with the sulfur atom in formula (VII-1).

[0120] R having one or more of the above acid dissociable groups 2A is a C 1-18 hydrocarbyl group which may have a substituent; any divalent carbon atom at any position except the terminal of the above R 2A may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); at least one or more hydrogen atoms of the above R 2A are preferably replaced by a polar group having a (t) acid dissociable group, a C 1-18 alkyl group, a C 3-18 alicyclic group, a C 6-18 aryl group, or a C 7-18 aralkyl group which may have a substituent; any divalent carbon atom at any position except the terminal of the above R 2A may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); at least one or more hydrogen atoms of the above R 2A are more preferably replaced by a polar group having a (t) acid dissociable group, is a C 6-18 aryl group or a C 7-18 aralkyl group which may have a substituent; the above R 2AThe divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the above R 2A It is more preferable that at least one or more hydrogen atoms of the above R are replaced by a polar group having a (t) acid dissociable group.

[0121] The above R 2A is characterized by having one or more acid dissociable groups, and for example, a polar group such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid dissociable group is introduced. Examples of the acid dissociable group include a tertiary carbon type acid dissociable group G A , an allyl type or benzyl type acid dissociable group G B , an acetal type acid dissociable group G C , an aminocarbonyl type acid dissociable group G D and the like.

[0122] Examples of R having one or more of the above acid dissociable groups 2A include, for example, the following. Note that * means the bonding part with the sulfur atom of the general formula (VII-1).

[0123]

Chemical formula

[0124] R 2B and R 2C are each independently a C 1-18 hydrocarbyl group which may have a substituent; the divalent carbon atoms at any position except the terminals of the above R 2B and R 2C may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the above R 2B and R 2CThe hydrogen atoms contained therein may be (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C in which at least a part of the hydrogen atoms may be substituted with the above (a) to (t), 1-18 a hydrocarbyl group, C 1-18 a hydrocarbyloxy group, C 1-18 a hydrocarbylcarbonyl group, C 1-18 a hydrocarbylcarbonyloxy group, C 1-18 a hydrocarbyloxycarbonyl group, C 1-18 a hydrocarbyloxycarbonyloxy group, or C 1-18 may be replaced with a hydrocarbylthio group, and the divalent carbon atoms at any position except the terminals of these substituents may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).) are preferred, a C which may have a substituent, 1-18 an alkyl group, C 3-18 an alicyclic group, C 6-18 an aryl group, or C 7-18 an aralkyl group; the R above 2B and R 2C the divalent carbon atoms at any position except the terminals may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the R above 2B and R 2CThe hydrogen atoms contained therein may be (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, C 1-18 hydrocarbyloxycarbonyloxy group, or C 1-18 may be replaced by a hydrocarbylthio group, and the divalent carbon atoms at any position except the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). Those are more preferred.

[0125] Also, R 2A , R 2B and R 2C any two of which may be directly bonded to each other by a single bond or a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3In the case of being linked via an alkylene group and forming a ring together with the sulfur atom in the formula (VII), examples include those having a thian-1-ium skeleton, a thiophene-1-ium skeleton, a 1,4-oxathian-4-ium skeleton, a 1,4-dithian-1-ium skeleton, a 1H-thiophene-1-ium skeleton, a benzo[b]thiophene-1-ium skeleton, a dibenzothiophenium skeleton, a 9,10-dihydrothioxanthenium skeleton, a 10H-phenoxathiin-10-ium skeleton, a 5H-thianthrene-5-ium skeleton, etc., and the following can be exemplified. Here, * means the bonding part with R 2A , R 2B or R 2C means the bonding part with.

[0126] [Chemical formula]

[0127] Examples of the organic sulfonium cation having one or more of the above acid dissociable groups include (3,5-dimethyl-4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl)diphenylsulfonium cation, (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, (3,5-dimethyl-4-(2-((1-methylcyclopentyl)oxy)-2-oxoethoxy)phenyl)diphenylsulfonium cation, (4-(2-(t-butoxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, (3,5-dimethyl-4-(2-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)-2-oxoethoxy)phenyl)diphenylsulfonium cation, 5-(3,5-dimethyl-4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)phenyl)-5H-dibenzothiophen-5-ium cation, (4-(2-((1-ethylcyclohexyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, 1-(4-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethoxy)naphthalen-1-yl)tetrahydro-1H-thiophen-1-ium cation, (4-(t-butoxy)-3,5-dimethylphenyl)diphenylsulfonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)dimethylsulfonium cation, 1-(4-methoxymethoxy)naphthalen-1-yl)tetrahydro-1H-thiophen-1-ium cation, 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)tetrahydro-1H-thiophen-1-ium cation, 1-(2-((2-methyladamantan-2-yl)oxy)-2-oxoethyl)hexahydrothiopyrylium cation, and the like.

[0128] Examples of the organic sulfonium cation having one or more of the above acid dissociable groups include the following.

[0129] [Chemical formula]

[0130] [1-1-2-1-2. Organic sulfonium dication having one or more acid-dissociable groups] The organic sulfonium dication having one or more acid-dissociable groups is not particularly limited, and known and commonly used ones can be used. Examples of the organic sulfonium dication having one or more acid-dissociable groups include, for example, the organic sulfonium dication represented by the following general formula (VII-2). [Chemical formula]

[0131] In the general formula (VII-2), R 3A , R 3B , R 3C and R 3D each independently represent a C 1-18 hydrocarbyl group which may have a substituent, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Any divalent carbon atom at a position other than the terminals of the above R 3A , R 3B , R 3C and R 3D may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced); K 3A , K 3B and L 3 each independently represent a C 1-18 hydrocarbylene group which may have a substituent, The above K 3A , K 3BAnd the divalent carbon atoms at any position of L may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); The above R 3A 、R 3B 、R 3C 、R 3D 、K 3A 、K 3B And L 3 The hydrogen atoms contained in are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C in which at least part of the hydrogen atoms may be substituted with the above (a) to (t) 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbylcarbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 Hydrocarbylthio group may be replaced, and the divalent carbon atoms at any position except the ends of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); Furthermore, the above R 3A 、R 3B 、R 3C 、R 3D 、K 3A 、K 3B And L 3At least one or more hydrogen atoms contained therein are replaced by a polar group having a (t) acid dissociable group; R 3A 、R 3B and K 3A Any two of, and / or, R 3C 、R 3D and K 3B Any two of them may be directly connected to each other by a single bond or a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 It may form a ring together with the sulfur atom in formula (VII-2) via an alkylene group.

[0132] The above R 3A ~R 3D are each independently a C 1-18 hydrocarbyl group which may have a substituent; any divalent carbon atom at a position other than the terminal of the above R 3A ~R 3D may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced); the hydrogen atoms contained in the above R 3A ~R 3D are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, in which at least part of the hydrogen atoms may be substituted with the above (a) to (t);1-18 A hydrocarbyloxycarbonyl group, C 1-18 A hydrocarbyloxycarbonyloxy group, or C 1-18 May be replaced by a hydrocarbylthio group. Any divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). Those are preferred, A C which may have a substituent 1-18 An alkyl group, C 3-18 An alicyclic group, C 6-18 An aryl group, or C 7-18 An aralkyl group; the above R 3A ~R 3D Any divalent carbon atom at any position except the terminal of may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the above R 3A ~R 3D The hydrogen atoms contained in are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C in which at least part of the hydrogen atoms are optionally substituted with the above (a) to (t) 1-18 A hydrocarbyl group, C 1-18 A hydrocarbyloxy group, C 1-18 A hydrocarbylcarbonyl group, C 1-18 A hydrocarbylcarbonyloxy group, C 1-18 A hydrocarbyloxycarbonyl group, C 1-18A hydrocarbyloxycarbonyl-oxy group, or a C 1-18 may be replaced by a hydrocarbylthio group, and the divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).) is more preferable.

[0133] The above K 3A , K 3B and L 3 each independently represent an alkylene group or an arylene group which may have a substituent; the divalent carbon atom at any position of the above K 1-18 , K 1-18 and L 3A may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the hydrogen atoms contained in the above K 3B , K 3 and L 3A may be replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid dissociable group. 3B and L 3 is preferably one that may be replaced.

[0134] R having one or more acid dissociable groups 3A , R 3B , R 3C , R 3D , K 3A , K 3B and / or L 3Examples include those having a polar group such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid dissociable group. Examples of the acid dissociable group include a tertiary carbon type acid dissociable group G A , an allyl type or benzyl type acid dissociable group G B , an acetal type acid dissociable group G C , an aminocarbonyl type acid dissociable group G D and the like. Examples of R 3A ~R 3D having one or more of the above acid dissociable groups are the same as those exemplified for R 2A having one or more acid dissociable groups above.

[0135] [1-1-2-1-3. Organic iodonium cation having one or more acid dissociable groups] The organic iodonium cation having one or more acid dissociable groups is not particularly limited, and known and commonly used ones can be used. Examples of the organic iodonium cation having one or more acid dissociable groups include, for example, an organic iodonium cation represented by the following general formula (VII-3). [Chemical formula]

[0136] In the general formula (VII-3), R 4A and R 4B each independently represent an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Any divalent carbon atom at a position other than the terminals of the above R 4A and R 4B may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced); The above R 4A and R 4BThe hydrogen atoms contained therein may be at least partially substituted with (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, or C 1-18 hydrocarbyloxycarbonyloxy group, and the divalent carbon atoms at any position except the ends of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); Also, one or more hydrogen atoms contained in the above R 4A are replaced by a polar group having an (t) acid dissociable group, Furthermore, R 4A and R 4B may be directly bonded to each other by a single bond or through a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or a C 1-3 alkylene group to form a ring together with the iodine atom in formula (VII-3).

[0137] As the above R 4A having one or more acid dissociable groups, it is a C 1-18 hydrocarbyl group which may have a substituent; the above R 4AThe divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the above R 4A It is preferable that at least one or more hydrogen atoms of the above R are replaced by a polar group having a (t) acid dissociable group, It may have a substituent and is a C 1-18 alkyl group, a C 3-18 alicyclic group, a C 6-18 aryl group, or a C 7-18 aralkyl group; the above R 4A The divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the above R 4A It is more preferable that at least one or more hydrogen atoms of the above R are replaced by a polar group having a (t) acid dissociable group, It may have a substituent and is a C 6-18 aryl group or a C 7-18 aralkyl group; the above R 4A The divalent carbon atoms at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the above R 4A It is even more preferable that at least one or more hydrogen atoms of the above R are replaced by a polar group having a (t) acid dissociable group.

[0138] The above R 4A is characterized by having one or more acid dissociable groups. For example, polar groups such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid dissociable group are introduced. Examples of the above acid dissociable group include a tertiary carbon type acid dissociable group G A , an allyl type or a benzyl type acid dissociable group GB , acetal-type acid dissociable group G C , aminocarbonyl-type acid dissociable group G D and the like can be mentioned. R having one or more of the above acid dissociable groups 4A As the R having one or more acid dissociable groups above 2A Those similar to those exemplified above can be exemplified.

[0139] R 4B is a hydrocarbyl group which may have a substituent; any divalent carbon atom at a position other than the terminal of the above R 1-18 may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not replaced simultaneously); the hydrogen atom contained in the above R 4B is (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C in which at least a part of the hydrogen atoms is substituted with the above (a) to (t) 4B hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, C 1-18 hydrocarbyloxycarbonyloxy group, or C 1-18 hydrocarbyloxycarbonyloxy group, or C 1-18It may be replaced by a hydrocarbylthio group, and the divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). Such is preferred. Optionally substituted C 1-18 alkyl group, C 3-18 alicyclic group, C 6-18 aryl group, or C 7-18 aralkyl group; any divalent carbon atom at a position except the terminal of the above R 4B may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the hydrogen atom contained in the above R 4B is (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) a C 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, C 1-18 hydrocarbyloxycarbonyloxy group, or C 1-18It may be replaced by a hydrocarbylthio group, and the divalent carbon atom at any position except the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). Those are more preferred.

[0140] [1-1-2-2. Other counter cations (A m+ )] The other counter cation (A m+ ) according to this embodiment is H + , a metal ion, an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication.

[0141] <Metal ion> The metal ion that can be used as "A m+ " is 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+ , etc. These metal ions may be single or a combination of two or more.

[0142] Examples of the metal ion include Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Al 3+ , Co 3+is preferred, and Na + , K + , Rb + , Cs + , Ca 2+ , Al 3+ , Co 3+ are more preferred.

[0143] <ammonium cation> The ammonium cation is not particularly limited, and known and commonly used ones can be used. The ammonium cation is not particularly limited. 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 mentioned. Note that the above R 5A ~R 5D represent the same ones as defined below.

[0144] As the ammonium cation, ammonium ion (NH4 + ), a quaternary ammonium cation is preferred, and in particular, ammonium ion (NH4 + ), an organic quaternary ammonium cation represented by the following general formula (VIII-1) is more preferred.

Chemical formula

[0145] In the general formula (VIII-1), R 5A ~R 5D are each independently C which may have a substituent1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, said R 5A ~R 5D Any divalent carbon atom at an arbitrary position except for the terminals of said R 5A ~R 5D may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced). 1-18 The hydrogen atom contained in 1-18 said R 1-18 ~R 1-18 is (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) at least a part of the hydrogen atom is a C 1-18 hydrocarbyl group, a C 1-18 hydrocarbyloxy group, a C 1-18 hydrocarbylcarbonyl group, a C 1-18 hydrocarbylcarbonyloxy group, a C 1-18 hydrocarbyloxycarbonyl group, a C 1-18 hydrocarbyloxycarbonyloxy group, a C 1-18 hydrocarbylamino group, a diC 1-18 hydrocarbylamino group, a C 1-18 hydrocarbylaminocarbonyl group, a diC 1-18 hydrocarbylaminocarbonyl group, a C 1-18A hydrocarbylaminocarbonylamino group, C 1-18 A hydrocarbyloxycarbonylamino group, or C 1-18 May be replaced by a hydrocarbylthio group, and any divalent carbon atom at any position except the ends of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); Furthermore, R 5A ~R 5D Any two of which may be directly connected to each other by a single bond or are a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 Linked via an alkylene group to form a ring together with the nitrogen atom in formula (VIII-1).

[0146] In general formula (VIII-1), R 5A ~R 5D Are each independently preferably a hydrocarbyl group which may have a substituent, and C 1-18 An alkyl group, C 1-12 An alkenyl group, C 1-12 An alkynyl group, C 1-12 An alicyclic group is more preferable. 1-12 Specific examples of the above organic quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, tetraheptylammonium cation, trimethylethylammonium cation, dimethyldiethylammonium cation, dimethylethylpropylammonium cation, methylethylpropylbutylammonium cation, trimethylphenylammonium cation, triethylhexylammonium cation, triethylcyclohexylammonium cation, dodecyltrimethylammonium cation and the like.

[0147]

[0148] ​ <ammonium dication> The ammonium dication is not particularly limited, and known and commonly used ones can be used. Examples of the ammonium dication include organic quaternary ammonium dications represented by the following general formula (VIII-2). [Chemical formula]

[0149] In general formula (VIII-2), R 6A ~R 6F each independently represents an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, at any position of the above R 6A ~R 6F any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced); L 6 represents an optionally substituted C 1-18 hydrocarbylene group, at any position of the above L 6 any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced); the above R 6A ~R 6F and L 6The hydrogen atoms contained therein are (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) at least a part of the hydrogen atoms may be substituted with the above (a) to (t), and the C 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, C 1-18 hydrocarbyloxycarbonyloxy group, C 1-18 hydrocarbylamino group, diC 1-18 hydrocarbylamino group, C 1-18 hydrocarbylaminocarbonyl group, diC 1-18 hydrocarbylaminocarbonyl group, C 1-18 hydrocarbylcarbonylamino group, C 1-18 hydrocarbylaminocarbonyloxy group, diC 1-18 hydrocarbylaminocarbonyloxy group, C 1-18 hydrocarbylaminocarbonylamino group, diC 1-18 hydrocarbylaminocarbonylamino group, C 1-18 hydrocarbyloxycarbonylamino group, or C 1-18 hydrocarbylthio group, and any divalent carbon atoms at positions other than the terminals of these substituents may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); R 6A ~R 6FAny two of them may be directly connected to each other by a single bond or through a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 and may form a ring together with the nitrogen atom in formula (VIII-2) via an alkylene group.

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

[0151] <Phosphonium cation> The phosphonium cation is not particularly limited, and known and commonly used ones can be used. Examples of the phosphonium cation include organic quaternary phosphonium cations represented by the following general formula (VIII-3).

Chemical formula

[0152] In the general formula (VIII-3), R 7A ~R 7D each independently represents a C 1-18 hydrocarbyl group which may have a substituent, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; At any position of the above R 7A ~R 7D except for the terminal, the divalent carbon atoms may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); At the above R 7A ~R7D The hydrogen atoms contained in (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u) at least a part of the hydrogen atoms may be substituted with the above (a) to (t), and the C 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, C 1-18 hydrocarbyloxycarbonyloxy group, C 1-18 hydrocarbylamino group, diC 1-18 hydrocarbylamino group, C 1-18 hydrocarbylaminocarbonyl group, diC 1-18 hydrocarbylaminocarbonyl group, C 1-18 hydrocarbylcarbonylamino group, C 1-18 hydrocarbylaminocarbonyloxy group, diC 1-18 hydrocarbylaminocarbonyloxy group, C 1-18 hydrocarbylaminocarbonylamino group, diC 1-18 hydrocarbylaminocarbonylamino group, C 1-18 hydrocarbyloxycarbonylamino group, or C 1-18 may be replaced with a hydrocarbylthio group, and the divalent carbon atoms at any position except the ends of these substituents may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); Furthermore, R 7A ~R 7DAny two of them are directly connected to each other by a single bond or are a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 and may form a ring together with the phosphorus atom in formula (VIII-3) via an alkylene group.

[0153] R in formula (VIII-3) 7A , R 7B , R 7C and R 7D are each independently preferably a hydrocarbyl group which may have a substituent, and more preferably a C 1-18 alkyl group, a C 1-12 alkenyl group, a C 1-12 alkynyl group, or an alicyclic group. 1-12 1-12 More preferably, it is an alicyclic group.

[0154] Specific examples of the above organic phosphonium cation 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, and the like.

[0155] <Phosphonium dication> The phosphonium dication is not particularly limited, and known and commonly used ones can be used. Examples of the phosphonium dication include organic quaternary phosphonium dications represented by the following general formula (VIII-4). [Chemical formula]

[0156] In the general formula (VIII-4), R 8A ~R 8F each independently represents an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, at any position of the above R 8A ~R 8F the divalent carbon atoms at any position except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). L 8 represents an optionally substituted C 1-18 hydrocarbylene group, at any position of the above L 8 the divalent carbon atoms may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); the above R 8A ~R 8F and L 8The hydrogen atoms contained therein may be at least one part of hydrogen atoms replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, (t) a polar group having an acid dissociable group, or (u); and the divalent carbon atoms at any position except the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); 1-18 hydrocarbyl group, C 1-18 hydrocarbyloxy group, C 1-18 hydrocarbylcarbonyl group, C 1-18 hydrocarbylcarbonyloxy group, C 1-18 hydrocarbyloxycarbonyl group, C 1-18 hydrocarbyloxycarbonyloxy group, C 1-18 hydrocarbylamino group, diC 1-18 hydrocarbylamino group, C 1-18 hydrocarbylaminocarbonyl group, diC 1-18 hydrocarbylaminocarbonyl group, C 1-18 hydrocarbylcarbonylamino group, C 1-18 hydrocarbylaminocarbonyloxy group, diC 1-18 hydrocarbylaminocarbonyloxy group, C 1-18 hydrocarbylaminocarbonylamino group, diC 1-18 hydrocarbylaminocarbonylamino group, C 1-18 hydrocarbyloxycarbonylamino group, or, C 1-18 may be replaced by a hydrocarbylthio group, and the divalent carbon atoms at any position except the terminals of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); R 8A ~R 8FAny two of them may be directly connected to each other by a single bond or through a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 via an alkylene group to form a ring together with the phosphorus atom in the formula (VIII-4).

[0157] The organic quaternary phosphonium dication represented by the general formula (VIII-4) is not particularly limited, and examples thereof include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylene bis(triphenylphosphonium) dication, pentamethylene bis(triphenylphosphonium) dication, and the like.

[0158] [1-1-2-3.A m+ and B n+ ratio] In the general formula (I), m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0. (A m+ ) a (B n+ ) b (C (am+bn)- ) (I) In addition, the mixture of heteropolyacid salts in which the defective site is modified may contain heteropolyacid salts in which a plurality of defective sites having different ratios of A m+ and B n+ are modified. In this case, the values of a and b can be determined, for example, by performing analysis by NMR, XRF analysis, XPS analysis, etc.

[0159] As the ratio of a to b, although it depends on the type of the heteropolyacid anion in which the defective site is modified, A m+ , B n+ etc., it is preferably a:b = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of 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 preferably, a is a real number from 0 to 4 and b is a real number from 2 to 8.

[0160] [Content of component (A) in 1-1-3.] 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 or the like and the film thickness to be applied. As the content of component (A) in the resist material, when the resist material is 100% by mass, it is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 10% by mass.

[0161] [1-2. (B) Acid diffusion controller] The resist material according to this embodiment may contain, as an optional component, a (B) acid diffusion controller that traps the acid generated by exposure, in addition to the heteropolyacid salt or a mixture thereof in which the (A) defect site is modified.

[0162] The acid diffusion controller is not particularly limited, and known and commonly used ones can be used. Examples of the acid diffusion controller include (B1) a photodegradable base that decomposes upon exposure to lose acid diffusion controllability, and (B2) a nitrogen-containing organic compound that does not correspond to component (B1). These may be used alone or in combination of two or more.

[0163] [1-2-1. (B1) Photodegradable base] (B1) The photodegradable base decomposes upon exposure to lose acid diffusion controllability, while acting as a quencher in the unexposed portion to control the diffusion of acid. Therefore, by incorporating (B1) the photodegradable base into the resist material, characteristics such as increased sensitivity, reduced roughness, and suppression of the occurrence of coating defects can be improved.

[0164] The above photo-dissociable base is not particularly limited, and known and commonly used ones can be used. Examples of the photo-dissociable base include, 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 ", "sulfonylamide salt compound B" represented by the following general formula (IX-3) C ", and the like. Hereinafter, the carboxylate anion, sulfonate anion, sulfonylamide anion, onium cation or dication (D p+ ) contained in the following general formulas (IX-1) to (IX-3) will be described respectively. [Chemical formula] [Chemical formula] [Chemical formula]

[0165] [1-2-1-1. Carboxylate compound B A As the above-mentioned (B1) photo-dissociable base, a salt of a carboxylate anion and an onium cation or dication (D A ) such as "carboxylate compound B" represented by the following general formula (IX-1) can be used. p+ [Chemical formula]

[0166] "R A b1 " may be a C optionally having a substituent 1-18 ​​A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced).

[0167] R A b1 As, it may be a C hydrocarbyl group which may have a substituent, 1-18 a hydrocarbyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced) is preferred, a C alkyl group which may have a substituent, C 1-18 an alkyl group, C 3-18 an alicyclic group, C 6-18 an aryl group, or a C 7-18 an aralkyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced) is more preferred.

[0168] <Carboxylate compound B A1 > The carboxylate compound B represented by the above general formula (IX-1) A may be a carboxylate compound B represented by the following general formula (IX-1-1). A1

Chemical formula

[0169] "X A " is a C alkyl group which may have a substituent, C 1-18 an alkyl group, C 3-18 an alicyclic group, C 6-18 ​An aryl group, or a C 7-18 aralkyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0170] X A As, it may be a C optionally having a substituent 3-18 alicyclic group, a C 6-18 aryl group, or a C 7-18 aralkyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), and it is preferably a C optionally having a substituent 3-18 alicyclic group, or a C 6-18 aryl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0171] "L A " is a group connecting X A and -COO - and, and a linking group represented by the following general formula (L A -1) to (L A -7) can be used.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0172] L A b1 and L A b2 are preferably a single bond or a C 1-8 alkylene group or a C 6-8 arylene group which may have a substituent, and more preferably a single bond or a C 1-8 alkylene group which may have a substituent.

[0173] [Examples of the carboxylate anion] The carboxylate anion of the above carboxylate compound B A or B A1 is not particularly limited, and examples thereof include trifluoroacetate anion, pentafluoropropionate anion, 2-methoxyacetate anion, 2-methoxy-2-methylpropionate anion, 2-hydroxyacetate anion, 2-hydroxy-2-methylpropionate anion, 2-acetoxyacetate anion, adamantane-1-carboxylate anion, 9,10-dihydro-9,10-ethanoanthracene-11-carboxylate anion, 9,10-dihydro-9,10-[1,2]benzenoanthracene-9-carboxylate anion, benzoate anion, salicylate anion, 3-hydroxybenzoate anion, 3-trifluoromethylbenzoate anion, and the like.

[0174]

Chem.

[0175]

Chem.

[0176]

Chem.

[0177] [1-2-1-2. Sulfonate Compound B B As the above-mentioned (B1) photo-disintegrating base, a salt of a sulfonic acid anion and an onium cation or dication (D B ) such as the "sulfonate compound B p+ " represented by the following general formula (IX-2) can be used.

Chem.

[0178] "R B b1 " is a C 1-18 hydrocarbyl group which may have a substituent, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, and any divalent carbon atoms except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (however, it is assumed that adjacent divalent carbon atoms are not simultaneously replaced).

[0179] R B b1 As, it is a C 1-18 ​A hydrocarbyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). Preferably, optionally substituted C 1-18 alkyl group, C 3-18 alicyclic group, C 6-18 aryl group, or C 7-18 aralkyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). More preferably,

[0180] <sulfonate compound B B1 > The sulfonate compound B represented by the above general formula (IX-2) B may be a sulfonate compound B represented by the following general formula (IX-2-1). B1

Chemical formula

[0181] 「X B 」 is optionally substituted C 1-18 alkyl group, C 3-18 alicyclic group, C 6-18 aryl group, or C 7-18 aralkyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0182] X B As, it may be optionally substituted C 3-18 alicyclic group, C 6-18 aryl group, or C​7-18 An aralkyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), is preferred. Optionally substituted C 3-18 alicyclic group, or C 6-18 An aryl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), is more preferred.

[0183] "L B " is a group that connects X B and -SO2-O - and can use a linking group represented by the following general formula (L B -1) to (L B -7).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0184] L B b1 and L B b2 As L 1-8 and L 6-8 it is preferably a single bond, or a C 1-8 alkylene group or C

[0185] <Examples of sulfonate anions> For the sulfonate anion of the above sulfonate compound B B or B B1 it is not particularly limited, and examples include camphorsulfonate anion, (adamantan-1-yl)methanesulfonate anion, (adamantan-1-carbonyloxy)ethane-1-sulfonate anion, cyclohexanesulfonate anion, 2-(cyclohexanecarbonyloxy)ethane-1-sulfonate anion, bicyclo[2.2.1]heptane-2-sulfonate anion, benzenesulfonate anion, 4-methylbenzenesulfonate anion, and the like.

[0186]

Chemical formula

[0187] [1-2-1-3. Sulfonylamide salt compound B C As the above (B1) photo-dissociable base, a salt of a sulfonylamide anion and an onium cation or dication (D C ) such as the "sulfonylamide salt compound B p+ " represented by the following general formula (IX-3) can be used.

Chemical formula

[0188] 「R C b1 」 is an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom except the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). 「R C b2 」 is an optionally substituted C 1-18 hydrocarbyl group, wherein any divalent carbon atom except the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0189] R C b1 Preferably, R 1-18 is an optionally substituted C hydrocarbyl group, wherein any divalent carbon atom except the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), 1-18 more preferably, it is an optionally substituted C 3-18 alkyl group, a C 6-18 cycloaliphatic group, a C 7-18 aryl group, or a C

[0190] R C b2Examples include a C which may have a substituent 1-18 alkyl group, a C 3-18 alicyclic group, where any divalent carbon atom except the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced). Such groups are preferred. C 1-12 It is more preferably a haloalkyl group, and C 1-5 even more preferably a fluorinated alkyl group.

[0191] <Sulfonylamide salt compound B C1 > The sulfonylamide salt compound B represented by the above general formula (IX-3) C may be a sulfonylamide salt compound B represented by the following general formula (IX-3-1). C1

Chemical formula

[0192] "X C " is a C which may have a substituent 1-18 alkyl group, a C 3-18 alicyclic group, a C 6-18 aryl group, or a C 7-18 aralkyl group, where any divalent carbon atom except the terminal ones may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced).

[0193] X C Examples include a C which may have a substituent 3-18 alicyclic group, a C 6-18 aryl group, or a C 7-18 ​An aralkyl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), is preferred. Optionally substituted C 3-18 alicyclic group, or C 6-18 aryl group, wherein any divalent carbon atom except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced), is more preferred.

[0194] "L C " is a group that connects X C and -N - -SO2-R C b2 and can use a linking group represented by the following general formula (L C -1) to (L C -7).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0195] L C b1 and L C b2 are preferably a single bond or a C alkylene group, C cycloalkylene group or C arylene group which may have a substituent, and more preferably a single bond or a C alkylene group or C cycloalkylene group which may have a substituent. 1-12 alkylene group, C 1-12 cycloalkylene group or C 6-12 arylene group, and more preferably a single bond or a C 1-8 alkylene group or C 1-8 cycloalkylene group.

[0196] <Exemplification of Sulfonylamide Anion> The above sulfonylamide salt compound B C or B C1 ​The sulfonylamide anion is not particularly limited, and examples thereof include 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]heptan-2-ylmethyl ((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1]heptan-7-ylmethyl ((trifluoromethyl)sulfonyl)amide anion, 2-((adamantane-1-carbonyl)oxy)ethyl ((trifluoromethyl)sulfonyl)amide anion, 2-(adamantane-1-carboxamido)ethyl ((trifluoromethyl)sulfonyl)amide anion, 2-(4-((adamantane-1-carbonyl)oxy)cyclohexyl)ethyl ((trifluoromethyl)sulfonyl)amide anion, 4-((adamantane-1-carbonyl)oxy)phenyl ((trifluoromethyl)sulfonyl)amide anion, and the like.

[0197] [Chemical formula]

[0198] [Chemical formula]

[0199] [Chemical formula]

[0200] [1-2-1-4. Onium Cation or Dication (D p+ )] As the cationic part of the above (B1) photodissociable base, an onium cation or dication D p+ can be used. Here, in the “(D p+ ) 1 / p ” represented by general formulas (IX-1) to (IX-3), (D p+ ) represents an onium cation or dication, and p represents an integer of 1 or 2. The above onium cation or dication is not particularly limited, and an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic quaternary ammonium cation, an organic quaternary ammonium dication, an organic phosphonium cation, an organic phosphonium dication, etc. can be used.

[0201] As the above onium cation or dication (D p+ ), for example, an organic sulfonium cation represented by the following general formula (X-1) can be used. [Chemical formula]

[0202] In general formula (X-1), R D 1A , R D 1B and R D 1C each independently represent an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Any divalent carbon atom at a position other than the terminals of the above R D 1A , R D 1B and R D 1C may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that two adjacent divalent carbon atoms are not simultaneously replaced); R D 1A, R D 1B and R D 1C Any two of them are directly linked to each other by a single bond or are a divalent linking group such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 and may form a ring together with the sulfur atom in formula (X-1) via an alkylene group.

[0203] In addition, as the above-mentioned onium cation or dication (D p+ ), for example, an organic sulfonium dication represented by the following general formula (X-2) can be used.

Chemical formula

[0204] In general formula (X-2), R D 2A , R D 2B , R D 2C and R D 2D each independently represents an optionally substituted C 1-18 hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, The above R D 2A , R D 2B , R D 2C and R D 2D Any divalent carbon atom at an arbitrary position except the terminal ends of them may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (however, it is assumed that two adjacent divalent carbon atoms are not simultaneously replaced); K D 2A , K D 2B and L D 2is, independently of each other, a C which may have a substituent 1-18 representing a hydrocarbylene group, said K D 2A , K D 2B and L D 2 Any divalent carbon atom at any position of may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (provided that two adjacent divalent carbon atoms are not simultaneously replaced); R D 2A , R D 2B and K D 2A Any two of, and / or, R D 2C , R D 2D and K D 2B may be directly connected to each other by a single bond or through a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or a C 1-3 alkylene group to form a ring together with the sulfur atom in formula (XI-2).

[0205] As the above-mentioned onium cation or dication (D p+ ), for example, an organic iodonium cation represented by the following general formula (X-3) can be used. [Chemical formula]

[0206] In general formula (X-3), R D 3A and R D 3B each independently represent a C hydrocarbyl group which may have a substituent, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, 1-18 and said R D ​3A and R D 3B Any divalent carbon atom at any position except the termini of and R may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not simultaneously replaced); R D 3A and R D 3B are directly connected to each other by a single bond or, via a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or a C 1-3 alkylene group, and may form a ring together with the iodine atom in formula (X-3).

[0207] [1-2-2. (B2) Nitrogen-containing organic compound] As other (B) acid diffusion control agents, nitrogen-containing organic compounds not corresponding to (B2)(B1) may be included. The nitrogen-containing organic compounds are not particularly limited, and for example, aliphatic amines, aromatic amines, heterocyclic amines, etc. can be used.

[0208] Examples of the nitrogen-containing organic compounds include aliphatic amines such as n-hexylamine, n-heptylamine, diethylamine, di-n-propylamine, di-n-butylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine; aromatic amines such as aniline, N-methylaniline, N-ethylamine, N,N-dimethylaniline, 4-methylaniline, pyrrole; 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, 1,4-diazabicyclo[2.2.2]octane, etc. These nitrogen-containing organic compounds may be used alone or in combination of two or more.

[0209] [1-2-3. Content of Component (B)] The content of the (B) acid diffusion controller contained in the resist material according to this embodiment is not particularly limited and can be appropriately selected according to the content, type, etc. of the (A) component. As the content of the (B) component in the resist material, it is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass, and even more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (A) component.

[0210] [1-3. Organic Solvent] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and known and commonly used ones can be used. The organic solvent is preferably an organic solvent that can be uniformly dissolved or dispersed when prepared with a heteropolyacid salt in which the (A) defect site is modified or a mixture thereof.

[0211] Examples of the organic solvent include, as polar solvents, for example, alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, nitrile solvents, aprotic polar solvents, etc., and hydrocarbon solvents, etc. as non-polar solvents. These organic solvents may be used alone or in combination of two or more.

[0212] Specific examples of the above polar solvents include, for example, alcohol 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); Ether 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.; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, furfural, etc.; Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, etc.; Ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, propylene glycol monomethyl ether acetate (PGMEA), etc.; Nitrile solvents such as acetonitrile, propionitrile, benzonitrile, etc.: Examples of aprotic polar solvents include γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, etc. Examples of nonpolar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, xylene, etc. The above organic solvents may be used alone or in combination of two or more.

[0213] As the organic solvent to be contained in the resist material according to this embodiment, a polar solvent is preferable from the viewpoint of coatability, and more preferably, an amide-based solvent, an ester-based solvent, an alcohol-based solvent, or a ketone-based solvent is included from the viewpoint of solubility. As the amide-based solvent, it is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. Further, as the ester-based solvent or alcohol-based solvent, it preferably has an ester bond and / or a hydroxyl group from the viewpoint of solubility. Among them, it is preferably at least one selected from the group consisting of propylene glycol monomethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, and propylene glycol monomethyl ether acetate.

[0214] The content of the organic solvent 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 or the like, the film thickness to be applied, and the like. As the content of the organic solvent in the resist material, it is preferable that the solid content concentration of the resist material is 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably in the range of 0.2 to 10% by mass.

[0215] [1-4. Others] In the resist material according to this embodiment, if desired, additives having miscibility, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc., can be appropriately added and contained. The resist material according to this embodiment preferably does not contain an epoxy resin. Further, it preferably does not contain hydrogen peroxide.

[0216] [2. Pattern formation method] The pattern formation method according to this embodiment includes a step of applying a resist material to a substrate, a step of exposing the resist film formed by the applying step, and a step of developing the exposed resist film.

[0217] [2-1. Coating Process] The pattern formation method according to this embodiment includes a step of applying a resist material onto a substrate.

[0218] [Substrate] The substrate used in this embodiment is not particularly limited, and known and commonly used substrates can be used. As the substrate, for example, a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, etc. may be used. The material of the substrate is not particularly limited, and examples thereof include metal substrates such as silicon wafers, copper, chromium, iron, and aluminum, and substrates made of inorganic substances such as glass, titanium oxide, and silicon dioxide. The size, shape, etc. of the substrate are not particularly limited, and the surface of the substrate may be smooth, may have a curved surface or unevenness, or may be a thin sheet-shaped substrate, etc.

[0219] The surface of the substrate may be subjected to surface treatment as necessary. In the case of a substrate having a hydroxyl group on its surface layer, the surface treatment of the substrate is performed using a silane-based coupling agent capable of reacting with the hydroxyl group, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic and enhancing the adhesion between the substrate and the metal compound-containing film. Examples of the above silane-based coupling agent include hexamethyldisilazane (HMDS).

[0220] [Coating Method] The method of applying the resist material onto the substrate is not particularly limited, and known and commonly used methods can be used. As the coating method, as the dry method, for example, CVD methods (chemical vapor deposition methods) such as thermal CVD, plasma CVD, and photo CVD; PVD methods (physical vapor deposition methods) such as vacuum evaporation, plasma-assisted evaporation, sputtering, and ion plating can be used. As the wet method, for example, coating methods such as spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing can be used.

[0221] As a method of applying the resist material according to this embodiment onto a substrate, from the viewpoint of forming a uniform film thickness or the like, it is preferable to use a wet method such as a spin coating method or screen printing, and it is more preferable to use the spin coating method. After forming the coating film, in order to remove the edge bead, a backside rinse, an edge bead removal step, or the like can be performed.

[0222] The method of drying the resist film formed by applying the resist material onto the substrate is not particularly limited, and for example, it can be performed using a heating device such as a hot plate (post-apply bake (PAB)), a decompression device, or the like. The baking conditions are not particularly limited and can be appropriately set according to the type and use of the resist film, etc. The baking temperature is preferably 80 to 300 °C, more preferably 80 to 200 °C, and even more preferably 80 to 130 °C. Also, the baking time is preferably 10 seconds to 300 seconds, more preferably 20 seconds to 180 seconds, and even more preferably 30 seconds to 120 seconds.

[0223] 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.

[0224] [2-2. Exposure process] The pattern formation method according to this embodiment includes a step of exposing the resist film formed by the above coating step.

[0225] As the exposure device in the exposure step of the resist film, for example, an ArF exposure device, an electron beam lithography device, an EUV exposure device, or the like can be used. Also, in the exposure step, exposure may be performed through a mask (mask pattern) in which a predetermined pattern is formed, or selective exposure may be performed by direct irradiation of an electron beam or the like without using a mask pattern.

[0226] 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, soft X-ray, etc. may be used.

[0227] In the case of an ArF excimer laser or a KrF excimer laser, the exposure dose on the resist film is preferably 1 to 200 mJ / cm 2 and more preferably 20 to 60 mJ / cm 2 In the case of extreme ultraviolet, the exposure dose is, for example, 500 mJ / cm 2 or less, preferably 0.1 to 200 mJ / cm 2 more preferably 3 to 100 mJ / cm 2 even more preferably 5 to 50 mJ / cm 2 In the case of an electron beam, it is preferably exposed at a dose of 3 μC / cm to 2 mC / cm at 50 kV and more preferably exposed at a dose of 10 μC / cm to 1.5 mC / cm 2 ~2 mC / cm 2 After the resist film is exposed, post-exposure baking (PEB) treatment may or may not be performed. The baking conditions are not particularly limited and can be appropriately set according to the type and use of the resist film. The baking temperature is preferably 80 to 300 °C, more preferably 80 to 200 °C, and even more preferably 80 to 130 °C using a heating device such as a hot plate. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds. 2 ~1.5 mC / cm 2 In the case of an electron beam, it is preferably exposed at a dose of 3 μC / cm to 2 mC / cm at 50 kV

[0228] After the resist film is exposed, post-exposure baking (PEB) treatment may or may not be performed. The baking conditions are not particularly limited and can be appropriately set according to the type and use of the resist film. The baking temperature is preferably 80 to 300 °C, more preferably 80 to 200 °C, and even more preferably 80 to 130 °C using a heating device such as a hot plate. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0229] [2-3. Development process] The pattern formation method according to this embodiment includes a step of developing the exposed resist film. In the development step, a pattern can be formed by developing the exposed resist film with a developer. When the exposed area remains as a pattern after development, it is a negative pattern formation process, and when the exposed area is removed after development, it is a positive pattern formation process. Whether to form a positive or negative pattern can be appropriately selected depending on the resist material or the developer. After the above development, it may be washed with a rinse solution and then dried, and in some cases, a baking process may be further performed.

[0230] As the developer used in this embodiment, an alkaline developer may be used as the developer for the alkaline development process, or a developer containing an organic solvent (organic-based developer) may be used as the developer for the organic solvent development process.

[0231] <Alkaline development process> The alkaline developer used in the alkaline development process is not particularly limited, and known and commonly used ones can be used. Examples of the alkaline developer include aqueous solutions containing one or more of quaternary ammonium salts such as tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide; inorganic alkalis such as sodium hydroxide and potassium hydroxide; alkanolamines such as dimethylethanolamine and triethanolamine.

[0232] Also, pure water can be used as the rinse solution in the alkaline development process.

[0233] <Organic solvent development process> Examples of the developer used in the organic solvent development process include developers containing one or more organic solvents such as polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.

[0234] Specific examples of the organic solvent include, for example, Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, furfural, etc.; Ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, propylene glycol monomethyl ether acetate (PGMEA), etc.; Alcohol 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), etc.; Nitrile solvents such as acetonitrile, propionitrile, benzonitrile, etc.: Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, etc.; Ether 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.; Hydrocarbon solvents such as n-pentane, n-hexane, toluene, xylene, etc.; And the like. These may be used alone or in combination of two or more.

[0235] Among these, as the organic solvent used in the developer, it is preferably a polar solvent, preferably containing an amide solvent, an alcohol solvent, and an ester solvent, and more preferably containing an amide solvent or an ester solvent and an alcohol solvent. As the amide solvent, it is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. As the ester solvent, it is preferably 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. As the alcohol solvent, it is preferably at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol.

[0236] When the developer contains both an amide solvent or an ester solvent and an alcohol solvent, the mixing ratio (weight ratio) of the amide solvent or the ester solvent to the alcohol solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0237] After developing with the above developer, it may have a step of washing with a rinse solution. The rinse solution is not particularly limited, and known and commonly used ones can be used. As the rinse solution, among the water or organic solvents contained in the above developer, those that are less likely to dissolve the resist pattern can be appropriately selected and used.

[0238] The rinsing liquid is not particularly limited. For example, at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents can be used. Among these, as the rinsing liquid, 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. It is more preferable to use at least one selected from the group consisting of alcohol solvents and ester solvents, and it is even more preferable to use at least one alcohol solvent.

[0239] As the alcohol solvent used in the rinsing liquid, a monohydric alcohol having 2 to 8 carbon atoms is preferable, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples of the monohydric alcohol include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, and the like. These organic solvents may be used alone or in combination of two or more.

[0240] <Development method using a developer and cleaning method using a rinsing liquid> The method of developing the exposed resist film using the above developer is not particularly limited, and a known and commonly used method can be used. Examples of the method of developing using the above developer include 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 on the surface of the resist film after exposure (spray method), and a method of discharging the above developer from a discharge nozzle at a constant speed toward the surface of the resist film on a substrate rotating at a constant speed (dynamic dispense method).

[0241] The method of cleaning the resist pattern with the above rinse liquid is not particularly limited, and known and commonly used methods can be used. Examples of the method of cleaning using the above rinse liquid include, for example, a method of immersing the resist pattern in the above rinse liquid for a certain period of time (dip method), a method of spraying the above rinse liquid on the surface of the resist pattern (spray method), and a method of discharging the above rinse liquid from a discharge nozzle at a constant speed toward the surface of the resist pattern rotating at a constant speed (dynamic dispense method), etc.

[0242] [3. Patterned structure] The patterned structure according to this embodiment is obtained by forming the above resist material on a substrate using the above pattern formation method.

[0243] The average thickness of part or all of the patterned structure according to this 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 an average thickness portion of 1 to 100 nm, more preferably an average thickness portion of 5 to 75 nm, and even more preferably an average thickness portion of 10 to 60 nm.

[0244] Also, the pitch of part or all of the patterned structure according to this 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 where the pitch is 100 nm or less, more preferably a portion where the pitch is 50 nm or less, and even more preferably a portion where the pitch is 20 nm or less. By forming a pattern of the resist material according to this embodiment using the above pattern formation method, it becomes possible to fabricate portions with pitches of 50 nm, 20 nm, and 15 nm in part or all of the patterned structure.

[0245] [4. Electron beam or EUV resist material] The resist material according to this embodiment contains a heteropolyacid salt or a mixture thereof in which the defect site is modified, and a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups in the cation part of the heteropolyacid salt or the mixture in which the defect site is modified is used. Thereby, the heteropolyacid salt or the mixture thereof in which the defect site is modified can exhibit the effects of both the function of a photoacid generator and the function of changing the solubility in a developer by the action of an acid. Therefore, the resist material according to this embodiment has good sensitivity to an electron beam and an EUV light source, and can be suitably used as a resist material corresponding to these exposure light sources.

Example

[0246] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited only to these examples.

[0247] [1. Synthesis of heteropolyacid salt (polyacid salt) in which the defect site is modified] Polyacid salts (A-1) to (A-7) were synthesized by the following methods, respectively.

[0248] <Production Example: Potassium undecatungstosilicate (α-K8[SiW 11 O 39 )> To 63 g of silicotungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H4[SiW 12 O 40 ·xH2O), 380 g of 1M acetic acid was added, and the reaction solution was heated to 45 °C. Potassium hydrogen carbonate (52 g) was added so that the pH became 6.0. Then, the reaction solution was cooled to room temperature and filtered by suction filtration to obtain 56 g of a crude product. 216 g of pure water was added to the obtained crude product and redissolved by heating to 73 °C. The solution was recrystallized by cooling at 4 °C for 16 hours, filtered by suction filtration, and vacuum dried to obtain 34 g of the target compound. 29 Si-NMR (119.22 MHz, D2O): δ (ppm) = -84.6 (s, 1Si). 183 W-NMR (20.84 MHz, D2O): δ (ppm) = -101.85 (s, 2W), -116.26 (s, 2W), -119.29 (s, 1W), -125.62 (s, 2W), -140.85 (s, 2W), -174.53 (s, 2W).

[0249] <Synthesis Example 1: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-diphenyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-1))>

Chemical Structure

[0250] <Synthesis 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 (Polyacid Salt (A-2))>

Chemical Structure

[0251] <Synthesis 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 (Polyacid Salt (A-3))>

Chemical Structure

[0252] <Synthesis 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 (Polyacid Salt (A-4))> [Chemical Formula] In Synthesis Example 1, the target compound, polyacid salt (A-4), was obtained in the same manner as above, except that 4-hydroxyphenyltrimethoxysilane was used as the starting compound instead of phenyltrimethoxysilane (PhSi(OCH3)3). 1 H-NMR (400 MHz, DMSO-d6): δ (ppm) = 0.77 - 0.81 (t, 12H), 1.48 - 1.75 (m, 24H), 1.90 - 1.93 (m, 16H), 2.29 (m, 24H), 4.55 (s, 8H), 6.76 (d, 4H), 7.54 (d, 4H), 7.59 (s, 8H), 7.76 - 7.82 (m, 40H), 9.56 (s, 2H). 29 Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -64.28 (s, 2Si), -85.00 (s, 1Si). ESI-MS: POSITIVE m / z 461.2 ([C 29 H 33 O3S] + ) NEGATIVE m / z 733.1 (median) ([C 12 H 10 O 42 Si3W 11 4- )

[0253] ​​<Synthesis Example 5: Tetrakis((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-dimethyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid salt (A-5))>

Chemical formula

[0254] <Synthesis Example 6: Tetrakis((4-(2-((2-methyladamantyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-diphenyldisiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid salt (A-6))>

Chemical formula

[0255] <Synthesis Example 7: Tetrakis(triphenylsulfonium) silicotungstate (Polyacid salt (A-7)>

Chemical formula

[0256] [2. Preparation of Test Resist Materials] As test resist materials, the polyacid salts (A-1) to (A-7) synthesized above, an acid diffusion control agent, and an organic solvent were blended so as to have the contents (unit: parts by mass) shown in Table 1 below, and test resist materials (R-1) to (R-11) were prepared.

[0257] Note that as the (B) acid diffusion control agent described in Table 1, the acid diffusion control agents (B-1) to (B-3) described below were used. · Acid diffusion control agent (B-1): An acid diffusion control agent that is a salt of a triphenylsulfonium cation represented by the following formula (B-1) and a salicylate anion [Chemical formula] · Acid diffusion control agent (B-2): An acid diffusion control agent that is a salt of a (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation represented by the following formula (B-2) and a salicylate anion [Chemical formula] · Acid diffusion control agent (B-3): An acid diffusion control agent that is a salt of a triphenylsulfonium cation represented by the following formula (B-3) and a heptafluorobutyrate anion [Chemical formula]

[0258] [Table 1] ​

[0259] [3. Formation of LS pattern] On an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS), resist materials (R-1) to (R-11) were applied using a spinner, and post-apply bake (PAB) treatment was performed on a hot plate at a temperature of 120 °C for 60 seconds and then dried to produce a resist film with a thickness of 50 nm. The thickness of the formed film was measured with a film thickness measuring device ("M-2000D" manufactured by J.A. Woollam).

[0260] Using an electron beam lithography apparatus F7000S-VD2 (manufactured by Advantest Corporation) for the above resist film, drawing (exposure) was performed at an acceleration voltage of 50 kV with a target size of a 1:1 line and space pattern with a line width of 50 nm (hereinafter also referred to as "LS pattern"). Thereafter, post-exposure bake (PEB) treatment was performed at 90 °C for 60 seconds. Next, development was performed for 60 seconds using a developer (NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) at 23 °C, and rinsing was performed for 15 seconds using pure water. From the above, a 1:1 LS pattern with a line width of 50 nm was formed, and LS patterns (LS-1) to (LS-11) corresponding to the test resist materials (R-1) to (R-11) were obtained. Note that all of the LS patterns (LS-1) to (LS-11) are positive patterns.

[0261] [4. Evaluation of the shape of the LS pattern] The shapes of the above LS patterns (LS-1) to (LS-11) were observed with a length-measuring SEM (scanning electron microscope, acceleration voltage 10 kV, product name: SU-5000, manufactured by Hitachi High-Technologies Corporation), and the shapes were evaluated according to the following criteria. The results are shown in Table 2. A: Almost no scalloping is observed in the LS pattern of the SEM image, and the resolution is excellent. B: Slight scalloping is observed in a part of the LS pattern of the SEM image. C: No LS pattern is formed (not resolved) throughout the SEM image.

[0262] [Table 2]

[0263] From the results in Table 2 above, it can be seen that by using resist materials (R-1) to (R-9) containing polyacid salts (A-1) to (A-6) having an acid-dissociable group in the cation part, an LS pattern with a line width of 50 nm and almost no footing can be obtained with good resolution ((LS-1) to (LS-9)). Also, when comparing the pattern resolution of (LS-1) and (LS-2), it can be seen that by using resist material R-2 containing an acid diffusion control agent (B-1) in addition to resist material (R-1) containing polyacid salt (A-1) having an acid-dissociable group in the cation part, an LS pattern with even better resolution can be obtained.

Claims

1. A resist material containing a heteropolyacid salt or a mixture thereof in which a defect site (A) represented by the general formula (I) is modified. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [In formula (I), A ｍ＋ each independently represents H ＋ , a metal ion, an ammonium cation, an ammonium dication, a phosphonium cation, or a phosphonium dication; B ｎ＋ each independently represents a sulfonium cation, a sulfonium dication, or an iodonium cation having one or more acid dissociable groups; C （ａｍ＋ｂｎ）－ represents a heteropolyacid anion in which the defective site in the heteropolyacid anion having the defective site is modified; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.]

2. The resist material according to claim 1, wherein the sulfonium cation, sulfonium dication, or iodonium dication having one or more acid-dissociable groups is an organic sulfonium cation, organic sulfonium dication, or organic iodonium cation having one or more acid-dissociable groups.

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

4. The resist material according to claim 1, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge.

5. The resist material according to claim 1, wherein the heteropolyacid anion having the defect site is a defective Keggin type heteropolyacid anion or a defective Dawson type heteropolyacid anion.

6. The resist material according to claim 1, wherein the modification is made by a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more organic groups are bonded, bonding to the heteropolyacid anion having the defect site through part or all of the heteroatoms.

7. The resist material according to claim 1, further containing (B) an acid diffusion controller.

8. The resist material according to claim 7, wherein the (B) acid diffusion controller is (B1) a photo-dissociable base.

9. The resist material according to claim 1, further containing an organic solvent.

10. The resist material according to any one of claims 1 to 9, which is an electron beam resist material or an EUV resist material.

11. A step of forming a resist film using the resist material according to any one of claims 1 to 9, A step of exposing the resist film, A step of developing the exposed resist film using a developer, A pattern forming method including the above steps.

12. The step of exposing the resist film is a step of exposing the resist film with an electron beam having a dose of 2 mC / cm ２ or less or with extreme ultraviolet light having a dose of 200 mJ / cm ２ or less. The pattern forming method according to claim 11

13. A patterned structure obtained by forming a pattern using the resist material according to any one of claims 1 to 9.

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