WO2023162838A1 - Active-ray-sensitive or radiation-sensitive resin composition, active-ray-sensitive or radiation-sensitive film, pattern formation method and electronic device manufacturing method - Google Patents

Active-ray-sensitive or radiation-sensitive resin composition, active-ray-sensitive or radiation-sensitive film, pattern formation method and electronic device manufacturing method Download PDF

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WO2023162838A1
WO2023162838A1 PCT/JP2023/005339 JP2023005339W WO2023162838A1 WO 2023162838 A1 WO2023162838 A1 WO 2023162838A1 JP 2023005339 W JP2023005339 W JP 2023005339W WO 2023162838 A1 WO2023162838 A1 WO 2023162838A1
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group
groups
sensitive
radiation
ring
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PCT/JP2023/005339
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French (fr)
Japanese (ja)
Inventor
英治 福▲崎▼
修平 山口
知昭 吉岡
太朗 三好
悠花 上農
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F24/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method.
  • immersion liquid a liquid with a high refractive index
  • Patent Document 1 describes a resin containing a repeating unit having an acid-decomposable group and a repeating unit derived from p-hydroxystyrene.
  • the present invention provides an actinic ray that is excellent in resolution, has excellent roughness performance, and can obtain an excellent pattern shape in extremely fine pattern formation (especially, line width or space width is 20 nm or less).
  • Actinic ray-sensitive or radiation-sensitive resin composition Actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition, Pattern using the actinic ray-sensitive or radiation-sensitive resin composition
  • An object is to provide a forming method and a method of manufacturing an electronic device.
  • A represents an aromatic ring group or an aromatic heterocyclic group.
  • X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a combination thereof. X may combine with the A ring to form a benzene ring.
  • Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom.
  • R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
  • R3 represents a hydrogen atom or a monovalent organic group.
  • R4 and R5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group.
  • L2 represents a single bond or an ester bond.
  • L 3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group.
  • R6 represents a hydroxyl group or a fluorinated alcohol group.
  • R7 represents a halogen atom.
  • m represents an integer of 1 or more.
  • n represents an integer of 0 or 1 or more.
  • R 61 to R 63 each independently represent a hydrogen atom, an organic group or a halogen atom.
  • R 62 may combine with Ar to form a ring, in which case R 62 represents a single bond or an alkylene group.
  • L represents a single bond or a divalent linking group.
  • Ar represents a (k+1)-valent aromatic ring group, and when combined with R 62 to form a ring, represents a (k+2)-valent aromatic ring group.
  • k represents an integer of 1 to 5;
  • R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
  • Each R 21 independently represents a hydrogen atom, an organic group, or a halogen atom.
  • R 21 may combine with each other to form a ring.
  • the actinic ray-sensitive properties are excellent in resolution, roughness performance, and excellent pattern shape.
  • a radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition, or pattern formation using the actinic ray-sensitive or radiation-sensitive resin composition Methods and methods of manufacturing electronic devices can be provided.
  • the present invention will be described in detail below. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the notation that does not describe substituted or unsubstituted includes groups containing substituents as well as groups that do not have substituents. do.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the term "organic group” as used herein refers to a group containing at least one carbon atom. As a substituent, a monovalent substituent is preferable unless otherwise specified.
  • the type of substituent, the position of the substituent, and the number of substituents when "may have a substituent” are not particularly limited.
  • the number of substituents can be, for example, one, two, three, or more.
  • substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.
  • the substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc.
  • halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • an alkoxy group such as
  • Alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; Arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkyl groups; Cycloalkyl groups; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; and combinations thereof.
  • actinic ray or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam).
  • light means actinic rays or radiation.
  • exposure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, and X-rays, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
  • the term "to” is used to include the numerical values before and after it as lower and upper limits.
  • the binding direction of the divalent linking groups indicated is not limited unless otherwise specified.
  • Y when Y is -COO-, Y may be -CO-O- or -O-CO- good too.
  • the compound may be "X—CO—O—Z” or "X—O—CO—Z.”
  • (meth)acrylate refers to acrylate and methacrylate
  • (meth)acryl refers to acrylic and methacrylic.
  • weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (hereinafter also referred to as "molecular weight distribution") (Mw/Mn) are measured by GPC (Gel Permeation Chromatography) equipment (Tosoh Corporation).
  • the acid dissociation constant (pKa) represents the pKa in an aqueous solution. is a calculated value.
  • Software Package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
  • pKa can also be determined by molecular orbital calculation.
  • a specific method there is a method of calculating the H 2 + dissociation free energy in an aqueous solution based on the thermodynamic cycle.
  • the H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and the method is not limited to this. Note that there are a plurality of software that can implement DFT, and Gaussian16 is an example.
  • pKa refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using Software Package 1, as described above. cannot be calculated, a value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted.
  • pKa refers to "pKa in aqueous solution” as described above, but when pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is adopted.
  • Solid content means the components that form the actinic ray-sensitive film, and does not include solvent. In addition, as long as it is a component that forms an actinic ray-sensitive film, it is regarded as a solid content even if the property is liquid.
  • the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "the composition of the present invention") according to the present invention is a resin (A ).
  • A represents an aromatic ring group or an aromatic heterocyclic group.
  • X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a combination thereof. X may combine with the A ring to form a benzene ring.
  • Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom.
  • R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
  • the repeating unit (a) contained in the resin (A) used in the composition of the present invention has a methylene structure bonded to two atoms selected from an oxygen atom and a sulfur atom.
  • it contains an acid-decomposable group having a cyclic protective structure in which two polar groups selected from groups such as thiol group, hydroxyl group and carboxyl group are protected by a methylene structure.
  • the repeating unit (a) having the above structure is presumed to react with an acid to decompose the methylene structure and deprotect, generate a polar group, and cause main chain cleavage. Therefore, in the resin (A), polar groups are generated by the acid generated by exposure, and the molecular weight is reduced by decomposition of the main chain. Therefore, before and after the exposure, the contrast of the solubility of the resin in the developer in the exposed area and the unexposed area can be made larger than before, and it is considered that the resolution is improved. Details of the following scheme will be described later.
  • the carbon atom in the methylene structure is a quaternary carbon atom
  • inclusion of this in the main chain suppresses the mobility of the main chain, increases the glass transition temperature (Tg) of the resin, and increases the sensitivity to actinic rays. It is thought that the diffusion of acid in the curable or radiation-sensitive film is suppressed, the resolution is further improved, and the roughness performance and pattern shape are also improved.
  • the composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition. is preferred. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development, preferably a resist composition for alkali development.
  • the composition of the present invention is typically a chemically amplified resist composition.
  • the composition of the present invention contains a resin containing repeating units (a) represented by the following general formula (a).
  • the repeating unit (a) is a repeating unit containing a group that is decomposed by the action of an acid to increase its polarity (hereinafter also referred to as "acid-decomposable group").
  • An acid-decomposable group is a group that is decomposed by the action of an acid to form a polar group.
  • the acid-decomposable group preferably has a structure in which the polar group is protected by a group (leaving group) that is eliminated by the action of an acid.
  • two polar groups have a structure protected by a methylene structure (the carbon atoms bonded to Y 1 and Y 2 ).
  • the resin (A) increases in polarity under the action of acid, increases in solubility in alkaline developing solutions, and decreases in solubility in organic solvents.
  • A represents an aromatic ring group or an aromatic heterocyclic group.
  • X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a combination thereof. X may combine with the A ring to form a benzene ring.
  • Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom.
  • R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
  • A represents an aromatic ring group or an aromatic heterocyclic group.
  • the aromatic ring group represented by A include aromatic ring groups having 6 to 18 carbon atoms such as benzene ring, naphthalene ring and anthracene ring.
  • aromatic heterocyclic groups represented by A include thiophene ring, furan ring, thiazole ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, and thiadiazole. ring and the like.
  • A may have a substituent.
  • Preferred substituents include, for example, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, alkoxy groups, halogen atoms and the like.
  • the alkyl group includes alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group and isopropyl group.
  • the alkenyl group includes alkenyl groups having 2 to 12 carbon atoms such as vinyl group and allyl group.
  • the alkynyl group includes alkynyl groups having 2 to 12 carbon atoms such as ethynyl group.
  • the cycloalkyl group may be monocyclic or polycyclic, and examples thereof include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl, cyclopentyl and cyclohexyl.
  • the aryl group includes an aryl group having 6 to 12 carbon atoms such as a phenyl group.
  • Alkoxy groups include alkyl groups having 1 to 12 carbon atoms such as methoxy, ethoxy and isopropoxy groups.
  • Halogen atoms include fluorine, chlorine, bromine, and iodine atoms. When A has multiple substituents, these substituents may combine with each other to form a ring.
  • the substituent is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorine atom, or an iodine atom.
  • A preferably represents an aromatic ring group, more preferably a benzene ring group.
  • X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a group formed by combining them.
  • the alkylene group represented by X is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, ethylene group, propylene group and butylene group, more preferably a methylene group or an ethylene group.
  • an alkenylene group represented by X an alkenylene group having 2 to 4 carbon atoms such as a vinylene group is preferable.
  • the alkynylene group represented by X is preferably an alkynylene group having 2 to 4 carbon atoms such as an ethynylene group.
  • X may combine with the A ring to form a benzene ring.
  • the repeating unit represented by the general formula (a) is a repeating unit represented by the following general formula (aa).
  • A, Y 1 , Y 2 , R 11 and R 12 in general formula (aa) are synonymous with A, Y 1 , Y 2 , R 11 and R 12 in general formula (a).
  • X may have a substituent, and examples of the substituent include the substituents that A described above can have.
  • X preferably represents a single bond, an alkylene group, or a carbonyl group, more preferably a single bond, a methylene group, an ethylene group, or a carbonyl group, and a methylene group, an ethylene group, or a carbonyl group. More preferably, it is particularly preferably a carbonyl group.
  • Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom. At least one of Y 1 and Y 2 is preferably an oxygen atom, and both are more preferably oxygen atoms.
  • R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
  • Examples of organic groups represented by R 11 and R 12 include alkyl groups, cycloalkyl groups, cyano groups and alkoxycarbonyl groups.
  • alkyl groups represented by R 11 and R 12 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. is preferably an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.
  • the cycloalkyl group represented by R 11 and R 12 may be monocyclic or polycyclic. Among them, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group are preferable.
  • the alkyl group contained in the alkoxycarbonyl group represented by R 11 and R 12 is preferably the same as the alkyl group for R 11 and R 12 above.
  • Halogen atoms represented by R 11 and R 12 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
  • Preferred substituents for R 11 and R 12 include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, and a thioether group. , acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups. The number of carbon atoms in the substituent is preferably 8 or less.
  • R 11 and R 12 are each independently preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, more preferably a hydrogen atom.
  • the repeating unit (a) having the above structure reacts with an acid to decompose the methylene structure and deprotect, generate a polar group, and cause main chain cleavage, as shown in the scheme below. guessed.
  • R 11 , R 12 , Y 1 , Y 2 , X and A are the same as R 11 , R 12 , Y 1 , Y 2 , X and A in the general formula (a) above.
  • H + acid protons
  • the Y-carbon bond is cleaved, the methylene structure is decomposed, and the carbon atom is cationized.
  • Water molecules attack the cation on the carbon and deprotonate it to form an alcohol.
  • a proton acts on this structure, the Y adjacent to the adjacent methylene structure and the proton combine to form a cation.
  • the repeating unit represented by general formula (a) is preferably a repeating unit represented by general formula (a-1) below.
  • R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
  • Each R 21 independently represents a hydrogen atom, an organic group, or a halogen atom.
  • R 21 may combine with each other to form a ring.
  • R 11 and R 12 in general formula (a-1) have the same definitions as R 11 and R 12 in general formula (a) above, and preferred examples are also the same.
  • each R 21 independently represents a hydrogen atom, an organic group, or a halogen atom.
  • the organic group for R 21 include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an alkoxy group. are alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, and alkoxy groups.
  • the halogen atom for R 21 include the halogen atom as a substituent when the above-mentioned A has a substituent.
  • a cyclic structure in which a plurality of R 21 are bonded to each other to form a ring includes a cyclopentyl group, a cyclohexyl group, and the like.
  • Each R 21 preferably independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine atom or an iodine atom.
  • repeating unit represented by formula (a) Specific examples of the repeating unit represented by formula (a) are shown below, but the present invention is not limited thereto. In the following specific examples, the structures of the raw material monomers (monomers represented by the above general formula (am)) of the repeating units represented by the general formula (a) are shown.
  • the content of the repeating unit (a) is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, relative to all repeating units in the resin (A).
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
  • the resin (A) may have a repeating unit having an acid-decomposable group in addition to the repeating unit (a) described above.
  • a repeating unit having an acid-decomposable group a repeating unit having an acid-decomposable group containing an unsaturated bond is preferable in addition to the repeating unit having an acid-decomposable group described below.
  • the acid-decomposable group preferably has a structure in which the polar group is protected with a group that is released by the action of an acid (leaving group).
  • the polar group is preferably an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Methylene groups, acidic groups such as tris(alkyl
  • the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
  • Examples of groups that leave by the action of an acid include groups represented by formulas (Y1) to (Y4).
  • Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
  • Formula (Y3) —C(R 36 )(R 37 )(OR 38 )
  • Rx 1 to Rx 3 each independently represent a hydrocarbon group, an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic) , an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic).
  • Rx 1 to Rx 3 are alkyl groups (linear or branched)
  • at least two of Rx 1 to Rx 3 are preferably methyl groups.
  • Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
  • Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
  • the alkyl groups of Rx 1 to Rx 3 are alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
  • the cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
  • one of the ring-constituting methylene groups may be replaced with a heteroatom such as an oxygen atom or a sulfur atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene group.
  • a heteroatom such as an oxygen atom or a sulfur atom
  • a heteroatom-containing group such as a carbonyl group
  • a vinylidene group one or more ethylene groups constituting the cycloalkane ring
  • the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
  • a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
  • the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
  • a polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
  • one of the methylene groups constituting the ring is a group containing a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced with In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
  • Rx 1 is a methyl group or an ethyl group
  • Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
  • composition of the present invention is a resist composition for EUV exposure
  • the ring formed by combining two atoms further has a fluorine atom or an iodine atom as a substituent.
  • R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may combine with each other to form a ring.
  • Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R 36 is a hydrogen atom.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
  • one or more of the methylene groups may be replaced with a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
  • R 38 may combine with another substituent of the main chain of the repeating unit to form a ring.
  • the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
  • monovalent organic groups represented by R 36 to R 38 and R 37 and R 38 are formed by binding to each other.
  • the ring also preferably has a fluorine atom or an iodine atom as a substituent.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group).
  • M represents a single bond or a divalent linking group.
  • Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
  • one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.
  • L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
  • L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
  • Secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups.
  • the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
  • the alkyl group, cycloalkyl group, aryl group, and group combining these represented by L 1 and L 2 are further It is also preferable to have a fluorine atom or an iodine atom as a substituent.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom and the iodine atom.
  • one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group.
  • composition of the present invention when the composition of the present invention is a resist composition for EUV exposure, an alkyl group optionally containing a heteroatom represented by Q, a cycloalkyl group optionally containing a heteroatom, or a heteroatom is In the aryl group, amino group, ammonium group, mercapto group, cyano group, aldehyde group, and groups in which these groups may be combined, the heteroatom is selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom. It is also preferred that the heteroatom is
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and Ar may combine with each other to form a non-aromatic ring.
  • Ar is preferably an aryl group.
  • the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group and aryl group represented by Rn are substituents It is also preferable to have a fluorine atom or an iodine atom as.
  • the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.
  • Groups that can be eliminated by the action of an acid also include a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1,4,4 A cyclohexyl group having a substituent (such as an alkyl group) such as a -tetramethylcyclohexyl group may also be used.
  • repeating unit having an acid-decomposable group a repeating unit represented by formula (A) is also preferable.
  • L 1 represents a divalent linking group optionally having a fluorine atom or an iodine atom
  • R 1 is a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group optionally having a fluorine atom or an iodine atom , or represents an aryl group optionally having a fluorine atom or an iodine atom
  • R 2 represents a leaving group optionally having a fluorine atom or an iodine atom which is eliminated by the action of an acid.
  • at least one of L 1 , R 1 and R 2 has a fluorine atom or an iodine atom.
  • the divalent linking group optionally having a fluorine atom or an iodine atom represented by L 1 includes -CO-, -O-, -S-, -SO-, -SO 2 -, fluorine atom or a hydrocarbon group optionally having an iodine atom (eg, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked.
  • L 1 is preferably -CO-, an arylene group, or an -arylene group - an alkylene group having a fluorine atom or an iodine atom -, and -CO- or an -arylene group - a fluorine atom or an iodine atom.
  • An alkylene group with - is more preferable.
  • a phenylene group is preferred as the arylene group.
  • Alkylene groups may be linear or branched. Although the number of carbon atoms in the alkylene group is not particularly limited, it is preferably 1-10, more preferably 1-3.
  • the total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
  • the alkyl group represented by R 1 may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom represented by R 1 is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and 1 to 3. More preferred.
  • the alkyl group represented by R 1 may contain a heteroatom such as an oxygen atom other than the halogen atom.
  • the leaving group optionally having a fluorine atom or an iodine atom represented by R 2 is represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom. groups.
  • a repeating unit having an acid-decomposable group a repeating unit represented by formula (AI) is also preferable.
  • Xa 1 represents a hydrogen atom or an optionally substituted alkyl group.
  • T represents a single bond or a divalent linking group.
  • Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl ( monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).
  • Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group and a group represented by -CH 2 -R 11 .
  • R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group.
  • Examples of the monovalent organic group represented by R 11 include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
  • Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
  • the divalent linking group for T includes an alkylene group, an aromatic ring group, a --COO--Rt-- group, and a --O--Rt-- group.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a -COO-Rt- group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - groups are more preferred.
  • the alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
  • Cycloalkyl groups of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
  • the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
  • a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.
  • Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
  • a cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring contains a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or It may be substituted with a vinylidene group.
  • Rx 1 is a methyl group or an ethyl group
  • Rx 2 and Rx 3 are preferably combined to form the above-mentioned cycloalkyl group.
  • substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • the repeating unit represented by the formula (AI) includes an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond. ) is preferred.
  • repeating units having an acid-decomposable group are shown below, but are not limited thereto.
  • Xa 1 represents H, CH 3 , CF 3 or CH 2 OH
  • Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.
  • Resin (A) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as the repeating unit having an acid-decomposable group.
  • a repeating unit represented by formula (B) is preferable.
  • Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group.
  • L represents a single bond or a divalent linking group which may have a substituent.
  • Ry 1 to Ry 3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group . However, at least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 may combine to form a monocyclic or polycyclic ring (a monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).
  • the optionally substituted alkyl group represented by Xb includes, for example, a methyl group and a group represented by —CH 2 —R 11 .
  • R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
  • Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
  • the divalent linking group of L includes -Rt- group, -CO- group, -COO-Rt- group, -COO-Rt-CO- group, -Rt-CO- group, and -O-Rt- groups.
  • Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, preferably an aromatic ring group.
  • L is preferably -Rt-, -CO-, -COO-Rt-CO- or -Rt-CO-.
  • Rt may have substituents such as halogen atoms, hydroxyl groups, and alkoxy groups.
  • the alkyl groups represented by Ry 1 to Ry 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
  • Cycloalkyl groups represented by Ry 1 to Ry 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Polycyclic cycloalkyl groups are preferred.
  • the aryl group represented by Ry 1 to Ry 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
  • a vinyl group is preferable as the alkenyl group for Ry 1 to Ry 3 .
  • An ethynyl group is preferred as the alkynyl group for Ry 1 to Ry 3 .
  • Cycloalkenyl groups represented by Ry 1 to Ry 3 are preferably monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, which partially contain a double bond.
  • the cycloalkyl group formed by combining two of Ry 1 to Ry 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
  • Polycyclic cycloalkyl groups such as a nyl group and an adamantyl group are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
  • a cycloalkyl group formed by combining two of Ry 1 to Ry 3 or a cycloalkenyl group for example, one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a carbonyl group, or —SO 2 It may be substituted with a group containing a heteroatom such as a - group and a -SO 3 - group, a vinylidene group, or a combination thereof.
  • one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group.
  • Ry 1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group
  • Ry 2 and Ry 3 combine to form the above-mentioned cycloalkyl
  • a preferred embodiment forms a group or a cycloalkenyl group.
  • substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • the repeating unit represented by the formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester-based repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a —CO— group.
  • repeating unit represented acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), acid-decomposable styrene carboxylic acid tertiary ester It is a repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
  • the content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on the total repeating units in the resin (A). is more preferred.
  • the upper limit thereof is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less, based on all repeating units in the resin (A).
  • repeating units having an acid-decomposable group containing an unsaturated bond are shown below, but are not limited thereto.
  • Xb and L 1 represent any of the substituents and linking groups described above
  • Ar represents an aromatic group
  • R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group.
  • a monocyclic or polycyclic aryl group is represented, and Q is a heteroatom such as an oxygen atom, a carbonyl group, a heteroatom-containing group such as a —SO 2 — group and a —SO 3 — group, a vinylidene group, or any of these represents a combination, and n, m and l represent integers of 0 or more.
  • the content of repeating units having an acid-decomposable group other than the repeating unit (a) is the content of repeating units having an acid-decomposable group including the repeating unit (a), which is the total number of repeating units in the resin (A). 15 mol % or more is preferable, 20 mol % or more is more preferable, and 30 mol % or more is still more preferable with respect to the unit.
  • the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
  • the resin (A) may contain at least one repeating unit selected from the group consisting of Group A below and/or at least one repeating unit selected from the group consisting of Group B below. good.
  • Group A A group consisting of the following repeating units (20) to (25).
  • a repeating unit having an acid group which will be described later
  • (23) a repeating unit having a photoacid-generating group which will be described later
  • the repeating units represented by formulas (A) to (E), which will be described later, are (25) reducing the mobility of the main chain corresponds to a repeating unit for Group B: A group consisting of the following repeating units (30) to (32).
  • the resin (A) preferably has an acid group, and preferably contains a repeating unit having an acid group, as described later.
  • the definition of the acid group will be explained later along with preferred embodiments of repeating units having an acid group.
  • the resin (A) may have at least one type of repeating unit selected from the group consisting of the A group.
  • the resin (A) has at least one repeating unit selected from the group consisting of Group A above. is preferred.
  • Resin (A) may contain at least one of a fluorine atom and an iodine atom.
  • the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
  • the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) It may contain two types of a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
  • Resin (A) may have a repeating unit having an aromatic group.
  • the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferred that the resin (A) has a repeating unit having an aromatic group.
  • the resin (A) may have at least one type of repeating unit selected from the group consisting of Group B above.
  • the resin (A) may have at least one repeating unit selected from the group consisting of Group B above. preferable.
  • the resin (A) preferably contains neither fluorine atoms nor silicon atoms.
  • Resin (A) preferably contains a repeating unit having an acid group.
  • an acid group having a pKa of 13 or less is preferable.
  • the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
  • the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable.
  • the acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
  • a fluoroalcohol group preferably a hexafluoroisopropanol group
  • a sulfonic acid group preferably a sulfonamide group
  • an isopropanol group preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
  • one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluor
  • the acid group is -C(CF 3 )(OH)-CF 2 - thus formed.
  • one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
  • the repeating unit having an acid group is different from the repeating unit having a structure in which the polar group is protected by a group that leaves under the action of an acid, and the repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. It is preferably a repeating unit.
  • a repeating unit having an acid group may have a fluorine atom or an iodine atom.
  • the resin (A) preferably has a repeating unit having a phenolic hydroxyl group in addition to the repeating unit (a) described above.
  • repeating unit having an acid group a repeating unit represented by the following general formula (B) is preferable.
  • R3 represents a hydrogen atom or a monovalent organic group.
  • a group represented by -L 4 -R 8 is preferable.
  • L4 represents a single bond or an ester group.
  • R8 includes an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.
  • R4 and R5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group.
  • a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • L2 represents a single bond or an ester bond.
  • L 3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group.
  • Aromatic hydrocarbon ring groups include a benzene ring group and a naphthalene ring group.
  • the alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.
  • R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R 6 is a hydroxyl group, L 3 is preferably an (n+m+1)-valent aromatic hydrocarbon ring group.
  • R7 represents a halogen atom.
  • a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • m represents an integer of 1 or more.
  • m is preferably an integer of 1-3, more preferably an integer of 1-2.
  • n represents an integer of 0 or 1 or more.
  • n is preferably an integer of 1-4. (n+m+1) is preferably an integer of 1-5.
  • repeating unit having an acid group a repeating unit represented by the following general formula (c) (repeating unit (c)) is also preferable. It is preferable that the resin (A) further contains a repeating unit (c) represented by the following general formula (c).
  • R 61 to R 63 each independently represent a hydrogen atom, an organic group or a halogen atom.
  • R 62 may combine with Ar to form a ring, in which case R 62 represents a single bond or an alkylene group.
  • L represents a single bond or a divalent linking group.
  • Ar represents a (k+1)-valent aromatic ring group, and when combined with R 62 to form a ring, represents a (k+2)-valent aromatic ring group.
  • k represents an integer of 1 to 5;
  • R 61 to R 63 each independently represent a hydrogen atom, an organic group or a halogen atom.
  • the organic group represented by R 61 to R 63 is, for example, an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group.
  • alkyl groups represented by R 61 to R 63 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. is preferably an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.
  • the cycloalkyl groups represented by R 61 to R 63 may be monocyclic or polycyclic. Among them, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group are preferable.
  • the alkyl group contained in the alkoxycarbonyl group represented by R 61 to R 63 is preferably the same as the alkyl group for R 61 to R 63 above.
  • the alkylene group for R 62 is preferably a group obtained by removing one arbitrary hydrogen atom from the alkyl group for R 61 to R 63 above.
  • Halogen atoms represented by R 61 to R 63 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
  • substituents for the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. , an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group.
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • Ar represents a (k+1)-valent aromatic ring group.
  • the divalent aromatic ring group when k is 1 may have a substituent, for example, a phenylene group, a tolylene group, a naphthylene group, and an arylene group having 6 to 18 carbon atoms such as an anthracenylene group.
  • a hetero ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring
  • a cyclic group is preferred.
  • Specific examples of the (k+1)-valent aromatic ring group when k is an integer of 2 or more include the above specific examples of the divalent aromatic ring group, with (k-1) any hydrogen atoms removed.
  • a group formed by The (k+1)-valent aromatic ring group may further have a substituent.
  • substituents that the (k+1)-valent aromatic ring group may have include halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, alkenyl groups, aralkyl groups, alkoxy groups, alkylcarbonyloxy groups, and alkylsulfonyloxy groups. , an alkyloxycarbonyl group or an aryloxycarbonyl group.
  • Ar is preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group.
  • the repeating unit represented by general formula (c) preferably has a hydroxystyrene structure. That is, Ar is preferably a benzene ring group, more preferably a phenylene group (a divalent benzene ring group).
  • L represents a single bond or a divalent linking group.
  • the divalent linking group represented by L includes *-X 4 -L 4 -**.
  • X 4 represents a single bond, -COO- or -CONR 64 -
  • R 64 represents a hydrogen atom or an alkyl group.
  • L4 represents a single bond or an alkylene group. * is a bond with a carbon atom of the main chain in general formula (c), and ** is a bond with Ar.
  • the alkyl group for R 64 in —CONR 64 — (R 64 represents a hydrogen atom or an alkyl group) represented by X 4 includes methyl, ethyl, propyl, isopropyl, n-butyl, sec -Butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and other alkyl groups having 20 or less carbon atoms, preferably alkyl groups having 8 or less carbon atoms.
  • X 4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.
  • the alkylene group for L4 is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group.
  • L is preferably a single bond, -COO- or -CONH-, more preferably a single bond.
  • k represents an integer of 1-5. k is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • repeating units having an acid group examples include a and a.
  • R represents a hydrogen atom or a methyl group
  • a represents an integer of 1-3.
  • the content of repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 70 mol % or less, more preferably 65 mol % or less, and still more preferably 60 mol % or less, based on all repeating units in the resin (A).
  • the resin (A) has neither an acid-decomposable group nor an acid group, apart from the above-described ⁇ repeating unit having an acid-decomposable group> and ⁇ repeating unit having an acid group>, and contains a fluorine atom and a bromine atom.
  • it may have a repeating unit having an iodine atom (hereinafter also referred to as unit X).
  • the ⁇ repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is a ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group> described later.
  • ⁇ repeating unit having photoacid-generating group> is a ⁇ repeating unit having photoacid-generating group>.
  • a repeating unit represented by formula (C) is preferable.
  • L5 represents a single bond or an ester group.
  • R9 represents a hydrogen atom or an alkyl group optionally having a fluorine atom or an iodine atom.
  • R 10 may have a hydrogen atom, an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, a fluorine atom or an iodine atom represents an aryl group or a group combining these;
  • repeating units having a fluorine atom or an iodine atom are shown below.
  • the content of the unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 50 mol % or less, more preferably 45 mol % or less, and still more preferably 40 mol % or less, relative to all repeating units in the resin (A).
  • the total content of repeating units containing at least one of a fluorine atom, a bromine atom and an iodine atom is preferably 10 mol% or more with respect to all repeating units of the resin (A). , more preferably 20 mol % or more, still more preferably 30 mol % or more, and particularly preferably 40 mol % or more.
  • the upper limit is not particularly limited, it is, for example, 100 mol % or less with respect to all repeating units of the resin (A).
  • the repeating unit containing at least one of a fluorine atom, a bromine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid-decomposable group, a fluorine atom, a bromine repeating units having an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.
  • Resin (A) may have a repeating unit (hereinafter also referred to as “unit Y”) having at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group. It is also preferable that the unit Y does not have a hydroxyl group and an acid group such as a hexafluoropropanol group.
  • the lactone group or sultone group may have a lactone structure or sultone structure.
  • the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
  • the resin (A) has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or any one of the following formulas (SL1-1) to (SL1-3). It preferably has a repeating unit having a lactone group or a sultone group obtained by removing one or more hydrogen atoms from a ring member atom of a sultone structure, and the lactone group or sultone group may be directly bonded to the main chain.
  • ring member atoms of a lactone group or a sultone group may constitute the main chain of resin (A).
  • the lactone structure or sultone structure may have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, and carboxyl groups. , halogen atoms, cyano groups, and acid-labile groups.
  • n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb 2 may be different, and multiple Rb 2 may combine to form a ring.
  • Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
  • a halogen atom for Rb 0 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Rb 0 is preferably a hydrogen atom or a methyl group.
  • Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these divalent linkages represents a group.
  • Ab is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -.
  • Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group or norbornylene group.
  • V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or formulas (SL1-1) to (SL1- 3) represents a group obtained by removing one hydrogen atom from a ring member atom of the sultone structure represented by any one of 3).
  • any optical isomer may be used. Moreover, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
  • a cyclic carbonate group is preferred.
  • a repeating unit having a cyclic carbonate group a repeating unit represented by the following formula (A-1) is preferable.
  • R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • n represents an integer of 0 or more.
  • R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
  • A represents a single bond or a divalent linking group.
  • the divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these.
  • a valent linking group is preferred.
  • Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.
  • Rx represents a hydrogen atom, -CH 3 , -CH 2 OH or -CF 3 .
  • the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in the resin (A).
  • the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
  • the resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as a "photoacid-generating group").
  • Repeating units having a photoacid-generating group include repeating units represented by formula (4).
  • R41 represents a hydrogen atom or a methyl group.
  • L41 represents a single bond or a divalent linking group.
  • L42 represents a divalent linking group.
  • R40 represents a structural site that is decomposed by exposure to actinic rays or radiation to generate an acid in the side chain. Examples of repeating units having a photoacid-generating group are shown below.
  • repeating unit represented by formula (4) includes, for example, repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327, and International Publication No. 2018/193954. Examples include repeating units described in paragraph [0094].
  • the content of the repeating unit having a photoacid-generating group is preferably 1 mol % or more, more preferably 5 mol % or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 40 mol % or less, more preferably 35 mol % or less, and still more preferably 30 mol % or less, based on all repeating units in the resin (A).
  • Resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
  • Repeating units represented by the following formulas (V-1) and (V-2) below are preferably different repeating units from the repeating units described above.
  • R 6 and R 7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is the number of carbon atoms; 1 to 6 alkyl groups or fluorinated alkyl groups), or a carboxyl group.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • n3 represents an integer of 0-6.
  • n4 represents an integer of 0-4.
  • X4 is a methylene group, an oxygen atom, or a sulfur atom.
  • the repeating units represented by formula (V-1) or (V-2) are exemplified below. Examples of the repeating unit represented by formula (V-1) or (V-2) include repeating units described in paragraph [0100] of WO 2018/193954.
  • the resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development.
  • Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C.
  • the Tg is preferably 400° C. or less, more preferably 350° C. or less, from the viewpoint of excellent dissolution rate in the developer.
  • Tg of repeating unit is calculated by the following method.
  • the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method.
  • the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated.
  • the Fox formula (described in Materials Letters 62 (2008) 3152, etc.) is used to calculate the Tg at each mass ratio, and these are totaled to obtain the Tg (°C) of the polymer.
  • the Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). Calculation of Tg by the Bicerano method can be performed using a polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
  • Methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e).
  • (a) introduction of bulky substituents into the main chain (b) introduction of multiple substituents into the main chain (c) introduction of substituents that induce interaction between the resin (A) into the vicinity of the main chain ( d) Main Chain Formation in Cyclic Structure (e) Linking of Cyclic Structure to Main Chain
  • the resin (A) preferably has a repeating unit exhibiting a homopolymer Tg of 130° C. or higher.
  • the type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited as long as it is a repeating unit having a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method.
  • the homopolymers correspond to repeating units exhibiting a homopolymer Tg of 130° C. or higher.
  • a specific example of means for achieving the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (A).
  • RA represents a group containing a polycyclic structure.
  • R x represents a hydrogen atom, a methyl group, or an ethyl group.
  • a group containing a polycyclic structure is a group containing multiple ring structures, and the multiple ring structures may or may not be condensed.
  • Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO2018/193954.
  • a specific example of means for achieving the above (b) is a method of introducing a repeating unit represented by the formula (B) into the resin (A).
  • R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
  • the type of other organic group is not particularly limited.
  • at least two of the organic groups have three or more constituent atoms excluding hydrogen atoms. is a substituent.
  • Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO2018/193954.
  • a specific example of means for achieving the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (A).
  • R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is hydrogen bonding hydrogen within 3 atoms from the main chain carbon It is a group containing atoms. Above all, it is preferable to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain side) in order to induce interaction between the main chains of the resin (A).
  • Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO2018/193954.
  • a specific example of means for achieving (d) above is a method of introducing a repeating unit represented by the formula (D) into the resin (A).
  • Cyclic represents a group forming a main chain with a cyclic structure.
  • the number of constituent atoms of the ring is not particularly limited.
  • Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO2018/193954.
  • a specific example of means for achieving (e) above is a method of introducing a repeating unit represented by formula (E) into the resin (A).
  • each Re independently represents a hydrogen atom or an organic group.
  • organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents.
  • a "Cyclic” is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO2018/193954.
  • the resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups.
  • the repeating unit having a lactone group, a sultone group, or a carbonate group that the resin (A) has include the repeating units described in the above ⁇ Repeating unit having a lactone group, sultone group, or carbonate group>.
  • the preferable content is also as described in ⁇ Repeating unit having lactone group, sultone group, or carbonate group>.
  • Resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the adhesion to the substrate and the compatibility with the developer.
  • a repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
  • a repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A-2014-098921.
  • Resin (A) may have a repeating unit having an alkali-soluble group.
  • the alkali-soluble group includes a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the ⁇ -position (e.g., hexafluoroisopropanol group). , is preferably a carboxyl group.
  • the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact holes is increased. Repeating units having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.
  • Resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure.
  • Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include, for example, 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth) Examples include repeating units derived from acrylates.
  • Resin (A) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.
  • R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
  • Ra represents a hydrogen atom, an alkyl group or a --CH 2 --O--Ra 2 group.
  • Ra2 represents a hydrogen atom, an alkyl group or an acyl group. Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A-2014-098921.
  • the resin (A) may have repeating units other than the repeating units described above.
  • the resin (A) has repeating units selected from the group consisting of repeating units having an oxathian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. You may have Specific examples of repeating units other than the repeating units described above are shown below.
  • the resin (A) may contain various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. may have
  • all repeating units are derived from a compound having an ethylenically unsaturated bond. It is preferably composed of repeating units. In particular, it is also preferred that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, and all of the repeating units are methacrylates. It is possible to use either one based on repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units be 50 mol % or less of the total repeating units.
  • Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
  • the weight average molecular weight of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, still more preferably 3,000 to 30,000, further preferably 5,000 as a polystyrene equivalent value by GPC method. ⁇ 15,000 is particularly preferred.
  • the dispersity (molecular weight distribution) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, still more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
  • the content of the resin (A) is preferably 40.0 to 99.9% by mass, more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition. .
  • the resin (A) may be used singly or in combination.
  • the composition of the present invention preferably contains a compound that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as a photoacid generator or photoacid generator (B)).
  • the photoacid generator (B) may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer (for example, resin (A) described above).
  • the form of a low-molecular-weight compound and the form of being incorporated into a part of a polymer for example, the resin (A) described above
  • the resin (A) described above may be used in combination.
  • the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. Although the lower limit is not particularly limited, 100 or more is preferable.
  • the photoacid generator (B) is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). good.
  • the photoacid generator (B) is preferably in the form of a low molecular weight compound.
  • Examples of the photoacid generator (B) include compounds (onium salts) represented by “M + X ⁇ ”, and compounds that generate an organic acid upon exposure are preferred.
  • Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), carbonylsulfonylimide, acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.
  • M + represents an organic cation.
  • the valence of the organic cation may be 1 or 2 or more.
  • a sulfonium cation or an iodonium cation is preferable.
  • a cation represented by the formula (ZaI) hereinafter also referred to as “cation (ZaI)
  • cation (ZaII) a cation represented by the formula (ZaII)
  • ZaIII a cation represented by the formula (ZaII)
  • R 201 , R 202 and R 203 each independently represent an organic group.
  • the number of carbon atoms in the organic groups for R 201 , R 202 and R 203 is preferably 1-30, more preferably 1-20.
  • Two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
  • Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, a butylene group and a pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. mentioned.
  • Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.
  • Cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in formula (ZaI) above is an aryl group.
  • R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
  • R 201 to R 203 is an aryl group, and the remaining two of R 201 to R 203 may combine to form a ring structure, in which an oxygen atom, a sulfur atom and an ester group , an amide group, or a carbonyl group.
  • the group formed by bonding two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, and —CH 2 —CH 2 —O—CH 2 —CH 2 —).
  • Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
  • the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene residues.
  • the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group or cyclohexyl group is more preferred.
  • substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 3 carbon atoms).
  • aryl groups eg, 6 to 14 carbon atoms
  • alkoxy groups eg, 1 to 15 carbon atoms
  • cycloalkylalkoxy groups eg, 1 to 15 carbon atoms
  • halogen atoms eg, fluorine and iodine
  • the substituent may further have a substituent
  • the alkyl group preferably has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
  • the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that is eliminated by the action of an acid.
  • the polar group and leaving group are as described above.
  • Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring.
  • Aromatic rings also include aromatic rings containing heteroatoms.
  • the number of carbon atoms in the organic group having no aromatic ring as R 201 to R 203 is preferably 1-30, more preferably 1-20.
  • R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or An alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
  • the alkyl groups and cycloalkyl groups of R 201 to R 203 are, for example, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, , butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group by any combination of substituents.
  • the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
  • R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkyl represents a carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group; R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
  • R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an ary
  • R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. It is also preferred that the substituents of R 1c to R 7c , R x and R y independently form an acid-decomposable group by any combination of substituents.
  • R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may combine with each other to form a ring.
  • the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined.
  • the ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • Examples of groups formed by bonding two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
  • the group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
  • Alkylene groups include methylene and ethylene groups.
  • R 1c to R 5c , R 6c , R 7c , R x , R y , and two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by combining each other with R x and R y may have a substituent.
  • the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
  • R 13 is a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (cycloalkyl may be the group itself, or may be a group partially containing a cycloalkyl group). These groups may have a substituent.
  • a halogen atom e.g., fluorine atom, iodine atom, etc.
  • R 14 is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl represents a group containing a group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When two or more R 14 are present, each independently represents the above group such as a hydroxyl group.
  • a halogen atom e.g., fluorine atom, iodine atom, etc.
  • Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be joined together to form a ring. When two R 15 are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R 15 are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R 15 groups may have a substituent.
  • the alkyl groups of R 13 , R 14 and R 15 may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1-10.
  • the alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. It is also preferred that each of the substituents of R 13 to R 15 , R x and R y independently forms an acid-decomposable group by any combination of substituents.
  • R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group for R 204 and R 205 may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
  • Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group for R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
  • the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
  • substituents that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. It is also preferred that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of substituents.
  • X ⁇ represents an organic anion.
  • the organic anion is not particularly limited, and includes organic anions having a valence of 1, 2 or more.
  • an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.
  • non-nucleophilic anions examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
  • sulfonate anions aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.
  • carboxylate anions aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions
  • sulfonylimide anions bis(alkylsulfonyl)imide anions
  • the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and may be a straight chain having 1 to 30 carbon atoms. Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferred.
  • the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
  • the aryl group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
  • the alkyl group, cycloalkyl group, and aryl group listed above may have a substituent.
  • the substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups ( preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group ( preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkylimino A sulfonyl group (preferably having 1
  • aralkyl group in the aralkylcarboxylate anion an aralkyl group having 7 to 14 carbon atoms is preferred.
  • Aralkyl groups having 7 to 14 carbon atoms include, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl groups.
  • Sulfonylimide anions include, for example, saccharin anions.
  • alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion an alkyl group having 1 to 5 carbon atoms is preferable.
  • substituents of these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups.
  • a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
  • the alkyl groups in the bis(alkylsulfonyl)imide anion may combine with each other to form a ring structure. This increases the acid strength.
  • non-nucleophilic anions include, for example, phosphorous fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ).
  • non-nucleophilic anions examples include aliphatic sulfonate anions in which at least the ⁇ -position of sulfonic acid is substituted with fluorine atoms, aromatic sulfonate anions in which fluorine atoms or groups having fluorine atoms are substituted, and alkyl groups in which fluorine atoms are present.
  • a bis(alkylsulfonyl)imide anion substituted with or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferred.
  • perfluoroaliphatic sulfonate anions preferably having 4 to 8 carbon atoms
  • benzenesulfonate anions having a fluorine atom are more preferable, nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluoro A benzenesulfonate anion or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is more preferred.
  • an anion represented by the following formula (AN1) is also preferable.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent.
  • the substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred.
  • groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.
  • Groups that are not electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR' or -NHCOR' each independently.
  • R' is a monovalent hydrocarbon group.
  • Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; ethynyl monovalent linear or branched hydrocarbon groups such as alkynyl groups such as groups, propynyl groups, and butynyl groups; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups Cycloalkyl group; monovalent alicyclic hydrocarbon group such as cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl aryl groups such as
  • L represents a divalent linking group.
  • divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups ( preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these.
  • the divalent linking group includes -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, and -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 - , or -COO-alkylene group- is more preferable.
  • a group represented by the following formula (AN1-1) is preferable. * a - (CR 2a 2 ) X - Q- (CR 2b 2 ) Y - * b (AN1-1)
  • * a represents the bonding position with R3 in formula (AN1).
  • * b represents the bonding position with -C(R 1 )(R 2 )- in formula (AN1).
  • X and Y each independently represent an integer of 0-10, preferably an integer of 0-3.
  • R 2a and R 2b each independently represent a hydrogen atom or a substituent. When multiple R 2a and R 2b are present, the multiple R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 directly bonded to —C(R 1 )(R 2 )— in formula (AN1) is other than a fluorine atom.
  • Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2- * B .
  • R3 represents an organic group.
  • the organic group is not particularly limited as long as it has 1 or more carbon atoms. branched chain alkyl group) or a cyclic group.
  • the organic group may or may not have a substituent.
  • the organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).
  • R 3 is preferably an organic group having a cyclic structure.
  • the cyclic structure may be monocyclic or polycyclic, and may have a substituent.
  • the ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1).
  • the organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), for example. Heteroatoms may replace one or more of the carbon atoms that form the ring structure.
  • the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group.
  • the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
  • the above hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
  • the cycloalkyl group may be monocyclic (such as cyclohexyl group) or polycyclic (such as adamantyl group), and preferably has 5 to 12 carbon atoms.
  • Examples of the lactone group and sultone group include structures represented by the above formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3). , preferably a group obtained by removing one hydrogen atom from a ring member atom constituting a lactone structure or a sultone structure.
  • the non-nucleophilic anion may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or cycloalkyl group.
  • an anion represented by the following formula (AN2) is also preferable.
  • o represents an integer of 1-3.
  • p represents an integer from 0 to 10;
  • q represents an integer from 0 to 10;
  • Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
  • the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
  • a perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 , and even more preferably both Xf are fluorine atoms.
  • R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R 4 and R 5 are present, each of R 4 and R 5 may be the same or different.
  • the alkyl groups represented by R 4 and R 5 preferably have 1 to 4 carbon atoms. The above alkyl group may have a substituent. Hydrogen atoms are preferred as R 4 and R 5 .
  • L represents a divalent linking group.
  • the definition of L is synonymous with L in formula (AN1).
  • W represents an organic group, preferably an organic group containing a cyclic structure.
  • a cyclic organic group is preferable.
  • Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
  • the alicyclic group may be monocyclic or polycyclic.
  • Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the polycyclic alicyclic group includes, for example, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group.
  • alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
  • Aryl groups may be monocyclic or polycyclic. Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
  • a heterocyclic group may be monocyclic or polycyclic. Especially, when it is a polycyclic heterocyclic group, diffusion of acid can be further suppressed.
  • a heterocyclic group may or may not have an aromatic character. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
  • Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
  • the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
  • the cyclic organic group may have a substituent.
  • substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide and sulfonate ester groups.
  • carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
  • Examples of anions represented by formula (AN2) include SO 3 ⁇ —CF 2 —CH 2 —OCO-(L) q′ —W, SO 3 ⁇ —CF 2 —CHF—CH 2 —OCO-(L) q ' -W, SO 3 - -CF 2 -COO-(L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q -W, or SO 3 - - CF 2 —CH(CF 3 )—OCO—(L) q′ —W is preferred.
  • L, q and W are the same as in formula (AN2).
  • q' represents an integer from 0 to 10;
  • an aromatic sulfonate anion represented by the following formula (AN3) is also preferable.
  • Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and -(D-B) group.
  • Substituents which may be further included include, for example, a fluorine atom and a hydroxyl group.
  • n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
  • D represents a single bond or a divalent linking group.
  • Divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more thereof.
  • B represents a hydrocarbon group.
  • B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an optionally substituted aryl group (such as a tricyclohexylphenyl group).
  • Disulfonamide anions are also preferred as non-nucleophilic anions.
  • a disulfonamide anion is, for example, an anion represented by N ⁇ (SO 2 —R q ) 2 .
  • R q represents an optionally substituted alkyl group, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.
  • Two R q may combine with each other to form a ring.
  • the group formed by bonding two R q together is preferably an optionally substituted alkylene group, preferably a fluoroalkylene group, more preferably a perfluoroalkylene group.
  • the alkylene group preferably has 2 to 4 carbon atoms.
  • Non-nucleophilic anions also include anions represented by the following formulas (d1-1) to (d1-4).
  • R 51 represents a hydrocarbon group (eg, an aryl group such as a phenyl group) optionally having a substituent (eg, hydroxyl group).
  • Z 2c represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon atom adjacent to S is not substituted with a fluorine atom).
  • the above hydrocarbon group for Z 2c may be linear or branched, and may have a cyclic structure.
  • the carbon atom in the hydrocarbon group (preferably the carbon atom that is a ring member atom when the hydrocarbon group has a cyclic structure) may be carbonyl carbon (--CO-).
  • Examples of the hydrocarbon group include a group having an optionally substituted norbornyl group.
  • a carbon atom forming the norbornyl group may be a carbonyl carbon.
  • Z 2c —SO 3 ⁇ in formula (d1-2) is preferably different from the anions represented by formulas (AN1) to (AN3) above.
  • Z 2c is preferably other than an aryl group.
  • the ⁇ -position and ⁇ -position atoms with respect to —SO 3 — in Z 2c are preferably atoms other than carbon atoms having a fluorine atom as a substituent.
  • the ⁇ -position atom and/or the ⁇ -position atom with respect to —SO 3 — is preferably a ring member atom in a cyclic group.
  • R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom)
  • Y 3 represents a linear, branched or cyclic alkylene group, an arylene group, or represents a carbonyl group
  • Rf represents a hydrocarbon group
  • R 53 and R 54 each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom). R 53 and R 54 may combine with each other to form a ring.
  • the organic anions may be used singly or in combination of two or more.
  • the photoacid generator (B) is also preferably a compound represented by the following general formula (1) (hereinafter also referred to as “compound (B)").
  • R 1 and R 5 each independently represent an aryl group or a heteroaryl group.
  • R 2 to R 4 each independently represent a hydrogen atom or a substituent.
  • M n+ represents a cation.
  • n represents an integer of 1 or more.
  • the aryl group for R 1 and R 5 includes, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and the like. can.
  • the heteroaryl group for R 1 and R 5 includes, for example, a heteroaryl group having 2 to 15 carbon atoms, such as a 5- to 10-membered ring, specifically , furyl group, thienyl group, pyrrolyl group, oxazolyl group, pyridyl group, quinolinyl group, carbazolyl group and the like.
  • R 2 to R 4 are not particularly limited as long as they are monovalent substituents, but examples include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as atoms and silicon atoms; and combinations of two or more of these.
  • alkyl groups for R 2 to R 4 include alkyl groups having 1 to 30 carbon atoms.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. and more preferably an alkyl group having 1 to 8 carbon atoms.
  • alkenyl groups for R 2 to R 4 include alkenyl groups having 2 to 30 carbon atoms, and alkenyl groups having 2 to 8 carbon atoms are preferred.
  • Cycloalkyl groups as R 2 to R 4 may be monocyclic or polycyclic. Although the number of carbon atoms in this cycloalkyl group is not particularly limited, it is preferably 3-8.
  • the aryl group for R 2 to R 4 includes, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and the like. can.
  • Halogen atoms for R 2 to R 4 include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Groups containing heteroatoms include, for example, hydroxyl group, carboxyl group, alkoxy group, thiol group, thioether group, nitro group, nitroso group, cyano group, amino group, acyloxy group, acylamide group, heteroaryl group, ether bond, carbonyl Conjugation and combinations of two or more of these are included.
  • the number of carbon atoms in the alkoxy group, acyloxy group and acylamide group is preferably 20 or less, more preferably 8 or less.
  • the alkoxy groups include, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butyroxy, t-butoxy and octyloxy groups. Among them, methoxy group, ethoxy group, propoxy group, isopropoxy group and t-butoxy group are particularly preferred.
  • the thioether group includes the same alkoxy groups, except that a sulfur atom is used instead of the oxygen atom.
  • Acyloxy groups include, for example, acetyloxy groups.
  • the acylamide group includes, for example, an acetylamide group.
  • Heteroaryl groups include the same heteroaryl groups as R 1 and R 5 .
  • the aryl group and heteroaryl group as R 1 and R 5 may further have a substituent.
  • Further substituents include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; A combination of Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; Similar to combinations of species or more.
  • the aryl group and heteroaryl group as R 1 and R 5 have multiple substituents, at least two of the multiple substituents may be bonded to each other to form a ring.
  • Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms as substituents of R 2 to R 4 further have substituents.
  • substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, groups, acyloxy groups, alkoxycarbonyl groups, cyano groups and nitro groups, and combinations of two or more of these.
  • R 1 and R 5 are a group containing a polar group described later, a group containing a group that is decomposed by the action of an acid to increase polarity, or decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer. It is possible to construct a group that includes a group that R 2 to R 4 above are a group containing a polar group described later, a group containing a group that is decomposed by the action of an acid to increase the polarity, or decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer. It is possible to construct a group that includes a group that includes a group that
  • R 3 preferably represents an aryl group.
  • the aryl group for R 3 include the same aryl groups as those for R 1 and R 5 .
  • the aryl group as R3 may further have a substituent.
  • the groups described above as specific examples of the substituents that R 1 and R 5 described above may further have can be mentioned.
  • the aryl group as R 3 has multiple substituents, at least two of the multiple substituents may be bonded to each other to form a ring.
  • At least one of R 1 to R 5 is a group containing a polar group, a group containing a group that is decomposed by the action of an acid to increase its polarity, or a group that is decomposed by the action of an alkaline developer. , is preferably a group containing a group that increases the solubility in an alkaline developer.
  • Examples of the polar group in the group containing a polar group as at least one of R 1 to R 5 include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonamide group, a sulfonylimide group, and (alkylsulfonyl) (alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, acidic groups such as a tris(alkylcarbonyl)methylene group and a tris(alkylsulfonyl)methylene group; and alcoholic hydroxyl groups.
  • the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It excludes aliphatic alcohols substituted with functional groups (eg, hexafluoroisopropanol groups, etc.).
  • the alcoholic hydroxyl group is preferably a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less.
  • the polar group is preferably a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).
  • a group having a carbonyl bond can also be mentioned as a group containing a polar group.
  • groups having a carbonyl bond include alkylcarbonyl groups and arylcarbonyl groups.
  • alkyl group include those similar to the alkyl groups for R 2 to R 4 .
  • the aryl group includes, for example, the same aryl groups as R 1 and R 5 .
  • a group having a carbonyl bond is a group in which the carbonyl bond and the ether bond are not adjacently bonded.
  • Alkylcarbonyl groups and arylcarbonyl groups as groups having a carbonyl bond may further have a substituent.
  • substituents include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; A combination of Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; Similar to combinations of species or more.
  • the group containing a polar group is not particularly limited, but an organic group containing a polar group can be mentioned.
  • Organic groups containing polar groups include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; A group having a polar group, which is a combination of more than one species, can be mentioned.
  • Examples of the group containing a polar group include an alkyl group containing a polar group and an aryl group containing a polar group.
  • Examples of the alkyl group in the alkyl group containing a polar group include those similar to the alkyl groups for R 2 to R 4 .
  • Examples of the aryl group in the aryl group containing a polar group include the same aryl groups as R 1 and R 5 .
  • the group containing the polar group may be the polar group itself.
  • At least one of R 1 to R 5 is a group containing a group that is decomposed by the action of an acid and increases in polarity (hereinafter also referred to as an "acid-decomposable group"). ) preferably has a structure in which the polar group is protected by a group (leaving group) that decomposes and leaves under the action of an acid.
  • the polar group the same polar group as in the group containing a polar group as at least one of R 1 to R 5 can be mentioned.
  • Groups that are decomposed and left by the action of an acid include, for example, groups represented by formulas (Y1) to (Y4).
  • Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
  • Formula (Y3) —C(R 36 )(R 37 )(OR 38 )
  • Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).
  • Rx 1 to Rx 3 are alkyl groups (linear or branched)
  • at least two of Rx 1 to Rx 3 are preferably methyl groups.
  • Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group
  • Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
  • Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
  • the alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
  • the cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
  • Cycloalkyl groups formed by combining two of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecanyl, and tetracyclododeca.
  • a polycyclic cycloalkyl group such as a nil group and an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
  • a cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. may be replaced.
  • Rx 1 is a methyl group or an ethyl group
  • Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
  • R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may combine with each other to form a ring.
  • Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R 36 is a hydrogen atom.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group).
  • M represents a single bond or a divalent linking group.
  • Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
  • one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group.
  • L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M and L 1 may combine to form a ring (preferably a 5- or 6-membered ring).
  • L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
  • Secondary alkyl groups include isopropyl, cyclohexyl and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups.
  • the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group or an aryl group.
  • Rn and Ar may combine with each other to form a non-aromatic ring.
  • Ar is more preferably an aryl group.
  • the acid-decomposable group preferably has an acetal structure.
  • the acetal structure is, for example, a structure in which a polar group such as a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group is protected with a group represented by the above formula (Y3).
  • the group containing an acid-decomposable group is not particularly limited as long as it is a group containing an acid-decomposable group, and an organic group containing an acid-decomposable group can be mentioned.
  • organic groups containing acid-decomposable groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; and a group having an acid-decomposable group.
  • Examples of the group containing an acid-decomposable group include an alkyl group containing an acid-decomposable group and an aryl group containing an acid-decomposable group.
  • Examples of the alkyl group in the alkyl group containing an acid-decomposable group include those similar to the alkyl groups for R 2 to R 4 .
  • Examples of the aryl group in the aryl group containing an acid-decomposable group include the same aryl groups as R 1 and R 5 .
  • the group containing an acid-decomposable group may be the acid-decomposable group itself.
  • At least one of R 1 to R 5 includes a group that is decomposed by the action of an alkaline developer and increases the solubility in the alkaline developer, and decomposes by the action of the alkaline developer and is dissolved in the alkaline developer.
  • a group that increases the solubility at is also called a "polar conversion group", and specific examples include a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O) -), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), sulfonate group (—SO 2 O—) and the like.
  • groups containing polar conversion groups include acyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, and imide groups.
  • the acyl group in the acyloxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
  • the alkoxy group in the alkoxycarbonyloxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
  • the aryl group in the aryloxycarbonyloxy group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the aryl group in the aryloxycarbonyl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the number of carbon atoms in the alkoxy group in the alkoxycarbonyl group is preferably 1-30, more preferably 1-8.
  • An imide group is a group obtained by removing one hydrogen atom from imide.
  • the acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group and imido group may further have a substituent.
  • substituents the groups described above as specific examples of the substituents that R 1 and R 5 described above may further have can be mentioned.
  • the polarity conversion group is a group represented by X in the partial structure represented by general formula (KA-1) or (KB-1).
  • X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: -COO-, an acid anhydride group: -C(O)OC(O)-, an acid imide group: -NHCONH-, Carboxylic acid thioester group: -COS-, carbonate group: -OC(O)O-, sulfate group: -OSO 2 O-, sulfonate group: -SO 2 O-.
  • Y 1 and Y 2 may be the same or different and represent an electron-withdrawing group.
  • the compound (B) has a group having a partial structure represented by general formula (KA-1) or (KB-1) as a group containing a polarity conversion group.
  • the partial structure represented by the general formula (KA-1), and the partial structure represented by (KB-1) when Y 1 and Y 2 are monovalent, the above partial structure is a bond is not present, the group having the above partial structure is a group having a monovalent or higher valence group from which at least one arbitrary hydrogen atom in the above partial structure is removed.
  • the partial structure represented by general formula (KA-1) is a structure that forms a ring structure together with a group as X.
  • X in general formula (KA-1) is preferably a carboxylate group (that is, when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate group.
  • a carboxylic acid ester group is more preferred.
  • the ring structure represented by general formula (KA-1) may have a substituent, for example, it may have nka substituents Z ka1 .
  • Z ka1 When there are more than one Z ka1 , each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group.
  • Z ka1 may be linked together to form a ring. Examples of the ring formed by combining Z ka1 include a cycloalkyl ring and a hetero ring (cyclic ether ring, lactone ring, etc.).
  • nka represents an integer from 0 to 10; It is preferably an integer of 0-8, more preferably an integer of 0-5, still more preferably an integer of 1-4, and most preferably an integer of 1-3.
  • the electron-withdrawing group for Z ka1 is the same as the electron-withdrawing group for Y 1 and Y 2 typified by a halogen atom.
  • the electron-withdrawing group may be substituted with another electron-withdrawing group.
  • Z ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron-withdrawing group, more preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group.
  • the ether group one substituted with an alkyl group, a cycloalkyl group, or the like, that is, an alkyl ether group or the like is preferable.
  • Preferred examples of the electron-withdrawing group are the same as the electron-withdrawing groups for Y 1 and Y 2 described later.
  • a halogen atom as Z ka1 includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the alkyl group as Z ka1 may have a substituent and may be linear or branched.
  • the linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, n-butyl, sec-butyl and t-butyl.
  • the branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and examples thereof include i-propyl, i-butyl, t-butyl, i-pentyl, t-pentyl, i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like.
  • the cycloalkyl group as Z ka1 may have a substituent, and may be monocyclic, polycyclic, or bridged.
  • a cycloalkyl group may have a bridged structure.
  • a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group and a cyclooctyl group.
  • Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure having 5 or more carbon atoms, preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl group, norbornyl group, isobornyl group, Campanyl group, dicyclopentyl group, ⁇ -pinel group, tricyclodecanyl group, tetocyclododecyl group, androstanyl group and the like.
  • the following structure is also preferable as the cycloalkyl group.
  • Some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.
  • Preferred alicyclic moieties include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecanyl. and the cyclododecanyl group.
  • adamantyl group More preferred are adamantyl group, decalin group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group and tricyclodecanyl group.
  • Substituents for these alicyclic structures include alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, and alkoxycarbonyl groups.
  • the alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl or butyl, more preferably methyl, ethyl, propyl or isopropyl.
  • Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy. Examples of substituents that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), and the like.
  • Examples of the lactone ring group for Z ka1 include groups obtained by removing a hydrogen atom from structures represented by any of (KA-1-1) to (KA-1-17) described later.
  • the aryl group for Z ka1 includes, for example, a phenyl group and a naphthyl group.
  • alkyl group, cycloalkyl group and aryl group of Z ka1 may further have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, benzyl aralkyl groups such as phenethyl group and cumyl group; acyl groups such as aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group and valeryl group; acyloxy groups such as butyryl
  • X in general formula (KA-1) is a carboxylic acid ester group
  • the partial structure represented by general formula (KA-1) is preferably a lactone ring, preferably a 5- to 7-membered lactone ring.
  • the 5- to 7-membered lactone ring as the partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro Other ring structures are preferably condensed to form a structure.
  • Peripheral ring structures to which the ring structure represented by general formula (KA-1) may be bound include, for example, those in (KA-1-1) to (KA-1-17) below, or I can list the thing which I followed.
  • Structures represented by any of the following (KA-1-1) to (KA-1-17) are more preferable as structures containing a lactone ring structure represented by general formula (KA-1).
  • the lactone structure may be directly bonded to the main chain.
  • Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14), (KA-1-17).
  • the structure containing the lactone ring structure may or may not have a substituent.
  • Preferred substituents include those similar to the substituents that the ring structure represented by the general formula (KA-1) may have.
  • Some lactone structures have an optically active form, but any optically active form may be used.
  • one type of optically active substance may be used alone, or a plurality of optically active substances may be mixed and used.
  • optical purity ee is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.
  • a carboxylic acid ester group (-COO-) can be preferably mentioned as X in the general formula (KB-1).
  • Y 1 and Y 2 in general formula (KB-1) each independently represent an electron-withdrawing group.
  • the electron-withdrawing group preferably has a partial structure represented by the following formula (EW).
  • * in formula (EW) represents a bond directly linked to (KA-1) or a bond directly linked to X in (KB-1).
  • n ew is the repeating number of the linking group represented by —C(R ew1 )(R ew2 )— and represents an integer of 0 or 1; When new is 0, it represents a single bond, indicating that Yew1 is directly bonded.
  • Y ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo(cyclo)alkyl group represented by —C(R f1 )(R f2 )—R f3 described later, a haloaryl group, an oxy group, a carbonyl group; , sulfonyl groups, sulfinyl groups, and combinations thereof, and the electron-withdrawing group may be, for example, the following structure.
  • the "halo(cyclo)alkyl group” represents an alkyl group and a cycloalkyl group which are at least partially halogenated.
  • R ew3 and R ew4 each independently represent an arbitrary structure.
  • R ew3 and R ew4 may have any structure, and the partial structure represented by the formula (EW) has electron-withdrawing properties, and is preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.
  • Y ew1 is a group having a valence of 2 or more, the remaining bond forms a bond with any atom or substituent.
  • Y ew1 is preferably a halogen atom, or a halo(cyclo)alkyl or haloaryl group represented by —C(R f1 )(R f2 )—R f3 .
  • R ew1 and R ew2 each independently represent an arbitrary substituent such as a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. At least two of R ew1 , R ew2 and Y ew1 may be linked together to form a ring.
  • R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a fluorine atom or a tri represents a fluoromethyl group.
  • R f2 and R f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R f2 and R f3 may be linked to form a ring.
  • Examples of the organic group include an alkyl group, a cycloalkyl group, an alkoxy group, and the like, which may be substituted with a halogen atom (preferably a fluorine atom), and more preferably R f2 and R f3 are (halo) is an alkyl group.
  • R f2 more preferably represents the same group as R f1 or is linked to R f3 to form a ring.
  • R f1 and R f3 may be linked to form a ring, and the ring to be formed includes a (halo)cycloalkyl ring, a (halo)aryl ring and the like.
  • the (halo)alkyl group for R f1 to R f3 includes, for example, the alkyl group for Z ka1 described above and a halogenated structure thereof.
  • the cycloalkyl group in Z ka1 described above is halogen structure, more preferably a fluorocycloalkyl group represented by -C (n) F (2n-2) H, and a perfluoroaryl group represented by -C (n) F (n-1) mentioned.
  • the number of carbon atoms n is not particularly limited, it is preferably 5 to 13, more preferably 6.
  • the ring which may be formed by combining at least two of R ew1 , R ew2 and Y ew1 is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group.
  • the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).
  • Part or all of the partial structure of general formula (KA-1) may also serve as an electron-withdrawing group as Y 1 or Y 2 in general formula (KB-1).
  • X in general formula (KA-1) is a carboxylic acid ester group
  • the carboxylic acid ester group functions as an electron-withdrawing group as Y 1 or Y 2 in general formula (KB-1). It is possible.
  • the group containing a polarity conversion group is not particularly limited, but an organic group containing a polarity conversion group can be mentioned.
  • organic groups containing polar conversion groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; A combination of two or more types and having a polar conversion group can be mentioned.
  • Examples of the group containing a polarity conversion group include an alkyl group containing a polarity conversion group and an aryl group containing a polarity conversion group.
  • Examples of the alkyl group in the alkyl group containing the polarity conversion group include those similar to the alkyl groups for R 2 to R 4 .
  • Examples of the aryl group in the aryl group containing a polarity conversion group include the same aryl groups as R 1 and R 5 .
  • R 1 , R 3 and R 5 are preferably groups represented by the following general formula (Ar).
  • R 6 to R 10 each independently represent a hydrogen atom or a substituent. At least one of R 6 to R 10 is a group containing a polar group, a group containing a group that is decomposed by the action of an acid to increase the polarity, or is decomposed by the action of an alkaline developer and has solubility in an alkaline developer. is a group containing increasing groups. * represents a bond to the benzene ring in general formula (1).
  • R 6 to R 10 are the same as those for R 2 to R 4 described above.
  • At least one of R 6 to R 10 is a group containing a polar group, a group containing a group that is decomposed by the action of an acid to increase the polarity, or is decomposed by the action of an alkaline developer and has solubility in an alkaline developer. is a group containing increasing groups.
  • the group containing a polar group is the same as the group containing a polar group as at least one of R 1 to R 5 .
  • the group containing a group which is decomposable by the action of an acid to increase its polarity is the same as the group containing a group which is decomposable by the action of an acid to increase its polarity as at least one of R 1 to R 5 .
  • a group containing a group that decomposes under the action of an alkaline developer and increases its solubility in an alkaline developer, as at least one of R 1 to R 5 decomposes under the action of an alkaline developer and dissolves in the alkaline developer. The same is true for groups containing groups that increase the solubility in.
  • R 1 , R 3 and R 5 are preferably groups represented by the following general formula (Ar1).
  • R 11 to R 15 each independently represent a hydrogen atom or a substituent, and at least one of R 11 to R 15 represents a substituent Y below.
  • * represents a bond to the benzene ring in general formula (1).
  • Substituent Y hydroxy group, carboxyl group, group having a carbonyl bond, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, or imido group
  • R 11 to R 15 are the same as those for R 2 to R 4 described above. At least one of R 11 to R 15 represents the substituent Y described above.
  • the group having a carbonyl bond as the substituent Y are the same as the specific examples of the group having a carbonyl bond as the group having the polar group described above.
  • the acyl group in the acyloxy group as the substituent Y preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
  • the alkoxy group in the alkoxycarbonyloxy group as the substituent Y preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
  • the aryl group in the aryloxycarbonyloxy group as the substituent Y preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the aryl group in the aryloxycarbonyl group as the substituent Y preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the number of carbon atoms of the alkoxy group in the alkoxycarbonyl group as the substituent Y is preferably 1-30, more preferably 1-8.
  • the imide group as the substituent Y is a group obtained by removing one hydrogen atom from imide.
  • a group having a carbonyl bond, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, and an imide group as the substituent Y may further have a substituent.
  • the groups described above as specific examples of the substituents that R 1 and R 5 described above may further have can be mentioned.
  • n in the anion part of the general formula (1) represents the number of anions. n represents an integer of 1 or more. Although the upper limit of n is not particularly limited, it is 4, for example. It is preferred that n is 1.
  • M n+ in the general formula (1) represents a cation.
  • n in the cation part of the general formula (1) represents the valence of the cation.
  • n represents an integer of 1 or more.
  • the upper limit of n is not particularly limited, it is 4, for example. It is preferred that n is 1.
  • the cation as M n+ is not particularly limited as long as it is a cation having a valence of 1 or more, but is preferably an onium cation, and preferably a cation represented by the above formula (ZaI) or formula (ZaII).
  • Preferred embodiments of the cation in formula (ZaI) include the cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described above.
  • the bivalent or higher cation when n is 2 or more may be a cation having a plurality of structures represented by formula (ZaI).
  • Such cations include, for example, at least one of R 201 to R 203 of the cation represented by formula (ZaI) and at least one of R 201 to R 203 of another cation represented by formula (ZaI).
  • Examples include divalent cations having a structure in which two are bonded via a single bond or a linking group.
  • M n+ (cation) in general formula (1) include specific examples of M + organic cations in the compound represented by “M + X ⁇ ” described above.
  • the pKa of the acid generated by the compound (B) is preferably -10 or more and 5 or less.
  • photoacid generator (B) Preferable examples of the photoacid generator (B) are shown below, but the present invention is not limited to these.
  • Me represents a methyl group.
  • Preferred examples of the photoacid generator (B) also include compounds in which the above anions and the above cations are combined.
  • Compound (B) can be synthesized, for example, by a method using a coupling reaction.
  • the counter cation can be converted into the desired cation M 2 + by, for example, a known anion exchange method described in JP-A-6-184170 or a conversion method using an ion exchange resin.
  • Examples of coupling reactions include the following.
  • X represents a halogen atom and A represents an alkyl group.
  • R represents a substituent.
  • Y represents a group that forms compound XY through a coupling reaction.
  • the content is not particularly limited, but since the cross-sectional shape of the formed pattern becomes more rectangular, the total solid content of the composition is , is preferably 0.5% by mass or more, more preferably 1.0% by mass or more.
  • the content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition.
  • the photoacid generator (B) may be used alone or in combination of two or more.
  • the composition of the present invention may contain an acid diffusion control agent.
  • the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
  • the type of acid diffusion controller is not particularly limited, and examples include basic compounds (CA), low-molecular-weight compounds (CB) having nitrogen atoms and groups that leave under the action of acids, and actinic rays or radiation. and a compound (CC) whose ability to control acid diffusion decreases or disappears upon irradiation.
  • a basic compound (CA) include, for example, those described in paragraphs [0132] to [0136] of WO2020/066824, and the basicity is reduced or reduced by exposure to actinic rays or radiation.
  • Specific examples of the disappearing basic compound (CE) include those described in paragraphs [0137] to [0155] of WO 2020/066824, and paragraph [0164] of WO 2020/066824.
  • CB low-molecular compound having a nitrogen atom and a group that leaves under the action of an acid
  • CD onium salt compound
  • paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1 paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1
  • paragraphs [0237190A1 and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents.
  • the content of the acid diffusion control agent (the total if there are more than one) is 0.1 to 15.0% relative to the total solid content of the composition. 0% by mass is preferred, and 1.0 to 15.0% by mass is more preferred.
  • one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.
  • the composition of the invention may further comprise a hydrophobic resin different from resin (A).
  • Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film. may not contribute to
  • the effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.
  • the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin. It is more preferable to have The hydrophobic resin preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Hydrophobic resins include compounds described in paragraphs [0275] to [0279] of WO2020/004306.
  • the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and 0.1 to 15.0% by mass, based on the total solid content of the composition. % by mass is more preferred.
  • the composition of the invention may contain a surfactant.
  • a surfactant When a surfactant is contained, it is possible to form a pattern with excellent adhesion and fewer development defects.
  • the surfactant is preferably a fluorine-based and/or silicon-based surfactant. Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/193954.
  • One type of these surfactants may be used alone, or two or more types may be used.
  • the content of the surfactant is preferably 0.0001 to 2.0% by mass, preferably 0.0005 to 1.0%, based on the total solid content of the composition. % by mass is more preferred, and 0.1 to 1.0% by mass is even more preferred.
  • the composition of the invention preferably contains a solvent.
  • Solvent consists of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from the group.
  • the solvent may further contain components other than components (M1) and (M2).
  • a combination of the above-described solvent and the above-described resin is preferable from the viewpoint of improving the coatability of the resist composition and reducing the number of development defects in the pattern. Since the solvent described above has a good balance of solubility, boiling point, and viscosity of the resin described above, it is possible to suppress unevenness in the thickness of the resist film and generation of deposits during spin coating. Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306, the contents of which are incorporated herein.
  • the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.
  • the content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. By doing so, the applicability of the composition can be further improved.
  • the solid content means all components other than the solvent, and as described above, it means the components that form the actinic ray-sensitive or radiation-sensitive film.
  • the solid content concentration is the mass percentage of the mass of other components excluding the solvent relative to the total mass of the composition of the present invention.
  • Total solid content refers to the total mass of components excluding the solvent from the total composition of the composition of the present invention.
  • the “solid content” is a component excluding the solvent, and may be solid or liquid at 25° C., for example.
  • the composition of the present invention contains a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light-absorbing agent, and/or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group) may further be included.
  • a dissolution-inhibiting compound for example, a phenolic compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group
  • the “dissolution-inhibiting compound” is a compound with a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
  • the composition of the specification is suitably used as a photosensitive composition for EUV exposure.
  • EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, so the number of incident photons is smaller when exposed with the same sensitivity. Therefore, the influence of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of LER and bridge defects.
  • photon shot noise there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.
  • the procedure of the pattern forming method using the composition of the present invention is not particularly limited, the pattern forming method preferably includes the following steps.
  • Step 1 A step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition
  • Step 2 A step of exposing the actinic ray-sensitive or radiation-sensitive film 3: Step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer
  • Step 1 is a step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention.
  • the actinic ray-sensitive or radiation-sensitive resin composition is applied onto the substrate. method.
  • the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
  • Filters are preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • the actinic ray-sensitive or radiation-sensitive resin composition can be applied onto a substrate (eg, silicon, silicon dioxide coating) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater.
  • the coating method is preferably spin coating using a spinner.
  • the rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
  • the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film.
  • various undercoat films inorganic film, organic film, antireflection film may be formed under the actinic ray-sensitive or radiation-sensitive film.
  • Heating can be carried out by a means provided in a normal exposure machine and/or a developing machine, and may be carried out using a hot plate or the like.
  • the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
  • the film thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, it is preferably 10 to 120 nm from the viewpoint of forming finer patterns with higher precision.
  • the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
  • the film thickness of the resist film is more preferably 10 to 120 nm, still more preferably 15 to 90 nm.
  • a topcoat composition may be used to form a topcoat on the upper layer of the resist film. It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film.
  • the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed. For example, it is preferable to form a topcoat containing a basic compound as described in JP-A-2013-61648 on the resist film.
  • Specific examples of basic compounds that the topcoat may contain include basic compounds that the actinic ray-sensitive or radiation-sensitive resin composition may contain.
  • the topcoat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
  • Step 2 is the step of exposing the actinic ray-sensitive or radiation-sensitive film.
  • the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask.
  • Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, 1 to 200 nm Particularly preferred are wavelengths of deep UV light, specifically KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), F2 excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.
  • baking is preferably performed before development. Baking accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape.
  • the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
  • the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called a post-exposure bake.
  • Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer to form a pattern.
  • the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
  • Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing the developer on the surface of the substrate for a certain period of time by raising the developer by surface tension (puddle method). method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). ). Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
  • the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
  • the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
  • alkaline aqueous solution containing alkali is not particularly limited, for example, quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. and an alkaline aqueous solution containing Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer.
  • the alkali concentration of the alkali developer is usually preferably 0.1 to 20% by mass.
  • the pH of the alkaline developer is preferably 10.0 to 15.0.
  • the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Preferably.
  • a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
  • the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
  • the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass with respect to the total amount of the developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.
  • the pattern forming method preferably includes a step of washing with a rinse after step 3.
  • Pure water is an example of the rinse solution used in the rinse step after the step of developing with an alkaline developer.
  • An appropriate amount of surfactant may be added to pure water.
  • An appropriate amount of surfactant may be added to the rinse solution.
  • the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used.
  • the rinse solution should contain at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. is preferred.
  • the method of the rinsing step is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. a method (dip method) and a method of spraying a rinse liquid onto the substrate surface (spray method).
  • the pattern forming method may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinse solution remaining between the patterns and inside the patterns due to baking are removed. In addition, this process smoothes the resist pattern, and has the effect of improving the roughness of the surface of the pattern.
  • the heating step after the rinsing step is usually carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
  • the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate.
  • the method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask.
  • a method of forming a pattern is preferred. Dry etching is preferably oxygen plasma etching.
  • composition of the present invention e.g., solvent, developer, rinse, composition for forming an antireflection film, composition for forming a topcoat, etc.
  • impurities such as The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
  • the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
  • metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
  • Methods for reducing impurities such as metals contained in various materials include, for example, a method of selecting raw materials with a low metal content as raw materials constituting various materials, and a method of filtering raw materials constituting various materials with a filter. and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).
  • impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination.
  • adsorbent known adsorbents can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • metal impurities such as metals contained in the various materials described above, it is necessary to prevent metal impurities from entering during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment.
  • the content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
  • the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
  • Organic processing liquids such as rinsing liquids should contain conductive compounds to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
  • the conductive compound is not particularly limited, and examples thereof include methanol.
  • the amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties.
  • the lower limit is not particularly limited, and is preferably 0.01% by mass or more.
  • chemical liquid pipe for example, SUS (stainless steel), antistatic treated polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.
  • Antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used for filters and O-rings.
  • the present specification also relates to an electronic device manufacturing method, including the pattern forming method described above, and an electronic device manufactured by this manufacturing method.
  • a preferred embodiment of the electronic device of the present specification includes a mode in which it is installed in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
  • cyclohexanone was added to give a solution with a monomer concentration of 30% by mass
  • dimethyl 2,2'-azobis(2-methylpropionate) was added at 8 mol% as an initiator, and the monomer solution was It was adjusted.
  • 0.1 times the weight of the monomer solution of cyclohexanone was heated to 85° C., and the monomer solution was added dropwise over 2 hours, followed by further reaction at 85° C. for 2 hours.
  • Resin (A) Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition] ⁇ Resin (A)>
  • the structures of the resins (A) used are shown below.
  • Resins A-1 to A-10 and A-12 to A-46 were synthesized in the same manner as resin A-11.
  • Table 1 shows the type and content of each repeating unit (content ratio (mol %)), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn).
  • repeating units (a-1) to (a-20) corresponding to repeating unit (a) shown in repeating unit 2 are raw material monomers (a-1) to (a-20) shown below, respectively.
  • each repeating unit shown in Table 1 The structural formula of each repeating unit shown in Table 1 is shown below.
  • the repeating unit corresponding to the repeating unit (a) shown in repeating unit 2 is shown as the structural formula of the corresponding raw material monomer.
  • Photoacid generator (B) The structure of the photoacid generator (B) used is shown below.
  • Compounds (B-1) to (B-80) are obtained by combining the cations listed in Table 2 and the anions listed in Table 2.
  • Me represents a methyl group and Bu represents an n-butyl group.
  • Me represents a methyl group and Bu represents an n-butyl group.
  • W-1 to W-4 below were used as surfactants.
  • W-1 Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine and silicon type)
  • W-2 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based)
  • W-3 Troisol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based)
  • EB exposure and development (4) Preparation of resist pattern
  • the resist film obtained in (3) above was subjected to pattern irradiation using an electron beam lithography system (F7000S manufactured by Advantest Co., Ltd., acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 100° C. for 600 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried.
  • TMAH tetramethylammonium hydroxide
  • the sensitivity was defined as the irradiation energy for resolving a 1:1 line and space pattern with a line width of 50 nm.
  • Roughness performance was evaluated by line width roughness (LWR) as follows.
  • ⁇ Pattern shape> The cross-sectional shape of a 1:1 line and space pattern with a line width of 50 nm at the irradiation dose showing the above sensitivity is observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.)
  • S-4800 manufactured by Hitachi, Ltd.
  • the ratio represented by [line width at the top part (surface part) of the line pattern / line width at the middle part of the line pattern (half the height of the line pattern)] is 1.1 or more, the "reverse Those with a ratio of 1.03 or more and less than 1.1 were evaluated as "slightly reverse taper", and those with a ratio of less than 1.03 were evaluated as "rectangular”.
  • the sensitivity was defined as the irradiation energy for resolving a 1:1 line and space pattern with a line width of 50 nm.
  • Roughness performance was evaluated by line width roughness (LWR) as follows.
  • ⁇ Pattern shape> The cross-sectional shape of a 1:1 line and space pattern with a line width of 50 nm at the irradiation dose showing the above sensitivity is observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.)
  • S-4800 manufactured by Hitachi, Ltd.
  • the ratio represented by [line width at the top part (surface part) of the line pattern / line width at the middle part of the line pattern (half the height of the line pattern)] is 1.1 or more, the "reverse Those with a ratio of 1.03 or more and less than 1.1 were evaluated as "slightly reverse taper", and those with a ratio of less than 1.03 were evaluated as "rectangular”.
  • the actinic ray-sensitive properties are excellent in resolution, roughness performance, and excellent pattern shape.
  • a radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition, or pattern formation using the actinic ray-sensitive or radiation-sensitive resin composition Methods and methods of manufacturing electronic devices can be provided.

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Abstract

The present invention provides: an active-ray-sensitive or radiation-sensitive resin composition comprising a resin (A) having repeating units (a) represented by a specific general formula (a); an active-ray-sensitive or radiation-sensitive film formed by using the active-ray-sensitive or radiation-sensitive resin composition; and a pattern formation method and electronic device manufacturing method using the active-ray-sensitive or radiation-sensitive resin composition.

Description

感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び電子デバイスの製造方法Actinic ray- or radiation-sensitive resin composition, actinic ray- or radiation-sensitive film, pattern forming method, and electronic device manufacturing method
　本発明は、感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び電子デバイスの製造方法に関する。 The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method.
　従来、ＩＣ（Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ）、ＬＳＩなどの半導体デバイスの製造プロセスにおいては、フォトレジスト組成物を用いたリソグラフィーによる微細加工が行われている。近年、集積回路の高集積化に伴い、サブミクロン領域又はクオーターミクロン領域の超微細パターン形成が要求されるようになってきている。それに伴い、露光波長もｇ線からｉ線に、更にＫｒＦエキシマレーザー光に、というように短波長化の傾向が見られ、現在では１９３ｎｍ波長を有するＡｒＦエキシマレーザーを光源とする露光機が開発されている。また、更に解像力を高める技術として、従来から投影レンズと試料の間に高屈折率の液体（以下、「液浸液」ともいう）で満たす、所謂、液浸法の開発が進んでいる。 Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication is performed by lithography using a photoresist composition. 2. Description of the Related Art In recent years, as integrated circuits have become more highly integrated, there has been a demand for ultra-fine pattern formation in the submicron region or quarter micron region. Along with this, there is a tendency for the exposure wavelength to become shorter, from the g-line to the i-line and then to the KrF excimer laser light. At present, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing. Further, as a technique for further improving the resolution, the so-called liquid immersion method, in which the space between the projection lens and the sample is filled with a liquid with a high refractive index (hereinafter also referred to as "immersion liquid"), has been developed.
　また、現在では、エキシマレーザー光以外にも、電子線（ＥＢ：Ｅｌｅｃｔｒｏｎ　Ｂｅａｍ）、Ｘ線及び極紫外線（ＥＵＶ：Ｅｘｔｒｅｍｅ　Ｕｌｔｒａｖｉｏｌｅｔ）等を用いたリソグラフィーも開発が進んでいる。これに伴い、各種の放射線に有効に感応し、感度及び解像度に優れた化学増幅型レジスト組成物や、これに用いる樹脂等が開発されている。 In addition to excimer laser light, lithography using electron beams (EB: Electron Beam), X-rays, extreme ultraviolet rays (EUV: Extreme Ultraviolet), etc. is currently under development. Along with this, chemically amplified resist compositions which effectively respond to various radiations and are excellent in sensitivity and resolution, as well as resins used therefor, have been developed.
　例えば、特許文献１には、酸分解性基を有する繰り返し単位とｐ－ヒドロキシスチレン由来の繰り返し単位とを含む樹脂が記載されている。 For example, Patent Document 1 describes a resin containing a repeating unit having an acid-decomposable group and a repeating unit derived from p-hydroxystyrene.
国際公開第２０２０／２３５６０８号WO2020/235608
　近年、パターンの微細化が進められており、このようなパターンを形成するための感活性光線性又は感放射線性樹脂組成物の諸性能について、更なる向上が求められている。
　特許文献１に記載されている従来技術によっても、特に解像性については不十分であり、改善の余地が残されていた。 In recent years, miniaturization of patterns has progressed, and further improvement is required for various properties of actinic ray-sensitive or radiation-sensitive resin compositions for forming such patterns.
Even with the conventional technique described in Patent Document 1, the resolution is particularly insufficient, leaving room for improvement.
　そこで、本発明は、極微細（特に、線幅又はスペース幅が２０ｎｍ以下）のパターン形成において、解像性に優れ、さらにラフネス性能にも優れ、優れたパターン形状を得ることができる感活性光線性又は感放射線性樹脂組成物、上記感活性光線性又は感放射線性樹脂組成物により形成された感活性光線性又は感放射線性膜、上記感活性光線性又は感放射線性樹脂組成物を用いるパターン形成方法及び電子デバイスの製造方法を提供することを課題とする。 Therefore, the present invention provides an actinic ray that is excellent in resolution, has excellent roughness performance, and can obtain an excellent pattern shape in extremely fine pattern formation (especially, line width or space width is 20 nm or less). Actinic ray-sensitive or radiation-sensitive resin composition, Actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition, Pattern using the actinic ray-sensitive or radiation-sensitive resin composition An object is to provide a forming method and a method of manufacturing an electronic device.
　本発明者らは、以下の構成により上記課題を解決できることを見出した。 The inventors have found that the above problems can be solved by the following configuration.
［１］
　下記一般式（ａ）で表される繰り返し単位（ａ）を含む樹脂（Ａ）を含有する感活性光線性又は感放射線性樹脂組成物。 [1]
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) containing a repeating unit (a) represented by the following general formula (a).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　一般式（ａ）中、Ａは芳香環基、又は芳香族ヘテロ環基を表す。Ｘは単結合、アルキレン基、アルケニレン基、アルキニレン基、カルボニル基、スルホニル基、又はそれらを組み合わせてなる基を表す。Ｘは、Ａ環と結合してベンゼン環を形成してもよい。Ｙ１及びＹ２はそれぞれ独立して、酸素原子又は硫黄原子を表す。Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。 In general formula (a), A represents an aromatic ring group or an aromatic heterocyclic group. X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a combination thereof. X may combine with the A ring to form a benzene ring. Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom. R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
［２］
　上記樹脂（Ａ）が、さらに酸基を有する繰り返し単位を含む［１］に記載の感活性光線性又は感放射線性樹脂組成物。 [2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin (A) further contains a repeating unit having an acid group.
［３］
　上記酸基を有する繰り返し単位が、フェノール性水酸基を有する繰り返し単位である［２］に記載の感活性光線性又は感放射線性樹脂組成物。 [3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit having an acid group is a repeating unit having a phenolic hydroxyl group.
［４］
　上記酸基を有する繰り返し単位が、下記一般式（Ｂ）で表される繰り返し単位である［２］に記載の感活性光線性又は感放射線性樹脂組成物。 [4]
The actinic ray-sensitive or radiation-sensitive resin composition according to [2], wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (B).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　一般式（Ｂ）中、Ｒ３は、水素原子、又は１価の有機基を表す。Ｒ４及びＲ５は、各々独立に、水素原子、ハロゲン原子、又はアルキル基を表す。Ｌ２は、単結合又はエステル結合を表す。Ｌ３は、（ｎ＋ｍ＋１）価の芳香族炭化水素環基、又は（ｎ＋ｍ＋１）価の脂環式炭化水素環基を表す。Ｒ６は、水酸基、又はフッ素化アルコール基を表す。Ｒ７は、ハロゲン原子を表す。ｍは、１以上の整数を表す。ｎは、０又は１以上の整数を表す。 In general formula (B), R3 represents a hydrogen atom or a monovalent organic group. R4 and R5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group. L2 represents a single bond or an ester bond. L 3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. R6 represents a hydroxyl group or a fluorinated alcohol group. R7 represents a halogen atom. m represents an integer of 1 or more. n represents an integer of 0 or 1 or more.
［５］
　上記酸基を有する繰り返し単位が、下記一般式（ｃ）で表される繰り返し単位である［２］又は［３］に記載の感活性光線性又は感放射線性樹脂組成物。 [5]
The actinic ray-sensitive or radiation-sensitive resin composition according to [2] or [3], wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (c).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　一般式（ｃ）中、Ｒ６１～Ｒ６３はそれぞれ独立して、水素原子、有機基又はハロゲン原子を表す。ただし、Ｒ６２はＡｒと結合して環を形成していてもよく、その場合のＲ６２は単結合またはアルキレン基を表す。Ｌは単結合、又は２価の連結基を表す。Ａｒは（ｋ＋１）価の芳香環基を表し、Ｒ６２と結合して環を形成する場合には（ｋ＋２）価の芳香環基を表す。ｋは、１～５の整数を表す。 In general formula (c), R 61 to R 63 each independently represent a hydrogen atom, an organic group or a halogen atom. However, R 62 may combine with Ar to form a ring, in which case R 62 represents a single bond or an alkylene group. L represents a single bond or a divalent linking group. Ar represents a (k+1)-valent aromatic ring group, and when combined with R 62 to form a ring, represents a (k+2)-valent aromatic ring group. k represents an integer of 1 to 5;
［６］
　一般式（ａ）中、Ｙ１及びＹ２がいずれも酸素原子を表す［１］～［５］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
［７］
　一般式（ａ）中、Ｘが単結合、メチレン基、エチレン基、又はカルボニル基を表す［１］～［６］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
［８］
　一般式（ａ）中、Ｘがメチレン基、エチレン基、又はカルボニル基を表す［１］～［７］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 [6]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein Y 1 and Y 2 both represent an oxygen atom in general formula (a).
[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein X in general formula (a) represents a single bond, a methylene group, an ethylene group, or a carbonyl group.
[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein in general formula (a), X represents a methylene group, an ethylene group, or a carbonyl group.
［９］
　一般式（ａ）中、Ｘがカルボニル基を表す［１］～［８］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
［１０］
　一般式（ａ）中、Ａが芳香環基を表す［１］～［９］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 [9]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein, in general formula (a), X represents a carbonyl group.
[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein A represents an aromatic ring group in general formula (a).
［１１］
　上記一般式（ａ）で表される繰り返し単位が、下記一般式（ａ－１）で表される繰り返し単位である［１］～［１０］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 [11]
Actinic ray-sensitive or according to any one of [1] to [10], wherein the repeating unit represented by the general formula (a) is a repeating unit represented by the following general formula (a-1) A radiation-sensitive resin composition.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（ａ－１）中、Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。Ｒ２１はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。Ｒ２１は互いに結合して環を形成しても良い。 In general formula (a-1), R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom. Each R 21 independently represents a hydrogen atom, an organic group, or a halogen atom. R 21 may combine with each other to form a ring.
［１２］
　［１］～［１１］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成された感活性光線性又は感放射線性膜。
［１３］
　［１］～［１１］のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物により、基板上に感活性光線性又は感放射線性膜を形成する工程と、
上記感活性光線性又は感放射線性膜を露光する露光工程と、
露光された上記感活性光線性又は感放射線性膜を現像液を用いて現像する現像工程と、を含むパターン形成方法。
［１４］
　［１３］に記載のパターン形成方法を含む電子デバイスの製造方法。 [12]
An actinic ray- or radiation-sensitive film formed using the actinic ray- or radiation-sensitive resin composition according to any one of [1] to [11].
[13]
forming an actinic ray-sensitive or radiation-sensitive film on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11];
an exposure step of exposing the actinic ray-sensitive or radiation-sensitive film;
and a developing step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
[14]
A method for manufacturing an electronic device, including the pattern forming method according to [13].
　本発明によれば、極微細（特に、線幅又はスペース幅が２０ｎｍ以下）のパターン形成において、解像性に優れ、さらにラフネス性能に優れ、優れたパターン形状を得ることができる感活性光線性又は感放射線性樹脂組成物、上記感活性光線性又は感放射線性樹脂組成物により形成された感活性光線性又は感放射線性膜、上記感活性光線性又は感放射線性樹脂組成物を用いるパターン形成方法及び電子デバイスの製造方法を提供することができる。 According to the present invention, in the formation of extremely fine patterns (in particular, line width or space width of 20 nm or less), the actinic ray-sensitive properties are excellent in resolution, roughness performance, and excellent pattern shape. Or a radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition, or pattern formation using the actinic ray-sensitive or radiation-sensitive resin composition Methods and methods of manufacturing electronic devices can be provided.
　以下、本発明について詳細に説明する。
　以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に限定されない。
　本明細書中における基（原子団）の表記について、本発明の趣旨に反しない限り、置換及び無置換を記していない表記は、置換基を有さない基と共に置換基を含む基をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。また、本明細書中において、「有機基」とは、少なくとも１個の炭素原子を含む基をいう。
　置換基としては、特に断らない限り、１価の置換基が好ましい。 The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
Regarding the notation of a group (atomic group) in the present specification, as long as it does not contradict the spirit of the present invention, the notation that does not describe substituted or unsubstituted includes groups containing substituents as well as groups that do not have substituents. do. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, the term "organic group" as used herein refers to a group containing at least one carbon atom.
As a substituent, a monovalent substituent is preferable unless otherwise specified.
　本明細書において、「置換基を有していてもよい」というときの置換基の種類、置換基の位置、及び、置換基の数は特に限定されない。置換基の数は例えば、１つ、２つ、３つ、又はそれ以上であってもよい。置換基の例としては水素原子を除く１価の非金属原子団を挙げることができ、例えば、以下の置換基Ｔから選択することができる。 In the present specification, the type of substituent, the position of the substituent, and the number of substituents when "may have a substituent" are not particularly limited. The number of substituents can be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.
（置換基Ｔ）
　置換基Ｔとしては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等のハロゲン原子；メトキシ基、エトキシ基及びｔｅｒｔ－ブトキシ基等のアルコキシ基；フェノキシ基及びｐ－トリルオキシ基等のアリールオキシ基；メトキシカルボニル基、ブトキシカルボニル基及びフェノキシカルボニル基等のアルコキシカルボニル基；アセトキシ基、プロピオニルオキシ基及びベンゾイルオキシ基等のアシルオキシ基；アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基及びメトキサリル基等のアシル基；メチルスルファニル基及びｔｅｒｔ－ブチルスルファニル基等のアルキルスルファニル基；フェニルスルファニル基及びｐ－トリルスルファニル基等のアリールスルファニル基；アルキル基；シクロアルキル基；アリール基；ヘテロアリール基；水酸基；カルボキシ基；ホルミル基；スルホ基；シアノ基；アルキルアミノカルボニル基；アリールアミノカルボニル基；スルホンアミド基；シリル基；アミノ基；モノアルキルアミノ基；ジアルキルアミノ基；アリールアミノ基、ニトロ基；ホルミル基；並びにこれらの組み合わせが挙げられる。 (substituent T)
The substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc. Alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; Arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkyl groups; Cycloalkyl groups; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; and combinations thereof.
　本明細書において、「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ：Ｅｘｔｒｅｍｅ　Ｕｌｔｒａｖｉｏｌｅｔ）、Ｘ線、及び、電子線（ＥＢ：Ｅｌｅｃｔｒｏｎ　Ｂｅａｍ）を意味する。
　本明細書において、「光」とは、活性光線又は放射線を意味する。
　本明細書において、「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線、及び、Ｘ線等による露光のみならず、電子線、及び、イオンビーム等の粒子線による描画も含む。
　本明細書において、「～」とは、その前後に記載される数値を下限値及び上限値として含む意味で使用される。 As used herein, "actinic ray" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam).
As used herein, "light" means actinic rays or radiation.
In the present specification, the term "exposure" means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, and X-rays, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
As used herein, the term "to" is used to include the numerical values before and after it as lower and upper limits.
　本明細書において、表記される２価の連結基の結合方向は、特に断らない限り制限されない。例えば、「Ｘ－Ｙ－Ｚ」なる式で表される化合物中の、Ｙが－ＣＯＯ－である場合、Ｙは、－ＣＯ－Ｏ－であってもよく、－Ｏ－ＣＯ－であってもよい。上記化合物は「Ｘ－ＣＯ－Ｏ－Ｚ」であってもよく、「Ｘ－Ｏ－ＣＯ－Ｚ」であってもよい。 In the present specification, the binding direction of the divalent linking groups indicated is not limited unless otherwise specified. For example, in the compound represented by the formula "XYZ", when Y is -COO-, Y may be -CO-O- or -O-CO- good too. The compound may be "X—CO—O—Z" or "X—O—CO—Z."
　本明細書において、（メタ）アクリレートはアクリレート及びメタクリレートを表し、（メタ）アクリルはアクリル及びメタクリルを表す。
　本明細書において、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、及び、分散度（以下「分子量分布」ともいう。）（Ｍｗ／Ｍｎ）は、ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）装置（東ソー社製ＨＬＣ－８１２０ＧＰＣ）によるＧＰＣ測定（溶媒：テトラヒドロフラン、流量（サンプル注入量）：１０μＬ、カラム：東ソー社製ＴＳＫ　ｇｅｌ　Ｍｕｌｔｉｐｏｒｅ　ＨＸＬ－Ｍ、カラム温度：４０℃、流速：１．０ｍＬ／分、検出器：示差屈折率検出器（Ｒｅｆｒａｃｔｉｖｅ　Ｉｎｄｅｘ　Ｄｅｔｅｃｔｏｒ））によるポリスチレン換算値として定義される。 As used herein, (meth)acrylate refers to acrylate and methacrylate, and (meth)acryl refers to acrylic and methacrylic.
In the present specification, weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (hereinafter also referred to as "molecular weight distribution") (Mw/Mn) are measured by GPC (Gel Permeation Chromatography) equipment (Tosoh Corporation). GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector : Defined as a polystyrene conversion value by a differential refractive index detector (Refractive Index Detector).
　本明細書において、酸解離定数（ｐＫａ）とは、水溶液中でのｐＫａを表し、具体的には、下記ソフトウェアパッケージ１を用いて、ハメットの置換基定数及び公知文献値のデータベースに基づいた値を、計算により求められる値である。
　ソフトウェアパッケージ１：　Ａｄｖａｎｃｅｄ　Ｃｈｅｍｉｓｔｒｙ　Ｄｅｖｅｌｏｐｍｅｎｔ　（ＡＣＤ／Ｌａｂｓ）　Ｓｏｆｔｗａｒｅ　Ｖ８．１４　ｆｏｒ　Ｓｏｌａｒｉｓ　（１９９４－２００７　ＡＣＤ／Ｌａｂｓ）。 As used herein, the acid dissociation constant (pKa) represents the pKa in an aqueous solution. is a calculated value.
Software Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
　ｐＫａは、分子軌道計算法によっても求められる。具体的な方法としては、熱力学サイクルに基づいて、水溶液中におけるＨ＋解離自由エネルギーを計算することで算出する手法が挙げられる。Ｈ＋解離自由エネルギーの計算方法については、例えばＤＦＴ（密度汎関数法）により計算することができるが、他にも様々な手法が文献等で報告されており、これに制限されない。なお、ＤＦＴを実施できるソフトウェアは複数存在するが、例えば、Ｇａｕｓｓｉａｎ１６が挙げられる。 pKa can also be determined by molecular orbital calculation. As a specific method, there is a method of calculating the H 2 + dissociation free energy in an aqueous solution based on the thermodynamic cycle. The H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and the method is not limited to this. Note that there are a plurality of software that can implement DFT, and Gaussian16 is an example.
　本明細書中において、ｐＫａとは、上述した通り、ソフトウェアパッケージ１を用いて、ハメットの置換基定数及び公知文献値のデータベースに基づいた値を計算により求められる値を指すが、この手法によりｐＫａが算出できない場合には、ＤＦＴ（密度汎関数法）に基づいてＧａｕｓｓｉａｎ１６により得られる値を採用するものとする。
　本明細書中において、ｐＫａは、上述した通り「水溶液中でのｐＫａ」を指すが、水溶液中でのｐＫａが算出できない場合には、「ジメチルスルホキシド（ＤＭＳＯ）溶液中でのｐＫａ」を採用するものとする。
　「固形分」とは、感活性光線性膜を形成する成分を意味し、溶剤は含まれない。また、感活性光線性膜を形成する成分であれば、その性状が液体状であっても、固形分とみなす。 In the present specification, pKa refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using Software Package 1, as described above. cannot be calculated, a value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted.
In this specification, pKa refers to "pKa in aqueous solution" as described above, but when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" is adopted. shall be
"Solid content" means the components that form the actinic ray-sensitive film, and does not include solvent. In addition, as long as it is a component that forms an actinic ray-sensitive film, it is regarded as a solid content even if the property is liquid.
［感活性光線性又は感放射線性樹脂組成物］
　本発明に係る感活性光線性又は感放射線性樹脂組成物（以下、「本発明の組成物」ともいう）は、下記一般式（ａ）で表される繰り返し単位（ａ）を含む樹脂（Ａ）を含有する。 [Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "the composition of the present invention") according to the present invention is a resin (A ).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　一般式（ａ）中、Ａは芳香環基、又は芳香族ヘテロ環基を表す。Ｘは単結合、アルキレン基、アルケニレン基、アルキニレン基、カルボニル基、スルホニル基、又はそれらを組み合わせてなる基を表す。Ｘは、Ａ環と結合してベンゼン環を形成してもよい。Ｙ１及びＹ２はそれぞれ独立して、酸素原子又は硫黄原子を表す。Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。 In general formula (a), A represents an aromatic ring group or an aromatic heterocyclic group. X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a combination thereof. X may combine with the A ring to form a benzene ring. Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom. R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
　このような構成によれば、極微細（特に、線幅又はスペース幅が２０ｎｍ以下）のパターン形成において、解像性に優れ、さらにラフネス性能に優れ、優れたパターン形状を得ることができる。
　本発明が上記効果を発現できるメカニズムは必ずしも明らかではないが、本発明者らは以下のように推察している。 According to such a configuration, it is possible to obtain an excellent pattern shape with excellent resolution and roughness performance in ultrafine pattern formation (in particular, line width or space width of 20 nm or less).
Although the mechanism by which the present invention can exhibit the above effects is not necessarily clear, the present inventors speculate as follows.
　本発明の組成物に用いる樹脂（Ａ）に含まれる繰り返し単位（ａ）は、酸素原子及び硫黄原子から選ばれる２つの原子に結合したメチレン構造を有している。換言すると、チオール基、水酸基、カルボキシル基といった基から選ばれる２つの極性基がメチレン構造によって保護された環状保護構造を有する酸分解性基を含んでいる。より具体的には、下記一般式（ａｍ）で表される、繰り返し単位（ａ）の原料モノマーにおいて、チオール基、水酸基、カルボキシル基といった基から選ばれる２つの極性基が－Ｃ（＝ＣＲ１１Ｒ１２）－で表されるメチリデン基含有メチレン構造によって保護された環状構造を有する酸分解性基が含まれており、重合反応により繰り返し単位（ａ）を形成している。 The repeating unit (a) contained in the resin (A) used in the composition of the present invention has a methylene structure bonded to two atoms selected from an oxygen atom and a sulfur atom. In other words, it contains an acid-decomposable group having a cyclic protective structure in which two polar groups selected from groups such as thiol group, hydroxyl group and carboxyl group are protected by a methylene structure. More specifically, in the raw material monomer of the repeating unit (a) represented by the following general formula (am), two polar groups selected from groups such as a thiol group, a hydroxyl group, and a carboxyl group are -C (=CR 11 It contains an acid-decomposable group having a cyclic structure protected by a methylidene group-containing methylene structure represented by R 12 )—, and forms the repeating unit (a) through a polymerization reaction.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記構造を有する繰り返し単位（ａ）は、下記スキームに示すように、酸と反応してメチレン構造が分解して脱保護し、極性基を発生させるとともに、主鎖開裂を引き起こすと推測される。そのため、樹脂（Ａ）は、露光により発生した酸によって極性基が生じるとともに、主鎖分解により分子量が低下する。よって、露光前後で、露光部及び未露光部における樹脂の現像液に対する溶解性のコントラストを従来よりも大きくすることができ、解像性が向上するものと考えられる。なお、下記スキームの詳細については後述する。 As shown in the scheme below, the repeating unit (a) having the above structure is presumed to react with an acid to decompose the methylene structure and deprotect, generate a polar group, and cause main chain cleavage. Therefore, in the resin (A), polar groups are generated by the acid generated by exposure, and the molecular weight is reduced by decomposition of the main chain. Therefore, before and after the exposure, the contrast of the solubility of the resin in the developer in the exposed area and the unexposed area can be made larger than before, and it is considered that the resolution is improved. Details of the following scheme will be described later.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　また、上記メチレン構造中の炭素原子は４級炭素原子であるため、これを主鎖に含むことにより主鎖の運動性が抑制され、樹脂のガラス転移温度（Ｔｇ）が高くなり、感活性光線性又は感放射線性膜中での酸の拡散が抑制され、解像性がさらに向上し、ラフネス性能やパターン形状についても良化するものと考えられる。 In addition, since the carbon atom in the methylene structure is a quaternary carbon atom, inclusion of this in the main chain suppresses the mobility of the main chain, increases the glass transition temperature (Tg) of the resin, and increases the sensitivity to actinic rays. It is thought that the diffusion of acid in the curable or radiation-sensitive film is suppressed, the resolution is further improved, and the roughness performance and pattern shape are also improved.
　本発明の組成物は、典型的には、レジスト組成物であり、ポジ型のレジスト組成物であっても、ネガ型のレジスト組成物であってもよく、ポジ型のレジスト組成物であることが好ましい。また、アルカリ現像用のレジスト組成物であっても、有機溶剤現像用のレジスト組成物であってもよく、アルカリ現像用のレジスト組成物であることが好ましい。本発明の組成物は、典型的には、化学増幅型のレジスト組成物である。 The composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition. is preferred. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development, preferably a resist composition for alkali development. The composition of the present invention is typically a chemically amplified resist composition.
　以下、本発明の組成物の各成分について詳述する。 Each component of the composition of the present invention will be described in detail below.
＜樹脂（Ａ）＞
（繰り返し単位（ａ））
　本発明の組成物は、下記一般式（ａ）で表される繰り返し単位（ａ）を含有する樹脂を含有する。
　繰り返し単位（ａ）は、酸の作用により分解し極性が増大する基（以下「酸分解性基」ともいう。）を含む繰り返し単位である。
　酸分解性基とは、酸の作用により分解して極性基を生じる基をいう。酸分解性基は、酸の作用により脱離する基（脱離基）で極性基が保護された構造を有することが好ましく、繰り返し単位（ａ）においては、水酸基、カルボキシル基、チオール基といった極性基のうち、２つの極性基がメチレン構造（Ｙ１、Ｙ２と結合する炭素原子）で保護された構造を有している。
　樹脂（Ａ）は、酸の作用により極性が増大し、アルカリ現像液に対する溶解度が増大し、有機溶剤に対する溶解度が減少する。 <Resin (A)>
(Repeating unit (a))
The composition of the present invention contains a resin containing repeating units (a) represented by the following general formula (a).
The repeating unit (a) is a repeating unit containing a group that is decomposed by the action of an acid to increase its polarity (hereinafter also referred to as "acid-decomposable group").
An acid-decomposable group is a group that is decomposed by the action of an acid to form a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected by a group (leaving group) that is eliminated by the action of an acid. Among the groups, two polar groups have a structure protected by a methylene structure (the carbon atoms bonded to Y 1 and Y 2 ).
The resin (A) increases in polarity under the action of acid, increases in solubility in alkaline developing solutions, and decreases in solubility in organic solvents.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　一般式（ａ）中、Ａは芳香環基、又は芳香族ヘテロ環基を表す。Ｘは単結合、アルキレン基、アルケニレン基、アルキニレン基、カルボニル基、スルホニル基、又はそれらを組み合わせてなる基を表す。Ｘは、Ａ環と結合してベンゼン環を形成してもよい。Ｙ１及びＹ２はそれぞれ独立して、酸素原子又は硫黄原子を表す。Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。 In general formula (a), A represents an aromatic ring group or an aromatic heterocyclic group. X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a combination thereof. X may combine with the A ring to form a benzene ring. Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom. R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
　一般式（ａ）中、Ａは芳香環基、又は芳香族ヘテロ環基を表す。
　Ａが表す芳香環基としては、例えば、ベンゼン環、ナフタレン環、アントラセン環等の炭素数６～１８の芳香環基が挙げられる。
　Ａが表す芳香族ヘテロ環基としては、例えば、チオフェン環、フラン環、チアゾール環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環等が挙げられる。 In general formula (a), A represents an aromatic ring group or an aromatic heterocyclic group.
Examples of the aromatic ring group represented by A include aromatic ring groups having 6 to 18 carbon atoms such as benzene ring, naphthalene ring and anthracene ring.
Examples of aromatic heterocyclic groups represented by A include thiophene ring, furan ring, thiazole ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, and thiadiazole. ring and the like.
　Ａは、置換基を有していてもよい。好ましい置換基としては、例えば、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基、ハロゲン原子等が挙げられる。
　アルキル基としては、メチル基、エチル基、イソプロピル基等の炭素数１～１２のアルキル基が挙げられる。
　アルケニル基としては、ビニル基、アリル基等の炭素数２～１２のアルケニル基が挙げられる。
　アルキニル基としては、エチニル基等の炭素数２～１２のアルキニル基が挙げられる。
　シクロアルキル基としては、単環でも多環でもよく、例えば、シクロプロピル基、シクロペンチル基、及びシクロヘキシル基等の炭素数３～１２のシクロアルキル基が挙げられる。
　アリール基としては、フェニル基等の炭素数６～１２のアリール基が挙げられる。
　アルコキシ基としては、メトキシ基、エトキシ基、イソプロポキシ基等の炭素数１～１２のアルキル基が挙げられる。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
　Ａが複数の置換基を有する場合、これらの置換基は互いに結合して環を形成しても良い。 A may have a substituent. Preferred substituents include, for example, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, alkoxy groups, halogen atoms and the like.
The alkyl group includes alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group and isopropyl group.
The alkenyl group includes alkenyl groups having 2 to 12 carbon atoms such as vinyl group and allyl group.
The alkynyl group includes alkynyl groups having 2 to 12 carbon atoms such as ethynyl group.
The cycloalkyl group may be monocyclic or polycyclic, and examples thereof include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl, cyclopentyl and cyclohexyl.
The aryl group includes an aryl group having 6 to 12 carbon atoms such as a phenyl group.
Alkoxy groups include alkyl groups having 1 to 12 carbon atoms such as methoxy, ethoxy and isopropoxy groups.
Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.
When A has multiple substituents, these substituents may combine with each other to form a ring.
　Ａが置換基を有する場合の置換基としては、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、フッ素原子、又はヨウ素原子が好ましい。 When A has a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorine atom, or an iodine atom.
　Ａは、芳香環基を表すことが好ましく、ベンゼン環基を表すことがより好ましい。 A preferably represents an aromatic ring group, more preferably a benzene ring group.
　一般式（ａ）中、Ｘは単結合、アルキレン基、アルケニレン基、アルキニレン基、カルボニル基、スルホニル基、又はそれらを組み合わせてなる基を表す。 In general formula (a), X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a group formed by combining them.
　Ｘが表すアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基等の炭素数１～４のアルキレン基が好ましく、メチレン基又はエチレン基がより好ましい。
　Ｘが表すアルケニレン基としては、ビニレン基等の炭素数２～４のアルケニレン基が好ましい。
　Ｘが表すアルキニレン基としては、エチニレン基等の炭素数２～４のアルキニレン基が好ましい。 The alkylene group represented by X is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, ethylene group, propylene group and butylene group, more preferably a methylene group or an ethylene group.
As the alkenylene group represented by X, an alkenylene group having 2 to 4 carbon atoms such as a vinylene group is preferable.
The alkynylene group represented by X is preferably an alkynylene group having 2 to 4 carbon atoms such as an ethynylene group.
　Ｘは、Ａ環と結合してベンゼン環を形成してもよい。具体的には、一般式（ａ）で表される繰り返し単位が、下記一般式（ａａ）で表される繰り返し単位である場合を意味する。 X may combine with the A ring to form a benzene ring. Specifically, it means that the repeating unit represented by the general formula (a) is a repeating unit represented by the following general formula (aa).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　一般式（ａａ）中のＡ、Ｙ１、Ｙ２、Ｒ１１、及びＲ１２は、一般式（ａ）中のＡ、Ｙ１、Ｙ２、Ｒ１１、及びＲ１２と同義である。 A, Y 1 , Y 2 , R 11 and R 12 in general formula (aa) are synonymous with A, Y 1 , Y 2 , R 11 and R 12 in general formula (a).
　Ｘは置換基を有していてもよく、置換基としては、例えば上述のＡが有し得る置換基が挙げられる。 X may have a substituent, and examples of the substituent include the substituents that A described above can have.
　Ｘは、単結合、アルキレン基、又はカルボニル基を表すことが好ましく、単結合、メチレン基、エチレン基、又はカルボニル基を表すことがより好ましく、メチレン基、エチレン基、又はカルボニル基を表すことがさらに好ましく、カルボニル基を表すことが特に好ましい。 X preferably represents a single bond, an alkylene group, or a carbonyl group, more preferably a single bond, a methylene group, an ethylene group, or a carbonyl group, and a methylene group, an ethylene group, or a carbonyl group. More preferably, it is particularly preferably a carbonyl group.
　一般式（ａ）中、Ｙ１及びＹ２はそれぞれ独立に、酸素原子又は硫黄原子を表す。Ｙ１及びＹ２は、少なくとも一方が酸素原子であることが好ましく、いずれも酸素原子を表すことがより好ましい。 In general formula (a), Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom. At least one of Y 1 and Y 2 is preferably an oxygen atom, and both are more preferably oxygen atoms.
　一般式（ａ）中、Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。 In general formula (a), R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
　Ｒ１１及びＲ１２が表す有機基としては、例えば、アルキル基、シクロアルキル基、シアノ基又はアルコキシカルボニル基が挙げられる。 Examples of organic groups represented by R 11 and R 12 include alkyl groups, cycloalkyl groups, cyano groups and alkoxycarbonyl groups.
　Ｒ１１及びＲ１２が表すアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、及び、ドデシル基等の炭素数２０以下のアルキル基が好ましく、炭素数８以下のアルキル基がより好ましく、炭素数３以下のアルキル基が更に好ましい。 Examples of alkyl groups represented by R 11 and R 12 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. is preferably an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.
　Ｒ１１及びＲ１２が表すシクロアルキル基としては、単環型でも、多環型でもよい。なかでも、シクロプロピル基、シクロペンチル基、及び、シクロヘキシル基等の炭素数３～８個で単環型のシクロアルキル基が好ましい。
　Ｒ１１及びＲ１２が表すアルコキシカルボニル基に含まれるアルキル基としては、上記Ｒ１１及びＲ１２におけるアルキル基と同様のものが好ましい。 The cycloalkyl group represented by R 11 and R 12 may be monocyclic or polycyclic. Among them, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group are preferable.
The alkyl group contained in the alkoxycarbonyl group represented by R 11 and R 12 is preferably the same as the alkyl group for R 11 and R 12 above.
　Ｒ１１及びＲ１２が表すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子が挙げられ、フッ素原子が好ましい。 Halogen atoms represented by R 11 and R 12 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
　上記Ｒ１１及びＲ１２における好ましい置換基としては、例えば、アルキル基、シクロアルキル基、アリール基、アミノ基、アミド基、ウレイド基、ウレタン基、水酸基、カルボキシル基、ハロゲン原子、アルコキシ基、チオエーテル基、アシル基、アシロキシ基、アルコキシカルボニル基、シアノ基、及び、ニトロ基が挙げられる。置換基の炭素数は８以下が好ましい。 Preferred substituents for R 11 and R 12 include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, and a thioether group. , acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups. The number of carbon atoms in the substituent is preferably 8 or less.
　Ｒ１１及びＲ１２はそれぞれ独立に、水素原子又は炭素数３以下のアルキル基であることが好ましく、水素原子であることがより好ましい。 R 11 and R 12 are each independently preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, more preferably a hydrogen atom.
　上述の通り、上記構造を有する繰り返し単位（ａ）は、下記スキームに示すように、酸と反応してメチレン構造が分解して脱保護し、極性基を発生させるとともに、主鎖開裂を引き起こすと推測される。 As described above, the repeating unit (a) having the above structure reacts with an acid to decompose the methylene structure and deprotect, generate a polar group, and cause main chain cleavage, as shown in the scheme below. guessed.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記スキーム中、Ｐｎ、Ｐｍは、ポリマー鎖を表す。
　Ｒ１１、Ｒ１２、Ｙ１、Ｙ２、Ｘ、及びＡは、それぞれ上記一般式（ａ）におけるＲ１１、Ｒ１２、Ｙ１、Ｙ２、Ｘ、及びＡと同様である。
　上記構造に酸を作用させると電子豊富なＹが酸のプロトン（Ｈ＋）と結合し、Ｙ－炭素結合が開裂、メチレン構造が分解して炭素原子がカチオン化される。炭素上カチオンを水分子が攻撃、脱プロトンにより、アルコール体となる。この構造にプロトンを作用させると、隣接するメチレン構造に隣接するＹとプロトンが結合し、カチオンとなる。この構造は不安定であり、中性状態に戻るため、アルコール水素が脱プロトンし、カルボニル結合に変化する。それに伴い、各炭素原子の共有結合の数が４となるよう、主鎖が開裂、連続してメチレン構造が開裂する。結果、ポリマー主鎖が酸の触媒作用により、開裂アルケニル体、カルボニル体となるものと推測される。 In the above scheme, Pn and Pm represent polymer chains.
R 11 , R 12 , Y 1 , Y 2 , X and A are the same as R 11 , R 12 , Y 1 , Y 2 , X and A in the general formula (a) above.
When acid is applied to the above structure, electron-rich Y bonds with acid protons (H + ), the Y-carbon bond is cleaved, the methylene structure is decomposed, and the carbon atom is cationized. Water molecules attack the cation on the carbon and deprotonate it to form an alcohol. When a proton acts on this structure, the Y adjacent to the adjacent methylene structure and the proton combine to form a cation. Since this structure is unstable and returns to the neutral state, the alcohol hydrogen deprotonates and changes to a carbonyl bond. Along with this, the main chain is cleaved so that the number of covalent bonds at each carbon atom is four, followed by methylene structures. As a result, it is presumed that the main chain of the polymer becomes a cleaved alkenyl derivative or a carbonyl derivative by the catalytic action of the acid.
　一般式（ａ）で表される繰り返し単位は、下記一般式（ａ－１）で表される繰り返し単位であることが好ましい。 The repeating unit represented by general formula (a) is preferably a repeating unit represented by general formula (a-1) below.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　一般式（ａ－１）中、Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。Ｒ２１はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。Ｒ２１は互いに結合して環を形成しても良い。 In general formula (a-1), R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom. Each R 21 independently represents a hydrogen atom, an organic group, or a halogen atom. R 21 may combine with each other to form a ring.
　一般式（ａ－１）中のＲ１１及びＲ１２は、上記一般式（ａ）中のＲ１１及びＲ１２と同義であり、好ましい例も同様である。 R 11 and R 12 in general formula (a-1) have the same definitions as R 11 and R 12 in general formula (a) above, and preferred examples are also the same.
　一般式（ａ－１）中、Ｒ２１はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。
　Ｒ２１における有機基としては、例えば、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基が挙げられ、具体的には、上述のＡが置換基を有する場合の置換基としてのアルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基の例が挙げられる。
　Ｒ２１におけるハロゲン原子としては、上述のＡが置換基を有する場合の置換基としてのハロゲン原子の例が挙げられる。
　複数のＲ２１が互いに結合して環を形成する場合の環状構造としては、シクロペンチル基又はシクロヘキシル基等が挙げられる。 In general formula (a-1), each R 21 independently represents a hydrogen atom, an organic group, or a halogen atom.
Examples of the organic group for R 21 include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and an alkoxy group. are alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, and alkoxy groups.
Examples of the halogen atom for R 21 include the halogen atom as a substituent when the above-mentioned A has a substituent.
A cyclic structure in which a plurality of R 21 are bonded to each other to form a ring includes a cyclopentyl group, a cyclohexyl group, and the like.
　Ｒ２１は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、フッ素原子、又はヨウ素原子を表すことが好ましい。 Each R 21 preferably independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorine atom or an iodine atom.
　以下、一般式（ａ）で表される繰り返し単位の具体例を示すが、本発明は、これに限定されるものではない。なお、以下の具体例においては、一般式（ａ）で表される繰り返し単位の原料モノマー（上記一般式（ａｍ）で表されるモノマー）の構造として示す。 Specific examples of the repeating unit represented by formula (a) are shown below, but the present invention is not limited thereto. In the following specific examples, the structures of the raw material monomers (monomers represented by the above general formula (am)) of the repeating units represented by the general formula (a) are shown.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　繰り返し単位（ａ）の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、１５モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上が更に好ましい。また、その上限値としては、樹脂（Ａ）中の全繰り返し単位に対して、９０モル％以下が好ましく、８０モル％以下がより好ましく、７０モル％以下が更に好ましく、６０モル％以下が特に好ましい。 The content of the repeating unit (a) is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, relative to all repeating units in the resin (A). The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
（酸分解性基を有する繰り返し単位）
　樹脂（Ａ）は、上述の繰り返し単位（ａ）以外にも、酸分解性基を有する繰り返し単位を有していてもよい。
　酸分解性基を有する繰り返し単位としては、後述する酸分解性基を有する繰り返し単位以外に、不飽和結合を含む酸分解性基を有する繰り返し単位が好ましい。 (Repeating unit having an acid-decomposable group)
The resin (A) may have a repeating unit having an acid-decomposable group in addition to the repeating unit (a) described above.
As the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond is preferable in addition to the repeating unit having an acid-decomposable group described below.
　酸分解性基は、酸の作用により脱離する基（脱離基）で極性基が保護された構造を有することが好ましい。
　極性基としては、アルカリ可溶性基が好ましく、例えば、カルボキシル基、フェノール性水酸基、フッ素化アルコール基、スルホン酸基、リン酸基、スルホンアミド基、スルホニルイミド基、（アルキルスルホニル）（アルキルカルボニル）メチレン基、（アルキルスルホニル）（アルキルカルボニル）イミド基、ビス（アルキルカルボニル）メチレン基、ビス（アルキルカルボニル）イミド基、ビス（アルキルスルホニル）メチレン基、ビス（アルキルスルホニル）イミド基、トリス（アルキルカルボニル）メチレン基、及び、トリス（アルキルスルホニル）メチレン基等の酸性基、並びに、アルコール性水酸基が挙げられる。
　なかでも、極性基としては、カルボキシル基、フェノール性水酸基、フッ素化アルコール基（好ましくはヘキサフルオロイソプロパノール基）、又は、スルホン酸基が好ましい。 The acid-decomposable group preferably has a structure in which the polar group is protected with a group that is released by the action of an acid (leaving group).
The polar group is preferably an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Methylene groups, acidic groups such as tris(alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups are included.
Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
　酸の作用により脱離する基としては、例えば、式（Ｙ１）～（Ｙ４）で表される基が挙げられる。
　式（Ｙ１）：－Ｃ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
　式（Ｙ２）：－Ｃ（＝Ｏ）ＯＣ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
　式（Ｙ３）：－Ｃ（Ｒ３６）（Ｒ３７）（ＯＲ３８）
　式（Ｙ４）：－Ｃ（Ｒｎ）（Ｈ）（Ａｒ） Examples of groups that leave by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C(Rx 1 )(Rx 2 )(Rx 3 )
Formula (Y2): -C(=O)OC(Rx 1 )(Rx 2 )(Rx 3 )
Formula (Y3): —C(R 36 )(R 37 )(OR 38 )
Formula (Y4): -C(Rn)(H)(Ar)
　式（Ｙ１）及び式（Ｙ２）中、Ｒｘ１～Ｒｘ３は、それぞれ独立に、炭化水素基を表し、アルキル基（直鎖状又は分岐鎖状）、シクロアルキル基（単環又は多環）、アルケニル基（直鎖状又は分岐鎖状）、又は、アリール基（単環又は多環）を表すことが好ましい。なお、Ｒｘ１～Ｒｘ３の全てがアルキル基（直鎖状又は分岐鎖状）である場合、Ｒｘ１～Ｒｘ３のうち少なくとも２つはメチル基であることが好ましい。
　なかでも、Ｒｘ１～Ｒｘ３は、それぞれ独立に、直鎖状又は分岐鎖状のアルキル基を表すことが好ましく、Ｒｘ１～Ｒｘ３は、それぞれ独立に、直鎖状のアルキル基を表すことがより好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して、単環又は多環を形成してもよい。
　Ｒｘ１～Ｒｘ３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、及び、ｔ－ブチル基等の炭素数１～５のアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、並びに、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。上記シクロアルキル基は、例えば、環を構成するメチレン基の１つが、酸素原子、硫黄原子等のヘテロ原子、カルボニル基等のヘテロ原子を含む基、又はビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の１つ以上が、ビニレン基で置き換わっていてもよい。
　Ｒｘ１～Ｒｘ３のアリール基としては、炭素数６～１０のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基が挙げられる。
　Ｒｘ１～Ｒｘ３のアルケニル基としては、ビニル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成される環としては、シクロアルキル基が好ましい。Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、若しくは、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、若しくは、アダマンチル基等の多環のシクロアルキル基が好ましく、炭素数５～６の単環のシクロアルキル基がより好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基は、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を含む基、又は、ビニリデン基で置き換わっていてもよい。これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の１つ以上が、ビニレン基で置き換わっていてもよい。
　式（Ｙ１）又は式（Ｙ２）で表される基は、例えば、Ｒｘ１がメチル基又はエチル基であり、Ｒｘ２とＲｘ３とが結合して上述のシクロアルキル基を形成している態様が好ましい。
　本発明の組成物が、例えば、ＥＵＶ露光用レジスト組成物である場合、Ｒｘ１～Ｒｘ３で表されるアルキル基、シクロアルキル基、アルケニル基、アリール基、及び、Ｒｘ１～Ｒｘ３の２つが結合して形成される環は、更に、置換基として、フッ素原子又はヨウ素原子を有していることも好ましい。 In formula (Y1) and formula (Y2), Rx 1 to Rx 3 each independently represent a hydrocarbon group, an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic) , an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups.
Among them, Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
The alkyl groups of Rx 1 to Rx 3 are alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
The cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred. In the cycloalkyl group, for example, one of the ring-constituting methylene groups may be replaced with a heteroatom such as an oxygen atom or a sulfur atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
The aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
A vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
The ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx 1 to Rx 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. A polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
In the cycloalkyl group formed by combining two of Rx 1 to Rx 3 , one of the methylene groups constituting the ring is a group containing a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced with In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
In the group represented by formula (Y1) or formula (Y2), for example, Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
For example, when the composition of the present invention is a resist composition for EUV exposure, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group represented by Rx 1 to Rx 3 , and 2 of Rx 1 to Rx 3 It is also preferred that the ring formed by combining two atoms further has a fluorine atom or an iodine atom as a substituent.
　式（Ｙ３）中、Ｒ３６～Ｒ３８は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｒ３７とＲ３８とは、互いに結合して環を形成してもよい。１価の有機基としては、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基が挙げられる。Ｒ３６は水素原子であることも好ましい。
　なお、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基には、酸素原子等のヘテロ原子及び／又はカルボニル基等のヘテロ原子を含む基が含まれていてもよい。例えば、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基において、メチレン基の１つ以上が、酸素原子等のヘテロ原子及び／又はカルボニル基等のヘテロ原子を含む基で置き換わっていてもよい。
　Ｒ３８は、繰り返し単位の主鎖が有する別の置換基と互いに結合して、環を形成してもよい。Ｒ３８と繰り返し単位の主鎖が有する別の置換基とが互いに結合して形成する基は、メチレン基等のアルキレン基が好ましい。
　本発明の組成物が、例えば、ＥＵＶ露光用レジスト組成物である場合、Ｒ３６～Ｒ３８で表される１価の有機基、及び、Ｒ３７とＲ３８とが互いに結合して形成される環は、更に、置換基として、フッ素原子又はヨウ素原子を有していることも好ましい。 In formula (Y3), R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group. R 37 and R 38 may combine with each other to form a ring. Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R 36 is a hydrogen atom.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more of the methylene groups may be replaced with a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group. good.
R 38 may combine with another substituent of the main chain of the repeating unit to form a ring. The group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
When the composition of the present invention is, for example, a resist composition for EUV exposure, monovalent organic groups represented by R 36 to R 38 and R 37 and R 38 are formed by binding to each other. The ring also preferably has a fluorine atom or an iodine atom as a substituent.
　式（Ｙ３）としては、下記式（Ｙ３－１）で表される基が好ましい。 As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　ここで、Ｌ１及びＬ２は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、又は、これらを組み合わせた基（例えば、アルキル基とアリール基とを組み合わせた基）を表す。
　Ｍは、単結合又は２価の連結基を表す。
　Ｑは、ヘテロ原子を含んでいてもよいアルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基、アルデヒド基、又は、これらを組み合わせた基（例えば、アルキル基とシクロアルキル基とを組み合わせた基）を表す。
　アルキル基及びシクロアルキル基は、例えば、メチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を含む基で置き換わっていてもよい。
　なお、Ｌ１及びＬ２のうち一方は水素原子であり、他方はアルキル基、シクロアルキル基、アリール基、又は、アルキレン基とアリール基とを組み合わせた基であることが好ましい。
　Ｑ、Ｍ、及びＬ１の少なくとも２つが結合して環（好ましくは、５員若しくは６員環）を形成してもよい。
　パターンの微細化の点では、Ｌ２が２級又は３級アルキル基であることが好ましく、３級アルキル基であることがより好ましい。２級アルキル基としては、イソプロピル基、シクロヘキシル基、及び、ノルボルニル基が挙げられ、３級アルキル基としては、ｔｅｒｔ－ブチル基、及び、アダマンタン基が挙げられる。これらの態様では、Ｔｇ（ガラス転移温度）及び活性化エネルギーが高くなるため、膜強度の担保に加え、かぶりの抑制ができる。 Here, L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group). .
M represents a single bond or a divalent linking group.
Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In alkyl groups and cycloalkyl groups, for example, one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.
One of L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
At least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
From the viewpoint of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
　本発明の組成物が、例えば、ＥＵＶ露光用レジスト組成物である場合、Ｌ１及びＬ２で表される、アルキル基、シクロアルキル基、アリール基、及び、これらを組み合わせた基は、更に、置換基として、フッ素原子又はヨウ素原子を有していることも好ましい。上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基には、フッ素原子及びヨウ素原子以外に、酸素原子等のヘテロ原子が含まれていることも好ましい。具体的には、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基は、例えば、メチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を含む基で置き換わっていてもよい。
　本発明の組成物が、例えば、ＥＵＶ露光用レジスト組成物である場合、Ｑで表されるヘテロ原子を含んでいてもよいアルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基、アルデヒド基、及び、これらを組み合わせた基において、ヘテロ原子としては、フッ素原子、ヨウ素原子及び酸素原子からなる群から選択されるヘテロ原子であることも好ましい。 When the composition of the present invention is, for example, a resist composition for EUV exposure, the alkyl group, cycloalkyl group, aryl group, and group combining these represented by L 1 and L 2 are further It is also preferable to have a fluorine atom or an iodine atom as a substituent. The alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom and the iodine atom. Specifically, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. may be
For example, when the composition of the present invention is a resist composition for EUV exposure, an alkyl group optionally containing a heteroatom represented by Q, a cycloalkyl group optionally containing a heteroatom, or a heteroatom is In the aryl group, amino group, ammonium group, mercapto group, cyano group, aldehyde group, and groups in which these groups may be combined, the heteroatom is selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom. It is also preferred that the heteroatom is
　式（Ｙ４）中、Ａｒは、芳香環基を表す。Ｒｎは、アルキル基、シクロアルキル基、又は、アリール基を表す。ＲｎとＡｒとは互いに結合して非芳香族環を形成してもよい。Ａｒとしては、アリール基が好ましい。
　本発明の組成物が、例えば、ＥＵＶ露光用レジスト組成物である場合、Ａｒで表される芳香環基、並びに、Ｒｎで表されるアルキル基、シクロアルキル基、及び、アリール基は、置換基としてフッ素原子又はヨウ素原子を有していることも好ましい。 In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may combine with each other to form a non-aromatic ring. Ar is preferably an aryl group.
For example, when the composition of the present invention is a resist composition for EUV exposure, the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group and aryl group represented by Rn are substituents It is also preferable to have a fluorine atom or an iodine atom as.
　繰り返し単位の酸分解性が優れる点から、極性基を保護する脱離基において、極性基（又はその残基）に非芳香族環が直接結合している場合、上記非芳香族環中の、上記極性基（又はその残基）と直接結合している環員原子に隣接する環員原子は、置換基としてフッ素原子等のハロゲン原子を有さないことも好ましい。 From the viewpoint of excellent acid decomposability of the repeating unit, when a non-aromatic ring is directly bonded to a polar group (or a residue thereof) in a leaving group that protects a polar group, in the non-aromatic ring, It is also preferable that the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.
　酸の作用により脱離する基は、他にも、３－メチル－２－シクロペンテニル基のような置換基（アルキル基等）を有する２－シクロペンテニル基、及び、１，１，４，４－テトラメチルシクロヘキシル基のような置換基（アルキル基等）を有するシクロヘキシル基でもよい。 Groups that can be eliminated by the action of an acid also include a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1,4,4 A cyclohexyl group having a substituent (such as an alkyl group) such as a -tetramethylcyclohexyl group may also be used.
　酸分解性基を有する繰り返し単位としては、式（Ａ）で表される繰り返し単位も好ましい。 As the repeating unit having an acid-decomposable group, a repeating unit represented by formula (A) is also preferable.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　Ｌ１は、フッ素原子又はヨウ素原子を有していてもよい２価の連結基を表し、Ｒ１は水素原子、フッ素原子、ヨウ素原子、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基、又は、フッ素原子若しくはヨウ素原子を有していてもよいアリール基を表し、Ｒ２は酸の作用によって脱離し、フッ素原子又はヨウ素原子を有していてもよい脱離基を表す。ただし、Ｌ１、Ｒ１、及びＲ２のうち少なくとも１つは、フッ素原子又はヨウ素原子を有する。
　Ｌ１で表される、フッ素原子又はヨウ素原子を有していてもよい２価の連結基としては、－ＣＯ－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、フッ素原子又はヨウ素原子を有していてもよい炭化水素基（例えば、アルキレン基、シクロアルキレン基、アルケニレン基、及び、アリーレン基等）、及び、これらの複数が連結した連結基が挙げられる。なかでも、Ｌ１としては、－ＣＯ－、アリーレン基、又は、－アリーレン基－フッ素原子若しくはヨウ素原子を有するアルキレン基－が好ましく、－ＣＯ－、又は、－アリーレン基－フッ素原子若しくはヨウ素原子を有するアルキレン基－がより好ましい。
　アリーレン基としては、フェニレン基が好ましい。
　アルキレン基は、直鎖状であっても、分岐鎖状であってもよい。アルキレン基の炭素数は特に制限されないが、１～１０が好ましく、１～３がより好ましい。
　フッ素原子又はヨウ素原子を有するアルキレン基に含まれるフッ素原子及びヨウ素原子の合計数は特に制限されないが、２以上が好ましく、２～１０がより好ましく、３～６が更に好ましい。 L 1 represents a divalent linking group optionally having a fluorine atom or an iodine atom, and R 1 is a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group optionally having a fluorine atom or an iodine atom , or represents an aryl group optionally having a fluorine atom or an iodine atom, and R 2 represents a leaving group optionally having a fluorine atom or an iodine atom which is eliminated by the action of an acid. However, at least one of L 1 , R 1 and R 2 has a fluorine atom or an iodine atom.
The divalent linking group optionally having a fluorine atom or an iodine atom represented by L 1 includes -CO-, -O-, -S-, -SO-, -SO 2 -, fluorine atom or a hydrocarbon group optionally having an iodine atom (eg, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked. Among them, L 1 is preferably -CO-, an arylene group, or an -arylene group - an alkylene group having a fluorine atom or an iodine atom -, and -CO- or an -arylene group - a fluorine atom or an iodine atom. An alkylene group with - is more preferable.
A phenylene group is preferred as the arylene group.
Alkylene groups may be linear or branched. Although the number of carbon atoms in the alkylene group is not particularly limited, it is preferably 1-10, more preferably 1-3.
The total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
　Ｒ１で表されるアルキル基は、直鎖状であっても、分岐鎖状であってもよい。アルキル基の炭素数は特に制限されないが、１～１０が好ましく、１～３がより好ましい。
　Ｒ１で表される、フッ素原子又はヨウ素原子を有するアルキル基に含まれる、フッ素原子及びヨウ素原子の合計数は特に制限されないが、１以上が好ましく、１～５がより好ましく、１～３が更に好ましい。
　Ｒ１で表されるアルキル基は、ハロゲン原子以外の酸素原子等のヘテロ原子を含んでいてもよい。 The alkyl group represented by R 1 may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-10, more preferably 1-3.
The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom represented by R 1 is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and 1 to 3. More preferred.
The alkyl group represented by R 1 may contain a heteroatom such as an oxygen atom other than the halogen atom.
　Ｒ２で表される、フッ素原子又はヨウ素原子を有していてもよい脱離基としては、上述した式（Ｙ１）～（Ｙ４）で表され、かつ、フッ素原子又はヨウ素原子を有する脱離基が挙げられる。 The leaving group optionally having a fluorine atom or an iodine atom represented by R 2 is represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom. groups.
　酸分解性基を有する繰り返し単位としては、式（ＡＩ）で表される繰り返し単位も好ましい。 As the repeating unit having an acid-decomposable group, a repeating unit represented by formula (AI) is also preferable.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式（ＡＩ）において、
　Ｘａ１は、水素原子、又は、置換基を有していてもよいアルキル基を表す。Ｔは、単結合、又は、２価の連結基を表す。Ｒｘ１～Ｒｘ３は、それぞれ独立に、アルキル基（直鎖状又は分岐鎖状）、シクロアルキル基（単環又は多環）、アルケニル基（直鎖状又は分岐鎖状）、又は、アリール（単環又は多環）基を表す。ただし、Ｒｘ１～Ｒｘ３の全てがアルキル基（直鎖状、又は分岐鎖状）である場合、Ｒｘ１～Ｒｘ３のうち少なくとも２つはメチル基であることが好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して、単環又は多環（単環又は多環のシクロアルキル基等）を形成してもよい。 In formula (AI),
Xa 1 represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl ( monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups.
Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).
　Ｘａ１により表される、置換基を有していてもよいアルキル基としては、例えば、メチル基又は－ＣＨ２－Ｒ１１で表される基が挙げられる。Ｒ１１は、ハロゲン原子（フッ素原子等）、水酸基、又は、１価の有機基を表す。Ｒ１１で表される１価の有機基としては、例えば、ハロゲン原子が置換していてもよい炭素数５以下のアルキル基、ハロゲン原子が置換していてもよい炭素数５以下のアシル基、及び、ハロゲン原子が置換していてもよい炭素数５以下のアルコキシ基が挙げられ、炭素数３以下のアルキル基が好ましく、メチル基がより好ましい。Ｘａ１としては、水素原子、メチル基、トリフルオロメチル基、又は、ヒドロキシメチル基が好ましい。 Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group and a group represented by -CH 2 -R 11 . R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples of the monovalent organic group represented by R 11 include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
　Ｔの２価の連結基としては、アルキレン基、芳香環基、－ＣＯＯ－Ｒｔ－基、及び、－Ｏ－Ｒｔ－基が挙げられる。式中、Ｒｔは、アルキレン基、又は、シクロアルキレン基を表す。
　Ｔは、単結合又は－ＣＯＯ－Ｒｔ－基が好ましい。Ｔが－ＣＯＯ－Ｒｔ－基を表す場合、Ｒｔとしては、炭素数１～５のアルキレン基が好ましく、－ＣＨ２－基、－（ＣＨ２）２－基、又は、－（ＣＨ２）３－基がより好ましい。 The divalent linking group for T includes an alkylene group, an aromatic ring group, a --COO--Rt-- group, and a --O--Rt-- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - groups are more preferred.
　Ｒｘ１～Ｒｘ３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、及び、ｔ－ブチル基等の炭素数１～４のアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のアリール基としては、炭素数６～１０のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基が挙げられる。
　Ｒｘ１～Ｒｘ３のアルケニル基としては、ビニル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基が好ましい。また、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基も好ましい。なかでも、炭素数５～６の単環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を含む基、又は、ビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の１つ以上が、ビニレン基で置き換わっていてもよい。
　式（ＡＩ）で表される繰り返し単位は、例えば、Ｒｘ１がメチル基又はエチル基であり、Ｒｘ２とＲｘ３とが結合して上述のシクロアルキル基を形成している態様が好ましい。 The alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
Cycloalkyl groups of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
The aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
A vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
The cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
A cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring contains a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or It may be substituted with a vinylidene group. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
In the repeating unit represented by formula (AI), for example, Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are preferably combined to form the above-mentioned cycloalkyl group.
　上記各基が置換基を有する場合、置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、水酸基、アルコキシ基（炭素数１～４）、カルボキシル基、及び、アルコキシカルボニル基（炭素数２～６）が挙げられる。置換基中の炭素数は、８以下が好ましい。 When each of the above groups has a substituent, examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.
　式（ＡＩ）で表される繰り返し単位としては、酸分解性（メタ）アクリル酸３級アルキルエステル系繰り返し単位（Ｘａ１が水素原子又はメチル基を表し、かつ、Ｔが単結合を表す繰り返し単位）が好ましい。 The repeating unit represented by the formula (AI) includes an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond. ) is preferred.
　酸分解性基を有する繰り返し単位の具体例を以下に示すが、これに限定されない。なお、式中、Ｘａ１は、Ｈ、ＣＨ３、ＣＦ３、又は、ＣＨ２ＯＨを表し、Ｒｘａ及びＲｘｂは、それぞれ独立に、炭素数１～５の直鎖状又は分岐鎖状のアルキル基を表す。 Specific examples of repeating units having an acid-decomposable group are shown below, but are not limited thereto. In the formula, Xa 1 represents H, CH 3 , CF 3 or CH 2 OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms. represents
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　樹脂（Ａ）は、酸分解性基を有する繰り返し単位として、不飽和結合を含む酸分解性基を有する繰り返し単位を有していてもよい。
　不飽和結合を含む酸分解性基を有する繰り返し単位としては、式（Ｂ）で表される繰り返し単位が好ましい。 Resin (A) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as the repeating unit having an acid-decomposable group.
As the repeating unit having an acid-decomposable group containing an unsaturated bond, a repeating unit represented by formula (B) is preferable.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（Ｂ）において、Ｘｂは、水素原子、ハロゲン原子、又は、置換基を有していてもよいアルキル基を表す。Ｌは、単結合、又は、置換基を有してもよい２価の連結基を表す。Ｒｙ１～Ｒｙ３は、それぞれ独立に、直鎖状若しくは分岐鎖状のアルキル基、単環状若しくは多環状のシクロアルキル基、アルケニル基、アルキニル基、又は、単環若しくは多環のアリール基を表す。ただし、Ｒｙ１～Ｒｙ３のうち少なくとも１つはアルケニル基、アルキニル基、単環若しくは多環のシクロアルケニル基、又は、単環若しくは多環のアリール基を表す。
　Ｒｙ１～Ｒｙ３の２つが結合して、単環又は多環（単環又は多環のシクロアルキル基、シクロアルケニル基等）を形成してもよい。 In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or a divalent linking group which may have a substituent. Ry 1 to Ry 3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group . However, at least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group.
Two of Ry 1 to Ry 3 may combine to form a monocyclic or polycyclic ring (a monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).
　Ｘｂにより表される、置換基を有していてもよいアルキル基としては、例えば、メチル基又は－ＣＨ２－Ｒ１１で表される基が挙げられる。Ｒ１１は、ハロゲン原子（フッ素原子等）、水酸基、又は、１価の有機基を表し、例えば、ハロゲン原子が置換していてもよい炭素数５以下のアルキル基、ハロゲン原子が置換していてもよい炭素数５以下のアシル基、及び、ハロゲン原子が置換していてもよい炭素数５以下のアルコキシ基が挙げられ、炭素数３以下のアルキル基が好ましく、メチル基がより好ましい。Ｘｂとしては、水素原子、フッ素原子、メチル基、トリフルオロメチル基、又は、ヒドロキシメチル基が好ましい。 The optionally substituted alkyl group represented by Xb includes, for example, a methyl group and a group represented by —CH 2 —R 11 . R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
　Ｌの２価の連結基としては、－Ｒｔ－基、－ＣＯ－基、－ＣＯＯ－Ｒｔ－基、－ＣＯＯ－Ｒｔ－ＣＯ－基、－Ｒｔ－ＣＯ－基、及び、－Ｏ－Ｒｔ－基が挙げられる。式中、Ｒｔは、アルキレン基、シクロアルキレン基、又は、芳香環基を表し、芳香環基が好ましい。
　Ｌとしては、－Ｒｔ－基、－ＣＯ－基、－ＣＯＯ－Ｒｔ－ＣＯ－基、又は、－Ｒｔ－ＣＯ－基が好ましい。Ｒｔは、ハロゲン原子、水酸基、アルコキシ基等の置換基を有していてもよい。 The divalent linking group of L includes -Rt- group, -CO- group, -COO-Rt- group, -COO-Rt-CO- group, -Rt-CO- group, and -O-Rt- groups. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, preferably an aromatic ring group.
L is preferably -Rt-, -CO-, -COO-Rt-CO- or -Rt-CO-. Rt may have substituents such as halogen atoms, hydroxyl groups, and alkoxy groups.
　Ｒｙ１～Ｒｙ３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、及び、ｔ－ブチル基等の炭素数１～４のアルキル基が好ましい。
　Ｒｙ１～Ｒｙ３のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、又はノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
　Ｒｙ１～Ｒｙ３のアリール基としては、炭素数６～１０のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基が挙げられる。
　Ｒｙ１～Ｒｙ３のアルケニル基としては、ビニル基が好ましい。
　Ｒｙ１～Ｒｙ３のアルキニル基としては、エチニル基が好ましい。
　Ｒｙ１～Ｒｙ３のシクロアルケニル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基の一部に二重結合を含む構造が好ましい。
　Ｒｙ１～Ｒｙ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。なかでも、炭素数５～６の単環のシクロアルキル基がより好ましい。
　Ｒｙ１～Ｒｙ３の２つが結合して形成されるシクロアルキル基、又は、シクロアルケニル基は、例えば、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、カルボニル基、－ＳＯ２－基及び－ＳＯ３－基等のヘテロ原子を含む基、ビニリデン基、又は、それらの組み合わせで置き換わっていてもよい。また、これらのシクロアルキル基又はシクロアルケニル基は、シクロアルカン環又はシクロアルケン環を構成するエチレン基の１つ以上が、ビニレン基で置き換わっていてもよい。
　式（Ｂ）で表される繰り返し単位は、例えば、Ｒｙ１がメチル基、エチル基、ビニル基、アリル基、又は、アリール基であり、Ｒｙ２とＲｙ３とが結合して上述のシクロアルキル基又はシクロアルケニル基を形成している態様が好ましい。 The alkyl groups represented by Ry 1 to Ry 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
Cycloalkyl groups represented by Ry 1 to Ry 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Polycyclic cycloalkyl groups are preferred.
The aryl group represented by Ry 1 to Ry 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
A vinyl group is preferable as the alkenyl group for Ry 1 to Ry 3 .
An ethynyl group is preferred as the alkynyl group for Ry 1 to Ry 3 .
Cycloalkenyl groups represented by Ry 1 to Ry 3 are preferably monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, which partially contain a double bond.
The cycloalkyl group formed by combining two of Ry 1 to Ry 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. Polycyclic cycloalkyl groups such as a nyl group and an adamantyl group are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
A cycloalkyl group formed by combining two of Ry 1 to Ry 3 or a cycloalkenyl group, for example, one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a carbonyl group, or —SO 2 It may be substituted with a group containing a heteroatom such as a - group and a -SO 3 - group, a vinylidene group, or a combination thereof. In these cycloalkyl groups or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group.
In the repeating unit represented by formula (B), for example, Ry 1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry 2 and Ry 3 combine to form the above-mentioned cycloalkyl A preferred embodiment forms a group or a cycloalkenyl group.
　上記各基が置換基を有する場合、置換基としては、例えば、アルキル基（炭素数１～４）、ハロゲン原子、水酸基、アルコキシ基（炭素数１～４）、カルボキシル基、及び、アルコキシカルボニル基（炭素数２～６）が挙げられる。置換基中の炭素数は、８以下が好ましい。 When each of the above groups has a substituent, examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.
　式（Ｂ）で表される繰り返し単位としては、好ましくは、酸分解性（メタ）アクリル酸３級エステル系繰り返し単位（Ｘｂが水素原子又はメチル基を表し、かつ、Ｌが－ＣＯ－基を表す繰り返し単位）、酸分解性ヒドロキシスチレン３級アルキルエーテル系繰り返し単位（Ｘｂが水素原子又はメチル基を表し、かつ、Ｌがフェニル基を表す繰り返し単位）、酸分解性スチレンカルボン酸３級エステル系繰り返し単位（Ｘｂが水素原子又はメチル基を表し、かつ、Ｌが－Ｒｔ－ＣＯ－基（Ｒｔは芳香族基）を表す繰り返し単位）である。 The repeating unit represented by the formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester-based repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a —CO— group. repeating unit represented), acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), acid-decomposable styrene carboxylic acid tertiary ester It is a repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
　不飽和結合を含む酸分解性基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、１５モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上が更に好ましい。また、その上限値としては、樹脂（Ａ）中の全繰り返し単位に対して、８０モル％以下が好ましく、７０モル％以下がより好ましく、６０モル％以下が更に好ましい。 The content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on the total repeating units in the resin (A). is more preferred. Moreover, the upper limit thereof is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less, based on all repeating units in the resin (A).
　不飽和結合を含む酸分解性基を有する繰り返し単位の具体例を以下に示すが、これに限定されない。なお、式中、Ｘｂ及びＬ１は上記記載の置換基、連結基のいずれかを表し、Ａｒは芳香族基を表し、Ｒは、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基、水酸基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ’’’又は－ＣＯＯＲ’’’、Ｒ’’’は炭素数１～２０のアルキル基又はフッ素化アルキル基）、又は、カルボキシル基等の置換基を表し、Ｒ’は直鎖状若しくは分岐鎖状のアルキル基、単環状若しくは多環状のシクロアルキル基、アルケニル基、アルキニル基、又は、単環若しくは多環のアリール基を表し、Ｑは酸素原子等のヘテロ原子、カルボニル基、－ＳＯ２－基及び－ＳＯ３－基等のヘテロ原子を含む基、ビニリデン基、又はそれらの組み合わせを表し、ｎ、ｍ及びｌは０以上の整数を表す。 Specific examples of repeating units having an acid-decomposable group containing an unsaturated bond are shown below, but are not limited thereto. In the formula, Xb and L 1 represent any of the substituents and linking groups described above, Ar represents an aromatic group, and R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group. , an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''', R''' having 1 to 20 carbon atoms an alkyl group or a fluorinated alkyl group), or a substituent such as a carboxyl group; Alternatively, a monocyclic or polycyclic aryl group is represented, and Q is a heteroatom such as an oxygen atom, a carbonyl group, a heteroatom-containing group such as a —SO 2 — group and a —SO 3 — group, a vinylidene group, or any of these represents a combination, and n, m and l represent integers of 0 or more.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　繰り返し単位（ａ）以外の、酸分解性基を有する繰り返し単位の含有量は、繰り返し単位（ａ）を含めた酸分解性基を有する繰り返し単位の含有量として、樹脂（Ａ）中の全繰り返し単位に対して、１５モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上が更に好ましい。また、その上限値としては、樹脂（Ａ）中の全繰り返し単位に対して、９０モル％以下が好ましく、８０モル％以下がより好ましく、７０モル％以下が更に好ましく、６０モル％以下が特に好ましい。 The content of repeating units having an acid-decomposable group other than the repeating unit (a) is the content of repeating units having an acid-decomposable group including the repeating unit (a), which is the total number of repeating units in the resin (A). 15 mol % or more is preferable, 20 mol % or more is more preferable, and 30 mol % or more is still more preferable with respect to the unit. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
　樹脂（Ａ）は、以下のＡ群からなる群から選択される少なくとも１種の繰り返し単位、及び／又は、以下のＢ群からなる群から選択される少なくとも１種の繰り返し単位を含んでいてもよい。
　Ａ群：以下の（２０）～（２５）の繰り返し単位からなる群。
　（２０）後述する、酸基を有する繰り返し単位
　（２１）後述する、酸分解性基及び酸基のいずれも有さず、フッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位
　（２２）後述する、ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位
　（２３）後述する、光酸発生基を有する繰り返し単位
　（２４）後述する、式（Ｖ－１）又は下記式（Ｖ－２）で表される繰り返し単位
　（２５）主鎖の運動性を低下させるための繰り返し単位
　なお、後述する、式（Ａ）～式（Ｅ）で表される繰り返し単位は、（２５）主鎖の運動性を低下させるための繰り返し単位に相当する。
　Ｂ群：以下の（３０）～（３２）の繰り返し単位からなる群。
　（３０）後述する、ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及びアルカリ可溶性基から選ばれる少なくとも１種類の基を有する繰り返し単位
　（３１）後述する、脂環式炭化水素構造を有し、酸分解性を示さない繰り返し単位
　（３２）後述する、水酸基及びシアノ基のいずれも有さない、式（ＩＩＩ）で表される繰り返し単位 The resin (A) may contain at least one repeating unit selected from the group consisting of Group A below and/or at least one repeating unit selected from the group consisting of Group B below. good.
Group A: A group consisting of the following repeating units (20) to (25).
(20) a repeating unit having an acid group, which will be described later; (21) a repeating unit, which has neither an acid-decomposable group nor an acid group, and has a fluorine atom, a bromine atom, or an iodine atom, as described later; a repeating unit having a lactone group, a sultone group, or a carbonate group; (23) a repeating unit having a photoacid-generating group, which will be described later; (25) a repeating unit for reducing the mobility of the main chain The repeating units represented by formulas (A) to (E), which will be described later, are (25) reducing the mobility of the main chain corresponds to a repeating unit for
Group B: A group consisting of the following repeating units (30) to (32).
(30) a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, which will be described later; (31) a repeating unit having an alicyclic hydrocarbon structure, which will be described later; (32) a repeating unit represented by the formula (III) having neither a hydroxyl group nor a cyano group, which will be described later
　樹脂（Ａ）は、酸基を有しているのが好ましく、後述するように、酸基を有する繰り返し単位を含むことが好ましい。なお、酸基の定義については、後段において酸基を有する繰り返し単位の好適態様と共に説明する。樹脂（Ａ）が酸基を有する場合、樹脂（Ａ）と光酸発生剤から発生する酸との相互作用性がより優れる。この結果として、酸の拡散がより一層抑制されて、形成されるパターンの断面形状がより矩形化し得る。 The resin (A) preferably has an acid group, and preferably contains a repeating unit having an acid group, as described later. The definition of the acid group will be explained later along with preferred embodiments of repeating units having an acid group. When the resin (A) has an acid group, the interaction between the resin (A) and the acid generated from the photoacid generator is more excellent. As a result, diffusion of acid is further suppressed, and the cross-sectional shape of the formed pattern can be made more rectangular.
　樹脂（Ａ）は上記Ａ群からなる群から選択される少なくとも１種の繰り返し単位を有してもよい。本発明の組成物がＥＵＶ露光用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂（Ａ）は上記Ａ群からなる群から選択される少なくとも１種の繰り返し単位を有することが好ましい。
　樹脂（Ａ）は、フッ素原子及びヨウ素原子の少なくとも一方を含んでもよい。本発明の組成物がＥＵＶ露光用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂（Ａ）は、フッ素原子及びヨウ素原子の少なくとも一方を含むことが好ましい。樹脂（Ａ）がフッ素原子及びヨウ素原子の両方を含む場合、樹脂（Ａ）は、フッ素原子及びヨウ素原子の両方を含む１つの繰り返し単位を有していてもよいし、樹脂（Ａ）は、フッ素原子を有する繰り返し単位とヨウ素原子を含む繰り返し単位との２種を含んでいてもよい。
　樹脂（Ａ）は、芳香族基を有する繰り返し単位を有してもよい。本発明の組成物がＥＵＶ露光用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂（Ａ）が、芳香族基を有する繰り返し単位を有することも好ましい。
　樹脂（Ａ）は上記Ｂ群からなる群から選択される少なくとも１種の繰り返し単位を有してもよい。本発明の組成物がＡｒＦ用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂（Ａ）は上記Ｂ群からなる群から選択される少なくとも１種の繰り返し単位を有することが好ましい。
　なお、本発明の組成物がＡｒＦ用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂（Ａ）は、フッ素原子及び珪素原子のいずれも含まないことが好ましい。 The resin (A) may have at least one type of repeating unit selected from the group consisting of the A group. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) has at least one repeating unit selected from the group consisting of Group A above. is preferred.
Resin (A) may contain at least one of a fluorine atom and an iodine atom. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) It may contain two types of a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
Resin (A) may have a repeating unit having an aromatic group. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferred that the resin (A) has a repeating unit having an aromatic group.
The resin (A) may have at least one type of repeating unit selected from the group consisting of Group B above. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) may have at least one repeating unit selected from the group consisting of Group B above. preferable.
When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably contains neither fluorine atoms nor silicon atoms.
（酸基を有する繰り返し単位）
　樹脂（Ａ）は、酸基を有する繰り返し単位を含むことが好ましい。
　酸基としては、ｐＫａが１３以下の酸基が好ましい。上記酸基の酸解離定数は、１３以下が好ましく、３～１３がより好ましく、５～１０が更に好ましい。
　樹脂（Ａ）が、ｐＫａが１３以下の酸基を有する場合、樹脂（Ａ）中における酸基の含有量は特に制限されないが、０．２～６．０ｍｍｏｌ／ｇの場合が多い。なかでも、０．８～６．０ｍｍｏｌ／ｇが好ましく、１．２～５．０ｍｍｏｌ／ｇがより好ましく、１．６～４．０ｍｍｏｌ／ｇが更に好ましい。酸基の含有量が上記範囲内であれば、現像が良好に進行し、形成されるパターン形状に優れ、解像性にも優れる。
　酸基としては、例えば、カルボキシル基、フェノール性水酸基、フッ化アルコール基（好ましくはヘキサフルオロイソプロパノール基）、スルホン酸基、スルホンアミド基、又はイソプロパノール基が好ましい。
　上記ヘキサフルオロイソプロパノール基は、フッ素原子の１つ以上（好ましくは１～２つ）が、フッ素原子以外の基（アルコキシカルボニル基等）で置換されてもよい。
酸基としては、このように形成された－Ｃ（ＣＦ３）（ＯＨ）－ＣＦ２－も好ましい。また、フッ素原子の１つ以上がフッ素原子以外の基に置換されて、－Ｃ（ＣＦ３）（ＯＨ）－ＣＦ２－を含む環を形成してもよい。
　酸基を有する繰り返し単位は、上述の酸の作用により脱離する基で極性基が保護された構造を有する繰り返し単位、及び後述するラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位とは異なる繰り返し単位であることが好ましい。
　酸基を有する繰り返し単位は、フッ素原子又はヨウ素原子を有していてもよい。 (Repeating unit having an acid group)
Resin (A) preferably contains a repeating unit having an acid group.
As the acid group, an acid group having a pKa of 13 or less is preferable. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
When the resin (A) has an acid group with a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable. If the content of the acid group is within the above range, the development proceeds satisfactorily, the formed pattern shape is excellent, and the resolution is also excellent.
The acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
In the hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group).
Also preferred as the acid group is -C(CF 3 )(OH)-CF 2 - thus formed. Also, one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
The repeating unit having an acid group is different from the repeating unit having a structure in which the polar group is protected by a group that leaves under the action of an acid, and the repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. It is preferably a repeating unit.
A repeating unit having an acid group may have a fluorine atom or an iodine atom.
　酸基としては、フェノール性水酸基が特に好ましい。
　樹脂（Ａ）は、前述の繰り返し単位（ａ）に加えて、更に、フェノール性水酸基を有する繰り返し単位を有することが好ましい。 As the acid group, a phenolic hydroxyl group is particularly preferred.
The resin (A) preferably has a repeating unit having a phenolic hydroxyl group in addition to the repeating unit (a) described above.
　酸基を有する繰り返し単位としては、下記一般式（Ｂ）で表される繰り返し単位が好ましい。 As the repeating unit having an acid group, a repeating unit represented by the following general formula (B) is preferable.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　Ｒ３は、水素原子、又は、１価の有機基を表す。
　１価の有機基としては、－Ｌ４－Ｒ８で表される基が好ましい。Ｌ４は、単結合、又は、エステル基を表す。Ｒ８は、アルキル基、シクロアルキル基、アリール基、又は、これらを組み合わせた基が挙げられる。 R3 represents a hydrogen atom or a monovalent organic group.
As the monovalent organic group, a group represented by -L 4 -R 8 is preferable. L4 represents a single bond or an ester group. R8 includes an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.
　Ｒ４及びＲ５は、各々独立に、水素原子、ハロゲン原子、又は、アルキル基を表す。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、又は、ヨウ素原子が挙げられる。 R4 and R5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group.
A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
　Ｌ２は、単結合、又は、エステル結合を表す。
　Ｌ３は、（ｎ＋ｍ＋１）価の芳香族炭化水素環基、又は、（ｎ＋ｍ＋１）価の脂環式炭化水素環基を表す。芳香族炭化水素環基としては、ベンゼン環基、及び、ナフタレン環基が挙げられる。脂環式炭化水素環基としては、単環であっても、多環であってもよく、例えば、シクロアルキル環基が挙げられる。
　Ｒ６は、水酸基、又は、フッ素化アルコール基（好ましくは、ヘキサフルオロイソプロパノール基）を表す。なお、Ｒ６が水酸基の場合、Ｌ３は（ｎ＋ｍ＋１）価の芳香族炭化水素環基であることが好ましい。
　Ｒ７は、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、又は、ヨウ素原子が挙げられる。
　ｍは、１以上の整数を表す。ｍは、１～３の整数が好ましく、１～２の整数が好ましい。
　ｎは、０又は１以上の整数を表す。ｎは、１～４の整数が好ましい。
　なお、（ｎ＋ｍ＋１）は、１～５の整数が好ましい。 L2 represents a single bond or an ester bond.
L 3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Aromatic hydrocarbon ring groups include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.
R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R 6 is a hydroxyl group, L 3 is preferably an (n+m+1)-valent aromatic hydrocarbon ring group.
R7 represents a halogen atom. A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
m represents an integer of 1 or more. m is preferably an integer of 1-3, more preferably an integer of 1-2.
n represents an integer of 0 or 1 or more. n is preferably an integer of 1-4.
(n+m+1) is preferably an integer of 1-5.
　酸基を有する繰り返し単位としては、下記一般式（ｃ）で表される繰り返し単位（繰り返し単位（ｃ））も好ましい。
　樹脂（Ａ）が、下記一般式（ｃ）で表される繰り返し単位（ｃ）をさらに含むことが好ましい。 As the repeating unit having an acid group, a repeating unit represented by the following general formula (c) (repeating unit (c)) is also preferable.
It is preferable that the resin (A) further contains a repeating unit (c) represented by the following general formula (c).
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　一般式（ｃ）中、Ｒ６１～Ｒ６３はそれぞれ独立して、水素原子、有機基又はハロゲン原子を表す。ただし、Ｒ６２はＡｒと結合して環を形成していてもよく、その場合のＲ６２は単結合またはアルキレン基を表す。Ｌは単結合、又は２価の連結基を表す。Ａｒは（ｋ＋１）価の芳香環基を表し、Ｒ６２と結合して環を形成する場合には（ｋ＋２）価の芳香環基を表す。ｋは、１～５の整数を表す。 In general formula (c), R 61 to R 63 each independently represent a hydrogen atom, an organic group or a halogen atom. However, R 62 may combine with Ar to form a ring, in which case R 62 represents a single bond or an alkylene group. L represents a single bond or a divalent linking group. Ar represents a (k+1)-valent aromatic ring group, and when combined with R 62 to form a ring, represents a (k+2)-valent aromatic ring group. k represents an integer of 1 to 5;
　一般式（ｃ）中、Ｒ６１～Ｒ６３はそれぞれ独立して、水素原子、有機基又はハロゲン原子を表す。
　Ｒ６１～Ｒ６３はが表す有機基としては、例えば、アルキル基、シクロアルキル基、シアノ基又はアルコキシカルボニル基を表す。 In general formula (c), R 61 to R 63 each independently represent a hydrogen atom, an organic group or a halogen atom.
The organic group represented by R 61 to R 63 is, for example, an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group.
　Ｒ６１～Ｒ６３が表すアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、及び、ドデシル基等の炭素数２０以下のアルキル基が好ましく、炭素数８以下のアルキル基がより好ましく、炭素数３以下のアルキル基が更に好ましい。 Examples of alkyl groups represented by R 61 to R 63 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. is preferably an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, and still more preferably an alkyl group having 3 or less carbon atoms.
　Ｒ６１～Ｒ６３が表すシクロアルキル基としては、単環型でも、多環型でもよい。なかでも、シクロプロピル基、シクロペンチル基、及び、シクロヘキシル基等の炭素数３～８個で単環型のシクロアルキル基が好ましい。
　Ｒ６１～Ｒ６３が表すアルコキシカルボニル基に含まれるアルキル基としては、上記Ｒ６１～Ｒ６３におけるアルキル基と同様のものが好ましい。 The cycloalkyl groups represented by R 61 to R 63 may be monocyclic or polycyclic. Among them, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group are preferable.
The alkyl group contained in the alkoxycarbonyl group represented by R 61 to R 63 is preferably the same as the alkyl group for R 61 to R 63 above.
　Ｒ６２はＡｒと結合して環を形成する場合の、Ｒ６２のアルキレン基としては、上記Ｒ６１～Ｒ６３におけるアルキル基から任意の水素原子を１つ除した基が好ましい。 When R 62 combines with Ar to form a ring, the alkylene group for R 62 is preferably a group obtained by removing one arbitrary hydrogen atom from the alkyl group for R 61 to R 63 above.
　Ｒ６１～Ｒ６３が表すハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子が挙げられ、フッ素原子が好ましい。 Halogen atoms represented by R 61 to R 63 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
　上記各基における好ましい置換基としては、例えば、アルキル基、シクロアルキル基、アリール基、アミノ基、アミド基、ウレイド基、ウレタン基、水酸基、カルボキシル基、ハロゲン原子、アルコキシ基、チオエーテル基、アシル基、アシロキシ基、アルコキシカルボニル基、シアノ基、及び、ニトロ基が挙げられる。置換基の炭素数は８以下が好ましい。 Preferable substituents for the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. , an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms in the substituent is preferably 8 or less.
　一般式（ｃ）中、Ａｒは、（ｋ＋１）価の芳香環基を表す。ｋが１である場合における２価の芳香環基は、置換基を有していてもよく、例えば、フェニレン基、トリレン基、ナフチレン基、及び、アントラセニレン基等の炭素数６～１８のアリーレン基、又は、チオフェン環、フラン環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環、及び、チアゾール環等のヘテロ環を含む芳香環基が好ましい。 In general formula (c), Ar represents a (k+1)-valent aromatic ring group. The divalent aromatic ring group when k is 1 may have a substituent, for example, a phenylene group, a tolylene group, a naphthylene group, and an arylene group having 6 to 18 carbon atoms such as an anthracenylene group. or an aromatic containing a hetero ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring A cyclic group is preferred.
　ｋが２以上の整数である場合における（ｋ＋１）価の芳香環基の具体例としては、２価の芳香環基の上記した具体例から、（ｋ－１）個の任意の水素原子を除してなる基が挙げられる。
　（ｋ＋１）価の芳香環基は、更に置換基を有していてもよい。 Specific examples of the (k+1)-valent aromatic ring group when k is an integer of 2 or more include the above specific examples of the divalent aromatic ring group, with (k-1) any hydrogen atoms removed. A group formed by
The (k+1)-valent aromatic ring group may further have a substituent.
　（ｋ＋１）価の芳香環基が有し得る置換基としては、例えば、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、アルケニル基、アラルキル基、アルコキシ基、アルキルカルボニルオキシ基、アルキルスルホニルオキシ基、アルキルオキシカルボニル基又はアリールオキシカルボニル基等が挙げられる。 Examples of substituents that the (k+1)-valent aromatic ring group may have include halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, alkenyl groups, aralkyl groups, alkoxy groups, alkylcarbonyloxy groups, and alkylsulfonyloxy groups. , an alkyloxycarbonyl group or an aryloxycarbonyl group.
　Ａｒとしては、炭素数６～１８の芳香環基が好ましく、ベンゼン環基、ナフタレン環基、及び、ビフェニレン環基がより好ましい。
　一般式（ｃ）で表される繰り返し単位は、ヒドロキシスチレン構造を備えていることが好ましい。即ち、Ａｒは、ベンゼン環基であることが好ましく、フェニレン基（２価のベンゼン環基）であることがより好ましい。 Ar is preferably an aromatic ring group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group.
The repeating unit represented by general formula (c) preferably has a hydroxystyrene structure. That is, Ar is preferably a benzene ring group, more preferably a phenylene group (a divalent benzene ring group).
　一般式（ｃ）中、Ｌは単結合、又は２価の連結基を表す。
　Ｌが表す２価の連結基としては、＊－Ｘ４－Ｌ４－＊＊が挙げられる。
　上記式中、Ｘ４は、単結合、－ＣＯＯ－、又は－ＣＯＮＲ６４－を表し、Ｒ６４は、水素原子又はアルキル基を表す。
　Ｌ４は、単結合又はアルキレン基を表す。
　＊は一般式（ｃ）中の主鎖の炭素原子との結合手、＊＊はＡｒとの結合手である。 In general formula (c), L represents a single bond or a divalent linking group.
The divalent linking group represented by L includes *-X 4 -L 4 -**.
In the above formula, X 4 represents a single bond, -COO- or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group.
L4 represents a single bond or an alkylene group.
* is a bond with a carbon atom of the main chain in general formula (c), and ** is a bond with Ar.
　Ｘ４により表される－ＣＯＮＲ６４－（Ｒ６４は、水素原子又はアルキル基を表す）におけるＲ６４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、及び、ドデシル基等の炭素数２０以下のアルキル基が挙げられ、炭素数８以下のアルキル基が好ましい。
　Ｘ４としては、単結合、－ＣＯＯ－、又は、－ＣＯＮＨ－が好ましく、単結合、又は、－ＣＯＯ－がより好ましい。 The alkyl group for R 64 in —CONR 64 — (R 64 represents a hydrogen atom or an alkyl group) represented by X 4 includes methyl, ethyl, propyl, isopropyl, n-butyl, sec -Butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and other alkyl groups having 20 or less carbon atoms, preferably alkyl groups having 8 or less carbon atoms.
X 4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.
　Ｌ４におけるアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、及び、オクチレン基等の炭素数１～８のアルキレン基が好ましい。 The alkylene group for L4 is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group.
　Ｌは単結合、－ＣＯＯ－、又は－ＣＯＮＨ－であることが好ましく、単結合であることがより好ましい。 L is preferably a single bond, -COO- or -CONH-, more preferably a single bond.
　一般式（ｃ）中、ｋは、１～５の整数を表す。
　ｋは、１～３の整数であることが好ましく、１又は２がより好ましく、１がさらに好ましい。 In general formula (c), k represents an integer of 1-5.
k is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
　以下、酸基を有する繰り返し単位を以下に例示する。式中、ａは１～３の整数を表す。 Examples of repeating units having an acid group are shown below. In the formula, a represents an integer of 1-3.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　なお、上記繰り返し単位のなかでも、以下に具体的に記載する繰り返し単位が好ましい。式中、Ｒは水素原子又はメチル基を表し、ａは１～３の整数を表す。 Among the above repeating units, repeating units specifically described below are preferable. In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer of 1-3.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　酸基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、１０モル％以上が好ましく、１５モル％以上がより好ましい。また、その上限値としては、樹脂（Ａ）中の全繰り返し単位に対して、７０モル％以下が好ましく、６５モル％以下がより好ましく、６０モル％以下が更に好ましい。 The content of repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 70 mol % or less, more preferably 65 mol % or less, and still more preferably 60 mol % or less, based on all repeating units in the resin (A).
（酸分解性基及び酸基のいずれも有さず、フッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位）
　樹脂（Ａ）は、上述した＜酸分解性基を有する繰り返し単位＞及び＜酸基を有する繰り返し単位＞とは別に、酸分解性基及び酸基のいずれも有さず、フッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位（以下、単位Ｘともいう。）を有していてもよい。ここで言う＜酸分解性基及び酸基のいずれも有さず、フッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位＞は、後述の＜ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位＞、及び＜光酸発生基を有する繰り返し単位＞等の、Ａ群に属する他の種類の繰り返し単位とは異なることが好ましい。 (Repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom)
The resin (A) has neither an acid-decomposable group nor an acid group, apart from the above-described <repeating unit having an acid-decomposable group> and <repeating unit having an acid group>, and contains a fluorine atom and a bromine atom. Alternatively, it may have a repeating unit having an iodine atom (hereinafter also referred to as unit X). The <repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is a <repeating unit having a lactone group, a sultone group, or a carbonate group> described later. , and <repeating unit having photoacid-generating group>.
　単位Ｘとしては、式（Ｃ）で表される繰り返し単位が好ましい。 As the unit X, a repeating unit represented by formula (C) is preferable.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　Ｌ５は、単結合、又はエステル基を表す。Ｒ９は、水素原子、又はフッ素原子若しくはヨウ素原子を有していてもよいアルキル基を表す。Ｒ１０は、水素原子、フッ素原子若しくはヨウ素原子を有していてもよいアルキル基、フッ素原子若しくはヨウ素原子を有していてもよいシクロアルキル基、フッ素原子若しくはヨウ素原子を有していてもよいアリール基、又はこれらを組み合わせた基を表す。 L5 represents a single bond or an ester group. R9 represents a hydrogen atom or an alkyl group optionally having a fluorine atom or an iodine atom. R 10 may have a hydrogen atom, an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, a fluorine atom or an iodine atom represents an aryl group or a group combining these;
　フッ素原子又はヨウ素原子を有する繰り返し単位を以下に例示する。 Examples of repeating units having a fluorine atom or an iodine atom are shown below.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　単位Ｘの含有量は、樹脂（Ａ）中の全繰り返し単位に対して、０モル％以上が好ましく、５モル％以上がより好ましく、１０モル％以上が更に好ましい。また、その上限値としては、樹脂（Ａ）中の全繰り返し単位に対して、５０モル％以下が好ましく、４５モル％以下がより好ましく、４０モル％以下が更に好ましい。 The content of the unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 50 mol % or less, more preferably 45 mol % or less, and still more preferably 40 mol % or less, relative to all repeating units in the resin (A).
　樹脂（Ａ）の繰り返し単位のうち、フッ素原子、臭素原子及びヨウ素原子の少なくとも１つを含む繰り返し単位の合計含有量は、樹脂（Ａ）の全繰り返し単位に対して、１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上が更に好ましく、４０モル％以上が特に好ましい。上限値は特に制限されないが、例えば、樹脂（Ａ）の全繰り返し単位に対して、１００モル％以下である。
　なお、フッ素原子、臭素原子及びヨウ素原子の少なくとも１つを含む繰り返し単位としては、例えば、フッ素原子、臭素原子又はヨウ素原子を有し、かつ、酸分解性基を有する繰り返し単位、フッ素原子、臭素原子又はヨウ素原子を有し、かつ、酸基を有する繰り返し単位、及びフッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位が挙げられる。 Among the repeating units of the resin (A), the total content of repeating units containing at least one of a fluorine atom, a bromine atom and an iodine atom is preferably 10 mol% or more with respect to all repeating units of the resin (A). , more preferably 20 mol % or more, still more preferably 30 mol % or more, and particularly preferably 40 mol % or more. Although the upper limit is not particularly limited, it is, for example, 100 mol % or less with respect to all repeating units of the resin (A).
The repeating unit containing at least one of a fluorine atom, a bromine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid-decomposable group, a fluorine atom, a bromine repeating units having an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.
（ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位）
　樹脂（Ａ）は、ラクトン基、スルトン基、及びカーボネート基からなる群から選択される少なくとも１種を有する繰り返し単位（以下、「単位Ｙ」ともいう。）を有していてもよい。
　単位Ｙは、水酸基、及びヘキサフルオロプロパノール基等の酸基を有さないことも好ましい。 (Repeating unit having a lactone group, a sultone group, or a carbonate group)
Resin (A) may have a repeating unit (hereinafter also referred to as “unit Y”) having at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group.
It is also preferable that the unit Y does not have a hydroxyl group and an acid group such as a hexafluoropropanol group.
　ラクトン基又はスルトン基としては、ラクトン構造又はスルトン構造を有していればよい。ラクトン構造又はスルトン構造は、５～７員環ラクトン構造又は５～７員環スルトン構造が好ましい。なかでも、ビシクロ構造若しくはスピロ構造を形成する形で５～７員環ラクトン構造に他の環構造が縮環しているもの、又はビシクロ構造若しくはスピロ構造を形成する形で５～７員環スルトン構造に他の環構造が縮環しているものがより好ましい。
　樹脂（Ａ）は、下記式（ＬＣ１－１）～（ＬＣ１－２１）のいずれかで表されるラクトン構造、又は下記式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造の環員原子から、水素原子を１つ以上引き抜いてなるラクトン基又はスルトン基を有する繰り返し単位を有することが好ましく、ラクトン基又はスルトン基が主鎖に直接結合していてもよい。例えば、ラクトン基又はスルトン基の環員原子が、樹脂（Ａ）の主鎖を構成してもよい。 The lactone group or sultone group may have a lactone structure or sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among them, a 5- to 7-membered ring lactone structure in which a bicyclo structure or spiro structure is formed and another ring structure is condensed with another ring structure, or a 5- to 7-membered ring sultone in a form to form a bicyclo structure or spiro structure. More preferably, the structure is condensed with another ring structure.
The resin (A) has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or any one of the following formulas (SL1-1) to (SL1-3). It preferably has a repeating unit having a lactone group or a sultone group obtained by removing one or more hydrogen atoms from a ring member atom of a sultone structure, and the lactone group or sultone group may be directly bonded to the main chain. For example, ring member atoms of a lactone group or a sultone group may constitute the main chain of resin (A).
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　上記ラクトン構造又はスルトン構造は、置換基（Ｒｂ２）を有していてもよい。好ましい置換基（Ｒｂ２）としては、炭素数１～８のアルキル基、炭素数４～７のシクロアルキル基、炭素数１～８のアルコキシ基、炭素数１～８のアルコキシカルボニル基、カルボキシル基、ハロゲン原子、シアノ基、及び酸分解性基が挙げられる。ｎ２は、０～４の整数を表す。ｎ２が２以上の時、複数存在するＲｂ２は、異なっていてもよく、複数存在するＲｂ２同士が結合して環を形成してもよい。 The lactone structure or sultone structure may have a substituent (Rb 2 ). Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, and carboxyl groups. , halogen atoms, cyano groups, and acid-labile groups. n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb 2 may be different, and multiple Rb 2 may combine to form a ring.
　式（ＬＣ１－１）～（ＬＣ１－２１）のいずれかで表されるラクトン構造、又は式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造を含む基を有する繰り返し単位としては、例えば、下記式（ＡＩ）で表される繰り返し単位が挙げられる。 Repeat having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) Examples of units include repeating units represented by the following formula (AI).
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
　式（ＡＩ）中、Ｒｂ０は、水素原子、ハロゲン原子、又は炭素数１～４のアルキル基を表す。Ｒｂ０のアルキル基が有していてもよい好ましい置換基としては、水酸基、及びハロゲン原子が挙げられる。
　Ｒｂ０のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。Ｒｂ０は、水素原子又はメチル基が好ましい。
　Ａｂは、単結合、アルキレン基、単環又は多環の脂環式炭化水素構造を有する２価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又はこれらを組み合わせた２価の連結基を表す。なかでも、Ａｂとしては、単結合、又は－Ａｂ１－ＣＯ２－で表される連結基が好ましい。Ａｂ１は、直鎖状若しくは分岐鎖状のアルキレン基、又は単環若しくは多環のシクロアルキレン基であり、メチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、又はノルボルニレン基が好ましい。
　Ｖは、式（ＬＣ１－１）～（ＬＣ１－２１）のいずれかで表されるラクトン構造の環員原子から水素原子を１つ引き抜いてなる基、又は式（ＳＬ１－１）～（ＳＬ１－３）のいずれかで表されるスルトン構造の環員原子から水素原子を１つ引き抜いてなる基を表す。 In formula (AI), Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
A halogen atom for Rb 0 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group.
Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these divalent linkages represents a group. Among them, Ab is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -. Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group or norbornylene group.
V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or formulas (SL1-1) to (SL1- 3) represents a group obtained by removing one hydrogen atom from a ring member atom of the sultone structure represented by any one of 3).
　ラクトン基又はスルトン基を有する繰り返し単位に、光学異性体が存在する場合、いずれの光学異性体を用いてもよい。また、１種の光学異性体を単独で用いても、複数の光学異性体を混合して用いてもよい。１種の光学異性体を主に用いる場合、その光学純度（ｅｅ）は９０以上が好ましく、９５以上がより好ましい。 When an optical isomer exists in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Moreover, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
　カーボネート基としては、環状炭酸エステル基が好ましい。
　環状炭酸エステル基を有する繰り返し単位としては、下記式（Ａ－１）で表される繰り返し単位が好ましい。 As the carbonate group, a cyclic carbonate group is preferred.
As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following formula (A-1) is preferable.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　式（Ａ－１）中、ＲＡ １は、水素原子、ハロゲン原子、又は１価の有機基（好ましくはメチル基）を表す。ｎは０以上の整数を表す。ＲＡ ２は、置換基を表す。ｎが２以上の場合、複数存在するＲＡ ２は、それぞれ同一でも異なっていてもよい。Ａは、単結合又は２価の連結基を表す。上記２価の連結基としては、アルキレン基、単環又は多環の脂環式炭化水素構造を有する２価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又はこれらを組み合わせた２価の連結基が好ましい。Ｚは、式中の－Ｏ－ＣＯ－Ｏ－で表される基と共に単環又は多環を形成する原子団を表す。 In formula (A-1), R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or more. R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these. A valent linking group is preferred. Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.
　単位Ｙを以下に例示する。式中、Ｒｘは、水素原子、－ＣＨ３、－ＣＨ２ＯＨまたは－ＣＦ３を表す。 The unit Y is exemplified below. In the formula, Rx represents a hydrogen atom, -CH 3 , -CH 2 OH or -CF 3 .
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　単位Ｙの含有量は、樹脂（Ａ）中の全繰り返し単位に対して、１モル％以上が好ましく、１０モル％以上がより好ましい。また、その上限値としては、樹脂（Ａ）中の全繰り返し単位に対して、８５モル％以下が好ましく、８０モル％以下がより好ましく、７０モル％以下が更に好ましく、６０モル％以下が特に好ましい。 The content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in the resin (A). The upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
（光酸発生基を有する繰り返し単位）
　樹脂（Ａ）は、上記以外の繰り返し単位として、活性光線又は放射線の照射により酸を発生する基（以下、「光酸発生基」ともいう）を有する繰り返し単位を有していてもよい。
　光酸発生基を有する繰り返し単位としては、式（４）で表される繰り返し単位が挙げられる。 (Repeating unit having a photoacid-generating group)
The resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as a "photoacid-generating group").
Repeating units having a photoacid-generating group include repeating units represented by formula (4).
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　Ｒ４１は、水素原子又はメチル基を表す。Ｌ４１は、単結合、又は２価の連結基を表す。Ｌ４２は、２価の連結基を表す。Ｒ４０は、活性光線又は放射線の照射により分解して側鎖に酸を発生させる構造部位を表す。
　光酸発生基を有する繰り返し単位を以下に例示する。 R41 represents a hydrogen atom or a methyl group. L41 represents a single bond or a divalent linking group. L42 represents a divalent linking group. R40 represents a structural site that is decomposed by exposure to actinic rays or radiation to generate an acid in the side chain.
Examples of repeating units having a photoacid-generating group are shown below.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　そのほか、式（４）で表される繰り返し単位としては、例えば、特開２０１４－０４１３２７号公報の段落［００９４］～［０１０５］に記載された繰り返し単位、及び国際公開第２０１８／１９３９５４号公報の段落［００９４］に記載された繰り返し単位が挙げられる。 In addition, the repeating unit represented by formula (4) includes, for example, repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327, and International Publication No. 2018/193954. Examples include repeating units described in paragraph [0094].
　光酸発生基を有する繰り返し単位の含有量は、樹脂（Ａ）中の全繰り返し単位に対して、１モル％以上が好ましく、５モル％以上がより好ましい。また、その上限値としては、樹脂（Ａ）中の全繰り返し単位に対して、４０モル％以下が好ましく、３５モル％以下がより好ましく、３０モル％以下が更に好ましい。 The content of the repeating unit having a photoacid-generating group is preferably 1 mol % or more, more preferably 5 mol % or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 40 mol % or less, more preferably 35 mol % or less, and still more preferably 30 mol % or less, based on all repeating units in the resin (A).
（式（Ｖ－１）又は下記式（Ｖ－２）で表される繰り返し単位）
　樹脂（Ａ）は、下記式（Ｖ－１）、又は下記式（Ｖ－２）で表される繰り返し単位を有していてもよい。
　下記式（Ｖ－１）、及び下記式（Ｖ－２）で表される繰り返し単位は上述の繰り返し単位とは異なる繰り返し単位であることが好ましい。 (Repeating unit represented by formula (V-1) or formula (V-2) below)
Resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
Repeating units represented by the following formulas (V-1) and (V-2) below are preferably different repeating units from the repeating units described above.
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　式中、
　Ｒ６及びＲ７は、それぞれ独立に、水素原子、水酸基、アルキル基、アルコキシ基、アシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基（－ＯＣＯＲ又は－ＣＯＯＲ：Ｒは炭素数１～６のアルキル基又はフッ素化アルキル基）、又はカルボキシル基を表す。アルキル基としては、炭素数１～１０の直鎖状、分岐鎖状又は環状のアルキル基が好ましい。
　ｎ３は、０～６の整数を表す。
　ｎ４は、０～４の整数を表す。
　Ｘ４は、メチレン基、酸素原子、又は硫黄原子である。
　式（Ｖ－１）又は（Ｖ－２）で表される繰り返し単位を以下に例示する。
　式（Ｖ－１）又は（Ｖ－２）で表される繰り返し単位としては、例えば、国際公開第２０１８／１９３９５４号の段落［０１００］に記載された繰り返し単位が挙げられる。 During the ceremony,
R 6 and R 7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is the number of carbon atoms; 1 to 6 alkyl groups or fluorinated alkyl groups), or a carboxyl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
n3 represents an integer of 0-6.
n4 represents an integer of 0-4.
X4 is a methylene group, an oxygen atom, or a sulfur atom.
The repeating units represented by formula (V-1) or (V-2) are exemplified below.
Examples of the repeating unit represented by formula (V-1) or (V-2) include repeating units described in paragraph [0100] of WO 2018/193954.
（主鎖の運動性を低下させるための繰り返し単位）
　樹脂（Ａ）は、発生酸の過剰な拡散又は現像時のパターン崩壊を抑制できる点から、ガラス転移温度（Ｔｇ）が高い方が好ましい。Ｔｇは、９０℃より大きいことが好ましく、１００℃より大きいことがより好ましく、１１０℃より大きいことが更に好ましく、１２５℃より大きいことが特に好ましい。なお、現像液への溶解速度が優れる点から、Ｔｇは４００℃以下が好ましく、３５０℃以下がより好ましい。
　なお、本明細書において、樹脂（Ａ）等のポリマーのガラス転移温度（Ｔｇ）（以下「繰り返し単位のＴｇ」）は、以下の方法で算出する。まず、ポリマー中に含まれる各繰り返し単位のみからなるホモポリマーのＴｇを、Ｂｉｃｅｒａｎｏ法によりそれぞれ算出する。次に、ポリマー中の全繰り返し単位に対する、各繰り返し単位の質量割合（％）を算出する。次に、Ｆｏｘの式（Ｍａｔｅｒｉａｌｓ　Ｌｅｔｔｅｒｓ　６２（２００８）３１５２等に記載）を用いて各質量割合におけるＴｇを算出して、それらを総和して、ポリマーのＴｇ（℃）とする。
　Ｂｉｃｅｒａｎｏ法は、Ｐｒｅｄｉｃｔｉｏｎ　ｏｆ　ｐｏｌｙｍｅｒ　ｐｒｏｐｅｒｔｉｅｓ，　Ｍａｒｃｅｌ　Ｄｅｋｋｅｒ　Ｉｎｃ，　Ｎｅｗ　Ｙｏｒｋ（１９９３）に記載されている。Ｂｉｃｅｒａｎｏ法によるＴｇの算出は、ポリマーの物性概算ソフトウェアＭＤＬ　Ｐｏｌｙｍｅｒ（ＭＤＬ　Ｉｎｆｏｒｍａｔｉｏｎ　Ｓｙｓｔｅｍｓ，　Ｉｎｃ．）を用いて行うことができる。 (Repeating unit for reducing the mobility of the main chain)
The resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development. Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. The Tg is preferably 400° C. or less, more preferably 350° C. or less, from the viewpoint of excellent dissolution rate in the developer.
In the present specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter "Tg of repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated. Next, the Fox formula (described in Materials Letters 62 (2008) 3152, etc.) is used to calculate the Tg at each mass ratio, and these are totaled to obtain the Tg (°C) of the polymer.
The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). Calculation of Tg by the Bicerano method can be performed using a polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
　樹脂（Ａ）のＴｇを大きくする（好ましくは、Ｔｇを９０℃超とする）には、樹脂（Ａ）の主鎖の運動性を低下させることが好ましい。樹脂（Ａ）の主鎖の運動性を低下させる方法は、以下の（ａ）～（ｅ）の方法が挙げられる。
（ａ）主鎖への嵩高い置換基の導入
（ｂ）主鎖への複数の置換基の導入
（ｃ）主鎖近傍への樹脂（Ａ）間の相互作用を誘発する置換基の導入
（ｄ）環状構造での主鎖形成
（ｅ）主鎖への環状構造の連結
　なお、樹脂（Ａ）は、ホモポリマーのＴｇが１３０℃以上を示す繰り返し単位を有することが好ましい。
　なお、ホモポリマーのＴｇが１３０℃以上を示す繰り返し単位の種類は特に制限されず、Ｂｉｃｅｒａｎｏ法により算出されるホモポリマーのＴｇが１３０℃以上である繰り返し単位であればよい。なお、後述する式（Ａ）～式（Ｅ）で表される繰り返し単位中の官能基の種類によっては、ホモポリマーのＴｇが１３０℃以上を示す繰り返し単位に該当する。 In order to increase the Tg of the resin (A) (preferably to make the Tg higher than 90°C), it is preferable to reduce the mobility of the main chain of the resin (A). Methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e).
(a) introduction of bulky substituents into the main chain (b) introduction of multiple substituents into the main chain (c) introduction of substituents that induce interaction between the resin (A) into the vicinity of the main chain ( d) Main Chain Formation in Cyclic Structure (e) Linking of Cyclic Structure to Main Chain The resin (A) preferably has a repeating unit exhibiting a homopolymer Tg of 130° C. or higher.
The type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited as long as it is a repeating unit having a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method. Depending on the type of functional group in the repeating units represented by the formulas (A) to (E) described below, the homopolymers correspond to repeating units exhibiting a homopolymer Tg of 130° C. or higher.
　上記（ａ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ａ）で表される繰り返し単位を導入する方法が挙げられる。 A specific example of means for achieving the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (A).
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　式（Ａ）、ＲＡは、多環構造を含む基を表す。Ｒｘは、水素原子、メチル基、又はエチル基を表す。多環構造を含む基とは、複数の環構造を含む基であり、複数の環構造は縮合していても、縮合していなくてもよい。
　式（Ａ）で表される繰り返し単位の具体例としては、国際公開第２０１８/１９３９５４号の段落［０１０７］～［０１１９］に記載のものが挙げられる。 Formula (A), RA represents a group containing a polycyclic structure. R x represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, and the multiple ring structures may or may not be condensed.
Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO2018/193954.
　上記（ｂ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｂ）で表される繰り返し単位を導入する方法が挙げられる。 A specific example of means for achieving the above (b) is a method of introducing a repeating unit represented by the formula (B) into the resin (A).
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　式（Ｂ）中、Ｒｂ１～Ｒｂ４は、それぞれ独立に、水素原子又は有機基を表し、Ｒｂ１～Ｒｂ４のうち少なくとも２つ以上が有機基を表す。
　有機基の少なくとも１つが、繰り返し単位中の主鎖に直接環構造が連結している基である場合、他の有機基の種類は特に制限されない。
　また、有機基のいずれも繰り返し単位中の主鎖に直接環構造が連結している基ではない場合、有機基の少なくとも２つ以上は、水素原子を除く構成原子の数が３つ以上である置換基である。
　式（Ｂ）で表される繰り返し単位の具体例としては、国際公開第２０１８/１９３９５４号の段落［０１１３］～［０１１５］に記載のものが挙げられる。 In formula (B), R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
When at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the type of other organic group is not particularly limited.
Further, when none of the organic groups is a group in which the ring structure is directly linked to the main chain in the repeating unit, at least two of the organic groups have three or more constituent atoms excluding hydrogen atoms. is a substituent.
Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO2018/193954.
　上記（ｃ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｃ）で表される繰り返し単位を導入する方法が挙げられる。 A specific example of means for achieving the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (A).
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　式（Ｃ）中、Ｒｃ１～Ｒｃ４は、それぞれ独立に、水素原子又は有機基を表し、Ｒｃ１～Ｒｃ４のうち少なくとも１つが、主鎖炭素から原子数３以内に水素結合性の水素原子を含む基である。なかでも、樹脂（Ａ）の主鎖間の相互作用を誘発するうえで、原子数２以内（より主鎖近傍側）に水素結合性の水素原子を有することが好ましい。
　式（Ｃ）で表される繰り返し単位の具体例としては、国際公開第２０１８／１９３９５４号の段落［０１１９］～［０１２１］に記載のものが挙げられる。 In formula (C), R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is hydrogen bonding hydrogen within 3 atoms from the main chain carbon It is a group containing atoms. Above all, it is preferable to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain side) in order to induce interaction between the main chains of the resin (A).
Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO2018/193954.
　上記（ｄ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｄ）で表される繰り返し単位を導入する方法が挙げられる。 A specific example of means for achieving (d) above is a method of introducing a repeating unit represented by the formula (D) into the resin (A).
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　式（Ｄ）中、「Ｃｙｃｌｉｃ」は、環状構造で主鎖を形成している基を表す。環の構成原子数は特に制限されない。
　式（Ｄ）で表される繰り返し単位の具体例としては、国際公開第２０１８/１９３９５４号の段落［０１２６］～［０１２７］に記載のものが挙げられる。 In formula (D), "Cyclic" represents a group forming a main chain with a cyclic structure. The number of constituent atoms of the ring is not particularly limited.
Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO2018/193954.
　上記（ｅ）の具体的な達成手段の一例としては、樹脂（Ａ）に式（Ｅ）で表される繰り返し単位を導入する方法が挙げられる。 A specific example of means for achieving (e) above is a method of introducing a repeating unit represented by formula (E) into the resin (A).
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　式（Ｅ）中、Ｒｅは、それぞれ独立に、水素原子又は有機基を表す。有機基としては、例えば、置換基を有してもよい、アルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基が挙げられる。
　「Ｃｙｃｌｉｃ」は、主鎖の炭素原子を含む環状基である。環状基に含まれる原子数は特に制限されない。
　式（Ｅ）で表される繰り返し単位の具体例としては、国際公開第２０１８／１９３９５４号の段落［０１３１］～［０１３３］に記載のものが挙げられる。 In formula (E), each Re independently represents a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents.
A "Cyclic" is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited.
Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO2018/193954.
（ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及びアルカリ可溶性基から選ばれる少なくとも１種類の基を有する繰り返し単位）
　樹脂（Ａ）は、ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及びアルカリ可溶性基から選ばれる少なくとも１種類の基を有する繰り返し単位を有していてもよい。
　樹脂（Ａ）が有するラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位としては、上述した＜ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位＞で説明した繰り返し単位が挙げられる。好ましい含有量も上述した＜ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位＞で説明した通りである。 (Repeating unit having at least one group selected from lactone group, sultone group, carbonate group, hydroxyl group, cyano group, and alkali-soluble group)
The resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups.
Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group that the resin (A) has include the repeating units described in the above <Repeating unit having a lactone group, sultone group, or carbonate group>. The preferable content is also as described in <Repeating unit having lactone group, sultone group, or carbonate group>.
　樹脂（Ａ）は、水酸基又はシアノ基を有する繰り返し単位を有していてもよい。これにより基板密着性、現像液親和性が向上する。
　水酸基又はシアノ基を有する繰り返し単位は、水酸基又はシアノ基で置換された脂環式炭化水素構造を有する繰り返し単位であることが好ましい。
　水酸基又はシアノ基を有する繰り返し単位は、酸分解性基を有さないことが好ましい。水酸基又はシアノ基を有する繰り返し単位としては、特開２０１４－０９８９２１号公報の段落［００８１］～［００８４］に記載のものが挙げられる。 Resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the adhesion to the substrate and the compatibility with the developer.
A repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
A repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A-2014-098921.
　樹脂（Ａ）は、アルカリ可溶性基を有する繰り返し単位を有していてもよい。
　アルカリ可溶性基としては、カルボキシル基、スルホンアミド基、スルホニルイミド基、ビススルホニルイミド基、及びα位が電子求引性基で置換された脂肪族アルコール基（例えば、ヘキサフルオロイソプロパノール基）が挙げられ、カルボキシル基が好ましい。樹脂（Ａ）がアルカリ可溶性基を有する繰り返し単位を含むことにより、コンタクトホール用途での解像性が増す。アルカリ可溶性基を有する繰り返し単位としては、特開２０１４－０９８９２１号公報の段落［００８５］及び［００８６］に記載のものが挙げられる。 Resin (A) may have a repeating unit having an alkali-soluble group.
The alkali-soluble group includes a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the α-position (e.g., hexafluoroisopropanol group). , is preferably a carboxyl group. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact holes is increased. Repeating units having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.
（脂環式炭化水素構造を有し、酸分解性を示さない繰り返し単位）
　樹脂（Ａ）は、脂環式炭化水素構造を有し、酸分解性を示さない繰り返し単位を有してもよい。これにより液浸露光時にレジスト膜から液浸液への低分子成分の溶出が低減できる。脂環式炭化水素構造を有し、酸分解性を示さない繰り返し単位として、例えば、１－アダマンチル（メタ）アクリレート、ジアマンチル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、又はシクロヘキシル（メタ）アクリレート由来の繰り返し単位が挙げられる。 (Repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid-decomposability)
Resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include, for example, 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth) Examples include repeating units derived from acrylates.
（水酸基及びシアノ基のいずれも有さない、式（ＩＩＩ）で表される繰り返し単位）
　樹脂（Ａ）は、水酸基及びシアノ基のいずれも有さない、式（ＩＩＩ）で表される繰り返し単位を有していてもよい。 (Repeating unit represented by formula (III) having neither hydroxyl group nor cyano group)
Resin (A) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　式（ＩＩＩ）中、Ｒ５は少なくとも１つの環状構造を有し、水酸基及びシアノ基のいずれも有さない炭化水素基を表す。
　Ｒａは水素原子、アルキル基又は－ＣＨ２－Ｏ－Ｒａ２基を表す。式中、Ｒａ２は、水素原子、アルキル基又はアシル基を表す。
　水酸基及びシアノ基のいずれも有さない、式（ＩＩＩ）で表される繰り返し単位としては、特開２０１４－０９８９２１号公報の段落［００８７］～［００９４］に記載のものが挙げられる。 In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group or a --CH 2 --O--Ra 2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group or an acyl group.
Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A-2014-098921.
（その他の繰り返し単位）
　更に、樹脂（Ａ）は、上述した繰り返し単位以外のその他の繰り返し単位を有してもよい。
　例えば樹脂（Ａ）は、オキサチアン環基を有する繰り返し単位、オキサゾロン環基を有する繰り返し単位、ジオキサン環基を有する繰り返し単位、及びヒダントイン環基を有する繰り返し単位からなる群から選択される繰り返し単位を有していてもよい。
　上述した繰り返し単位以外のその他の繰り返し単位の具体例を以下に例示する。 (Other repeating units)
Furthermore, the resin (A) may have repeating units other than the repeating units described above.
For example, the resin (A) has repeating units selected from the group consisting of repeating units having an oxathian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. You may have
Specific examples of repeating units other than the repeating units described above are shown below.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　樹脂（Ａ）は、上記の繰り返し構造単位以外に、ドライエッチング耐性、標準現像液適性、基板密着性、レジストプロファイル、解像性、耐熱性、及び感度等を調節する目的で様々な繰り返し構造単位を有していてもよい。 In addition to the repeating structural units described above, the resin (A) may contain various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. may have
　樹脂（Ａ）としては、特に、本発明の組成物がＡｒＦ用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、繰り返し単位の全てが、エチレン性不飽和結合を有する化合物に由来する繰り返し単位で構成されることが好ましい。特に、繰り返し単位の全てが（メタ）アクリレート系繰り返し単位で構成されることも好ましい。繰り返し単位の全てが（メタ）アクリレート系繰り返し単位で構成される場合、繰り返し単位の全てがメタクリレート系繰り返し単位であるもの、繰り返し単位の全てがアクリレート系繰り返し単位であるもの、繰り返し単位の全てがメタクリレート系繰り返し単位とアクリレート系繰り返し単位とによるもののいずれのものでも用いることができ、アクリレート系繰り返し単位が全繰り返し単位の５０モル％以下であることが好ましい。 As the resin (A), especially when the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, all repeating units are derived from a compound having an ethylenically unsaturated bond. It is preferably composed of repeating units. In particular, it is also preferred that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, and all of the repeating units are methacrylates. It is possible to use either one based on repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units be 50 mol % or less of the total repeating units.
　樹脂（Ａ）は、常法に従って（例えばラジカル重合）合成できる。
　ＧＰＣ法によりポリスチレン換算値として、樹脂（Ａ）の重量平均分子量は、３０，０００以下が好ましく、１，０００～３０，０００がより好ましく、３，０００～３０，０００が更に好ましく、５，０００～１５，０００が特に好ましい。
　樹脂（Ａ）の分散度（分子量分布）は、１～５が好ましく、１～３がより好ましく、１．２～３．０が更に好ましく、１．２～２．０が特に好ましい。分散度が小さいものほど、解像度、及びレジスト形状がより優れ、更に、レジストパターンの側壁がよりスムーズであり、ラフネス性にもより優れる。 Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
The weight average molecular weight of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, still more preferably 3,000 to 30,000, further preferably 5,000 as a polystyrene equivalent value by GPC method. ~15,000 is particularly preferred.
The dispersity (molecular weight distribution) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, still more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
　本発明の組成物において、樹脂（Ａ）の含有量は、組成物の全固形分に対して、４０．０～９９．９質量％が好ましく、６０．０～９０．０質量％がより好ましい。
　樹脂（Ａ）は、１種で使用してもよいし、複数併用してもよい。 In the composition of the present invention, the content of the resin (A) is preferably 40.0 to 99.9% by mass, more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition. .
The resin (A) may be used singly or in combination.
＜光酸発生剤（Ｂ）＞
　本発明の組成物は、活性光線又は放射線の照射により酸を発生する化合物（以下、光酸発生剤、光酸発生剤（Ｂ）ともいう）を含むことが好ましい。
　光酸発生剤（Ｂ）は、低分子化合物の形態であってもよく、重合体（例えば、上述の樹脂（Ａ））の一部に組み込まれた形態であってもよい。また、低分子化合物の形態と重合体（例えば、上述の樹脂（Ａ））の一部に組み込まれた形態とを併用してもよい。
　光酸発生剤（Ｂ）が、低分子化合物の形態である場合、光酸発生剤の分子量は３０００以下が好ましく、２０００以下がより好ましく、１０００以下が更に好ましい。下限は特に制限されないが、１００以上が好ましい。
　光酸発生剤（Ｂ）が、重合体の一部に組み込まれた形態である場合、樹脂（Ａ）の一部に組み込まれてもよく、樹脂（Ａ）とは異なる樹脂に組み込まれてもよい。
　本明細書において、光酸発生剤（Ｂ）は、低分子化合物の形態であることが好ましい。 <Photoacid generator (B)>
The composition of the present invention preferably contains a compound that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as a photoacid generator or photoacid generator (B)).
The photoacid generator (B) may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer (for example, resin (A) described above). Moreover, the form of a low-molecular-weight compound and the form of being incorporated into a part of a polymer (for example, the resin (A) described above) may be used in combination.
When the photoacid generator (B) is in the form of a low-molecular-weight compound, the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. Although the lower limit is not particularly limited, 100 or more is preferable.
When the photoacid generator (B) is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). good.
In this specification, the photoacid generator (B) is preferably in the form of a low molecular weight compound.
　光酸発生剤（Ｂ）としては、例えば、「Ｍ＋　Ｘ－」で表される化合物（オニウム塩）が挙げられ、露光により有機酸を発生する化合物であることが好ましい。
　上記有機酸として、例えば、スルホン酸（脂肪族スルホン酸、芳香族スルホン酸、及びカンファースルホン酸等）、カルボン酸（脂肪族カルボン酸、芳香族カルボン酸、及びアラルキルカルボン酸等）、カルボニルスルホニルイミド酸、ビス（アルキルスルホニル）イミド酸、及びトリス（アルキルスルホニル）メチド酸が挙げられる。 Examples of the photoacid generator (B) include compounds (onium salts) represented by “M + X − ”, and compounds that generate an organic acid upon exposure are preferred.
Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), carbonylsulfonylimide, acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.
　「Ｍ＋　Ｘ－」で表される化合物において、Ｍ＋は、有機カチオンを表す。
　有機カチオンとしては特に制限されない。有機カチオンの価数は、１又は２価以上であってもよい。
　上記有機カチオンとしては、スルホニウムカチオン又は、ヨードニウムカチオンが好ましい。
　なかでも、上記有機カチオンとしては、式（ＺａＩ）で表されるカチオン（以下「カチオン（ＺａＩ）」ともいう。）、又は、式（ＺａＩＩ）で表されるカチオン（以下「カチオン（ＺａＩＩ）」ともいう。）が好ましい。 In the compound represented by "M + X - ", M + represents an organic cation.
There are no particular restrictions on the organic cation. The valence of the organic cation may be 1 or 2 or more.
As the organic cation, a sulfonium cation or an iodonium cation is preferable.
Among them, as the organic cation, a cation represented by the formula (ZaI) (hereinafter also referred to as "cation (ZaI)"), or a cation represented by the formula (ZaII) (hereinafter referred to as "cation (ZaII)" Also called.) is preferable.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　上記式（ＺａＩ）において、Ｒ２０１、Ｒ２０２、及びＲ２０３は、それぞれ独立に、有機基を表す。
　Ｒ２０１、Ｒ２０２、及びＲ２０３としての有機基の炭素数は、１～３０が好ましく、１～２０がより好ましい。Ｒ２０１～Ｒ２０３のうち２つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル基、アミド基、又はカルボニル基を含んでいてもよい。Ｒ２０１～Ｒ２０３の内の２つが結合して形成する基としては、例えば、アルキレン基（例えば、ブチレン基及びペンチレン基）、及び－ＣＨ２－ＣＨ２－Ｏ－ＣＨ２－ＣＨ２－が挙げられる。 In formula (ZaI) above, R 201 , R 202 and R 203 each independently represent an organic group.
The number of carbon atoms in the organic groups for R 201 , R 202 and R 203 is preferably 1-30, more preferably 1-20. Two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, a butylene group and a pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. mentioned.
　式（ＺａＩ）における有機カチオンの好適な態様としては、後述する、カチオン（ＺａＩ－１）、カチオン（ＺａＩ－２）、カチオン（ＺａＩ－３ｂ）、カチオン（ＺａＩ－４ｂ）が挙げられる。 Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.
　まず、カチオン（ＺａＩ－１）について説明する。
　カチオン（ＺａＩ－１）は、上記式（ＺａＩ）のＲ２０１～Ｒ２０３の少なくとも１つがアリール基である、アリールスルホニウムカチオンである。
　アリールスルホニウムカチオンは、Ｒ２０１～Ｒ２０３の全てがアリール基でもよいし、Ｒ２０１～Ｒ２０３の一部がアリール基であり、残りがアルキル基又はシクロアルキル基であってもよい。
　Ｒ２０１～Ｒ２０３のうちの１つがアリール基であり、Ｒ２０１～Ｒ２０３のうちの残りの２つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル基、アミド基、又はカルボニル基を含んでいてもよい。Ｒ２０１～Ｒ２０３のうちの２つが結合して形成する基としては、例えば、１つ以上のメチレン基が酸素原子、硫黄原子、エステル基、アミド基、及び／又はカルボニル基で置換されていてもよいアルキレン基（例えば、ブチレン基、ペンチレン基、及び－ＣＨ２－ＣＨ２－Ｏ－ＣＨ２－ＣＨ２－）が挙げられる。
　アリールスルホニウムカチオンとしては、トリアリールスルホニウムカチオン、ジアリールアルキルスルホニウムカチオン、アリールジアルキルスルホニウムカチオン、ジアリールシクロアルキルスルホニウムカチオン、及びアリールジシクロアルキルスルホニウムカチオンが挙げられる。 First, the cation (ZaI-1) will be described.
Cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in formula (ZaI) above is an aryl group.
In the arylsulfonium cation, all of R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
One of R 201 to R 203 is an aryl group, and the remaining two of R 201 to R 203 may combine to form a ring structure, in which an oxygen atom, a sulfur atom and an ester group , an amide group, or a carbonyl group. The group formed by bonding two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, and —CH 2 —CH 2 —O—CH 2 —CH 2 —).
Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
　アリールスルホニウムカチオンに含まれるアリール基としては、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。アリール基は、酸素原子、窒素原子、又は硫黄原子等を有するヘテロ環構造を有するアリール基であってもよい。ヘテロ環構造としては、ピロール残基、フラン残基、チオフェン残基、インドール残基、ベンゾフラン残基、及びベンゾチオフェン残基が挙げられる。アリールスルホニウムカチオンが２つ以上のアリール基を有する場合に、２つ以上あるアリール基は同一であっても異なっていてもよい。
　アリールスルホニウムカチオンが必要に応じて有しているアルキル基又はシクロアルキル基は、炭素数１～１５の直鎖状アルキル基、炭素数３～１５の分岐鎖状アルキル基、又は炭素数３～１５のシクロアルキル基が好ましく、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、シクロプロピル基、シクロブチル基、又はシクロヘキシル基がより好ましい。 The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group or cyclohexyl group is more preferred.
　Ｒ２０１～Ｒ２０３のアリール基、アルキル基、及びシクロアルキル基が有していてもよい置換基としては、アルキル基（例えば、炭素数１～１５）、シクロアルキル基（例えば、炭素数３～１５）、アリール基（例えば、炭素数６～１４）、アルコキシ基（例えば、炭素数１～１５）、シクロアルキルアルコキシ基（例えば、炭素数１～１５）、ハロゲン原子（例えば、フッ素及びヨウ素）、水酸基、カルボキシル基、エステル基、スルフィニル基、スルホニル基、アルキルチオ基、又はフェニルチオ基が好ましい。
　上記置換基は可能な場合更に置換基を有していてもよく、上記アルキル基が置換基としてハロゲン原子を有して、トリフルオロメチル基等のハロゲン化アルキル基となっていることも好ましい。
　上記置換基は任意の組み合わせにより、酸分解性基を形成することも好ましい。
　なお、酸分解性基とは、酸の作用により分解して極性基を生じる基を意図し、酸の作用により脱離する基で極性基が保護された構造であることが好ましい。上記の極性基及び脱離基としては、上述の通りである。 Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 3 carbon atoms). 15), aryl groups (eg, 6 to 14 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), cycloalkylalkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms (eg, fluorine and iodine) , hydroxyl group, carboxyl group, ester group, sulfinyl group, sulfonyl group, alkylthio group or phenylthio group.
If possible, the substituent may further have a substituent, and the alkyl group preferably has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
It is also preferable to form an acid-decomposable group by any combination of the above substituents.
The acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that is eliminated by the action of an acid. The polar group and leaving group are as described above.
　次に、カチオン（ＺａＩ－２）について説明する。
　カチオン（ＺａＩ－２）は、式（ＺａＩ）におけるＲ２０１～Ｒ２０３が、それぞれ独立に、芳香環を有さない有機基を表すカチオンである。芳香環とは、ヘテロ原子を含む芳香族環も包含する。
　Ｒ２０１～Ｒ２０３としての芳香環を有さない有機基の炭素数は、１～３０が好ましく、１～２０がより好ましい。
　Ｒ２０１～Ｒ２０３としては、それぞれ独立に、アルキル基、シクロアルキル基、アリル基、又はビニル基が好ましく、直鎖状又は分岐鎖状の２－オキソアルキル基、２－オキソシクロアルキル基、又はアルコキシカルボニルメチル基がより好ましく、直鎖状又は分岐鎖状の２－オキソアルキル基が更に好ましい。 Next, the cation (ZaI-2) will be explained.
Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring. Aromatic rings also include aromatic rings containing heteroatoms.
The number of carbon atoms in the organic group having no aromatic ring as R 201 to R 203 is preferably 1-30, more preferably 1-20.
R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or An alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
　Ｒ２０１～Ｒ２０３のアルキル基及びシクロアルキル基は、例えば、炭素数１～１０の直鎖状アルキル基又は炭素数３～１０の分岐鎖状アルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基、及びペンチル基）、並びに、炭素数３～１０のシクロアルキル基（例えば、シクロペンチル基、シクロヘキシル基、及びノルボルニル基）が挙げられる。
　Ｒ２０１～Ｒ２０３は、ハロゲン原子、アルコキシ基（例えば、炭素数１～５）、水酸基、シアノ基、又はニトロ基によって更に置換されていてもよい。
　Ｒ２０１～Ｒ２０３の置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。 The alkyl groups and cycloalkyl groups of R 201 to R 203 are, for example, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, , butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group by any combination of substituents.
　次に、カチオン（ＺａＩ－３ｂ）について説明する。
　カチオン（ＺａＩ－３ｂ）は、下記式（ＺａＩ－３ｂ）で表されるカチオンである。 Next, the cation (ZaI-3b) will be explained.
The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
　式（ＺａＩ－３ｂ）中、Ｒ１ｃ～Ｒ５ｃは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アルキルカルボニルオキシ基、シクロアルキルカルボニルオキシ基、ハロゲン原子、水酸基、ニトロ基、アルキルチオ基、又はアリールチオ基を表す。
　Ｒ６ｃ及びＲ７ｃは、それぞれ独立に、水素原子、アルキル基（例えば、ｔ－ブチル基等）、シクロアルキル基、ハロゲン原子、シアノ基、又はアリール基を表す。
　Ｒｘ及びＲｙは、それぞれ独立に、アルキル基、シクロアルキル基、２－オキソアルキル基、２－オキソシクロアルキル基、アルコキシカルボニルアルキル基、アリル基、又はビニル基を表す。
　Ｒ１ｃ～Ｒ７ｃ、並びに、Ｒｘ及びＲｙの置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。 In formula (ZaI-3b), R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkyl represents a carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group;
R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
It is also preferred that the substituents of R 1c to R 7c , R x and R y independently form an acid-decomposable group by any combination of substituents.
　Ｒ１ｃ～Ｒ５ｃ中のいずれか２つ以上、Ｒ５ｃとＲ６ｃ、Ｒ６ｃとＲ７ｃ、Ｒ５ｃとＲｘ、及びＲｘとＲｙは、それぞれ互いに結合して環を形成してもよく、この環は、それぞれ独立に、酸素原子、硫黄原子、ケトン基、エステル結合、又はアミド結合を含んでいてもよい。
　上記環としては、芳香族又は非芳香族の炭化水素環、芳香族又は非芳香族のヘテロ環、及びこれらの環が２つ以上組み合わされてなる多環縮合環が挙げられる。環としては、３～１０員環が挙げられ、４～８員環が好ましく、５又は６員環がより好ましい。 Any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may combine with each other to form a ring. The rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.
　Ｒ１ｃ～Ｒ５ｃ中のいずれか２つ以上、Ｒ６ｃとＲ７ｃ、及びＲｘとＲｙが結合して形成する基としては、ブチレン基及びペンチレン基等のアルキレン基が挙げられる。このアルキレン基中のメチレン基が酸素原子等のヘテロ原子で置換されていてもよい。
　Ｒ５ｃとＲ６ｃ、及びＲ５ｃとＲｘが結合して形成する基としては、単結合又はアルキレン基が好ましい。アルキレン基としては、メチレン基及びエチレン基が挙げられる。 Examples of groups formed by bonding two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
The group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group. Alkylene groups include methylene and ethylene groups.
　Ｒ１ｃ～Ｒ５ｃ、Ｒ６ｃ、Ｒ７ｃ、Ｒｘ、Ｒｙ、並びに、Ｒ１ｃ～Ｒ５ｃ中のいずれか２つ以上、Ｒ５ｃとＲ６ｃ、Ｒ６ｃとＲ７ｃ、Ｒ５ｃとＲｘ、及びＲｘとＲｙがそれぞれ互いに結合して形成する環は、置換基を有していてもよい。 R 1c to R 5c , R 6c , R 7c , R x , R y , and two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by combining each other with R x and R y may have a substituent.
　次に、カチオン（ＺａＩ－４ｂ）について説明する。
　カチオン（ＺａＩ－４ｂ）は、下記式（ＺａＩ－４ｂ）で表されるカチオンである。 Next, the cation (ZaI-4b) will be explained.
The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　式（ＺａＩ－４ｂ）中、ｌは０～２の整数を表し、ｒは０～８の整数を表す。
　Ｒ１３は、水素原子、ハロゲン原子(例えば、フッ素原子及びヨウ素原子等)、水酸基、アルキル基、ハロゲン化アルキル基、アルコキシ基、カルボキシル基、アルコキシカルボニル基、又はシクロアルキル基を含む基（シクロアルキル基そのものであってもよく、シクロアルキル基を一部に含む基であってもよい）を表す。これらの基は置換基を有してもよい。
　Ｒ１４は、水酸基、ハロゲン原子(例えば、フッ素原子及びヨウ素原子等)、アルキル基、ハロゲン化アルキル基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、又はシクロアルキル基を含む基（シクロアルキル基そのものであってもよく、シクロアルキル基を一部に含む基であってもよい）を表す。これらの基は置換基を有してもよい。Ｒ１４は、複数存在する場合は、それぞれ独立して、水酸基等の上記基を表す。
　Ｒ１５は、それぞれ独立して、アルキル基、シクロアルキル基、又はナフチル基を表す。２つのＲ１５が互いに結合して環を形成してもよい。２つのＲ１５が互いに結合して環を形成するとき、環骨格内に、酸素原子、又は窒素原子等のヘテロ原子を含んでもよい。
　一態様において、２つのＲ１５がアルキレン基であり、互いに結合して環構造を形成することが好ましい。なお、上記アルキル基、上記シクロアルキル基、及び上記ナフチル基、並びに、２つのＲ１５が互いに結合して形成する環は置換基を有してもよい。 In formula (ZaI-4b), l represents an integer of 0-2 and r represents an integer of 0-8.
R 13 is a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (cycloalkyl may be the group itself, or may be a group partially containing a cycloalkyl group). These groups may have a substituent.
R 14 is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl represents a group containing a group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When two or more R 14 are present, each independently represents the above group such as a hydroxyl group.
Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be joined together to form a ring. When two R 15 are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
In one aspect, two R 15 are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R 15 groups may have a substituent.
　式（ＺａＩ－４ｂ）において、Ｒ１３、Ｒ１４、及びＲ１５のアルキル基は、直鎖状又は分岐鎖状であってもよい。アルキル基の炭素数は、１～１０が好ましい。アルキル基は、メチル基、エチル基、ｎ－ブチル基、又はｔ－ブチル基等が好ましい。
　Ｒ１３～Ｒ１５、並びに、Ｒｘ及びＲｙの各置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。 In formula (ZaI-4b), the alkyl groups of R 13 , R 14 and R 15 may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.
It is also preferred that each of the substituents of R 13 to R 15 , R x and R y independently forms an acid-decomposable group by any combination of substituents.
　次に、式（ＺａＩＩ）について説明する。
　式（ＺａＩＩ）中、Ｒ２０４及びＲ２０５は、それぞれ独立に、アリール基、アルキル基又はシクロアルキル基を表す。
　Ｒ２０４及びＲ２０５のアリール基としては、フェニル基、又はナフチル基が好ましく、フェニル基がより好ましい。Ｒ２０４及びＲ２０５のアリール基は、酸素原子、窒素原子、又は硫黄原子等を有するヘテロ環を有するアリール基であってもよい。ヘテロ環を有するアリール基の骨格としては、例えば、ピロール、フラン、チオフェン、インドール、ベンゾフラン、及びベンゾチオフェンが挙げられる。
　Ｒ２０４及びＲ２０５のアルキル基及びシクロアルキル基としては、炭素数１～１０の直鎖状アルキル基又は炭素数３～１０の分岐鎖状アルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基、又はペンチル基）、又は炭素数３～１０のシクロアルキル基（例えばシクロペンチル基、シクロヘキシル基、又はノルボルニル基）が好ましい。 Next, formula (ZaII) will be described.
In formula (ZaII), R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group for R 204 and R 205 may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group for R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
　Ｒ２０４及びＲ２０５のアリール基、アルキル基、及びシクロアルキル基は、それぞれ独立に、置換基を有していてもよい。Ｒ２０４及びＲ２０５のアリール基、アルキル基、及びシクロアルキル基が有していてもよい置換基としては、例えば、アルキル基（例えば、炭素数１～１５）、シクロアルキル基（例えば、炭素数３～１５）、アリール基（例えば、炭素数６～１５）、アルコキシ基（例えば、炭素数１～１５）、ハロゲン原子、水酸基、及びフェニルチオ基が挙げられる。また、Ｒ２０４及びＲ２０５の置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。 The aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may each independently have a substituent. Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. It is also preferred that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of substituents.
　以下に有機カチオンの具体例を示すが、本発明は、これに限定されない。 Specific examples of organic cations are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　「Ｍ＋　Ｘ－」で表される化合物において、Ｘ－は、有機アニオンを表す。
　有機アニオンとしては、特に制限されず、１又は２価以上の有機アニオンが挙げられる。
　有機アニオンとしては、求核反応を起こす能力が著しく低いアニオンが好ましく、非求核性アニオンがより好ましい。 In the compound represented by “M + X − ”, X − represents an organic anion.
The organic anion is not particularly limited, and includes organic anions having a valence of 1, 2 or more.
As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.
　非求核性アニオンとしては、例えば、スルホン酸アニオン（脂肪族スルホン酸アニオン、芳香族スルホン酸アニオン、及びカンファースルホン酸アニオン等）、カルボン酸アニオン（脂肪族カルボン酸アニオン、芳香族カルボン酸アニオン、及びアラルキルカルボン酸アニオン等）、スルホニルイミドアニオン、ビス（アルキルスルホニル）イミドアニオン、及びトリス（アルキルスルホニル）メチドアニオンが挙げられる。 Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
　脂肪族スルホン酸アニオン及び脂肪族カルボン酸アニオンにおける脂肪族部位は、直鎖状又は分岐鎖状のアルキル基であっても、シクロアルキル基であってもよく、炭素数１～３０の直鎖状又は分岐鎖状のアルキル基、又は、炭素数３～３０のシクロアルキル基が好ましい。
　上記アルキル基は、例えば、フルオロアルキル基（フッ素原子以外の置換基を有していてもよい。パーフルオロアルキル基であってもよい）であってもよい。 The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and may be a straight chain having 1 to 30 carbon atoms. Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferred.
The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
　芳香族スルホン酸アニオン及び芳香族カルボン酸アニオンにおけるアリール基としては、炭素数６～１４のアリール基が好ましく、例えば、フェニル基、トリル基、及び、ナフチル基が挙げられる。 The aryl group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
　上記で挙げたアルキル基、シクロアルキル基、及び、アリール基は、置換基を有していてもよい。置換基としては特に制限されないが、例えば、ニトロ基、フッ素原子及び塩素原子等のハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基（炭素数１～１５が好ましい）、アルキル基（炭素数１～１０が好ましい）、シクロアルキル基（炭素数３～１５が好ましい）、アリール基（炭素数６～１４が好ましい）、アルコキシカルボニル基（炭素数２～７が好ましい）、アシル基（炭素数２～１２が好ましい）、アルコキシカルボニルオキシ基（炭素数２～７が好ましい）、アルキルチオ基（炭素数１～１５が好ましい）、アルキルスルホニル基（炭素数１～１５が好ましい）、アルキルイミノスルホニル基（炭素数１～１５が好ましい）、及び、アリールオキシスルホニル基（炭素数６～２０が好ましい）が挙げられる。 The alkyl group, cycloalkyl group, and aryl group listed above may have a substituent. The substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups ( preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group ( preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkylimino A sulfonyl group (preferably having 1 to 15 carbon atoms) and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms) can be mentioned.
　アラルキルカルボン酸アニオンにおけるアラルキル基としては、炭素数７～１４のアラルキル基が好ましい。
　炭素数７～１４のアラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ナフチルエチル基、及び、ナフチルブチル基が挙げられる。 As the aralkyl group in the aralkylcarboxylate anion, an aralkyl group having 7 to 14 carbon atoms is preferred.
Aralkyl groups having 7 to 14 carbon atoms include, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl groups.
　スルホニルイミドアニオンとしては、例えば、サッカリンアニオンが挙げられる。 　Sulfonylimide anions include, for example, saccharin anions.
　ビス（アルキルスルホニル）イミドアニオン、及び、トリス（アルキルスルホニル）メチドアニオンにおけるアルキル基としては、炭素数１～５のアルキル基が好ましい。これらのアルキル基の置換基としては、ハロゲン原子、ハロゲン原子で置換されたアルキル基、アルコキシ基、アルキルチオ基、アルキルオキシスルホニル基、アリールオキシスルホニル基、及び、シクロアルキルアリールオキシスルホニル基が挙げられ、フッ素原子又はフッ素原子で置換されたアルキル基が好ましい。
　また、ビス（アルキルスルホニル）イミドアニオンにおけるアルキル基は、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。 As the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of substituents of these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may combine with each other to form a ring structure. This increases the acid strength.
　その他の非求核性アニオンとしては、例えば、フッ素化燐（例えば、ＰＦ６ －）、フッ素化ホウ素（例えば、ＢＦ４ －）、及び、フッ素化アンチモン（例えば、ＳｂＦ６ －）が挙げられる。 Other non-nucleophilic anions include, for example, phosphorous fluorides (eg, PF 6 − ), boron fluorides (eg, BF 4 − ), and antimony fluorides (eg, SbF 6 − ).
　非求核性アニオンとしては、スルホン酸の少なくともα位がフッ素原子で置換された脂肪族スルホン酸アニオン、フッ素原子若しくはフッ素原子を有する基で置換された芳香族スルホン酸アニオン、アルキル基がフッ素原子で置換されたビス（アルキルスルホニル）イミドアニオン、又は、アルキル基がフッ素原子で置換されたトリス（アルキルスルホニル）メチドアニオンが好ましい。なかでも、パーフルオロ脂肪族スルホン酸アニオン（炭素数４～８が好ましい）、又は、フッ素原子を有するベンゼンスルホン酸アニオンがより好ましく、ノナフルオロブタンスルホン酸アニオン、パーフルオロオクタンスルホン酸アニオン、ペンタフルオロベンゼンスルホン酸アニオン、又は、３，５－ビス（トリフルオロメチル）ベンゼンスルホン酸アニオンが更に好ましい。 Examples of non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of sulfonic acid is substituted with fluorine atoms, aromatic sulfonate anions in which fluorine atoms or groups having fluorine atoms are substituted, and alkyl groups in which fluorine atoms are present. A bis(alkylsulfonyl)imide anion substituted with or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferred. Among them, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) or benzenesulfonate anions having a fluorine atom are more preferable, nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluoro A benzenesulfonate anion or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is more preferred.
　非求核性アニオンとしては、下記式（ＡＮ１）で表されるアニオンも好ましい。 As the non-nucleophilic anion, an anion represented by the following formula (AN1) is also preferable.
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
　式（ＡＮ１）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、又は置換基を表す。
　置換基は特に制限されないが、電子求引性基ではない基が好ましい。電子求引性基ではない基としては、例えば、炭化水素基、水酸基、オキシ炭化水素基、オキシカルボニル炭化水素基、アミノ基、炭化水素置換アミノ基、及び、炭化水素置換アミド基が挙げられる。
　電子求引性基ではない基としては、それぞれ独立に、－Ｒ’、－ＯＨ、－ＯＲ’、－ＯＣＯＲ’、－ＮＨ２、－ＮＲ’２、－ＮＨＲ’、又は、－ＮＨＣＯＲ’が好ましい。Ｒ’は、１価の炭化水素基である。 In formula (AN1), R 1 and R 2 each independently represent a hydrogen atom or a substituent.
The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.
Groups that are not electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR' or -NHCOR' each independently. . R' is a monovalent hydrocarbon group.
　上記Ｒ’で表される１価の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、及びブチル基等のアルキル基；エテニル基、プロペニル基、及びブテニル基等のアルケニル基；エチニル基、プロピニル基、及びブチニル基等のアルキニル基等の１価の直鎖状又は分岐鎖状の炭化水素基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、及びアダマンチル基等のシクロアルキル基；シクロプロペニル基、シクロブテニル基、シクロペンテニル基、及びノルボルネニル基等のシクロアルケニル基等の１価の脂環炭化水素基；フェニル基、トリル基、キシリル基、メシチル基、ナフチル基、メチルナフチル基、アントリル基、及びメチルアントリル基等のアリール基；ベンジル基、フェネチル基、フェニルプロピル基、ナフチルメチル基、及びアントリルメチル基等のアラルキル基等の１価の芳香族炭化水素基が挙げられる。
　なかでも、Ｒ１及びＲ２は、それぞれ独立に、炭化水素基（シクロアルキル基が好ましい）又は水素原子が好ましい。 Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; ethynyl monovalent linear or branched hydrocarbon groups such as alkynyl groups such as groups, propynyl groups, and butynyl groups; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups Cycloalkyl group; monovalent alicyclic hydrocarbon group such as cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl aryl groups such as naphthyl group, anthryl group and methylanthryl group; monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and anthrylmethyl group; mentioned.
Among them, R 1 and R 2 are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.
　Ｌは、２価の連結基を表す。
　Ｌが複数存在する場合、Ｌは、それぞれ同一でも異なっていてもよい。
　２価の連結基としては、例えば、－Ｏ－ＣＯ－Ｏ－、－ＣＯＯ－、－ＣＯＮＨ－、－ＣＯ－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、アルキレン基（炭素数１～６が好ましい）、シクロアルキレン基（炭素数３～１５が好ましい）、アルケニレン基（炭素数２～６が好ましい）、及び、これらの複数を組み合わせた２価の連結基が挙げられる。なかでも、２価の連結基としては、－Ｏ－ＣＯ－Ｏ－、－ＣＯＯ－、－ＣＯＮＨ－、－ＣＯ－、－Ｏ－、－ＳＯ２－、－Ｏ－ＣＯ－Ｏ－アルキレン基－、－ＣＯＯ－アルキレン基－、又は、－ＣＯＮＨ－アルキレン基－が好ましく、－Ｏ－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｏ－アルキレン基－、－ＣＯＯ－、－ＣＯＮＨ－、－ＳＯ２－、又は、－ＣＯＯ－アルキレン基－がより好ましい。 L represents a divalent linking group.
When there are multiple L's, each L may be the same or different.
Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups ( preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these. . Among them, the divalent linking group includes -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, and -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 - , or -COO-alkylene group- is more preferable.
　Ｌとしては、例えば、下記式（ＡＮ１－１）で表される基が好ましい。
　＊ａ－（ＣＲ２ａ ２）Ｘ－Ｑ－（ＣＲ２ｂ ２）Ｙ－＊ｂ　　　（ＡＮ１－１） As L, for example, a group represented by the following formula (AN1-1) is preferable.
* a - (CR 2a 2 ) X - Q- (CR 2b 2 ) Y - * b (AN1-1)
　式（ＡＮ１－１）中、＊ａは、式（ＡＮ１）におけるＲ３との結合位置を表す。
　＊ｂは、式（ＡＮ１）における－Ｃ（Ｒ１）（Ｒ２）－との結合位置を表す。
　Ｘ及びＹは、それぞれ独立に、０～１０の整数を表し、０～３の整数が好ましい。
　Ｒ２ａ及びＲ２ｂは、それぞれ独立に、水素原子又は置換基を表す。
　Ｒ２ａ及びＲ２ｂがそれぞれ複数存在する場合、複数存在するＲ２ａ及びＲ２ｂは、それぞれ同一でも異なっていてもよい。
　ただし、Ｙが１以上の場合、式（ＡＮ１）における－Ｃ（Ｒ１）（Ｒ２）－と直接結合するＣＲ２ｂ ２におけるＲ２ｂは、フッ素原子以外である。
　Ｑは、＊Ａ－Ｏ－ＣＯ－Ｏ－＊Ｂ、＊Ａ－ＣＯ－＊Ｂ、＊Ａ－ＣＯ－Ｏ－＊Ｂ、＊Ａ－Ｏ－ＣＯ－＊Ｂ、＊Ａ－Ｏ－＊Ｂ、＊Ａ－Ｓ－＊Ｂ、又は、＊Ａ－ＳＯ２－＊Ｂを表す。
　ただし、式（ＡＮ１－１）中のＸ＋Ｙが１以上、かつ、式（ＡＮ１－１）中のＲ２ａ及びＲ２ｂのいずれもが全て水素原子である場合、Ｑは、＊Ａ－Ｏ－ＣＯ－Ｏ－＊Ｂ、＊Ａ－ＣＯ－＊Ｂ、＊Ａ－Ｏ－ＣＯ－＊Ｂ、＊Ａ－Ｏ－＊Ｂ、＊Ａ－Ｓ－＊Ｂ、又は、＊Ａ－ＳＯ２－＊Ｂを表す。
　＊Ａは、式（ＡＮ１）におけるＲ３側の結合位置を表し、＊Ｂは、式（ＡＮ１）における－ＳＯ３ －側の結合位置を表す。 In formula (AN1-1), * a represents the bonding position with R3 in formula (AN1).
* b represents the bonding position with -C(R 1 )(R 2 )- in formula (AN1).
X and Y each independently represent an integer of 0-10, preferably an integer of 0-3.
R 2a and R 2b each independently represent a hydrogen atom or a substituent.
When multiple R 2a and R 2b are present, the multiple R 2a and R 2b may be the same or different.
However, when Y is 1 or more, R 2b in CR 2b 2 directly bonded to —C(R 1 )(R 2 )— in formula (AN1) is other than a fluorine atom.
Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2- * B .
However, when X + Y in formula (AN1-1) is 1 or more, and both R 2a and R 2b in formula (AN1-1) are hydrogen atoms, Q is * A —O—CO -O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2- * B represents
* A represents the bonding position on the R 3 side in formula (AN1), and * B represents the bonding position on the —SO 3 — side in formula (AN1).
　式（ＡＮ１）中、Ｒ３は、有機基を表す。
　上記有機基は、炭素原子を１以上有していれば特に制限はなく、直鎖状の基（例えば、直鎖状のアルキル基）でも、分岐鎖状の基（例えば、ｔ－ブチル基等の分岐鎖状のアルキル基）でもよく、環状の基であってもよい。上記有機基は、置換基を有していても、有していなくてもよい。上記有機基は、ヘテロ原子（酸素原子、硫黄原子、及び／又は、窒素原子等）を有していても、有してなくてもよい。 In formula (AN1), R3 represents an organic group.
The organic group is not particularly limited as long as it has 1 or more carbon atoms. branched chain alkyl group) or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).
　なかでも、Ｒ３は、環状構造を有する有機基であることが好ましい。上記環状構造は、単環でも多環でもよく、置換基を有していてもよい。環状構造を含む有機基における環は、式（ＡＮ１）中のＬと直接結合していることが好ましい。
　上記環状構造を有する有機基は、例えば、ヘテロ原子（酸素原子、硫黄原子、及び／又は、窒素原子等）を有していても、有してなくてもよい。ヘテロ原子は、環状構造を形成する炭素原子の１つ以上と置換していてもよい。
　上記環状構造を有する有機基は、例えば、環状構造の炭化水素基、ラクトン環基、及び、スルトン環基が好ましい。なかでも、上記環状構造を有する有機基は、環状構造の炭化水素基が好ましい。
　上記環状構造の炭化水素基は、単環又は多環のシクロアルキル基が好ましい。これらの基は、置換基を有していてもよい。
　上記シクロアルキル基は、単環（シクロヘキシル基等）でも多環（アダマンチル基等）でもよく、炭素数は５～１２が好ましい。
　上記ラクトン基及びスルトン基としては、例えば、上述した式（ＬＣ１－１）～（ＬＣ１－２１）で表される構造、及び、式（ＳＬ１－１）～（ＳＬ１－３）で表される構造のいずれかにおいて、ラクトン構造又はスルトン構造を構成する環員原子から、水素原子を１つ除いてなる基が好ましい。 Among them, R 3 is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1).
The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), for example. Heteroatoms may replace one or more of the carbon atoms that form the ring structure.
The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among them, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
The above hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
The cycloalkyl group may be monocyclic (such as cyclohexyl group) or polycyclic (such as adamantyl group), and preferably has 5 to 12 carbon atoms.
Examples of the lactone group and sultone group include structures represented by the above formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3). , preferably a group obtained by removing one hydrogen atom from a ring member atom constituting a lactone structure or a sultone structure.
　非求核性アニオンとしては、ベンゼンスルホン酸アニオンであってもよく、分岐鎖状のアルキル基又はシクロアルキル基によって置換されたベンゼンスルホン酸アニオンであることが好ましい。 The non-nucleophilic anion may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or cycloalkyl group.
　非求核性アニオンとしては、下記式（ＡＮ２）で表されるアニオンも好ましい。 As the non-nucleophilic anion, an anion represented by the following formula (AN2) is also preferable.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
　式（ＡＮ２）中、ｏは、１～３の整数を表す。ｐは、０～１０の整数を表す。ｑは、０～１０の整数を表す。 In formula (AN2), o represents an integer of 1-3. p represents an integer from 0 to 10; q represents an integer from 0 to 10;
　Ｘｆは、水素原子、フッ素原子、少なくとも１つのフッ素原子で置換されたアルキル基、又はフッ素原子を有さない有機基を表す。このアルキル基の炭素数は、１～１０が好ましく、１～４がより好ましい。少なくとも１つのフッ素原子で置換されたアルキル基としては、パーフルオロアルキル基が好ましい。
　Ｘｆは、フッ素原子又は炭素数１～４のパーフルオロアルキル基であることが好ましく、フッ素原子又はＣＦ３であることがより好ましく、双方のＸｆがフッ素原子であることが更に好ましい。 Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 , and even more preferably both Xf are fluorine atoms.
　Ｒ４及びＲ５は、それぞれ独立に、水素原子、フッ素原子、アルキル基、又は、少なくとも１つのフッ素原子で置換されたアルキル基を表す。Ｒ４及びＲ５が複数存在する場合、Ｒ４及びＲ５は、それぞれ同一でも異なっていてもよい。
　Ｒ４及びＲ５で表されるアルキル基は、炭素数１～４が好ましい。上記アルキル基は置換基を有していてもよい。Ｒ４及びＲ５としては、水素原子が好ましい。 R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R 4 and R 5 are present, each of R 4 and R 5 may be the same or different.
The alkyl groups represented by R 4 and R 5 preferably have 1 to 4 carbon atoms. The above alkyl group may have a substituent. Hydrogen atoms are preferred as R 4 and R 5 .
　Ｌは、２価の連結基を表す。Ｌの定義は、式（ＡＮ１）中のＬと同義である。 　L represents a divalent linking group. The definition of L is synonymous with L in formula (AN1).
　Ｗは、有機基を表し、環状構造を含む有機基を表すことが好ましい。なかでも、環状の有機基であることが好ましい。
　環状の有機基としては、例えば、脂環基、アリール基、及び、複素環基が挙げられる。
　脂環基は、単環であってもよく、多環であってもよい。単環の脂環基としては、例えば、シクロペンチル基、シクロヘキシル基、及び、シクロオクチル基等の単環のシクロアルキル基が挙げられる。多環の脂環基としては、例えば、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が挙げられる。なかでも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の炭素数７以上の嵩高い構造を有する脂環基が好ましい。 W represents an organic group, preferably an organic group containing a cyclic structure. Among them, a cyclic organic group is preferable.
Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
The alicyclic group may be monocyclic or polycyclic. Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic alicyclic group includes, for example, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
　アリール基は、単環又は多環であってもよい。上記アリール基としては、例えば、フェニル基、ナフチル基、フェナントリル基、及び、アントリル基が挙げられる。
　複素環基は、単環又は多環であってもよい。なかでも、多環の複素環基である場合、より酸の拡散を抑制できる。複素環基は、芳香族性を有していてもよいし、芳香族性を有していなくてもよい。芳香族性を有している複素環としては、例えば、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及び、ピリジン環が挙げられる。芳香族性を有していない複素環としては、例えば、テトラヒドロピラン環、ラクトン環、スルトン環、及び、デカヒドロイソキノリン環が挙げられる。複素環基における複素環としては、フラン環、チオフェン環、ピリジン環、又は、デカヒドロイソキノリン環が好ましい。 Aryl groups may be monocyclic or polycyclic. Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
A heterocyclic group may be monocyclic or polycyclic. Especially, when it is a polycyclic heterocyclic group, diffusion of acid can be further suppressed. A heterocyclic group may or may not have an aromatic character. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
　上記環状の有機基は、置換基を有していてもよい。上記置換基としては、例えば、アルキル基（直鎖状及び分岐鎖状のいずれであってもよく、炭素数１～１２が好ましい）、シクロアルキル基（単環、多環、及び、スピロ環のいずれであってもよく、炭素数３～２０が好ましい）、アリール基（炭素数６～１４が好ましい）、水酸基、アルコキシ基、エステル基、アミド基、ウレタン基、ウレイド基、チオエーテル基、スルホンアミド基、及び、スルホン酸エステル基が挙げられる。なお、環状の有機基を構成する炭素（環形成に寄与する炭素）はカルボニル炭素であってもよい。 The cyclic organic group may have a substituent. Examples of the substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide and sulfonate ester groups. In addition, carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic|annular organic group.
　式（ＡＮ２）で表されるアニオンとしては、ＳＯ３ －－ＣＦ２－ＣＨ２－ＯＣＯ－（Ｌ）ｑ’－Ｗ、ＳＯ３ －－ＣＦ２－ＣＨＦ－ＣＨ２－ＯＣＯ－（Ｌ）ｑ’－Ｗ、ＳＯ３ －－ＣＦ２－ＣＯＯ－（Ｌ）ｑ’－Ｗ、ＳＯ３ －－ＣＦ２－ＣＦ２－ＣＨ２－ＣＨ２－（Ｌ）ｑ－Ｗ、又は、ＳＯ３ －－ＣＦ２－ＣＨ（ＣＦ３）－ＯＣＯ－（Ｌ）ｑ’－Ｗが好ましい。ここで、Ｌ、ｑ及びＷは、式（ＡＮ２）と同様である。ｑ’は、０～１０の整数を表す。 Examples of anions represented by formula (AN2) include SO 3 − —CF 2 —CH 2 —OCO-(L) q′ —W, SO 3 − —CF 2 —CHF—CH 2 —OCO-(L) q ' -W, SO 3 - -CF 2 -COO-(L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q -W, or SO 3 - - CF 2 —CH(CF 3 )—OCO—(L) q′ —W is preferred. Here, L, q and W are the same as in formula (AN2). q' represents an integer from 0 to 10;
　非求核性アニオンとしては、下記式（ＡＮ３）で表される芳香族スルホン酸アニオンも好ましい。 As the non-nucleophilic anion, an aromatic sulfonate anion represented by the following formula (AN3) is also preferable.
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
　式（ＡＮ３）中、Ａｒは、アリール基（フェニル基等）を表し、スルホン酸アニオン、及び、－（Ｄ－Ｂ）基以外の置換基を更に有していてもよい。更に有してもよい置換基としては、例えば、フッ素原子及び水酸基が挙げられる。
　ｎは、０以上の整数を表す。ｎとしては、１～４が好ましく、２～３がより好ましく、３が更に好ましい。 In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and -(D-B) group. Substituents which may be further included include, for example, a fluorine atom and a hydroxyl group.
n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
　Ｄは、単結合又は２価の連結基を表す。２価の連結基としては、エーテル基、チオエーテル基、カルボニル基、スルホキシド基、スルホン基、スルホン酸エステル基、エステル基、及び、これらの２種以上の組み合わせからなる基が挙げられる。 D represents a single bond or a divalent linking group. Divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more thereof.
　Ｂは、炭化水素基を表す。
　Ｂとしては、脂肪族炭化水素基が好ましく、イソプロピル基、シクロヘキシル基、又は更に置換基を有してもよいアリール基（トリシクロヘキシルフェニル基等）がより好ましい。 B represents a hydrocarbon group.
B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an optionally substituted aryl group (such as a tricyclohexylphenyl group).
　非求核性アニオンとしては、ジスルホンアミドアニオンも好ましい。
　ジスルホンアミドアニオンは、例えば、Ｎ－（ＳＯ２－Ｒｑ）２で表されるアニオンである。
　ここで、Ｒｑは置換基を有していてもよいアルキル基を表し、フルオロアルキル基が好ましく、パーフルオロアルキル基がより好ましい。２個のＲｑは互いに結合して環を形成してもよい。２個のＲｑが互いに結合して形成される基は、置換基を有していてもよいアルキレン基が好ましく、フルオロアルキレン基が好ましく、パーフルオロアルキレン基が更に好ましい。上記アルキレン基の炭素数は２～４が好ましい。 Disulfonamide anions are also preferred as non-nucleophilic anions.
A disulfonamide anion is, for example, an anion represented by N − (SO 2 —R q ) 2 .
Here, R q represents an optionally substituted alkyl group, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. Two R q may combine with each other to form a ring. The group formed by bonding two R q together is preferably an optionally substituted alkylene group, preferably a fluoroalkylene group, more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.
　また、非求核性アニオンとしては、下記式（ｄ１－１）～（ｄ１－４）で表されるアニオンも挙げられる。 Non-nucleophilic anions also include anions represented by the following formulas (d1-1) to (d1-4).
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
　式（ｄ１－１）中、Ｒ５１は置換基（例えば、水酸基）を有していてもよい炭化水素基（例えば、フェニル基等のアリール基）を表す。 In formula (d1-1), R 51 represents a hydrocarbon group (eg, an aryl group such as a phenyl group) optionally having a substituent (eg, hydroxyl group).
　式（ｄ１－２）中、Ｚ２ｃは置換基を有していてもよい炭素数１～３０の炭化水素基（ただし、Ｓに隣接する炭素原子にはフッ素原子が置換されない）を表す。
　Ｚ２ｃにおける上記炭化水素基は、直鎖状でも分岐鎖状でもよく、環状構造を有していてもよい。また、上記炭化水素基における炭素原子（好ましくは、上記炭化水素基が環状構造を有する場合における、環員原子である炭素原子）は、カルボニル炭素（－ＣＯ－）であってもよい。上記炭化水素基としては、例えば、置換基を有していてもよいノルボルニル基を有する基が挙げられる。上記ノルボルニル基を形成する炭素原子は、カルボニル炭素であってもよい。
　式（ｄ１－２）中の「Ｚ２ｃ－ＳＯ３ －」は、上述の式（ＡＮ１）～（ＡＮ３）で表されるアニオンとは異なることが好ましい。例えば、Ｚ２ｃは、アリール基以外が好ましい。例えば、Ｚ２ｃにおける、－ＳＯ３ －に対してα位及びβ位の原子は、置換基としてフッ素原子を有する炭素原子以外の原子が好ましい。例えば、Ｚ２ｃは、－ＳＯ３ －に対してα位の原子及び／又はβ位の原子は環状基中の環員原子であることが好ましい。 In formula (d1-2), Z 2c represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon atom adjacent to S is not substituted with a fluorine atom).
The above hydrocarbon group for Z 2c may be linear or branched, and may have a cyclic structure. In addition, the carbon atom in the hydrocarbon group (preferably the carbon atom that is a ring member atom when the hydrocarbon group has a cyclic structure) may be carbonyl carbon (--CO--). Examples of the hydrocarbon group include a group having an optionally substituted norbornyl group. A carbon atom forming the norbornyl group may be a carbonyl carbon.
“Z 2c —SO 3 − ” in formula (d1-2) is preferably different from the anions represented by formulas (AN1) to (AN3) above. For example, Z 2c is preferably other than an aryl group. For example, the α-position and β-position atoms with respect to —SO 3 — in Z 2c are preferably atoms other than carbon atoms having a fluorine atom as a substituent. For example, in Z 2c , the α-position atom and/or the β-position atom with respect to —SO 3 — is preferably a ring member atom in a cyclic group.
　式（ｄ１－３）中、Ｒ５２は有機基（好ましくはフッ素原子を有する炭化水素基）を表し、Ｙ３は直鎖状、分岐鎖状、若しくは、環状のアルキレン基、アリーレン基、又は、カルボニル基を表し、Ｒｆは炭化水素基を表す。 In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 represents a linear, branched or cyclic alkylene group, an arylene group, or represents a carbonyl group, and Rf represents a hydrocarbon group.
　式（ｄ１－４）中、Ｒ５３及びＲ５４は、それぞれ独立に、有機基（好ましくはフッ素原子を有する炭化水素基）を表す。Ｒ５３及びＲ５４は互いに結合して環を形成していてもよい。 In formula (d1-4), R 53 and R 54 each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom). R 53 and R 54 may combine with each other to form a ring.
　有機アニオンは、１種単独で使用してもよく、２種以上を使用してもよい。 The organic anions may be used singly or in combination of two or more.
（一般式（１）で表される化合物）
　光酸発生剤（Ｂ）は下記一般式（１）で表される化合物（「以下、化合物（Ｂ）」ともいう）であることも好ましい。 (Compound represented by general formula (1))
The photoacid generator (B) is also preferably a compound represented by the following general formula (1) (hereinafter also referred to as "compound (B)").
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
　一般式（１）中、Ｒ１及びＲ５は、それぞれ独立にアリール基又はヘテロアリール基を表す。Ｒ２～Ｒ４は、それぞれ独立に水素原子又は置換基を表す。Ｍｎ＋はカチオンを表す。ｎは１以上の整数を表す。 In general formula (1), R 1 and R 5 each independently represent an aryl group or a heteroaryl group. R 2 to R 4 each independently represent a hydrogen atom or a substituent. M n+ represents a cation. n represents an integer of 1 or more.
　Ｒ１及びＲ５としてのアリール基としては、例えば、炭素数６～１５個のアリール基を挙げることができ、具体的には、フェニル基、ナフチル基、アントリル基等を好ましい例として挙げることができる。
　Ｒ１及びＲ５としてのヘテロアリール基としては、例えば、炭素数２～１５個のヘテロアリール基を挙げることができ、５員環～１０員環のものを挙げることができ、具体的には、フリル基、チエニル基、ピロリル基、オキサゾリル基、ピリジル基、キノリニル基、カルバゾリル基等が挙げられる。
　Ｒ２～Ｒ４としての置換基としては、１価の置換基であれば特に限定されないが、例えば、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせが挙げられる。 The aryl group for R 1 and R 5 includes, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and the like. can.
The heteroaryl group for R 1 and R 5 includes, for example, a heteroaryl group having 2 to 15 carbon atoms, such as a 5- to 10-membered ring, specifically , furyl group, thienyl group, pyrrolyl group, oxazolyl group, pyridyl group, quinolinyl group, carbazolyl group and the like.
The substituents for R 2 to R 4 are not particularly limited as long as they are monovalent substituents, but examples include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as atoms and silicon atoms; and combinations of two or more of these.
　Ｒ２～Ｒ４としてのアルキル基は、例えば、炭素数１～３０のアルキル基を挙げることができる。アルキル基として好ましくはメチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基、ドデシル基など炭素数１～２０のアルキル基であり、より好ましくは炭素数１～８のアルキル基である。 Examples of alkyl groups for R 2 to R 4 include alkyl groups having 1 to 30 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group. and more preferably an alkyl group having 1 to 8 carbon atoms.
　Ｒ２～Ｒ４としてのアルケニル基は、例えば、炭素数２～３０のアルケニル基を挙げることができ、炭素数２～８のアルケニル基は好ましい。
　Ｒ２～Ｒ４としてのシクロアルキル基は、単環型であってもよく、多環型であってもよい。このシクロアルキル基の炭素数は、特に限定されないが、好ましくは３～８である。 Examples of alkenyl groups for R 2 to R 4 include alkenyl groups having 2 to 30 carbon atoms, and alkenyl groups having 2 to 8 carbon atoms are preferred.
Cycloalkyl groups as R 2 to R 4 may be monocyclic or polycyclic. Although the number of carbon atoms in this cycloalkyl group is not particularly limited, it is preferably 3-8.
　Ｒ２～Ｒ４としてのアリール基としては、例えば、炭素数６～１５個のアリール基を挙げることができ、具体的には、フェニル基、ナフチル基、アントリル基等を好ましい例として挙げることができる。
　Ｒ２～Ｒ４としてのハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等を挙げることができる。 The aryl group for R 2 to R 4 includes, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, and the like. can.
Halogen atoms for R 2 to R 4 include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
　ヘテロ原子を含む基としては、例えば、水酸基、カルボキシル基、アルコキシ基、チオール基、チオエーテル基、ニトロ基、ニトロソ基、シアノ基、アミノ基、アシルオキシ基、アシルアミド基、ヘテロアリール基、エーテル結合、カルボニル結合、及び、これらの２種以上の組み合わせが挙げられる。 Groups containing heteroatoms include, for example, hydroxyl group, carboxyl group, alkoxy group, thiol group, thioether group, nitro group, nitroso group, cyano group, amino group, acyloxy group, acylamide group, heteroaryl group, ether bond, carbonyl Conjugation and combinations of two or more of these are included.
　アルコキシ基、アシルオキシ基及びアシルアミド基の炭素数は、好ましくは２０以下とし、更に好ましくは８以下とする。このアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ｎ－ブチロキシ基、ｔ－ブトキシ基及びオクチロキシ基が挙げられる。中でも、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基及びｔ－ブトキシ基が特に好ましい。なお、チオエーテル基についても、酸素原子の代わりに硫黄原子を用いることを除いては、アルコキシ基と同様のものが挙げられる。アシルオキシ基としては、例えば、アセチルオキシ基が挙げられる。アシルアミド基としては、例えば、アセチルアミド基が挙げられる。
　ヘテロアリール基としては、Ｒ１及びＲ５としてのヘテロアリール基と同様のものを挙げることができる。 The number of carbon atoms in the alkoxy group, acyloxy group and acylamide group is preferably 20 or less, more preferably 8 or less. The alkoxy groups include, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butyroxy, t-butoxy and octyloxy groups. Among them, methoxy group, ethoxy group, propoxy group, isopropoxy group and t-butoxy group are particularly preferred. The thioether group includes the same alkoxy groups, except that a sulfur atom is used instead of the oxygen atom. Acyloxy groups include, for example, acetyloxy groups. The acylamide group includes, for example, an acetylamide group.
Heteroaryl groups include the same heteroaryl groups as R 1 and R 5 .
　Ｒ１及びＲ５としてのアリール基、ヘテロアリール基は、更に置換基を有していても良い。更なる置換基としては、例えば、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせが挙げられる。
　アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせは、それぞれ、Ｒ２～Ｒ４としての置換基の具体例における、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせと同様である。
　Ｒ１及びＲ５としてのアリール基、ヘテロアリール基が複数の置換基を有する場合、複数の置換基における少なくとも２つは互いに結合して環を形成しても良い。 The aryl group and heteroaryl group as R 1 and R 5 may further have a substituent. Further substituents include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; A combination of
Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; Similar to combinations of species or more.
When the aryl group and heteroaryl group as R 1 and R 5 have multiple substituents, at least two of the multiple substituents may be bonded to each other to form a ring.
　Ｒ２～Ｒ４の置換基としてのアルキル基；アルケニル基；シクロアルキル基；アリール基；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基は、更に置換基を有していても良い。更なる置換基としては、例えば、アルキル基、アルケニル基、シクロアルキル基、アリール基、アミノ基、アミド基、ウレイド基、ウレタン基、ヒドロキシ基、カルボキシ基、ハロゲン原子、アルコキシ基、チオエーテル基、アシル基、アシロキシ基、アルコキシカルボニル基、シアノ基及びニトロ基、並びにこれらの２種以上の組合せが挙げられる。 Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms as substituents of R 2 to R 4 further have substituents. can be Further substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, groups, acyloxy groups, alkoxycarbonyl groups, cyano groups and nitro groups, and combinations of two or more of these.
　上記Ｒ１及びＲ５は、後述の極性基を含む基、酸の作用により分解し極性が増大する基を含む基、又はアルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基を構成することができる。
　上記Ｒ２～Ｒ４は、後述の極性基を含む基、酸の作用により分解し極性が増大する基を含む基、又はアルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基を構成することができる。 The above R 1 and R 5 are a group containing a polar group described later, a group containing a group that is decomposed by the action of an acid to increase polarity, or decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer. It is possible to construct a group that includes a group that
R 2 to R 4 above are a group containing a polar group described later, a group containing a group that is decomposed by the action of an acid to increase the polarity, or decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer. It is possible to construct a group that includes a group that
　上記一般式（１）中、Ｒ３がアリール基を表すことが好ましい。
　Ｒ３としてのアリール基は、Ｒ１及びＲ５としてのアリール基と同様のものを挙げることができる。
　Ｒ３としてのアリール基は、更に置換基を有していても良い。更なる置換基としては、上述したＲ１及びＲ５とが更に有していても良い置換基の具体例として前述した各基を挙げることができる。
　Ｒ３としてのアリール基が複数の置換基を有する場合、複数の置換基における少なくとも２つは互いに結合して環を形成しても良い。 In general formula (1) above, R 3 preferably represents an aryl group.
Examples of the aryl group for R 3 include the same aryl groups as those for R 1 and R 5 .
The aryl group as R3 may further have a substituent. As the further substituents, the groups described above as specific examples of the substituents that R 1 and R 5 described above may further have can be mentioned.
When the aryl group as R 3 has multiple substituents, at least two of the multiple substituents may be bonded to each other to form a ring.
　上記一般式（１）中、Ｒ１～Ｒ５のうち少なくとも一つは、極性基を含む基、酸の作用により分解し極性が増大する基を含む基、又はアルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基であることが好ましい。 In the general formula (1), at least one of R 1 to R 5 is a group containing a polar group, a group containing a group that is decomposed by the action of an acid to increase its polarity, or a group that is decomposed by the action of an alkaline developer. , is preferably a group containing a group that increases the solubility in an alkaline developer.
　Ｒ１～Ｒ５のうち少なくとも一つとしての、極性基を含む基における極性基としては、例えば、カルボキシル基、フェノール性水酸基、フッ素化アルコール基、スルホンアミド基、スルホニルイミド基、（アルキルスルホニル）（アルキルカルボニル）メチレン基、（アルキルスルホニル）（アルキルカルボニル）イミド基、ビス（アルキルカルボニル）メチレン基、ビス（アルキルカルボニル）イミド基、ビス（アルキルスルホニル）メチレン基、ビス（アルキルスルホニル）イミド基、トリス（アルキルカルボニル）メチレン基、及び、トリス（アルキルスルホニル）メチレン基等の酸性基、並びに、アルコール性水酸基等が挙げられる。 Examples of the polar group in the group containing a polar group as at least one of R 1 to R 5 include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonamide group, a sulfonylimide group, and (alkylsulfonyl) (alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, acidic groups such as a tris(alkylcarbonyl)methylene group and a tris(alkylsulfonyl)methylene group; and alcoholic hydroxyl groups.
　なお、アルコール性水酸基とは、炭化水素基に結合した水酸基であって、芳香環上に直接結合した水酸基（フェノール性水酸基）以外の水酸基をいい、水酸基としてα位がフッ素原子などの電子求引性基で置換された脂肪族アルコール（例えば、ヘキサフルオロイソプロパノール基など）は除く。アルコール性水酸基としては、ｐＫａ（酸解離定数）が１２以上２０以下の水酸基であることが好ましい。
　中でも、極性基としては、カルボキシル基、フェノール性水酸基、又はフッ素化アルコール基（好ましくはヘキサフルオロイソプロパノール基）が好ましい。 The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It excludes aliphatic alcohols substituted with functional groups (eg, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less.
Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).
　極性基を含む基として、カルボニル結合を有する基も挙げることができる。
　カルボニル結合を有する基としては、例えば、アルキルカルボニル基、アリールカルボニル基等を挙げることができる。
　アルキル基としては、例えば、Ｒ２～Ｒ４としてのアルキル基と同様のものを挙げることができる。
　アリール基としては、例えば、Ｒ１及びＲ５としてのアリール基と同様のものを挙げることができる。
　カルボニル結合を有する基は、カルボニル結合とエーテル結合が隣接して結合しない基である。 A group having a carbonyl bond can also be mentioned as a group containing a polar group.
Examples of groups having a carbonyl bond include alkylcarbonyl groups and arylcarbonyl groups.
Examples of the alkyl group include those similar to the alkyl groups for R 2 to R 4 .
The aryl group includes, for example, the same aryl groups as R 1 and R 5 .
A group having a carbonyl bond is a group in which the carbonyl bond and the ether bond are not adjacently bonded.
　カルボニル結合を有する基としての、アルキルカルボニル基、アリールカルボニル基は更に置換基を有していても良い。
　更なる置換基としては、例えば、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせが挙げられる。
　アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせは、それぞれ、Ｒ２～Ｒ４としての置換基の具体例における、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせと同様である。 Alkylcarbonyl groups and arylcarbonyl groups as groups having a carbonyl bond may further have a substituent.
Further substituents include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; A combination of
Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; Similar to combinations of species or more.
　極性基を含む基としては、特に限定されないが、極性基を含む有機基を挙げることができる。極性基を含む有機基としては、例えば、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせであって、極性基を有するようにした基が挙げられる。
　アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせは、それぞれ、Ｒ２～Ｒ４としての置換基の具体例における、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせと同様である。 The group containing a polar group is not particularly limited, but an organic group containing a polar group can be mentioned. Organic groups containing polar groups include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; A group having a polar group, which is a combination of more than one species, can be mentioned.
Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; Similar to combinations of species or more.
　極性基を含む基としては、例えば、極性基を含むアルキル基、極性基を含むアリール基を挙げることができる。
　極性基を含むアルキル基におけるアルキル基としては、例えば、Ｒ２～Ｒ４としてのアルキル基と同様のものを挙げることができる。
　極性基を含むアリール基におけるアリール基としては、例えば、Ｒ１及びＲ５としてのアリール基と同様のものを挙げることができる。
　また、極性基を含む基が、極性基自体であっても良い。 Examples of the group containing a polar group include an alkyl group containing a polar group and an aryl group containing a polar group.
Examples of the alkyl group in the alkyl group containing a polar group include those similar to the alkyl groups for R 2 to R 4 .
Examples of the aryl group in the aryl group containing a polar group include the same aryl groups as R 1 and R 5 .
Also, the group containing the polar group may be the polar group itself.
　Ｒ１～Ｒ５のうち少なくとも一つとしての、酸の作用により分解し極性が増大する基を含む基における酸の作用により分解し極性が増大する基（以下、「酸分解性基」とも言う）は、極性基が酸の作用により分解し脱離する基（脱離基）で保護された構造を有することが好ましい。
　極性基としては、Ｒ１～Ｒ５のうち少なくとも一つとしての、極性基を含む基における極性基と同様のものを挙げることができる。 At least one of R 1 to R 5 is a group containing a group that is decomposed by the action of an acid and increases in polarity (hereinafter also referred to as an "acid-decomposable group"). ) preferably has a structure in which the polar group is protected by a group (leaving group) that decomposes and leaves under the action of an acid.
As the polar group, the same polar group as in the group containing a polar group as at least one of R 1 to R 5 can be mentioned.
　酸の作用により分解し脱離する基（脱離基）としては、例えば、式（Ｙ１）～（Ｙ４）で表される基が挙げられる。
式（Ｙ１）：－Ｃ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
式（Ｙ２）：－Ｃ（＝Ｏ）ＯＣ（Ｒｘ１）（Ｒｘ２）（Ｒｘ３）
式（Ｙ３）：－Ｃ（Ｒ３６）（Ｒ３７）（ＯＲ３８）
式（Ｙ４）：－Ｃ（Ｒｎ）（Ｈ）（Ａｒ） Groups that are decomposed and left by the action of an acid (leaving groups) include, for example, groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C(Rx 1 )(Rx 2 )(Rx 3 )
Formula (Y2): -C(=O)OC(Rx 1 )(Rx 2 )(Rx 3 )
Formula (Y3): —C(R 36 )(R 37 )(OR 38 )
Formula (Y4): -C(Rn)(H)(Ar)
　式（Ｙ１）及び式（Ｙ２）中、Ｒｘ１～Ｒｘ３は、各々独立に、アルキル基（直鎖状若しくは分岐鎖状）又はシクロアルキル基（単環若しくは多環）を表す。なお、Ｒｘ１～Ｒｘ３の全てがアルキル基（直鎖若しくは分岐）である場合、Ｒｘ１～Ｒｘ３のうち少なくとも２つはメチル基であることが好ましい。
　なかでも、Ｒｘ１～Ｒｘ３は、各々独立に、直鎖状又は分岐鎖状のアルキル基を表すことが好ましく、Ｒｘ１～Ｒｘ３は、各々独立に、直鎖状のアルキル基を表すことがより好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して、単環又は多環を形成してもよい。
　Ｒｘ１～Ｒｘ３のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、及び、ｔ－ブチル基等の炭素数１～４のアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、並びに、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、並びに、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましく、炭素数５～６の単環のシクロアルキル基がより好ましい。
　Ｒｘ１～Ｒｘ３の２つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
　式（Ｙ１）又は式（Ｙ２）で表される基は、例えば、Ｒｘ１がメチル基又はエチル基であり、Ｒｘ２とＲｘ３とが結合して上述のシクロアルキル基を形成している態様が好ましい。 In formulas (Y1) and (Y2), Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups.
Among them, Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
The alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
The cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
Cycloalkyl groups formed by combining two of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecanyl, and tetracyclododeca. A polycyclic cycloalkyl group such as a nil group and an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
A cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. may be replaced.
In the group represented by formula (Y1) or formula (Y2), for example, Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
　式（Ｙ３）中、Ｒ３６～Ｒ３８は、各々独立に、水素原子又は１価の有機基を表す。Ｒ３７とＲ３８とは、互いに結合して環を形成してもよい。１価の有機基としては、アルキル基、シクロアルキル基、アリール基、アラルキル基、及び、アルケニル基等が挙げられる。Ｒ３６は水素原子であることも好ましい。 In formula (Y3), R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group. R 37 and R 38 may combine with each other to form a ring. Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R 36 is a hydrogen atom.
　式（Ｙ３）としては、下記式（Ｙ３－１）で表される基が好ましい。 As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
　ここで、Ｌ１及びＬ２は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、又は、これらを組み合わせた基（例えば、アルキル基とアリール基とを組み合わせた基）を表す。
　Ｍは、単結合又は２価の連結基を表す。
　Ｑは、ヘテロ原子を含んでいてもよいアルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基、アルデヒド基、又は、これらを組み合わせた基（例えば、アルキル基とシクロアルキル基とを組み合わせた基）を表す。
　アルキル基及びシクロアルキル基は、例えば、メチレン基の１つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
　なお、Ｌ１及びＬ２のうち一方は水素原子であり、他方はアルキル基、シクロアルキル基、アリール基、又は、アルキレン基とアリール基とを組み合わせた基であることが好ましい。
　Ｑ、Ｍ、及び、Ｌ１の少なくとも２つが結合して環（好ましくは、５員若しくは６員環）を形成してもよい。
　パターンの微細化の点では、Ｌ２が２級又は３級アルキル基であることが好ましく、３級アルキル基であることがより好ましい。２級アルキル基としては、イソプロピル基、シクロヘキシル基又はノルボルニル基が挙げられ、３級アルキル基としては、ｔｅｒｔ－ブチル基又はアダマンタン基を挙げることができる。これらの態様では、Ｔｇ（ガラス転移温度）や活性化エネルギーが高くなるため、膜強度の担保に加え、かぶりの抑制ができる。 Here, L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group). .
M represents a single bond or a divalent linking group.
Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In alkyl groups and cycloalkyl groups, for example, one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group.
One of L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
At least two of Q, M and L 1 may combine to form a ring (preferably a 5- or 6-membered ring).
From the viewpoint of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Secondary alkyl groups include isopropyl, cyclohexyl and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
　式（Ｙ４）中、Ａｒは、芳香環基を表す。Ｒｎは、アルキル基、シクロアルキル基又はアリール基を表す。ＲｎとＡｒとは互いに結合して非芳香族環を形成してもよい。Ａｒはより好ましくはアリール基である。 In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may combine with each other to form a non-aromatic ring. Ar is more preferably an aryl group.
　酸分解性基は、アセタール構造を有することが好ましい。アセタール構造は、例えば、カルボキシル基、フェノール性水酸基、フッ素化アルコール基などの極性基が、上記式（Ｙ３）で表される基で保護された構造である。 The acid-decomposable group preferably has an acetal structure. The acetal structure is, for example, a structure in which a polar group such as a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group is protected with a group represented by the above formula (Y3).
　酸分解性基を含む基としては、酸分解性基を含む基であれば特に限定されないが、酸分解性基を含む有機基を挙げることができる。酸分解性基を含む有機基としては、例えば、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせであって、酸分解性基を有するようにした基が挙げられる。
　アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせは、それぞれ、Ｒ２～Ｒ４としての置換基の具体例における、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせと同様である。 The group containing an acid-decomposable group is not particularly limited as long as it is a group containing an acid-decomposable group, and an organic group containing an acid-decomposable group can be mentioned. Examples of organic groups containing acid-decomposable groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; and a group having an acid-decomposable group.
Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; Similar to combinations of species or more.
　酸分解性基を含む基としては、例えば、酸分解性基を含むアルキル基、酸分解性基を含むアリール基を挙げることができる。
　酸分解性基を含むアルキル基におけるアルキル基としては、例えば、Ｒ２～Ｒ４としてのアルキル基と同様のものを挙げることができる。
　酸分解性基を含むアリール基におけるアリール基としては、例えば、Ｒ１及びＲ５としてのアリール基と同様のものを挙げることができる。
　また、酸分解性基を含む基が、酸分解性基自体であっても良い。 Examples of the group containing an acid-decomposable group include an alkyl group containing an acid-decomposable group and an aryl group containing an acid-decomposable group.
Examples of the alkyl group in the alkyl group containing an acid-decomposable group include those similar to the alkyl groups for R 2 to R 4 .
Examples of the aryl group in the aryl group containing an acid-decomposable group include the same aryl groups as R 1 and R 5 .
Also, the group containing an acid-decomposable group may be the acid-decomposable group itself.
　Ｒ１～Ｒ５のうち少なくとも一つとしての、アルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基におけるアルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基は、「極性変換基」とも呼ばれ、具体例としては、ラクトン基、カルボン酸エステル基（－ＣＯＯ－）、酸無水物基（－Ｃ（Ｏ）ＯＣ（Ｏ）－）、酸イミド基（－ＮＨＣＯＮＨ－）、カルボン酸チオエステル基（－ＣＯＳ－）、炭酸エステル基（－ＯＣ（Ｏ）Ｏ－）、硫酸エステル基（－ＯＳＯ２Ｏ－）、スルホン酸エステル基（－ＳＯ２Ｏ－）などが挙げられる。 At least one of R 1 to R 5 includes a group that is decomposed by the action of an alkaline developer and increases the solubility in the alkaline developer, and decomposes by the action of the alkaline developer and is dissolved in the alkaline developer. A group that increases the solubility at is also called a "polar conversion group", and specific examples include a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O) -), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO 2 O-), sulfonate group (—SO 2 O—) and the like.
　極性変換基を含む基としては、例えば、アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、イミド基が挙げられる。 Examples of groups containing polar conversion groups include acyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, and imide groups.
　アシルオキシ基におけるアシル基の炭素数は、好ましくは１～３０であり、更に好ましくは１～８である。
　アルコキシカルボニルオキシ基におけるアルコキシ基の炭素数は、好ましくは１～３０であり、更に好ましくは１～８である。 The acyl group in the acyloxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
The alkoxy group in the alkoxycarbonyloxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
　アリールオキシカルボニルオキシ基におけるアリール基の炭素数は、好ましくは６～１４であり、更に好ましくは６～１０である。
　アリールオキシカルボニル基におけるアリール基の炭素数は、好ましくは６～１４であり、更に好ましくは６～１０である。
　アルコキシカルボニル基におけるアルコキシ基の炭素数は、好ましくは１～３０であり、更に好ましくは１～８である。
　イミド基は、イミドから水素原子を一つ除した基である。 The aryl group in the aryloxycarbonyloxy group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
The aryl group in the aryloxycarbonyl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group is preferably 1-30, more preferably 1-8.
An imide group is a group obtained by removing one hydrogen atom from imide.
　アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、及びイミド基は更に置換基を有していても良い。
　更なる置換基としては、上述したＲ１及びＲ５とが更に有していても良い置換基の具体例として前述した各基を挙げることができる。 The acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group and imido group may further have a substituent.
As the further substituents, the groups described above as specific examples of the substituents that R 1 and R 5 described above may further have can be mentioned.
　本発明の一つの好ましい態様としては、極性変換基としては、一般式（ＫＡ－１）又は（ＫＢ－１）で表される部分構造におけるＸで表される基である。 In one preferred embodiment of the present invention, the polarity conversion group is a group represented by X in the partial structure represented by general formula (KA-1) or (KB-1).
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
　一般式（ＫＡ－１）又は（ＫＢ－１）におけるＸは、カルボン酸エステル基：－ＣＯＯ－、酸無水物基：－Ｃ（Ｏ）ＯＣ（Ｏ）－、酸イミド基：－ＮＨＣＯＮＨ－、カルボン酸チオエステル基：－ＣＯＳ－、炭酸エステル基：－ＯＣ（Ｏ）Ｏ－、硫酸エステル基：－ＯＳＯ２Ｏ－、スルホン酸エステル基：－ＳＯ２Ｏ－を表す。
　Ｙ１及びＹ２は、それぞれ同一でも異なっても良く、電子求引性基を表す。
　なお、本発明の一つの好ましい態様として、上記化合物（Ｂ）が極性変換基を含む基として、一般式（ＫＡ－１）又は（ＫＢ－１）で表される部分構造を有する基を有するが、一般式（ＫＡ－１）で表される部分構造、Ｙ１及びＹ２が１価である場合の（ＫＢ－１）で表される部分構造の場合のように、上記部分構造が結合手を有しない場合は、上記部分構造を有する基とは、上記部分構造における任意の水素原子を少なくとも１つ除いた１価以上の基を有する基である。 X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: -COO-, an acid anhydride group: -C(O)OC(O)-, an acid imide group: -NHCONH-, Carboxylic acid thioester group: -COS-, carbonate group: -OC(O)O-, sulfate group: -OSO 2 O-, sulfonate group: -SO 2 O-.
Y 1 and Y 2 may be the same or different and represent an electron-withdrawing group.
In one preferred embodiment of the present invention, the compound (B) has a group having a partial structure represented by general formula (KA-1) or (KB-1) as a group containing a polarity conversion group. , the partial structure represented by the general formula (KA-1), and the partial structure represented by (KB-1) when Y 1 and Y 2 are monovalent, the above partial structure is a bond is not present, the group having the above partial structure is a group having a monovalent or higher valence group from which at least one arbitrary hydrogen atom in the above partial structure is removed.
　一般式（ＫＡ－１）で表される部分構造は、Ｘとしての基とともに環構造を形成する構造である。
　一般式（ＫＡ－１）におけるＸとして好ましくは、カルボン酸エステル基（即ち、ＫＡ－１としてラクトン環構造を形成する場合）、及び酸無水物基、炭酸エステル基である。より好ましくはカルボン酸エステル基である。
　一般式（ＫＡ－１）で表される環構造は、置換基を有していてもよく、例えば、置換基Ｚｋａ１をｎｋａ個有していてもよい。
　Ｚｋａ１は、複数ある場合はそれぞれ独立して、アルキル基、シクロアルキル基、エーテル基、ヒドロキシル基、アミド基、アリール基、ラクトン環基、又は電子求引性基を表す。
　Ｚｋａ１同士が連結して環を形成しても良い。Ｚｋａ１同士が連結して形成する環としては、例えば、シクロアルキル環、ヘテロ環（環状エーテル環、ラクトン環など）が挙げられる。
　ｎｋａは０～１０の整数を表す。好ましくは０～８の整数、より好ましくは０～５の整数、更に好ましくは１～４の整数、最も好ましくは１～３の整数である。 The partial structure represented by general formula (KA-1) is a structure that forms a ring structure together with a group as X.
X in general formula (KA-1) is preferably a carboxylate group (that is, when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate group. A carboxylic acid ester group is more preferred.
The ring structure represented by general formula (KA-1) may have a substituent, for example, it may have nka substituents Z ka1 .
When there are more than one Z ka1 , each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group.
Z ka1 may be linked together to form a ring. Examples of the ring formed by combining Z ka1 include a cycloalkyl ring and a hetero ring (cyclic ether ring, lactone ring, etc.).
nka represents an integer from 0 to 10; It is preferably an integer of 0-8, more preferably an integer of 0-5, still more preferably an integer of 1-4, and most preferably an integer of 1-3.
　Ｚｋａ１としての電子求引性基は、ハロゲン原子に代表される後述のＹ１及びＹ２としての電子求引性基と同様である。
　なお、上記電子求引性基は、別の電子求引性基で置換されていてもよい。 The electron-withdrawing group for Z ka1 is the same as the electron-withdrawing group for Y 1 and Y 2 typified by a halogen atom.
In addition, the electron-withdrawing group may be substituted with another electron-withdrawing group.
　Ｚｋａ１は好ましくは、アルキル基、シクロアルキル基、エーテル基、ヒドロキシル基、又は電子求引性基であり、より好ましくは、アルキル基、シクロアルキル基又は電子求引性基である。なお、エーテル基としては、アルキル基又はシクロアルキル基等で置換されたもの、すなわち、アルキルエーテル基等が好ましい。電子求引性基の好ましい例は、後述のＹ１及びＹ２としての電子求引性基と同様である。
　Ｚｋａ１としてのハロゲン原子はフッ素原子、塩素原子、臭素原子及びヨウ素原子等が挙げられ、フッ素原子が好ましい。
　Ｚｋａ１としてのアルキル基は置換基を有していてもよく、直鎖、分岐のいずれでもよい。直鎖アルキル基としては、好ましくは炭素数１～３０、更に好ましくは１～２０であり、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デカニル基等が挙げられる。分岐アルキル基としては、好ましくは炭素数３～３０、更に好ましくは３～２０であり、例えば、ｉ－プロピル基、ｉ－ブチル基、ｔ－ブチル基、ｉ－ペンチル基、ｔ－ペンチル基、ｉ－ヘキシル基、ｔ－ヘキシル基、ｉ－ヘプチル基、ｔ－ヘプチル基、ｉ－オクチル基、ｔ－オクチル基、ｉ－ノニル基、ｔ－デカノイル基等が挙げられる。メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｔ－ブチル基などの炭素数１～４のものが好ましい。
　Ｚｋａ１としてのシクロアルキル基は、置換基を有していてもよく、単環型でもよく、多環型でもよく、有橋式であってもよい。例えば、シクロアルキル基は橋かけ構造を有していてもよい。単環型としては、炭素数３～８のシクロアルキル基が好ましく、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロブチル基、シクロオクチル基等を挙げることができる。多環型としては、炭素数５以上のビシクロ、トリシクロ、テトラシクロ構造等を有する基を挙げることができ、炭素数６～２０のシクロアルキル基が好ましく、例えば、アダマンチル基、ノルボルニル基、イソボロニル基、カンファニル基、ジシクロペンチル基、α－ピネル基、トリシクロデカニル基、テトシクロドデシル基、アンドロスタニル基等が挙げられる。シクロアルキル基としては下記構造も好ましい。なお、シクロアルキル基中の炭素原子の一部が、酸素原子等のヘテロ原子によって置換されていてもよい。 Z ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron-withdrawing group, more preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group. As the ether group, one substituted with an alkyl group, a cycloalkyl group, or the like, that is, an alkyl ether group or the like is preferable. Preferred examples of the electron-withdrawing group are the same as the electron-withdrawing groups for Y 1 and Y 2 described later.
A halogen atom as Z ka1 includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
The alkyl group as Z ka1 may have a substituent and may be linear or branched. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, n-butyl, sec-butyl and t-butyl. group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and examples thereof include i-propyl, i-butyl, t-butyl, i-pentyl, t-pentyl, i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. Those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group are preferred.
The cycloalkyl group as Z ka1 may have a substituent, and may be monocyclic, polycyclic, or bridged. For example, a cycloalkyl group may have a bridged structure. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure having 5 or more carbon atoms, preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl group, norbornyl group, isobornyl group, Campanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, androstanyl group and the like. The following structure is also preferable as the cycloalkyl group. Some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
　上記脂環部分の好ましいものとしては、アダマンチル基、ノルアダマンチル基、デカリン基、トリシクロデカニル基、テトラシクロドデカニル基、ノルボルニル基、セドロール基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデカニル基、シクロドデカニル基を挙げることができる。より好ましくは、アダマンチル基、デカリン基、ノルボルニル基、セドロール基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデカニル基、シクロドデカニル基、トリシクロデカニル基である。
　これらの脂環式構造の置換基としては、アルキル基、ハロゲン原子、水酸基、アルコキシ基、カルボキシル基、アルコキシカルボニル基が挙げられる。アルキル基としてはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基等の低級アルキル基が好ましく、更に好ましくはメチル基、エチル基、プロピル基、イソプロピル基を表す。上記アルコキシ基としては、好ましくはメトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数１～４個のものを挙げることができる。アルキル基及びアルコキシ基が有してもよい置換基としては、水酸基、ハロゲン原子、アルコキシ基（好ましくは炭素数１～４）等を挙げることができる。 Preferred alicyclic moieties include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecanyl. and the cyclododecanyl group. More preferred are adamantyl group, decalin group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group and tricyclodecanyl group.
Substituents for these alicyclic structures include alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, and alkoxycarbonyl groups. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl or butyl, more preferably methyl, ethyl, propyl or isopropyl. Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy. Examples of substituents that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), and the like.
　Ｚka１のラクトン環基としては、後述する（ＫＡ－１－１）～（ＫＡ－１－１７）のいずれかで表される構造から水素原子を除した基が挙げられる。 Examples of the lactone ring group for Z ka1 include groups obtained by removing a hydrogen atom from structures represented by any of (KA-1-1) to (KA-1-17) described later.
　Ｚka１のアリール基としては、例えば、フェニル基及びナフチル基が挙げられる。 The aryl group for Z ka1 includes, for example, a phenyl group and a naphthyl group.
　Ｚka１のアルキル基、シクロアルキル基及びアリール基が更に有し得る置換基としては、水酸基、ハロゲン原子（フッ素、塩素、臭素、ヨウ素）、ニトロ基、シアノ基、上記のアルキル基、メトキシ基、エトキシ基、ヒドロキシエトキシ基、プロポキシ基、ヒドロキシプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔ－ブトキシ基等のアルコキシ基、メトキシカルボニル基、エトキシカルボニル基等のアルコキシカルボニル基、ベンジル基、フエネチル基、クミル基等のアラルキル基、アラルキルオキシ基、ホルミル基、アセチル基、ブチリル基、ベンゾイル基、シアナミル基、バレリル基等のアシル基、ブチリルオキシ基等のアシロキシ基、上記のアルケニル基、ビニルオキシ基、プロペニルオキシ基、アリルオキシ基、ブテニルオキシ基等のアルケニルオキシ基、上記のアリール基、フエノキシ基等のアリールオキシ基、ベンゾイルオキシ基等のアリールオキシカルボニル基等を挙げることができる。 Examples of substituents that the alkyl group, cycloalkyl group and aryl group of Z ka1 may further have include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, benzyl aralkyl groups such as phenethyl group and cumyl group; acyl groups such as aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group and valeryl group; acyloxy groups such as butyryloxy group; Alkenyloxy groups such as vinyloxy group, propenyloxy group, allyloxy group and butenyloxy group; aryloxy groups such as the above aryl groups and phenoxy groups; and aryloxycarbonyl groups such as benzoyloxy group.
　一般式（ＫＡ－１）におけるＸがカルボン酸エステル基であり、一般式（ＫＡ－１）が示す部分構造がラクトン環であることが好ましく、５～７員環ラクトン環であることが好ましい。
　なお、下記（ＫＡ－１－１）～（ＫＡ－１－１７）におけるように、一般式（ＫＡ－１）で表される部分構造としての５～７員環ラクトン環に、ビシクロ構造、スピロ構造を形成する形で他の環構造が縮環していることが好ましい。
　一般式（ＫＡ－１）で表される環構造が結合してもよい周辺の環構造については、例えば、下記（ＫＡ－１－１）～（ＫＡ－１－１７）におけるもの、又はこれに準じたものを挙げることができる。 X in general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by general formula (KA-1) is preferably a lactone ring, preferably a 5- to 7-membered lactone ring.
As in the following (KA-1-1) to (KA-1-17), the 5- to 7-membered lactone ring as the partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro Other ring structures are preferably condensed to form a structure.
Peripheral ring structures to which the ring structure represented by general formula (KA-1) may be bound include, for example, those in (KA-1-1) to (KA-1-17) below, or I can list the thing which I followed.
　一般式（ＫＡ－１）が示すラクトン環構造を含有する構造として、下記（ＫＡ－１－１）～（ＫＡ－１－１７）のいずれかで表される構造がより好ましい。なお、ラクトン構造が主鎖に直接結合していてもよい。好ましい構造としては、（ＫＡ－１－１）、（ＫＡ－１－４）、（ＫＡ－１－５）、（ＫＡ－１－６）、（ＫＡ－１－１３）、（ＫＡ－１－１４）、（ＫＡ－１－１７）である。 Structures represented by any of the following (KA-1-1) to (KA-1-17) are more preferable as structures containing a lactone ring structure represented by general formula (KA-1). In addition, the lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14), (KA-1-17).
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
　上記ラクトン環構造を含有する構造は、置換基を有していても有していなくてもよい。好ましい置換基としては、上記一般式（ＫＡ－１）が示す環構造が有してもよい置換基と同様のものが挙げられる。 The structure containing the lactone ring structure may or may not have a substituent. Preferred substituents include those similar to the substituents that the ring structure represented by the general formula (KA-1) may have.
　ラクトン構造は光学活性体が存在するものもあるが、いずれの光学活性体を用いてもよい。また、１種の光学活性体を単独で用いても、複数の光学活性体を混合して用いてもよい。１種の光学活性体を主に用いる場合、その光学純度（ｅｅ）が９０％以上のものが好ましく、より好ましくは９５％以上、最も好ましくは９８％以上である。 Some lactone structures have an optically active form, but any optically active form may be used. In addition, one type of optically active substance may be used alone, or a plurality of optically active substances may be mixed and used. When one kind of optically active substance is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.
　一般式（ＫＢ－１）のＸとして好ましくは、カルボン酸エステル基（－ＣＯＯ－）を挙げることができる。 A carboxylic acid ester group (-COO-) can be preferably mentioned as X in the general formula (KB-1).
　一般式（ＫＢ－１）におけるＹ１及びＹ２は、それぞれ独立に、電子求引性基を表す。 Y 1 and Y 2 in general formula (KB-1) each independently represent an electron-withdrawing group.
　電子求引性基は、下記式（ＥＷ）で示す部分構造であることが好ましい。式（ＥＷ）における＊は（ＫＡ－１）に直結している結合手、又は（ＫＢ－１）中のＸに直結している結合手を表す。 The electron-withdrawing group preferably has a partial structure represented by the following formula (EW). * in formula (EW) represents a bond directly linked to (KA-1) or a bond directly linked to X in (KB-1).
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000074
　式（ＥＷ）中、
　ｎｅｗは－Ｃ（Ｒｅｗ１）（Ｒｅｗ２）－で表される連結基の繰り返し数であり、０又は１の整数を表す。ｎｅｗが０の場合は単結合を表し、直接Ｙｅｗ１が結合していることを示す。
　Ｙｅｗ１は、ハロゲン原子、シアノ基、ニトリル基、ニトロ基、後述の－Ｃ（Ｒｆ１）（Ｒｆ２）－Ｒｆ３で表されるハロ（シクロ）アルキル基、ハロアリール基、オキシ基、カルボニル基、スルホニル基、スルフィニル基、及びこれらの組み合わせをあげることができ、電子求引性基は例えば下記構造であってもよい。なお、「ハロ（シクロ）アルキル基」とは、少なくとも一部がハロゲン化したアルキル基及びシクロアルキル基を表す。Ｒｅｗ３、Ｒｅｗ４は、各々独立して任意の構造を表す。Ｒｅｗ３、Ｒｅｗ４はどのような構造でも式（ＥＷ）で表される部分構造は電子求引性を有し、好ましくはアルキル基、シクロアルキル基、フッ化アルキル基である。 In formula (EW),
n ew is the repeating number of the linking group represented by —C(R ew1 )(R ew2 )— and represents an integer of 0 or 1; When new is 0, it represents a single bond, indicating that Yew1 is directly bonded.
Y ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo(cyclo)alkyl group represented by —C(R f1 )(R f2 )—R f3 described later, a haloaryl group, an oxy group, a carbonyl group; , sulfonyl groups, sulfinyl groups, and combinations thereof, and the electron-withdrawing group may be, for example, the following structure. In addition, the "halo(cyclo)alkyl group" represents an alkyl group and a cycloalkyl group which are at least partially halogenated. R ew3 and R ew4 each independently represent an arbitrary structure. R ew3 and R ew4 may have any structure, and the partial structure represented by the formula (EW) has electron-withdrawing properties, and is preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
　Ｙｅｗ１が２価以上の基である場合、残る結合手は、任意の原子又は置換基との結合を形成するものである。
　Ｙｅｗ１は、好ましくはハロゲン原子、又は、－Ｃ（Ｒｆ１）（Ｒｆ２）－Ｒｆ３で表されるハロ（シクロ）アルキル基又はハロアリール基である。
　Ｒｅｗ１、Ｒｅｗ２は、各々独立して任意の置換基を表し、例えば水素原子、アルキル基、シクロアルキル基又はアリール基を表す。
　Ｒｅｗ１、Ｒｅｗ２及びＹｅｗ１の少なくとも２つが互いに連結して環を形成していてもよい。 When Y ew1 is a group having a valence of 2 or more, the remaining bond forms a bond with any atom or substituent.
Y ew1 is preferably a halogen atom, or a halo(cyclo)alkyl or haloaryl group represented by —C(R f1 )(R f2 )—R f3 .
R ew1 and R ew2 each independently represent an arbitrary substituent such as a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
At least two of R ew1 , R ew2 and Y ew1 may be linked together to form a ring.
　ここでＲｆ１はハロゲン原子、パーハロアルキル基、パーハロシクロアルキル基、又はパーハロアリール基を表し、より好ましくはフッ素原子、パーフルオロアルキル基又はパーフルオロシクロアルキル基、更に好ましくはフッ素原子又はトリフルオロメチル基を表す。
　Ｒｆ２、Ｒｆ３は各々独立して水素原子、ハロゲン原子又は有機基を表し、Ｒｆ２とＲｆ３とが連結して環を形成してもよい。有機基としては例えばアルキル基、シクロアルキル基、アルコキシ基等を表し、これらはハロゲン原子（好ましくはフッ素原子）で置換されていても良く、より好ましくは、Ｒｆ２、Ｒｆ３は、（ハロ）アルキル基である。Ｒｆ２はＲｆ１と同様の基を表すか、又はＲｆ３と連結して環を形成していることがより好ましい。
　Ｒｆ１とＲｆ３とは連結して環を形成してもよく、形成する環としては、（ハロ）シクロアルキル環、（ハロ）アリール環等が挙げられる。
　Ｒｆ１～Ｒｆ３における（ハロ）アルキル基としては、例えば前述したＺｋａ１におけるアルキル基、及びこれがハロゲン化した構造が挙げられる。
　Ｒｆ１～Ｒｆ３における、又は、Ｒｆ２とＲｆ３とが連結して形成する環における（パー）ハロシクロアルキル基及び（パー）ハロアリール基としては、例えば前述したＺｋａ１におけるシクロアルキル基がハロゲン化した構造、より好ましくは－Ｃ（ｎ）Ｆ（２ｎ－２）Ｈで表されるフルオロシクロアルキル基、及び、－Ｃ（ｎ）Ｆ（ｎ－１）で表されるパーフルオロアリール基が挙げられる。ここで炭素数ｎは特に限定されないが、５～１３のものが好ましく、６がより好ましい。 Here, R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a fluorine atom or a tri represents a fluoromethyl group.
R f2 and R f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R f2 and R f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, an alkoxy group, and the like, which may be substituted with a halogen atom (preferably a fluorine atom), and more preferably R f2 and R f3 are (halo) is an alkyl group. R f2 more preferably represents the same group as R f1 or is linked to R f3 to form a ring.
R f1 and R f3 may be linked to form a ring, and the ring to be formed includes a (halo)cycloalkyl ring, a (halo)aryl ring and the like.
The (halo)alkyl group for R f1 to R f3 includes, for example, the alkyl group for Z ka1 described above and a halogenated structure thereof.
As the (per)halocycloalkyl group and (per)haloaryl group in R f1 to R f3 or in the ring formed by connecting R f2 and R f3 , for example, the cycloalkyl group in Z ka1 described above is halogen structure, more preferably a fluorocycloalkyl group represented by -C (n) F (2n-2) H, and a perfluoroaryl group represented by -C (n) F (n-1) mentioned. Although the number of carbon atoms n is not particularly limited, it is preferably 5 to 13, more preferably 6.
　Ｒｅｗ１、Ｒｅｗ２及びＹｅｗ１の少なくとも２つが互いに連結して形成してもよい環としては、好ましくはシクロアルキル基又はヘテロ環基が挙げられ、ヘテロ環基としてはラクトン環基が好ましい。ラクトン環としては、例えば上記式（ＫＡ－１－１）～（ＫＡ－１－１７）で表される構造が挙げられる。 The ring which may be formed by combining at least two of R ew1 , R ew2 and Y ew1 is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).
　なお、上記化合物（Ｂ）中に、一般式（ＫＡ－１）で表される部分構造を複数、一般式（ＫＢ－１）で表される部分構造を複数、あるいは、一般式（ＫＡ－１）の部分構造と一般式（ＫＢ－１）の両方を有していてもよい。
　なお、一般式（ＫＡ－１）の部分構造の一部又は全部が、一般式（ＫＢ－１）におけるＹ１又はＹ２としての電子求引性基を兼ねてもよい。例えば、一般式（ＫＡ－１）のＸがカルボン酸エステル基である場合、そのカルボン酸エステル基は一般式（ＫＢ－１）におけるＹ１又はＹ２としての電子求引性基として機能することもあり得る。 In the compound (B), a plurality of partial structures represented by general formula (KA-1), a plurality of partial structures represented by general formula (KB-1), or a plurality of partial structures represented by general formula (KA-1 ) and general formula (KB-1).
Part or all of the partial structure of general formula (KA-1) may also serve as an electron-withdrawing group as Y 1 or Y 2 in general formula (KB-1). For example, when X in general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron-withdrawing group as Y 1 or Y 2 in general formula (KB-1). It is possible.
　極性変換基を含む基としては、特に限定されないが、極性変換基を含む有機基を挙げることができる。極性変換基を含む有機基としては、例えば、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせであって、極性変換基を有するようにした基が挙げられる。
　アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせは、それぞれ、Ｒ２～Ｒ４としての置換基の具体例における、アルキル基；アルケニル基；シクロアルキル基；アリール基；ハロゲン原子；酸素原子、硫黄原子、窒素原子及びケイ素原子等のヘテロ原子を含む基；並びにこれらの２種以上の組み合わせと同様である。 The group containing a polarity conversion group is not particularly limited, but an organic group containing a polarity conversion group can be mentioned. Examples of organic groups containing polar conversion groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; A combination of two or more types and having a polar conversion group can be mentioned.
Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen, sulfur, nitrogen and silicon atoms; Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; Similar to combinations of species or more.
　極性変換基を含む基としては、例えば、極性変換基を含むアルキル基、極性変換基を含むアリール基等を挙げることができる。
　極性変換基を含むアルキル基におけるアルキル基としては、例えば、Ｒ２～Ｒ４としてのアルキル基と同様のものを挙げることができる。
　極性変換基を含むアリール基におけるアリール基としては、例えば、Ｒ１及びＲ５としてのアリール基と同様のものを挙げることができる。 Examples of the group containing a polarity conversion group include an alkyl group containing a polarity conversion group and an aryl group containing a polarity conversion group.
Examples of the alkyl group in the alkyl group containing the polarity conversion group include those similar to the alkyl groups for R 2 to R 4 .
Examples of the aryl group in the aryl group containing a polarity conversion group include the same aryl groups as R 1 and R 5 .
　上記一般式（１）中、Ｒ１、Ｒ３、及びＲ５が、下記一般式（Ａｒ）で表される基であることが好ましい。 In general formula (1) above, R 1 , R 3 and R 5 are preferably groups represented by the following general formula (Ar).
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
　一般式（Ａｒ）中、Ｒ６～Ｒ１０は、それぞれ独立に水素原子又は置換基を表す。Ｒ６～Ｒ１０のうち少なくとも一つは、極性基を含む基、酸の作用により分解し極性が増大する基を含む基、又はアルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基である。*は、一般式（１）におけるベンゼン環への結合手を表す。 In general formula (Ar), R 6 to R 10 each independently represent a hydrogen atom or a substituent. At least one of R 6 to R 10 is a group containing a polar group, a group containing a group that is decomposed by the action of an acid to increase the polarity, or is decomposed by the action of an alkaline developer and has solubility in an alkaline developer. is a group containing increasing groups. * represents a bond to the benzene ring in general formula (1).
　Ｒ６～Ｒ１０としての置換基の具体例は、上述のＲ２～Ｒ４としての置換基の具体例と同様である。
　Ｒ６～Ｒ１０のうち少なくとも一つは、極性基を含む基、酸の作用により分解し極性が増大する基を含む基、又はアルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基である。
　極性基を含む基は、Ｒ１～Ｒ５のうち少なくとも一つとしての、極性基を含む基と同様である。
　酸の作用により分解し極性が増大する基を含む基は、Ｒ１～Ｒ５のうち少なくとも一つとしての、酸の作用により分解し極性が増大する基を含む基と同様である。
　アルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基は、Ｒ１～Ｒ５のうち少なくとも一つとしての、アルカリ現像液の作用により分解し、アルカリ現像液中での溶解度が増大する基を含む基と同様である。 Specific examples of substituents for R 6 to R 10 are the same as those for R 2 to R 4 described above.
At least one of R 6 to R 10 is a group containing a polar group, a group containing a group that is decomposed by the action of an acid to increase the polarity, or is decomposed by the action of an alkaline developer and has solubility in an alkaline developer. is a group containing increasing groups.
The group containing a polar group is the same as the group containing a polar group as at least one of R 1 to R 5 .
The group containing a group which is decomposable by the action of an acid to increase its polarity is the same as the group containing a group which is decomposable by the action of an acid to increase its polarity as at least one of R 1 to R 5 .
A group containing a group that decomposes under the action of an alkaline developer and increases its solubility in an alkaline developer, as at least one of R 1 to R 5 , decomposes under the action of an alkaline developer and dissolves in the alkaline developer. The same is true for groups containing groups that increase the solubility in.
　また、上記一般式（１）中、Ｒ１、Ｒ３、及びＲ５が、下記一般式（Ａｒ１）で表される基であることが好ましい。 Moreover, in the general formula (1), R 1 , R 3 and R 5 are preferably groups represented by the following general formula (Ar1).
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
　一般式（Ａｒ１）中、
　Ｒ１１～Ｒ１５は、それぞれ独立に水素原子又は置換基を表し、Ｒ１１～Ｒ１５のうち少なくとも一つは、下記置換基Ｙを表す。*は、一般式（１）におけるベンゼン環への結合手を表す。
　置換基Ｙ：　ヒドロキシ基、カルボキシル基、カルボニル結合を有する基、アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、又はイミド基 In the general formula (Ar1),
R 11 to R 15 each independently represent a hydrogen atom or a substituent, and at least one of R 11 to R 15 represents a substituent Y below. * represents a bond to the benzene ring in general formula (1).
Substituent Y: hydroxy group, carboxyl group, group having a carbonyl bond, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, or imido group
　Ｒ１１～Ｒ１５としての置換基の具体例は、上述のＲ２～Ｒ４としての置換基の具体例と同様である。
　Ｒ１１～Ｒ１５のうち少なくとも一つは、上記置換基Ｙを表す。 Specific examples of substituents for R 11 to R 15 are the same as those for R 2 to R 4 described above.
At least one of R 11 to R 15 represents the substituent Y described above.
　置換基Ｙとしてのカルボニル結合を有する基の具体例は、上述の極性基を有する基としてのカルボニル結合を有する基の具体例と同様である。
　置換基Ｙとしてのアシルオキシ基におけるアシル基の炭素数は、好ましくは１～３０であり、更に好ましくは１～８である。
　置換基Ｙとしてのアルコキシカルボニルオキシ基におけるアルコキシ基の炭素数は、好ましくは１～３０であり、更に好ましくは１～８である。
　置換基Ｙとしてのアリールオキシカルボニルオキシ基におけるアリール基の炭素数は、好ましくは６～１４であり、更に好ましくは６～１０である。
　置換基Ｙとしてのアリールオキシカルボニル基におけるアリール基の炭素数は、好ましくは６～１４であり、更に好ましくは６～１０である。
　置換基Ｙとしてのアルコキシカルボニル基におけるアルコキシ基の炭素数は、好ましくは１～３０であり、更に好ましくは１～８である。
　置換基Ｙとしてのイミド基は、イミドから水素原子を一つ除した基である。 Specific examples of the group having a carbonyl bond as the substituent Y are the same as the specific examples of the group having a carbonyl bond as the group having the polar group described above.
The acyl group in the acyloxy group as the substituent Y preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
The alkoxy group in the alkoxycarbonyloxy group as the substituent Y preferably has 1 to 30 carbon atoms, more preferably 1 to 8 carbon atoms.
The aryl group in the aryloxycarbonyloxy group as the substituent Y preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
The aryl group in the aryloxycarbonyl group as the substituent Y preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.
The number of carbon atoms of the alkoxy group in the alkoxycarbonyl group as the substituent Y is preferably 1-30, more preferably 1-8.
The imide group as the substituent Y is a group obtained by removing one hydrogen atom from imide.
　置換基Ｙとしての、カルボニル結合を有する基、アシルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アリールオキシカルボニル基、アルコキシカルボニル基、及びイミド基は更に置換基を有していても良い。
　更なる置換基としては、上述したＲ１及びＲ５とが更に有していても良い置換基の具体例として前述した各基を挙げることができる。 A group having a carbonyl bond, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, and an imide group as the substituent Y may further have a substituent.
As the further substituents, the groups described above as specific examples of the substituents that R 1 and R 5 described above may further have can be mentioned.
　一般式（１）のアニオン部におけるｎは、アニオンの個数を表す。ｎは１以上の整数を表す。ｎの上限値は特に限定されないが、例えば、４である。
　ｎが１であることが好ましい。 n in the anion part of the general formula (1) represents the number of anions. n represents an integer of 1 or more. Although the upper limit of n is not particularly limited, it is 4, for example.
It is preferred that n is 1.
　上記一般式（１）におけるＭｎ＋はカチオンを表す。
　一般式（１）のカチオン部におけるｎは、カチオンの価数を表す。ｎは１以上の整数を表す。ｎの上限値は特に限定されないが、例えば、４である。
　ｎが１であることが好ましい。
　Ｍｎ＋としてのカチオンは、１価以上のカチオンであれば、特に限定されないが、オニウムカチオンが好ましく、上記式（ＺａＩ）、又は式（ＺａＩＩ）で表されるカチオンが好ましい。 M n+ in the general formula (1) represents a cation.
n in the cation part of the general formula (1) represents the valence of the cation. n represents an integer of 1 or more. Although the upper limit of n is not particularly limited, it is 4, for example.
It is preferred that n is 1.
The cation as M n+ is not particularly limited as long as it is a cation having a valence of 1 or more, but is preferably an onium cation, and preferably a cation represented by the above formula (ZaI) or formula (ZaII).
　式（ＺａＩ）におけるカチオンの好適な態様としては、上述の、カチオン（ＺａＩ－１）、カチオン（ＺａＩ－２）、カチオン（ＺａＩ－３ｂ）、カチオン（ＺａＩ－４ｂ）が挙げられる。
　ｎが２以上の場合における２価以上のカチオンは、式（ＺａＩ）で表される構造を複数有するカチオンであってもよい。このようなカチオンとしては、例えば、式（ＺａＩ）で表されるカチオンのＲ２０１～Ｒ２０３の少なくとも１つと、式（ＺａＩ）で表されるもうひとつのカチオンのＲ２０１～Ｒ２０３の少なくとも一つとが、単結合又は連結基を介して結合した構造を有する２価のカチオンなどを挙げることができる。 Preferred embodiments of the cation in formula (ZaI) include the cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described above.
The bivalent or higher cation when n is 2 or more may be a cation having a plurality of structures represented by formula (ZaI). Such cations include, for example, at least one of R 201 to R 203 of the cation represented by formula (ZaI) and at least one of R 201 to R 203 of another cation represented by formula (ZaI). Examples include divalent cations having a structure in which two are bonded via a single bond or a linking group.
　一般式（１）におけるＭｎ＋（カチオン）の好ましい例としては、上述の「Ｍ＋　Ｘ－」で表される化合物における、Ｍ＋の有機カチオンの具体例が挙げられる。 Preferable examples of M n+ (cation) in general formula (1) include specific examples of M + organic cations in the compound represented by “M + X − ” described above.
　一般式（１）におけるアニオン部分の好ましい例を以下に示すが、本発明はこれらに限定されるものではない。Ｍｅは、メチル基を表す。 Preferred examples of the anion moiety in general formula (1) are shown below, but the present invention is not limited to these. Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000080
 
Figure JPOXMLDOC01-appb-C000080
 
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000082
 
Figure JPOXMLDOC01-appb-C000082
 
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
　上記化合物（Ｂ）が発生する酸のｐＫａが－１０以上５以下であることが好ましい。 The pKa of the acid generated by the compound (B) is preferably -10 or more and 5 or less.
　光酸発生剤（Ｂ）の好ましい例を以下に示すが、本発明はこれらに限定されるものではない。Ｍｅはメチル基を表す。また、光酸発生剤（Ｂ）の好ましい例としては、上記のアニオンと上記のカチオンを組み合わせた化合物も挙げることができる。 Preferable examples of the photoacid generator (B) are shown below, but the present invention is not limited to these. Me represents a methyl group. Preferred examples of the photoacid generator (B) also include compounds in which the above anions and the above cations are combined.
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000088
　化合物（Ｂ）は、例えば、カップリング反応を使用する方法により合成することができる。 Compound (B) can be synthesized, for example, by a method using a coupling reaction.
　カップリング反応は、例えば、鈴木カップリング等を適用することができる。対カチオンは、例えば、特開平６－１８４１７０号公報等に記載の公知のアニオン交換法やイオン交換樹脂による変換法により、所望のカチオンＭ＋に変換することが出来る。
　カップリング反応としては、例えば以下を挙げることができる。 For the coupling reaction, for example, Suzuki coupling or the like can be applied. The counter cation can be converted into the desired cation M 2 + by, for example, a known anion exchange method described in JP-A-6-184170 or a conversion method using an ion exchange resin.
Examples of coupling reactions include the following.
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
　Ｘはハロゲン原子を表し、Ａはアルキル基を表す。Ｒは置換基を表す。
　Ｙはカップリング反応により化合物ＸＹを形成する基を表す。 X represents a halogen atom and A represents an alkyl group. R represents a substituent.
Y represents a group that forms compound XY through a coupling reaction.
　本発明の組成物が光酸発生剤（Ｂ）を含む場合、その含有量は特に制限されないが、形成されるパターンの断面形状がより矩形化する点で、組成物の全固形分に対して、０．５質量％以上が好ましく、１．０質量％以上がより好ましい。上記含有量は、組成物の全固形分に対して、５０．０質量％以下が好ましく、３０．０質量％以下がより好ましく、２５．０質量％以下が更に好ましい。
　光酸発生剤（Ｂ）は、１種単独で使用してもよく、２種以上を使用してもよい。 When the composition of the present invention contains the photoacid generator (B), the content is not particularly limited, but since the cross-sectional shape of the formed pattern becomes more rectangular, the total solid content of the composition is , is preferably 0.5% by mass or more, more preferably 1.0% by mass or more. The content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition.
The photoacid generator (B) may be used alone or in combination of two or more.
＜酸拡散制御剤（Ｃ）＞
　本発明の組成物は、酸拡散制御剤を含んでいてもよい。
　酸拡散制御剤は、露光時に光酸発生剤等から発生する酸をトラップし、余分な発生酸による、未露光部における酸分解性樹脂の反応を抑制するクエンチャーとして作用する。
　酸拡散制御剤の種類は特に制限されず、例えば、塩基性化合物（ＣＡ）、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物（ＣＢ）、及び、活性光線又は放射線の照射により酸拡散制御能が低下又は消失する化合物（ＣＣ）が挙げられる。
　化合物（ＣＣ）としては、光酸発生剤に対して相対的に弱酸となるオニウム塩化合物（ＣＤ）、及び、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物（ＣＥ）が挙げられる。
　塩基性化合物（ＣＡ）の具体例としては、例えば、国際公開第２０２０／０６６８２４号の段落［０１３２］～［０１３６］に記載のものが挙げられ、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物（ＣＥ）の具体例としては、国際公開第２０２０／０６６８２４号の段落［０１３７］～［０１５５］に記載のもの、及び国際公開第２０２０／０６６８２４号公報の段落［０１６４］に記載のものが挙げられ、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物（ＣＢ）の具体例としては、国際公開第２０２０／０６６８２４号の段落［０１５６］～［０１６３］に記載のものが挙げられる。
　光酸発生剤に対して相対的に弱酸となるオニウム塩化合物（ＣＤ）の具体例としては、例えば、国際公開第２０２０／１５８３３７号の段落［０３０５］～［０３１４］に記載のものが挙げられる。 <Acid diffusion control agent (C)>
The composition of the present invention may contain an acid diffusion control agent.
The acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
The type of acid diffusion controller is not particularly limited, and examples include basic compounds (CA), low-molecular-weight compounds (CB) having nitrogen atoms and groups that leave under the action of acids, and actinic rays or radiation. and a compound (CC) whose ability to control acid diffusion decreases or disappears upon irradiation.
As the compound (CC), an onium salt compound (CD), which becomes a relatively weak acid with respect to the photoacid generator, and a basic compound (CE), whose basicity is reduced or lost by irradiation with actinic rays or radiation. mentioned.
Specific examples of the basic compound (CA) include, for example, those described in paragraphs [0132] to [0136] of WO2020/066824, and the basicity is reduced or reduced by exposure to actinic rays or radiation. Specific examples of the disappearing basic compound (CE) include those described in paragraphs [0137] to [0155] of WO 2020/066824, and paragraph [0164] of WO 2020/066824. Specific examples of the low-molecular compound (CB) having a nitrogen atom and a group that leaves under the action of an acid include paragraphs [0156] to [0163] of International Publication No. 2020/066824. ] include those described in .
Specific examples of the onium salt compound (CD), which is a relatively weak acid with respect to the photoacid generator, include those described in paragraphs [0305] to [0314] of International Publication No. 2020/158337. .
　上記以外にも、例えば、米国特許出願公開２０１６／００７０１６７Ａ１号の段落［０６２７］～［０６６４］、米国特許出願公開２０１５／０００４５４４Ａ１号の段落［００９５］～［０１８７］、米国特許出願公開２０１６／０２３７１９０Ａ１号の段落［０４０３］～［０４２３］、及び米国特許出願公開２０１６／０２７４４５８Ａ１号の段落［０２５９］～［０３２８］に開示された公知の化合物を酸拡散制御剤として好適に使用できる。 In addition to the above, for example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1 and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents.
　本発明の組成物に酸拡散制御剤が含まれる場合、酸拡散制御剤の含有量（複数種存在する場合はその合計）は、組成物の全固形分に対して、０．１～１５．０質量％が好ましく、１．０～１５．０質量％がより好ましい。
　本発明の組成物において、酸拡散制御剤は１種単独で使用してもよいし、２種以上を併用してもよい。 When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (the total if there are more than one) is 0.1 to 15.0% relative to the total solid content of the composition. 0% by mass is preferred, and 1.0 to 15.0% by mass is more preferred.
In the composition of the present invention, one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.
＜疎水性樹脂（Ｄ）＞
　本発明の組成物は、更に、樹脂（Ａ）とは異なる疎水性樹脂を含んでいてもよい。
　疎水性樹脂はレジスト膜の表面に偏在するように設計されることが好ましいが、界面活性剤とは異なり、必ずしも分子内に親水基を有する必要はなく、極性物質及び非極性物質の均一な混合に寄与しなくてもよい。
　疎水性樹脂の添加による効果として、水に対するレジスト膜表面の静的及び動的な接触角の制御、並びに、アウトガスの抑制が挙げられる。 <Hydrophobic resin (D)>
The composition of the invention may further comprise a hydrophobic resin different from resin (A).
Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film. may not contribute to
The effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.
　疎水性樹脂は、膜表層への偏在化の点から、フッ素原子、珪素原子、及び、樹脂の側鎖部分に含まれたＣＨ３部分構造のいずれか１種以上を有するのが好ましく、２種以上を有することがより好ましい。上記疎水性樹脂は、炭素数５以上の炭化水素基を有することが好ましい。これらの基は樹脂の主鎖中に有していても、側鎖に置換していてもよい。
　疎水性樹脂としては、国際公開第２０２０／００４３０６号の段落［０２７５］～［０２７９］に記載される化合物が挙げられる。 From the viewpoint of uneven distribution on the film surface layer, the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin. It is more preferable to have The hydrophobic resin preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain.
Hydrophobic resins include compounds described in paragraphs [0275] to [0279] of WO2020/004306.
　本発明の組成物が疎水性樹脂を含む場合、疎水性樹脂の含有量は、組成物の全固形分に対して、０．０１～２０．０質量％が好ましく、０．１～１５．０質量％がより好ましい。 When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and 0.1 to 15.0% by mass, based on the total solid content of the composition. % by mass is more preferred.
＜界面活性剤（Ｅ）＞
　本発明の組成物は、界面活性剤を含んでいてもよい。界面活性剤を含むと、密着性により優れ、現像欠陥のより少ないパターンを形成することができる。
　界面活性剤は、フッ素系及び／又はシリコン系界面活性剤が好ましい。
　フッ素系及び／又はシリコン系界面活性剤としては、国際公開第２０１８／１９３９５４号の段落［０２１８］及び［０２１９］に開示された界面活性剤が挙げられる。 <Surfactant (E)>
The composition of the invention may contain a surfactant. When a surfactant is contained, it is possible to form a pattern with excellent adhesion and fewer development defects.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/193954.
　これら界面活性剤は、１種を単独で用いてもよく、２種以上を使用してもよい。 One type of these surfactants may be used alone, or two or more types may be used.
　本発明の組成物が界面活性剤を含む場合、界面活性剤の含有量は、組成物の全固形分に対して、０．０００１～２．０質量％が好ましく、０．０００５～１．０質量％がより好ましく、０．１～１．０質量％が更に好ましい。 When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0% by mass, preferably 0.0005 to 1.0%, based on the total solid content of the composition. % by mass is more preferred, and 0.1 to 1.0% by mass is even more preferred.
＜溶剤（Ｆ）＞
　本発明の組成物は、溶剤を含むことが好ましい。
　溶剤は、（Ｍ１）プロピレングリコールモノアルキルエーテルカルボキシレート、並びに、（Ｍ２）プロピレングリコールモノアルキルエーテル、乳酸エステル、酢酸エステル、アルコキシプロピオン酸エステル、鎖状ケトン、環状ケトン、ラクトン、及びアルキレンカーボネートからなる群より選択される少なくとも１つの少なくとも一方を含んでいることが好ましい。なお、上記溶剤は、成分（Ｍ１）及び（Ｍ２）以外の成分を更に含んでいてもよい。 <Solvent (F)>
The composition of the invention preferably contains a solvent.
Solvent consists of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from the group. The solvent may further contain components other than components (M1) and (M2).
　上述した溶剤と上述した樹脂とを組み合わせると、レジスト組成物の塗布性の向上、及び、パターンの現像欠陥数の低減の観点で好ましい。上述した溶剤は、上述した樹脂の溶解性、沸点及び粘度のバランスが良いため、レジスト膜の膜厚のムラ及びスピンコート中の析出物の発生等を抑制することができる。
　成分（Ｍ１）及び成分（Ｍ２）の詳細は、国際公開第２０２０／００４３０６号の段落［０２１８］～［０２２６］に記載され、これらの内容は本明細書に組み込まれる。 A combination of the above-described solvent and the above-described resin is preferable from the viewpoint of improving the coatability of the resist composition and reducing the number of development defects in the pattern. Since the solvent described above has a good balance of solubility, boiling point, and viscosity of the resin described above, it is possible to suppress unevenness in the thickness of the resist film and generation of deposits during spin coating.
Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306, the contents of which are incorporated herein.
　溶剤が成分（Ｍ１）及び（Ｍ２）以外の成分を更に含む場合、成分（Ｍ１）及び（Ｍ２）以外の成分の含有量は、溶剤の全量に対して、５～３０質量％が好ましい。 When the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.
　本発明の組成物中の溶剤の含有量は、固形分濃度が０．５～３０質量％となるように定めるのが好ましく、１～２０質量％となるように定めることがより好ましい。こうすると、組成物の塗布性を更に向上させられる。 The content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. By doing so, the applicability of the composition can be further improved.
　なお、固形分とは、溶剤以外の全ての成分を意味するものであり、上述の通り、感活性光線性又は感放射線性膜を形成する成分を意味する。
　固形分濃度とは、本発明の組成物の総質量に対する、溶剤を除く他の成分の質量の質量百分率である。
　「全固形分」とは、本発明の組成物の全組成から溶剤を除いた成分の総質量をいう。また、「固形分」とは、上述のように、溶剤を除いた成分であり、例えば、２５℃において固体であっても、液体であってもよい。 The solid content means all components other than the solvent, and as described above, it means the components that form the actinic ray-sensitive or radiation-sensitive film.
The solid content concentration is the mass percentage of the mass of other components excluding the solvent relative to the total mass of the composition of the present invention.
"Total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition of the present invention. Moreover, as described above, the “solid content” is a component excluding the solvent, and may be solid or liquid at 25° C., for example.
＜その他の添加剤＞
　本発明の組成物は、溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤、及び／又は、現像液に対する溶解性を促進させる化合物（例えば、分子量１０００以下のフェノール化合物、又は、カルボキシル基を含んだ脂環族若しくは脂肪族化合物）を更に含んでいてもよい。 <Other additives>
The composition of the present invention contains a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light-absorbing agent, and/or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group) may further be included.
　上記「溶解阻止化合物」とは、酸の作用により分解して有機系現像液中での溶解度が減少する、分子量３０００以下の化合物である。 The "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
　本明細書の組成物は、ＥＵＶ露光用感光性組成物として好適に用いられる。
　ＥＵＶ光は波長１３．５ｎｍであり、ＡｒＦ（波長１９３ｎｍ）光等に比べて、より短波長であるため、同じ感度で露光された際の入射フォトン数が少ない。そのため、確率的にフォトンの数がばらつく“フォトンショットノイズ”の影響が大きく、ＬＥＲの悪化及びブリッジ欠陥を招く。フォトンショットノイズを減らすには、露光量を大きくして入射フォトン数を増やす方法があるが、高感度化の要求とトレードオフとなる。 The composition of the specification is suitably used as a photosensitive composition for EUV exposure.
EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, so the number of incident photons is smaller when exposed with the same sensitivity. Therefore, the influence of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of LER and bridge defects. To reduce the photon shot noise, there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.
［感活性光線性又は感放射線性膜、パターン形成方法］
　上記本発明の組成物を用いたパターン形成方法の手順は特に制限されないが、以下の工程を有するパターン形成方法であることが好ましい。
工程１：感活性光線性又は感放射線性樹脂組成物により、基板上に感活性光線性又は感放射線性膜を形成する工程
工程２：上記感活性光線性又は感放射線性膜を露光する工程
工程３：露光された感活性光線性又は感放射線性膜を現像液を用いて現像する工程
　以下、上記それぞれの工程の手順について詳述する。 [Actinic ray-sensitive or radiation-sensitive film, pattern forming method]
Although the procedure of the pattern forming method using the composition of the present invention is not particularly limited, the pattern forming method preferably includes the following steps.
Step 1: A step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition Step 2: A step of exposing the actinic ray-sensitive or radiation-sensitive film 3: Step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer Below, the procedure of each of the above steps will be described in detail.
（工程１：感活性光線性又は感放射線性膜形成工程）
　工程１は、本発明の組成物により、基板上に感活性光線性又は感放射線性膜を形成する工程である。 (Step 1: actinic ray-sensitive or radiation-sensitive film forming step)
Step 1 is a step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention.
　感活性光線性又は感放射線性樹脂組成物により基板上に感活性光線性又は感放射線性膜を形成する方法としては、例えば、感活性光線性又は感放射線性樹脂組成物を基板上に塗布する方法が挙げられる。
　なお、塗布前に感活性光線性又は感放射線性樹脂組成物を必要に応じてフィルター濾過することが好ましい。フィルターのポアサイズは、０．１μｍ以下が好ましく、０．０５μｍ以下がより好ましく、０．０３μｍ以下が更に好ましい。フィルターは、ポリテトラフルオロエチレン製、ポリエチレン製、又は、ナイロン製が好ましい。 As a method for forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition, for example, the actinic ray-sensitive or radiation-sensitive resin composition is applied onto the substrate. method.
In addition, it is preferable to filter the actinic ray-sensitive or radiation-sensitive resin composition with a filter as necessary before coating. The pore size of the filter is preferably 0.1 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less. Filters are preferably made of polytetrafluoroethylene, polyethylene, or nylon.
　感活性光線性又は感放射線性樹脂組成物は、集積回路素子の製造に使用されるような基板（例：シリコン、二酸化シリコン被覆）上に、スピナー又はコーター等の適当な塗布方法により塗布できる。塗布方法は、スピナーを用いたスピン塗布が好ましい。スピナーを用いたスピン塗布をする際の回転数は、１０００～３０００ｒｐｍが好ましい。
　感活性光線性又は感放射線性樹脂組成物の塗布後、基板を乾燥し、感活性光線性又は感放射線性膜を形成してもよい。なお、必要により、感活性光線性又は感放射線性膜の下層に、各種下地膜（無機膜、有機膜、反射防止膜）を形成してもよい。 The actinic ray-sensitive or radiation-sensitive resin composition can be applied onto a substrate (eg, silicon, silicon dioxide coating) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. The coating method is preferably spin coating using a spinner. The rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
After applying the actinic ray-sensitive or radiation-sensitive resin composition, the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoat films (inorganic film, organic film, antireflection film) may be formed under the actinic ray-sensitive or radiation-sensitive film.
　乾燥方法としては、例えば、加熱して乾燥する方法が挙げられる。加熱は通常の露光機、及び／又は、現像機に備わっている手段で実施でき、ホットプレート等を用いて実施してもよい。加熱温度は８０～１５０℃が好ましく、８０～１４０℃がより好ましく、８０～１３０℃が更に好ましい。加熱時間は３０～１０００秒が好ましく、６０～８００秒がより好ましく、６０～６００秒が更に好ましい。 As a drying method, for example, a method of heating and drying can be mentioned. Heating can be carried out by a means provided in a normal exposure machine and/or a developing machine, and may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
　感活性光線性又は感放射線性膜（典型的には、レジスト膜）の膜厚は特に制限されないが、より高精度な微細パターンを形成できる点から、１０～１２０ｎｍが好ましい。なかでも、ＥＵＶ露光とする場合、レジスト膜の膜厚としては、１０～６５ｎｍがより好ましく、１５～５０ｎｍが更に好ましい。ＡｒＦ液浸露光とする場合、レジスト膜の膜厚としては、１０～１２０ｎｍがより好ましく、１５～９０ｎｍが更に好ましい。 Although the film thickness of the actinic ray-sensitive or radiation-sensitive film (typically, resist film) is not particularly limited, it is preferably 10 to 120 nm from the viewpoint of forming finer patterns with higher precision. In particular, when EUV exposure is used, the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. In the case of ArF liquid immersion exposure, the film thickness of the resist film is more preferably 10 to 120 nm, still more preferably 15 to 90 nm.
　なお、レジスト膜の上層にトップコート組成物を用いてトップコートを形成してもよい。
　トップコート組成物は、レジスト膜と混合せず、更にレジスト膜上層に均一に塗布できることが好ましい。トップコートは、特に限定されず、従来公知のトップコートを、従来公知の方法によって形成でき、例えば、特開２０１４－０５９５４３号公報の段落［００７２］～［００８２］の記載に基づいてトップコートを形成できる。
　例えば、特開２０１３－６１６４８号公報に記載されたような塩基性化合物を含むトップコートを、レジスト膜上に形成することが好ましい。トップコートが含み得る塩基性化合物の具体的な例は、感活性光線性又は感放射線性樹脂組成物が含んでいてもよい塩基性化合物が挙げられる。
　トップコートは、エーテル結合、チオエーテル結合、水酸基、チオール基、カルボニル結合、及びエステル結合からなる群より選択される基又は結合を少なくとも１つ含む化合物を含むことも好ましい。 A topcoat composition may be used to form a topcoat on the upper layer of the resist film.
It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film. The topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed.
For example, it is preferable to form a topcoat containing a basic compound as described in JP-A-2013-61648 on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that the actinic ray-sensitive or radiation-sensitive resin composition may contain.
The topcoat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
（工程２：露光工程）
　工程２は、感活性光線性又は感放射線性膜を露光する工程である。
　露光の方法としては、形成した感活性光線性又は感放射線性膜に所定のマスクを通して活性光線又は放射線を照射する方法が挙げられる。
　活性光線又は放射線としては、赤外光、可視光、紫外光、遠紫外光、極紫外光、Ｘ線、及び電子線が挙げられ、２５０ｎｍ以下が好ましく、２２０ｎｍ以下がより好ましく、１～２００ｎｍの波長の遠紫外光、具体的には、ＫｒＦエキシマレーザー（２４８ｎｍ）、ＡｒＦエキシマレーザー（１９３ｎｍ）、Ｆ２エキシマレーザー（１５７ｎｍ）、ＥＵＶ（１３．５ｎｍ）、Ｘ線、及び電子ビームが特に好ましい。 (Step 2: Exposure step)
Step 2 is the step of exposing the actinic ray-sensitive or radiation-sensitive film.
Examples of the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask.
Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, 1 to 200 nm Particularly preferred are wavelengths of deep UV light, specifically KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), F2 excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.
　露光後、現像を行う前にベーク（加熱）を行うことが好ましい。ベークにより露光部の反応が促進され、感度及びパターン形状がより良好となる。
　加熱温度は８０～１５０℃が好ましく、８０～１４０℃がより好ましく、８０～１３０℃が更に好ましい。
　加熱時間は１０～１０００秒が好ましく、１０～１８０秒がより好ましく、３０～１２０秒が更に好ましい。
　加熱は通常の露光機及び／又は現像機に備わっている手段で実施でき、ホットプレート等を用いて行ってもよい。
　この工程は露光後ベークともいう。 After exposure, baking (heating) is preferably performed before development. Baking accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape.
The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds.
Heating can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like.
This step is also called a post-exposure bake.
（工程３：現像工程）
　工程３は、現像液を用いて、露光された感活性光線性又は感放射線性膜を現像し、パターンを形成する工程である。
　現像液は、アルカリ現像液であっても、有機溶剤を含有する現像液（以下、有機系現像液ともいう）であってもよい。 (Step 3: Development step)
Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer to form a pattern.
The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
　現像方法としては、例えば、現像液が満たされた槽中に基板を一定時間浸漬する方法（ディップ法）、基板表面に現像液を表面張力によって盛り上げて一定時間静置して現像する方法（パドル法）、基板表面に現像液を噴霧する方法（スプレー法）、及び一定速度で回転している基板上に一定速度で現像液吐出ノズルをスキャンしながら現像液を吐出しつづける方法（ダイナミックディスペンス法）が挙げられる。
　また、現像を行う工程の後に、他の溶剤に置換しながら、現像を停止する工程を実施してもよい。
　現像時間は未露光部の樹脂が十分に溶解する時間であれば特に制限はなく、１０～３００秒が好ましく、２０～１２０秒がより好ましい。
　現像液の温度は０～５０℃が好ましく、１５～３５℃がより好ましい。 Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing the developer on the surface of the substrate for a certain period of time by raising the developer by surface tension (puddle method). method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). ).
Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
The development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
　アルカリ現像液は、アルカリを含むアルカリ水溶液を用いることが好ましい。アルカリ水溶液の種類は特に制限されないが、例えば、テトラメチルアンモニウムヒドロキシドに代表される４級アンモニウム塩、無機アルカリ、１級アミン、２級アミン、３級アミン、アルコールアミン、又は、環状アミン等を含むアルカリ水溶液が挙げられる。中でも、アルカリ現像液は、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）に代表される４級アンモニウム塩の水溶液であることが好ましい。アルカリ現像液には、アルコール類、界面活性剤等を適当量添加してもよい。アルカリ現像液のアルカリ濃度は、通常、０．１～２０質量％であることが好ましい。アルカリ現像液のｐＨは、通常、１０．０～１５．０であることが好ましい。 It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. Although the type of alkaline aqueous solution is not particularly limited, for example, quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. and an alkaline aqueous solution containing Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer. The alkali concentration of the alkali developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10.0 to 15.0.
　有機系現像液は、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、及び炭化水素系溶剤からなる群より選択される少なくとも１種の有機溶剤を含有する現像液であることが好ましい。 The organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Preferably.
　上記の溶剤は、複数混合してもよいし、上記以外の溶剤又は水と混合してもよい。現像液全体としての含水率は、５０質量％未満が好ましく、２０質量％未満がより好ましく、１０質量％未満が更に好ましく、実質的に水分を含有しないのが特に好ましい。
　有機系現像液に対する有機溶剤の含有量は、現像液の全量に対して、５０質量％以上１００質量％以下が好ましく、８０質量％以上１００質量％以下がより好ましく、９０質量％以上１００質量％以下が更に好ましく、９５質量％以上１００質量％以下が特に好ましい。 A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass with respect to the total amount of the developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.
（他の工程）
　上記パターン形成方法は、工程３の後に、リンス液を用いて洗浄する工程を含むことが好ましい。 (Other processes)
The pattern forming method preferably includes a step of washing with a rinse after step 3.
　アルカリ現像液を用いて現像する工程の後のリンス工程に用いるリンス液としては、例えば、純水が挙げられる。なお、純水には、界面活性剤を適当量添加してもよい。
　リンス液には、界面活性剤を適当量添加してもよい。 Pure water is an example of the rinse solution used in the rinse step after the step of developing with an alkaline developer. An appropriate amount of surfactant may be added to pure water.
An appropriate amount of surfactant may be added to the rinse solution.
　有機系現像液を用いた現像工程の後のリンス工程に用いるリンス液は、パターンを溶解しないものであれば特に制限はなく、一般的な有機溶剤を含む溶液を使用できる。リンス液は、炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤、及びエーテル系溶剤からなる群より選択される少なくとも１種の有機溶剤を含有するリンス液を用いることが好ましい。 The rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse solution should contain at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. is preferred.
　リンス工程の方法は特に限定されず、例えば、一定速度で回転している基板上にリンス液を吐出しつづける方法（回転塗布法）、リンス液が満たされた槽中に基板を一定時間浸漬する方法（ディップ法）、及び基板表面にリンス液を噴霧する方法（スプレー法）が挙げられる。
　また、パターン形成方法は、リンス工程の後に加熱工程（Ｐｏｓｔ　Ｂａｋｅ）を含んでいてもよい。本工程により、ベークによりパターン間及びパターン内部に残留した現像液及びリンス液が除去される。また、本工程により、レジストパターンがなまされ、パターンの表面荒れが改善される効果もある。リンス工程の後の加熱工程は、通常４０～２５０℃（好ましくは９０～２００℃）で、通常１０秒間～３分間（好ましくは３０秒間～１２０秒間）行う。 The method of the rinsing step is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. a method (dip method) and a method of spraying a rinse liquid onto the substrate surface (spray method).
Also, the pattern forming method may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinse solution remaining between the patterns and inside the patterns due to baking are removed. In addition, this process smoothes the resist pattern, and has the effect of improving the roughness of the surface of the pattern. The heating step after the rinsing step is usually carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
　また、形成されたパターンをマスクとして、基板のエッチング処理を実施してもよい。つまり、工程３にて形成されたパターンをマスクとして、基板（又は、下層膜及び基板）を加工して、基板にパターンを形成してもよい。
　基板（又は、下層膜及び基板）の加工方法は特に限定されないが、工程３で形成されたパターンをマスクとして、基板（又は、下層膜及び基板）に対してドライエッチングを行うことにより、基板にパターンを形成する方法が好ましい。ドライエッチングは、酸素プラズマエッチングが好ましい。 Also, the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate.
The method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask. A method of forming a pattern is preferred. Dry etching is preferably oxygen plasma etching.
　本発明の組成物、及び本明細書のパターン形成方法において使用される各種材料（例えば、溶剤、現像液、リンス液、反射防止膜形成用組成物、トップコート形成用組成物等）は、金属等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量は、１質量ｐｐｍ以下が好ましく、１０質量ｐｐｂ以下がより好ましく、１００質量ｐｐｔ以下が更に好ましく、１０質量ｐｐｔ以下が特に好ましく、１質量ｐｐｔ以下が最も好ましい。下限は特に制限させず、０質量ｐｐｔ以上が好ましい。ここで、金属不純物としては、例えば、Ｎａ、Ｋ、Ｃａ、Ｆｅ、Ｃｕ、Ｍｇ、Ａｌ、Ｌｉ、Ｃｒ、Ｎｉ、Ｓｎ、Ａｇ、Ａｓ、Ａｕ、Ｂａ、Ｃｄ、Ｃｏ、Ｐｂ、Ｔｉ、Ｖ、Ｗ、及びＺｎが挙げられる。 Various materials used in the composition of the present invention and the pattern forming method of the present specification (e.g., solvent, developer, rinse, composition for forming an antireflection film, composition for forming a topcoat, etc.) It is preferable not to contain impurities such as The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit is not particularly limited, and is preferably 0 mass ppt or more. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
　各種材料から金属等の不純物を除去する方法としては、例えば、フィルターを用いた濾過が挙げられる。フィルターを用いた濾過の詳細は、国際公開第２０２０／００４３０６号の段落［０３２１］に記載される。 　An example of a method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using filters are described in paragraph [0321] of WO2020/004306.
　各種材料に含まれる金属等の不純物を低減する方法としては、例えば、各種材料を構成する原料として金属含有量が少ない原料を選択する方法、各種材料を構成する原料に対してフィルター濾過を行う方法、及び装置内をテフロン（登録商標）でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う方法が挙げられる。 Methods for reducing impurities such as metals contained in various materials include, for example, a method of selecting raw materials with a low metal content as raw materials constituting various materials, and a method of filtering raw materials constituting various materials with a filter. and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).
　フィルター濾過の他、吸着材による不純物の除去を行ってもよく、フィルター濾過と吸着材とを組み合わせて使用してもよい。吸着材としては、公知の吸着材を使用でき、例えば、シリカゲル及びゼオライト等の無機系吸着材、並びに、活性炭等の有機系吸着材を使用できる。上記各種材料に含まれる金属等の不純物を低減するためには、製造工程における金属不純物の混入を防止する必要がある。製造装置から金属不純物が十分に除去されたかどうかは、製造装置の洗浄に使用された洗浄液中に含まれる金属成分の含有量を測定して確認できる。使用後の洗浄液に含まれる金属成分の含有量は、１００質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）以下が好ましく、１０質量ｐｐｔ以下がより好ましく、１質量ｐｐｔ以下が更に好ましい。下限は特に制限させず、０質量ｐｐｔ以上が好ましい。 In addition to filter filtration, impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the various materials described above, it is necessary to prevent metal impurities from entering during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment. The content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less. The lower limit is not particularly limited, and is preferably 0 mass ppt or more.
　リンス液等の有機系処理液には、静電気の帯電、引き続き生じる静電気放電に伴う、薬液配管及び各種パーツ（フィルター、Ｏ－リング、及び、チューブ等）の故障を防止するため、導電性の化合物を添加してもよい。導電性の化合物は特に制限されないが、例えば、メタノールが挙げられる。添加量は特に制限されないが、好ましい現像特性又はリンス特性を維持する点で、１０質量％以下が好ましく、５質量％以下がより好ましい。下限は特に制限させず、０．０１質量％以上が好ましい。
　薬液配管としては、例えば、ＳＵＳ（ステンレス鋼）、又は、帯電防止処理の施されたポリエチレン、ポリプロピレン、若しくは、フッ素樹脂（ポリテトラフルオロエチレン、又は、パーフルオロアルコキシ樹脂等）で被膜された各種配管を使用できる。フィルター及びＯ－リングに関しても同様に、帯電防止処理の施されたポリエチレン、ポリプロピレン、又は、フッ素樹脂（ポリテトラフルオロエチレン、又は、パーフルオロアルコキシ樹脂等）を使用できる。 Organic processing liquids such as rinsing liquids should contain conductive compounds to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. may be added. The conductive compound is not particularly limited, and examples thereof include methanol. The amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties. The lower limit is not particularly limited, and is preferably 0.01% by mass or more.
As the chemical liquid pipe, for example, SUS (stainless steel), antistatic treated polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. Antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used for filters and O-rings.
［電子デバイスの製造方法］
　本明細書は、上記したパターン形成方法を含む、電子デバイスの製造方法、及びこの製造方法により製造された電子デバイスにも関する。
　本明細書の電子デバイスの好適態様としては、電気電子機器（家電、ＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ）、メディア関連機器、光学用機器及び通信機器等）に搭載される態様が挙げられる。 [Method for manufacturing electronic device]
The present specification also relates to an electronic device manufacturing method, including the pattern forming method described above, and an electronic device manufactured by this manufacturing method.
A preferred embodiment of the electronic device of the present specification includes a mode in which it is installed in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
　以下に実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。 The present invention will be described in more detail below based on examples. Materials, usage amounts, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below.
＜合成例１：樹脂Ａ－１１の合成＞
（モノマー（ａ－１）の合成）
　Ｐｏｌｙｍ．　Ｃｈｅｍ．　２０１９，　１０，　２７６４に記載の方法に従って合成した。 <Synthesis Example 1: Synthesis of Resin A-11>
(Synthesis of monomer (a-1))
Polym. Chem. 2019, 10, synthesized according to the method described in 2764.
（樹脂Ａ－１１の合成） (Synthesis of resin A-11)
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
　モノマーとして（Ｍ－１）、（Ｍ－２）、（ａ－１）を用い、各モノマーを（Ｍ－１）：（Ｍ－２）：（ａ－１）＝６５／１０／２５のモル比になるように混合し、シクロヘキサノンをモノマー濃度が３０質量％の溶液になるように加え、開始剤ジメチル２，２’－アゾビス（２－メチルプロピオネート）を８ｍｏｌ％添加し、モノマー溶液を調整した。窒素雰囲気下、上記モノマー溶液の０．１質量倍のシクロヘキサノンを８５℃に加熱し、モノマー溶液を２時間かけて滴下した後、さらに２時間８５℃で反応させた。得られた樹脂の溶液を酢酸エチル：ｎ－ヘプタン＝１：９（質量比）混合溶媒中に滴下し、樹脂を沈殿させ、ろ過、回収後、真空乾燥し、収率６６％で樹脂Ａ－１１を得た。 Using (M-1), (M-2), and (a-1) as monomers, each monomer is (M-1): (M-2): (a-1) = 65/10/25 moles ratio, cyclohexanone was added to give a solution with a monomer concentration of 30% by mass, dimethyl 2,2'-azobis(2-methylpropionate) was added at 8 mol% as an initiator, and the monomer solution was It was adjusted. Under a nitrogen atmosphere, 0.1 times the weight of the monomer solution of cyclohexanone was heated to 85° C., and the monomer solution was added dropwise over 2 hours, followed by further reaction at 85° C. for 2 hours. The resulting resin solution was added dropwise to a mixed solvent of ethyl acetate:n-heptane=1:9 (mass ratio) to precipitate the resin, followed by filtration, recovery, and vacuum drying. 11 was obtained.
［感活性光線性又は感放射線性樹脂組成物の各種成分］
＜樹脂（Ａ）＞
　使用した樹脂（Ａ）（樹脂Ａ－１～Ａ－４６）の構造を以下に示す。
　モノマー（ａ－１）以外の一般式（ａ）で表される繰り返し単位の原料モノマーについては、Ｐｏｌｙｍ．　Ｃｈｅｍ．　２０１６，　７，　４４２７　２の記載や、国際公開第２０２１／０７１４３２号等を参考に合成した。樹脂Ａ－１～Ａ－１０、Ａ―１２～Ａ－４６は、上記樹脂Ａ－１１と同様の方法で合成したものを用いた。
　表１に各繰り返し単位の種類及び含有量（含有比率（モル％））、重量平均分子量（Ｍｗ）、及び分散度（Ｍｗ／Ｍｎ）を示す。
　表１中、繰り返し単位２に示す繰り返し単位（ａ）に相当する繰り返し単位（ａ－１）～（ａ－２０）は、それぞれ、後掲する原料モノマー（ａ－１）～（ａ－２０）に由来する繰り返し単位である。
　樹脂Ａ－１～Ａ－４６の重量平均分子量（Ｍｗ）及び分散度（Ｍｗ／Ｍｎ）はＧＰＣ（キャリア：テトラヒドロフラン（ＴＨＦ））により測定した（ポリスチレン換算量である）。また、各繰り返し単位の比率は、１３Ｃ－ＮＭＲ（ｎｕｃｌｅａｒ　ｍａｇｎｅｔｉｃ　ｒｅｓｏｎａｎｃｅ）により測定した。 [Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition]
<Resin (A)>
The structures of the resins (A) used (resins A-1 to A-46) are shown below.
For the raw material monomer of the repeating unit represented by the general formula (a) other than the monomer (a-1), see Polym. Chem. 2016, 7, 4427 2, and International Publication No. 2021/071432. Resins A-1 to A-10 and A-12 to A-46 were synthesized in the same manner as resin A-11.
Table 1 shows the type and content of each repeating unit (content ratio (mol %)), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn).
In Table 1, repeating units (a-1) to (a-20) corresponding to repeating unit (a) shown in repeating unit 2 are raw material monomers (a-1) to (a-20) shown below, respectively. is a repeating unit derived from
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of Resins A-1 to A-46 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). Also, the ratio of each repeating unit was measured by 13 C-NMR (nuclear magnetic resonance).
Figure JPOXMLDOC01-appb-T000091
Figure JPOXMLDOC01-appb-T000091
　表１に示される各繰り返し単位の構造式を以下に示す。繰り返し単位２に示す繰り返し単位（ａ）に相当する繰り返し単位については、対応する原料モノマーの構造式として示す。 The structural formula of each repeating unit shown in Table 1 is shown below. The repeating unit corresponding to the repeating unit (a) shown in repeating unit 2 is shown as the structural formula of the corresponding raw material monomer.
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
　比較例には、下記の樹脂（ＡＸ－１）～（ＡＸ－３）を用いた。各繰り返し単位の含有量（含有比率（モル％））、重量平均分子量（Ｍｗ）、及び分散度（Ｍｗ／Ｍｎ）を示す。重量平均分子量（Ｍｗ）及び分散度（Ｍｗ／Ｍｎ）はＧＰＣ（キャリア：テトラヒドロフラン（ＴＨＦ））により測定した（ポリスチレン換算量である）。また、各繰り返し単位の比率は、１３Ｃ－ＮＭＲ（ｎｕｃｌｅａｒ　ｍａｇｎｅｔｉｃ　ｒｅｓｏｎａｎｃｅ）により測定した。 In Comparative Examples, the following resins (AX-1) to (AX-3) were used. The content of each repeating unit (content ratio (mol %)), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) are shown. The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). Also, the ratio of each repeating unit was measured by 13 C-NMR (nuclear magnetic resonance).
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000096
〔光酸発生剤（Ｂ）〕
　使用した光酸発生剤（Ｂ）の構造を以下に示す。
　化合物（Ｂ－１）～（Ｂ－８０）は、表２に記載のカチオンと表２に記載のアニオンを組み合わせてなるものである。
　組成物の調製には、上記化合物のうち、化合物（Ｂ－３）、（Ｂ－４）、（Ｂ－７）、（Ｂ－８）、（Ｂ－１１）、（Ｂ－１２）、（Ｂ－１５）、（Ｂ－１７）～（Ｂ－１９）、（Ｂ－２９）～（Ｂ－３２）、（Ｂ－３５）～（Ｂ－３７）、（Ｂ－４３）～（Ｂ－４９）、（Ｂ－５３）、（Ｂ－５６）、（Ｂ－５８）、（Ｂ－６２）、（Ｂ－６３）、（Ｂ－６６）、（Ｂ－６７）、（Ｂ－７０）、（Ｂ－７２）、（Ｂ－７３）、（Ｂ－７６）、（Ｂ－７７）、及び（Ｂ－８０）を用いた。 [Photoacid generator (B)]
The structure of the photoacid generator (B) used is shown below.
Compounds (B-1) to (B-80) are obtained by combining the cations listed in Table 2 and the anions listed in Table 2.
For the preparation of the composition, among the above compounds, compounds (B-3), (B-4), (B-7), (B-8), (B-11), (B-12), ( B-15), (B-17) ~ (B-19), (B-29) ~ (B-32), (B-35) ~ (B-37), (B-43) ~ (B- 49), (B-53), (B-56), (B-58), (B-62), (B-63), (B-66), (B-67), (B-70) , (B-72), (B-73), (B-76), (B-77), and (B-80) were used.
Figure JPOXMLDOC01-appb-T000097
Figure JPOXMLDOC01-appb-T000097
　表２に記載のカチオンの構造を以下に示す。Ｍｅはメチル基を表し、Ｂｕは、ｎ－ブチル基を表す。 The structures of the cations listed in Table 2 are shown below. Me represents a methyl group and Bu represents an n-butyl group.
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
　表２に記載のアニオンの構造を以下に示す。Ｍｅはメチル基を表し、Ｂｕは、ｎ－ブチル基を表す。 The structures of the anions listed in Table 2 are shown below. Me represents a methyl group and Bu represents an n-butyl group.
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000104
〔酸拡散制御剤〕
　使用した酸拡散制御剤の構造を以下に示す。 [Acid diffusion control agent]
The structure of the acid diffusion control agent used is shown below.
Figure JPOXMLDOC01-appb-C000105
Figure JPOXMLDOC01-appb-C000105
〔界面活性剤〕
　界面活性剤としては、下記Ｗ－１～Ｗ－４を用いた。
　Ｗ－１：メガファックＲ０８（大日本インキ化学工業（株）製；フッ素及びシリコン系）
　Ｗ－２：ポリシロキサンポリマーＫＰ－３４１（信越化学工業（株）製；シリコン系）　Ｗ－３：トロイゾルＳ－３６６（トロイケミカル（株）製；フッ素系）
　Ｗ－４：ＰＦ６３２０（ＯＭＮＯＶＡ社製；フッ素系） [Surfactant]
W-1 to W-4 below were used as surfactants.
W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine and silicon type)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based) W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)
〔溶剤〕
　使用した溶剤を以下に示す。
　Ｓ－１：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）
　Ｓ－２：ジアセトンアルコール（ＤＡＡ）
　Ｓ－３：プロピレングリコールモノメチルエーテル（ＰＧＭＥ）
　Ｓ－４：乳酸エチル（ＥＬ）
　Ｓ－５：３－エトキシプロピオン酸エチル（ＥＥＰ）
　Ｓ－６：２－ヘプタノン（ＭＡＫ）
　Ｓ－７：３－メトキシプロピオン酸メチル（ＭＭＰ）
　Ｓ－８：酢酸３－メトキシブチル
　Ｓ－９：γ－ブチロラクトン 〔solvent〕
The solvents used are shown below.
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: diacetone alcohol (DAA)
S-3: Propylene glycol monomethyl ether (PGME)
S-4: ethyl lactate (EL)
S-5: Ethyl 3-ethoxypropionate (EEP)
S-6: 2-heptanone (MAK)
S-7: methyl 3-methoxypropionate (MMP)
S-8: 3-methoxybutyl acetate S-9: γ-butyrolactone
［レジスト組成物の塗液調製及び塗設］
（１）支持体の準備
　酸化窒化Ｃｒを蒸着した８インチウェハー（通常のフォトマスクブランクスに使用する遮蔽膜処理を施した物）を準備した。
（２）レジスト組成物の調製
　表３に示す成分を同表に示す溶剤に溶解させて、同表に示す固形分濃度にて溶液を調製し、これを０．０３μｍのポアサイズを有するポリエチレンフィルターで濾過してレジスト組成物を調製した。
　なお、下記表３において、溶剤以外の各成分の含有量（質量％）は、全固形分に対する含有比率を意味する。また、下記表３には用いた溶剤の全溶剤に対する含有比率（質量％）を記載した。
（３）レジスト膜の作製
　上記８インチウェハー上に東京エレクトロン製スピンコーターＭａｒｋ８を用いてレジスト組成物を塗布し、１２０℃、６００秒間ホットプレート上で乾燥して、膜厚１００ｎｍのレジスト膜を得た。すなわち、レジスト塗布ウェハーを得た。 [Preparation and application of coating solution of resist composition]
(1) Preparation of support An 8-inch wafer (having undergone a shielding film treatment used for a normal photomask blank) on which Cr oxynitride was deposited was prepared.
(2) Preparation of resist composition The components shown in Table 3 were dissolved in the solvent shown in the same table to prepare a solution with the solid content concentration shown in the same table, and this was passed through a polyethylene filter having a pore size of 0.03 µm. A resist composition was prepared by filtration.
In Table 3 below, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. In addition, Table 3 below shows the content ratio (% by mass) of the solvent used with respect to the total solvent.
(3) Preparation of resist film On the above 8-inch wafer, a resist composition is applied using a Tokyo Electron spin coater Mark 8 and dried on a hot plate at 120 ° C. for 600 seconds to obtain a resist film with a thickness of 100 nm. Ta. That is, a resist-coated wafer was obtained.
Figure JPOXMLDOC01-appb-T000106
Figure JPOXMLDOC01-appb-T000106
Figure JPOXMLDOC01-appb-T000107
Figure JPOXMLDOC01-appb-T000107
［ＥＢ露光及び現像］
（４）レジストパターンの作製
　上記（３）で得られたレジスト膜に電子線描画装置（（株）アドバンテスト製；Ｆ７０００Ｓ、加速電圧５０ＫｅＶ）を用いて、パターン照射を行った。照射後に、１００℃、６００秒ホットプレート上で加熱し、２．３８質量％テトラメチルアンモニウムハイドロオキサイド（ＴＭＡＨ）水溶液を用いて６０秒間浸漬した後、３０秒間、水でリンスして乾燥した。 [EB exposure and development]
(4) Preparation of resist pattern The resist film obtained in (3) above was subjected to pattern irradiation using an electron beam lithography system (F7000S manufactured by Advantest Co., Ltd., acceleration voltage 50 KeV). After irradiation, it was heated on a hot plate at 100° C. for 600 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried.
［評価］
（５）レジストパタ－ンの評価
　得られたパターンを下記の方法で、解像性、ラフネス性能、パターン形状について評価した。結果を後掲の表４に示す。 [evaluation]
(5) Evaluation of resist pattern The resulting pattern was evaluated for resolution, roughness performance and pattern shape by the following methods. The results are shown in Table 4 below.
　線幅５０ｎｍの１：１ラインアンドスペースパターンを解像する時の照射エネルギーを感度（Ｅｏｐ）とした。 The sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line and space pattern with a line width of 50 nm.
　＜Ｌ／Ｓ解像性＞
　上記感度（Ｅｏｐ）を示す露光量における限界解像力（ラインとスペース（ライン：スペース＝１：１）が分離解像する最小の線幅）を解像力（ｎｍ）とした。 <L/S resolution>
The limit resolving power (the minimum line width at which a line and a space (line:space=1:1) are separated and resolved) at the exposure dose showing the sensitivity (Eop) was taken as the resolving power (nm).
＜ラフネス性能＞
　ラフネス性能は、以下のようにラインウィズスラフネス（ＬＷＲ）にて評価した。
　ラインウィズスラフネスは、上記Ｅｏｐにおいて、線幅５０ｎｍのラインアンドスペースパターン（ライン：スペース＝１：１）の長手方向０．５μｍの任意の５０点について、線幅を計測し、その標準偏差を求め、３σ（ｎｍ）を算出した。値が小さいほど良好な性能であることを示す。 <Roughness performance>
Roughness performance was evaluated by line width roughness (LWR) as follows.
The line width roughness is obtained by measuring the line width at arbitrary 50 points in the longitudinal direction of 0.5 μm of a line and space pattern (line: space = 1: 1) with a line width of 50 nm in the above Eop, and calculating the standard deviation. 3σ (nm) was calculated. A smaller value indicates better performance.
＜パタ－ン形状＞
　上記の感度を示す照射量における線幅５０ｎｍの１：１ラインアンドスペースパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－４８００）を用いて観察したラインパターンの断面形状において、［ラインパターンのトップ部（表面部）における線幅／ラインパターンの中部（ラインパターンの高さの半分の高さ位置）における線幅］で表される比率が１．１以上のものを「逆テーパー」とし、該比率が１．０３以上１．１未満のものを「やや逆テーパー」とし、該比率が１．０３未満のものを「矩形」として、評価を行った。 <Pattern shape>
The cross-sectional shape of a 1:1 line and space pattern with a line width of 50 nm at the irradiation dose showing the above sensitivity is observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.) In the cross-sectional shape of the line pattern, If the ratio represented by [line width at the top part (surface part) of the line pattern / line width at the middle part of the line pattern (half the height of the line pattern)] is 1.1 or more, the "reverse Those with a ratio of 1.03 or more and less than 1.1 were evaluated as "slightly reverse taper", and those with a ratio of less than 1.03 were evaluated as "rectangular".
Figure JPOXMLDOC01-appb-T000108
Figure JPOXMLDOC01-appb-T000108
　表４の結果より、本発明の組成物によれば、極微細（特に、線幅又はスペース幅が２０ｎｍ以下）のパターン形成において、優れた解像性、優れたラフネス性能を有し、優れたパターン形状を得ることができることがわかる。 From the results of Table 4, according to the composition of the present invention, in ultrafine (especially line width or space width of 20 nm or less) pattern formation, excellent resolution, excellent roughness performance, excellent It can be seen that a pattern shape can be obtained.
［極紫外線（ＥＵＶ）露光及び現像］
（４）レジストパターンの作製
　上記（３）で得られたレジスト膜の塗布されたウェハを、ＥＵＶ露光装置（Ｅｘｉｔｅｃｈ社製　Ｍｉｃｒｏ　Ｅｘｐｏｓｕｒｅ　Ｔｏｏｌ、ＮＡ（開口数）０．３、Ｑｕａｄｒｕｐｏｌｅ、アウターシグマ０．６８、インナーシグマ０．３６）を用い、露光マスク（ライン／スペース＝１／１）を使用して、パターン露光を行った。露光後、ホットプレート上で、１００℃で９０秒間加熱した後、２．３８質量％のテトラメチルアンモニウムハイドロオキサイド（ＴＭＡＨ）水溶液を用いて６０秒間浸漬した後、３０秒間、水でリンスした。その後、４０００ｒｐｍの回転数で３０秒間ウェハを回転させた後、９５℃で６０秒間ベークを行い乾燥した。 [Extreme ultraviolet (EUV) exposure and development]
(4) Preparation of resist pattern The wafer coated with the resist film obtained in (3) above was exposed to an EUV exposure apparatus (Micro Exposure Tool manufactured by Exitech, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.3). 68, inner sigma 0.36), and an exposure mask (line/space=1/1) was used for pattern exposure. After exposure, the film was heated on a hot plate at 100° C. for 90 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then rinsed with water for 30 seconds. After that, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then dried by baking at 95° C. for 60 seconds.
［評価］
（５）レジストパタ－ンの評価
　得られたパターンを下記の方法で、解像性、ラフネス性能、及びパターン形状について評価した。結果を後掲の表５に示す。 [evaluation]
(5) Evaluation of resist pattern The resulting pattern was evaluated for resolution, roughness performance, and pattern shape by the following methods. The results are shown in Table 5 below.
　線幅５０ｎｍの１：１ラインアンドスペースパターンを解像する時の照射エネルギーを感度（Ｅｏｐ）とした。 The sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line and space pattern with a line width of 50 nm.
　＜Ｌ／Ｓ解像性＞
　上記感度（Ｅｏｐ）を示す露光量における限界解像力（ラインとスペース（ライン：スペース＝１：１）が分離解像する最小の線幅）を解像力（ｎｍ）とした。 <L/S resolution>
The limit resolving power (the minimum line width at which a line and a space (line:space=1:1) are separated and resolved) at the exposure dose showing the sensitivity (Eop) was taken as the resolving power (nm).
＜ラフネス性能＞
　ラフネス性能は、以下のようにラインウィズスラフネス（ＬＷＲ）にて評価した。
　ラインウィズスラフネスは、上記Ｅｏｐにおいて、線幅５０ｎｍのラインアンドスペースパターン（ライン：スペース＝１：１）の長手方向０．５μｍの任意の５０点について、線幅を計測し、その標準偏差を求め、３σ（ｎｍ）を算出した。値が小さいほど良好な性能であることを示す。 <Roughness performance>
Roughness performance was evaluated by line width roughness (LWR) as follows.
The line width roughness is obtained by measuring the line width at arbitrary 50 points in the longitudinal direction of 0.5 μm of a line and space pattern (line: space = 1: 1) with a line width of 50 nm in the above Eop, and calculating the standard deviation. 3σ (nm) was calculated. A smaller value indicates better performance.
＜パタ－ン形状＞
　上記の感度を示す照射量における線幅５０ｎｍの１：１ラインアンドスペースパターンの断面形状を走査型電子顕微鏡（（株）日立製作所製Ｓ－４８００）を用いて観察したラインパターンの断面形状において、［ラインパターンのトップ部（表面部）における線幅／ラインパターンの中部（ラインパターンの高さの半分の高さ位置）における線幅］で表される比率が１．１以上のものを「逆テーパー」とし、該比率が１．０３以上１．１未満のものを「やや逆テーパー」とし、該比率が１．０３未満のものを「矩形」として、評価を行った。 <Pattern shape>
The cross-sectional shape of a 1:1 line and space pattern with a line width of 50 nm at the irradiation dose showing the above sensitivity is observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.) In the cross-sectional shape of the line pattern, If the ratio represented by [line width at the top part (surface part) of the line pattern / line width at the middle part of the line pattern (half the height of the line pattern)] is 1.1 or more, the "reverse Those with a ratio of 1.03 or more and less than 1.1 were evaluated as "slightly reverse taper", and those with a ratio of less than 1.03 were evaluated as "rectangular".
Figure JPOXMLDOC01-appb-T000109
Figure JPOXMLDOC01-appb-T000109
　表５の結果より、本発明の組成物によれば、極微細（特に、線幅又はスペース幅が２０ｎｍ以下）のパターン形成において、優れた解像性、優れたラフネス性能を有し、優れたパターン形状を得ることができることがわかる。 From the results of Table 5, according to the composition of the present invention, in ultrafine (especially line width or space width of 20 nm or less) pattern formation, excellent resolution, excellent roughness performance, excellent It can be seen that a pattern shape can be obtained.
　本発明によれば、極微細（特に、線幅又はスペース幅が２０ｎｍ以下）のパターン形成において、解像性に優れ、さらにラフネス性能に優れ、優れたパターン形状を得ることができる感活性光線性又は感放射線性樹脂組成物、上記感活性光線性又は感放射線性樹脂組成物により形成された感活性光線性又は感放射線性膜、上記感活性光線性又は感放射線性樹脂組成物を用いるパターン形成方法及び電子デバイスの製造方法を提供することができる。 According to the present invention, in the formation of extremely fine patterns (in particular, line width or space width of 20 nm or less), the actinic ray-sensitive properties are excellent in resolution, roughness performance, and excellent pattern shape. Or a radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition, or pattern formation using the actinic ray-sensitive or radiation-sensitive resin composition Methods and methods of manufacturing electronic devices can be provided.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０２２年２月２４日出願の日本特許出願（特願２０２２－０２７３４７）に基づくものであり、その内容はここに参照として取り込まれる。
 
   Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2022-027347) filed on February 24, 2022, the content of which is incorporated herein by reference.

Claims (14)

  1. 　下記一般式（ａ）で表される繰り返し単位（ａ）を含む樹脂（Ａ）を含有する感活性光線性又は感放射線性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
    　一般式（ａ）中、Ａは芳香環基、又は芳香族ヘテロ環基を表す。Ｘは単結合、アルキレン基、アルケニレン基、アルキニレン基、カルボニル基、スルホニル基、又はそれらを組み合わせてなる基を表す。Ｘは、Ａ環と結合してベンゼン環を形成してもよい。Ｙ１及びＹ２はそれぞれ独立して、酸素原子又は硫黄原子を表す。Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。     An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) containing a repeating unit (a) represented by the following general formula (a).
    Figure JPOXMLDOC01-appb-C000001
    In general formula (a), A represents an aromatic ring group or an aromatic heterocyclic group. X represents a single bond, an alkylene group, an alkenylene group, an alkynylene group, a carbonyl group, a sulfonyl group, or a combination thereof. X may combine with the A ring to form a benzene ring. Y 1 and Y 2 each independently represent an oxygen atom or a sulfur atom. R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom.
  2. 　前記樹脂（Ａ）が、さらに酸基を有する繰り返し単位を含む請求項１に記載の感活性光線性又は感放射線性樹脂組成物。 The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) further contains a repeating unit having an acid group.
  3. 　前記酸基を有する繰り返し単位が、フェノール性水酸基を有する繰り返し単位である請求項２に記載の感活性光線性又は感放射線性樹脂組成物。 The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit having an acid group is a repeating unit having a phenolic hydroxyl group.
  4. 　前記酸基を有する繰り返し単位が、下記一般式（Ｂ）で表される繰り返し単位である請求項２に記載の感活性光線性又は感放射線性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
    　一般式（Ｂ）中、Ｒ３は、水素原子、又は１価の有機基を表す。Ｒ４及びＲ５は、各々独立に、水素原子、ハロゲン原子、又はアルキル基を表す。Ｌ２は、単結合又はエステル結合を表す。Ｌ３は、（ｎ＋ｍ＋１）価の芳香族炭化水素環基、又は（ｎ＋ｍ＋１）価の脂環式炭化水素環基を表す。Ｒ６は、水酸基、又はフッ素化アルコール基を表す。Ｒ７は、ハロゲン原子を表す。ｍは、１以上の整数を表す。ｎは、０又は１以上の整数を表す。     3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (B).
    Figure JPOXMLDOC01-appb-C000002
    In general formula (B), R3 represents a hydrogen atom or a monovalent organic group. R4 and R5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group. L2 represents a single bond or an ester bond. L 3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. R6 represents a hydroxyl group or a fluorinated alcohol group. R7 represents a halogen atom. m represents an integer of 1 or more. n represents an integer of 0 or 1 or more.
  5. 　前記酸基を有する繰り返し単位が、下記一般式（ｃ）で表される繰り返し単位である請求項２に記載の感活性光線性又は感放射線性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000003
    　一般式（ｃ）中、Ｒ６１～Ｒ６３はそれぞれ独立して、水素原子、有機基又はハロゲン原子を表す。ただし、Ｒ６２はＡｒと結合して環を形成していてもよく、その場合のＲ６２は単結合またはアルキレン基を表す。Ｌは単結合、又は２価の連結基を表す。Ａｒは（ｋ＋１）価の芳香環基を表し、Ｒ６２と結合して環を形成する場合には（ｋ＋２）価の芳香環基を表す。ｋは、１～５の整数を表す。     3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit having an acid group is a repeating unit represented by the following general formula (c).
    Figure JPOXMLDOC01-appb-C000003
    In general formula (c), R 61 to R 63 each independently represent a hydrogen atom, an organic group or a halogen atom. However, R 62 may combine with Ar to form a ring, in which case R 62 represents a single bond or an alkylene group. L represents a single bond or a divalent linking group. Ar represents a (k+1)-valent aromatic ring group, and when combined with R 62 to form a ring, represents a (k+2)-valent aromatic ring group. k represents an integer of 1 to 5;
  6. 　一般式（ａ）中、Ｙ１及びＹ２がいずれも酸素原子を表す請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein both Y 1 and Y 2 in general formula (a) represent an oxygen atom.
  7. 　一般式（ａ）中、Ｘが単結合、メチレン基、エチレン基、又はカルボニル基を表す請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein X in general formula (a) represents a single bond, a methylene group, an ethylene group, or a carbonyl group.
  8. 　一般式（ａ）中、Ｘがメチレン基、エチレン基、又はカルボニル基を表す請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein X in general formula (a) represents a methylene group, an ethylene group, or a carbonyl group.
  9. 　一般式（ａ）中、Ｘがカルボニル基を表す請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein X in general formula (a) represents a carbonyl group.
  10. 　一般式（ａ）中、Ａが芳香環基を表す請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein A in general formula (a) represents an aromatic ring group.
  11. 　前記一般式（ａ）で表される繰り返し単位が、下記一般式（ａ－１）で表される繰り返し単位である請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
    　一般式（ａ－１）中、Ｒ１１及びＲ１２はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。Ｒ２１はそれぞれ独立して、水素原子、有機基、又はハロゲン原子を表す。Ｒ２１は互いに結合して環を形成しても良い。     Actinic ray-sensitive or radiation-sensitive according to any one of claims 1 to 5, wherein the repeating unit represented by the general formula (a) is a repeating unit represented by the following general formula (a-1). elastic resin composition.
    Figure JPOXMLDOC01-appb-C000004
    In general formula (a-1), R 11 and R 12 each independently represent a hydrogen atom, an organic group, or a halogen atom. Each R 21 independently represents a hydrogen atom, an organic group, or a halogen atom. R 21 may combine with each other to form a ring.
  12. 　請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成された感活性光線性又は感放射線性膜。 An actinic ray- or radiation-sensitive film formed using the actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 5.
  13. 　請求項１～５のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物により、基板上に感活性光線性又は感放射線性膜を形成する工程と、
    前記感活性光線性又は感放射線性膜を露光する露光工程と、
    露光された前記感活性光線性又は感放射線性膜を現像液を用いて現像する現像工程と、を含むパターン形成方法。     A step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5;
    an exposure step of exposing the actinic ray-sensitive or radiation-sensitive film;
    and a developing step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
  14. 　請求項１３に記載のパターン形成方法を含む電子デバイスの製造方法。
     
     
          A method for manufacturing an electronic device, comprising the pattern forming method according to claim 13 .
PCT/JP2023/005339 2022-02-24 2023-02-15 Active-ray-sensitive or radiation-sensitive resin composition, active-ray-sensitive or radiation-sensitive film, pattern formation method and electronic device manufacturing method WO2023162838A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01130976A (en) * 1987-11-16 1989-05-23 Dainippon Printing Co Ltd Sheet to be thermally transferred
WO2011027782A1 (en) * 2009-09-01 2011-03-10 旭硝子株式会社 Coating material composition for liquid immersion exposure apparatus, laminate, method for forming laminate, and liquid immersion exposure apparatus
CN106986969A (en) * 2017-04-28 2017-07-28 华南理工大学 A kind of main chain degradation-type polyacrylic acid resin of copper and preparation method and application
WO2020004306A1 (en) * 2018-06-28 2020-01-02 富士フイルム株式会社 Active ray-sensitive or radiation-sensitive resin composition, pattern formation method, electronic device manufacturing method, resin
WO2020137918A1 (en) * 2018-12-28 2020-07-02 富士フイルム株式会社 Negative-type active-ray-sensitive or radiation-sensitive resin composition for organic solvent development, resist film, pattern-forming method, and electronic device production method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01130976A (en) * 1987-11-16 1989-05-23 Dainippon Printing Co Ltd Sheet to be thermally transferred
WO2011027782A1 (en) * 2009-09-01 2011-03-10 旭硝子株式会社 Coating material composition for liquid immersion exposure apparatus, laminate, method for forming laminate, and liquid immersion exposure apparatus
CN106986969A (en) * 2017-04-28 2017-07-28 华南理工大学 A kind of main chain degradation-type polyacrylic acid resin of copper and preparation method and application
WO2020004306A1 (en) * 2018-06-28 2020-01-02 富士フイルム株式会社 Active ray-sensitive or radiation-sensitive resin composition, pattern formation method, electronic device manufacturing method, resin
WO2020137918A1 (en) * 2018-12-28 2020-07-02 富士フイルム株式会社 Negative-type active-ray-sensitive or radiation-sensitive resin composition for organic solvent development, resist film, pattern-forming method, and electronic device production method

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