WO2024014462A1 - Composition de réserve, procédé de formation de motif de réserve, composé et composé polymère - Google Patents

Composition de réserve, procédé de formation de motif de réserve, composé et composé polymère Download PDF

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Publication number
WO2024014462A1
WO2024014462A1 PCT/JP2023/025597 JP2023025597W WO2024014462A1 WO 2024014462 A1 WO2024014462 A1 WO 2024014462A1 JP 2023025597 W JP2023025597 W JP 2023025597W WO 2024014462 A1 WO2024014462 A1 WO 2024014462A1
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group
substituent
carbon atoms
hydrocarbon group
formula
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PCT/JP2023/025597
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Japanese (ja)
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秀一 石井
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東京応化工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • C08F12/00—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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08F22/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/24—Esters containing sulfur
    • 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
    • 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 a resist composition, a resist pattern forming method, a compound, and a polymer compound.
  • Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with minute dimensions.
  • chemically amplified resist compositions have conventionally been used that contain a base component whose solubility in a developer changes due to the action of an acid, and an acid generator component that generates an acid upon exposure. is used.
  • the present invention has been made in view of the above circumstances, and includes a resist composition that achieves high sensitivity and has good lithography properties, a resist pattern forming method using the resist composition, and a manufacturing method of the resist composition.
  • An object of the present invention is to provide a polymer compound that can be used for the synthesis of the polymer, and a compound that can be used for the synthesis of the polymer.
  • a first aspect of the present invention is a resist composition that generates an acid upon exposure to light and whose solubility in a developing solution changes due to the action of the acid.
  • the resist composition contains a resin component (A1) having a structural unit (a0) derived from a compound represented by the following general formula (a0-1).
  • W 01 represents a polymerizable group-containing group.
  • La 01 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • La 02 represents a divalent linking group.
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 01 represents a divalent linking group or a single bond.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group. However, both Ya 01 and Va 01 do not form a single bond.
  • Ra 01 represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • m is an integer of 1 or more, and M m+ is an m-valent cation.
  • a second aspect of the present invention includes a step of forming a resist film on a support using the resist composition according to the first aspect, a step of exposing the resist film, and a step of exposing the resist film to light after the exposure.
  • This is a resist pattern forming method that includes a step of developing and forming a resist pattern.
  • the third aspect of the present invention is a compound represented by the following general formula (m0-1).
  • W 01 represents a polymerizable group-containing group.
  • La 01 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • La 02 represents a divalent linking group.
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 01 represents a divalent linking group or a single bond.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group. However, both Ya 01 and Va 01 do not form a single bond.
  • Ra 01 is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • m is an integer of 1 or more, and M m+ is an m-valent cation.
  • a fourth aspect of the present invention is a polymer compound having a structural unit derived from the compound according to the third aspect.
  • a resist composition that can achieve high sensitivity and have good lithography properties, a resist pattern forming method using the resist composition, a polymer compound that can be used for manufacturing the resist composition, and Compounds that can be used for polymer synthesis can be provided.
  • alkyl group includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
  • alkylene group includes linear, branched, and cyclic divalent saturated hydrocarbon groups.
  • halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Constant unit means a monomer unit (monomer unit) that constitutes a high molecular compound (resin, polymer, copolymer).
  • substituent there are cases in which a hydrogen atom (-H) is substituted with a monovalent group and a case in which a methylene group (-CH 2 -) is substituted with a divalent group. including both.
  • Exposure is a concept that includes radiation irradiation in general.
  • an "acid-decomposable group” is a group having acid-decomposability that allows at least a portion of the bonds in the structure of the acid-decomposable group to be cleaved by the action of an acid.
  • acid-decomposable groups whose polarity increases due to the action of an acid include groups that decompose under the action of an acid to produce a polar group.
  • the polar group include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO 3 H).
  • the acid-decomposable group includes a group in which the polar group is protected with an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
  • Acid-dissociable group means (i) a group having acid-dissociable properties that allows the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group to be cleaved by the action of an acid; (ii) A group in which the bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group can be cleaved by further decarboxylation reaction after some bonds are cleaved by the action of an acid. , refers to both.
  • the acid-dissociable group constituting the acid-dissociable group needs to be a group with lower polarity than the polar group generated by dissociation of the acid-dissociable group.
  • the “base material component” is an organic compound that has film-forming ability.
  • Organic compounds used as base material components are broadly classified into non-polymers and polymers.
  • the non-polymer those having a molecular weight of 500 or more and less than 4,000 are usually used (hereinafter referred to as "low-molecular compound”).
  • “resin”, “high molecular compound”, or “polymer” refers to a polymer having a molecular weight of 1000 or more.
  • the molecular weight of the polymer the weight average molecular weight calculated by GPC (gel permeation chromatography) in terms of polystyrene is used.
  • “Derived structural unit” means a structural unit formed by cleavage of multiple bonds between carbon atoms, for example, ethylenic double bonds.
  • the hydrogen atom bonded to the ⁇ -position carbon atom may be substituted with a substituent.
  • the substituent (R ⁇ x ) that substitutes the hydrogen atom bonded to the ⁇ -position carbon atom is an atom or group other than a hydrogen atom.
  • derivative is a concept that includes target compounds in which the hydrogen atom at the ⁇ -position is substituted with other substituents such as alkyl groups and halogenated alkyl groups, as well as derivatives thereof. These derivatives include those in which the hydrogen atom of the hydroxyl group of the target compound is replaced with an organic group; the hydrogen atom at the ⁇ position may be substituted with a substituent; Good target compounds include those to which a substituent other than a hydroxyl group is bonded.
  • the ⁇ -position refers to the first carbon atom adjacent to a functional group, unless otherwise specified.
  • substituent for substituting the hydrogen atom at the ⁇ -position of hydroxystyrene include those similar to R ⁇ x .
  • the resist composition of this embodiment generates acid upon exposure, and its solubility in a developer changes due to the action of the acid.
  • a resist composition contains a base component (A) (hereinafter also referred to as "component (A)”) whose solubility in a developer changes due to the action of an acid.
  • component (A) generates acid upon exposure.
  • component (A1) which will be described later, is a resin that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid.
  • a resist film is formed using the resist composition of the present embodiment and the resist film is selectively exposed, for example, acid is generated from the component (A) in the exposed portion of the resist film. While the solubility of component (A) in the developing solution changes due to the action of the acid, the solubility of component (A) in the developing solution does not change in the unexposed areas of the resist film. There is a difference in solubility in the developer between the two. Therefore, when the resist film is developed, if the resist composition is positive type, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern, and if the resist composition is negative type, the resist film is not formed. The exposed portion is dissolved and removed to form a negative resist pattern.
  • the resist composition of this embodiment may be a positive resist composition or a negative resist composition. Furthermore, the resist composition of the present embodiment may be used in an alkaline development process using an alkaline developer in the development process during resist pattern formation, and the development process includes a developer containing an organic solvent (organic developer). It may be used for a solvent development process using.
  • organic developer organic developer
  • component (A) includes a resin component (A1) whose solubility in a developer changes due to the action of an acid (hereinafter also referred to as "component (A1)").
  • component (A1) the resin component (A1) whose solubility in a developer changes due to the action of an acid (hereinafter also referred to as "component (A1)").
  • component (A1) the polarity of the base material component changes before and after exposure, so that good development contrast can be obtained not only in an alkaline development process but also in a solvent development process.
  • component (A) other high molecular compounds and/or low molecular compounds may be used in combination with component (A1).
  • one type of component (A) may be used alone, or two or more types may be used in combination.
  • Component (A1) is a resin component whose solubility in a developer changes due to the action of acid.
  • Component (A1) has a structural unit (a0) derived from a compound represented by the general formula (a0-1) described below. In addition to the structural unit (a0), the component (A1) may have other structural units as necessary.
  • the structural unit (a0) is a structural unit derived from a compound represented by the following general formula (a0-1).
  • W 01 represents a polymerizable group-containing group.
  • La 01 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • La 02 represents a divalent linking group.
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 01 represents a divalent linking group or a single bond.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group. However, both Ya 01 and Va 01 do not form a single bond.
  • Ra 01 represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • m is an integer of 1 or more, and M m+ is an m-valent cation.
  • W 01 represents a polymerizable group-containing group.
  • a "polymerizable group” is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and refers to a group containing multiple bonds between carbon atoms such as an ethylenic double bond.
  • Examples of the polymerizable group include vinyl group, allyl group, acryloyl group, methacryloyl group, fluorovinyl group, difluorovinyl group, trifluorovinyl group, difluorotrifluoromethylvinyl group, trifluoroallyl group, perfluoroallyl group, Trifluoromethylacryloyl group, nonylfluorobutylacryloyl group, vinyl ether group, fluorine-containing vinyl ether group, allyl ether group, fluorine-containing allyl ether group, styryl group, vinylnaphthyl group, fluorine-containing styryl group, fluorine-containing vinylnaphthyl group, norbornyl group , a fluorine-containing norbornyl group, a silyl group, and the like.
  • the polymerizable group-containing group may be a group consisting only of a polymerizable group, or may be a group consisting of a polymerizable group and a group other than the polymerizable group.
  • groups other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.
  • Examples of the divalent linking group in Ya x0 include a divalent hydrocarbon group that may have a substituent, a divalent linking group containing a hetero atom, and the like.
  • La 01 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • An aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
  • the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituents.
  • the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene.
  • the aromatic hydrocarbon group includes a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring (arylene group); an aromatic compound containing two or more aromatic hydrocarbon rings (e.g. biphenyl, fluorene, etc.) Examples include a group obtained by removing two hydrogen atoms from .
  • the alkylene group bonded to the aryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
  • the aromatic hydrocarbon group may or may not have a substituent.
  • the substituent is, for example, a substituent that replaces a hydrogen atom possessed by an aromatic hydrocarbon group.
  • a hydrogen atom bonded to an aromatic hydrocarbon ring in an aromatic hydrocarbon group may be substituted with a substituent.
  • the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
  • the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.
  • the alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group. , methoxy group, and ethoxy group are more preferred.
  • the halogen atom as the substituent is preferably a fluorine atom or an iodine atom. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.
  • the alicyclic hydrocarbon group in La 01 may be a polycyclic group or a monocyclic group.
  • the monocyclic alicyclic hydrocarbon group a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable.
  • the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
  • the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically Examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
  • the alicyclic hydrocarbon group may or may not have a substituent.
  • substituents include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
  • alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those listed as the substituent for the aromatic hydrocarbon group above.
  • La 01 is preferably an aromatic hydrocarbon group that may have a substituent.
  • a group obtained by removing two carbon atoms from a benzene ring which may have a substituent is more preferable.
  • La 02 represents a divalent linking group.
  • the divalent linking group in La 02 include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a heteroatom.
  • the divalent linking group in La 02 is preferably a divalent linking group containing a hetero atom.
  • the divalent hydrocarbon group is preferably a linear or branched aliphatic hydrocarbon group.
  • the linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and has 1 to 4 carbon atoms. 3 is particularly preferred.
  • the branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, particularly preferably 3 carbon atoms. .
  • the linear or branched hydrocarbon group may be saturated or unsaturated, but saturated is preferred.
  • H may be substituted with a substituent such as an alkyl group or an acyl group.
  • the substituent alkyl group, acyl group, etc. preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
  • Y21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, even more preferably a linear alkylene group having 1 to 5 carbon atoms, and a methylene group or an ethylene group. Particularly preferred.
  • Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group.
  • the alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
  • m" is an integer of 0 to 3, preferably an integer of 0 to 2, and 0 or 1 is more preferred, and 1 is particularly preferred.
  • a' is 1 to is an integer of 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even more preferably 1 or 2, and most preferably 1.
  • b' is an integer of 1 to 10, and An integer of 1 to 5 is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is even more preferred, and 1 is most preferred.
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • the aromatic hydrocarbon group in Ar 01 include the same aromatic hydrocarbon groups as in La 01 above.
  • Ar 01 a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring is preferable.
  • the aromatic carbocyclic ring include those mentioned above for La 01 .
  • Ar 01 a group obtained by removing two hydrogen atoms from a benzene ring which may have a substituent is preferable.
  • the aromatic hydrocarbon group in Ar 01 may or may not have a substituent.
  • substituents include the same substituents that the aromatic hydrocarbon group in La 01 may have.
  • the aromatic hydrocarbon group in Ar 01 more preferably has an iodine atom as a substituent from the viewpoint of improving sensitivity and reducing roughness.
  • the iodine atom may be a substituent that replaces a hydrogen atom in an aromatic hydrocarbon ring.
  • Examples of the number of iodine atoms as a substituent include 1 to 4, 1 to 3, 2, or 1. The greater the number of iodine atoms as substituents, the easier it is to achieve high sensitivity.
  • Ya 01 represents a divalent linking group or a single bond.
  • Examples of the divalent linking group in Ya 01 include those similar to the divalent linking group in La 02 .
  • a divalent linking group containing a hetero atom is preferably mentioned.
  • Examples of the divalent linking group containing a hetero atom include those similar to the divalent linking group containing a hetero atom in La 01 above.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group.
  • the alkylene group in Va 01 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.
  • the alkylene group in Va 01 may be linear or branched, but preferably linear.
  • Examples of the fluorinated alkylene group in Va 01 include groups in which some or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms.
  • the fluorinated alkylene group in Va 01 include -CFH-, -CH 2 -CFH-, -CH(CF 3 )-, and -CH 2 -CH(CF 3 )-.
  • the fluorinated alkylene group is preferably -CFH- or -CH 2 -CFH-.
  • Va 01 is preferably an alkylene group having 1 to 4 carbon atoms or a fluorinated alkylene group having 1 to 4 carbon atoms; More preferred are methylene group, ethylene group, and -CHF-.
  • both Ya 01 and Va 01 do not form a single bond. That is, when Ya 01 is a single bond, Va 01 is an alkylene group or a fluorinated alkylene group. When Va 01 is a single bond, Ya 01 is a divalent linking group.
  • Ra 01 is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • the fluorinated alkyl group in Ra 01 may be linear or branched, but linear is preferred.
  • the fluorinated alkyl group in Ra 01 preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group.
  • Ra 01 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, and further preferably a fluorine atom or a trifluoromethyl group.
  • a fluorine atom is particularly preferable.
  • the structural unit (a0) is preferably a structural unit represented by the following general formula (a0-1-1).
  • R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • Yx 01 represents a divalent linking group or a single bond containing a heteroatom.
  • La 011 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • La 021 represents a divalent linking group.
  • Ar 011 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 011 represents a divalent linking group or a single bond.
  • Va 011 represents a single bond, an alkylene group or a fluorinated alkylene group. However, both Ya 011 and Va 011 do not form a single bond.
  • Ra 011 is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • m is an integer of 1 or more, and M m+ is an m-valent cation.
  • R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • the alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and the like.
  • the halogenated alkyl group having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
  • the halogen atom is preferably a fluorine atom.
  • R is preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.
  • Yx 01 represents a divalent linking group or a single bond containing a hetero atom.
  • the divalent linking group containing a hetero atom include those similar to the divalent linking group containing a hetero atom in La 02 above.
  • La 011 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • Examples of La 011 include those similar to La 01 in the above general formula (a0-1).
  • La 011 is preferably an aromatic hydrocarbon group which may have a substituent, and more preferably a group obtained by removing two hydrogen atoms from a benzene ring which may have a substituent.
  • La 021 represents a divalent linking group.
  • Examples of the divalent linking group in La 021 include those similar to La 02 in the above general formula (a0-1).
  • Ar 011 represents an aromatic hydrocarbon group which may have a substituent.
  • Ar 011 include those similar to Ar 01 in the above general formula (a0-1).
  • Ar 011 a group obtained by removing two hydrogen atoms from a benzene ring which may have a substituent is preferable.
  • the aromatic hydrocarbon group in Ar 011 preferably has an iodine atom as a substituent.
  • Ya 011 represents a divalent linking group or a single bond.
  • Examples of the divalent linking group in Ya 011 include those similar to Ya 01 in the above general formula (a0-1).
  • Va 011 represents a single bond, an alkylene group or a fluorinated alkylene group.
  • Examples of the alkylene group and fluorinated alkylene group in Va 011 include those similar to Va 01 in the above general formula (a0-1).
  • Va 011 is preferably a methylene group, an ethylene group, or -CHF-.
  • both Ya 011 and Va 011 do not form a single bond. That is, when Ya 011 is a single bond, Va 011 is an alkylene group or a fluorinated alkylene group. When Va 011 is a single bond, Ya 011 is a divalent linking group.
  • Ra 011 represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • fluorinated alkyl group having 1 to 5 carbon atoms in Ra 011 include those similar to Ra 01 in the above general formula (a0-1).
  • Ra 011 is preferably a fluorine atom or a trifluoromethyl group, more preferably a fluorine atom.
  • the structural unit (a0) is preferably a structural unit represented by the following general formula (a0-1-1-1).
  • R, Yx 01 , La 021 , and Ra 011 are the same as R, Yx 01 , La 021 , and Ra 011 in the general formula (a0-1-1), respectively.
  • La 0 represents an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring.
  • R a represents a hydrogen atom or an alkyl group.
  • Ra 021 and Ra 022 each independently represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • X 0 represents an iodine atom.
  • Rx 01 represents a substituent other than an iodine atom.
  • Rx 02 represents a substituent.
  • k1 and k2 each independently represent an integer from 0 to 4, and k1+k2 ⁇ 4.
  • k3 is an integer of 0 or more as long as the valence allows.
  • k4 represents an integer from 1 to 5
  • k5 represents 0 or 1
  • k6 represents an integer from 0 to 5.
  • the plurality of Ra 021s may be the same or different.
  • a plurality of Ra 022 may be the same or different.
  • L 01 is a single bond
  • k5 and k6 will never both be 0.
  • m is an integer of 1 or more
  • M m+ is an m-valent cation.
  • R, Yx 01 , La 021 and Ra 011 are different from R, Yx 01 , La 021 and Ra 011 in the general formula (a0-1-1). Each is the same.
  • La 0 represents an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring.
  • the aromatic hydrocarbon ring in La 0 may be monocyclic or polycyclic. Specific examples of the aromatic hydrocarbon ring in La 0 include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like.
  • the aromatic hydrocarbon ring in La 0 is preferably a benzene ring.
  • the aliphatic hydrocarbon ring in La 0 may be monocyclic or polycyclic.
  • Examples of aliphatic hydrocarbon rings in La 0 include monocycloalkane rings such as cyclopentane ring and cyclohexane ring; adamantane ring, norbornane ring, isobornane ring, tricyclo[5.2.1.0 2,6 ]decane ring, and tetracycloalkane ring. Examples include polycycloalkane rings such as a cyclododecane ring.
  • the aliphatic hydrocarbon ring in La 0 is preferably an adamantane ring.
  • La 0 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.
  • R a represents a hydrogen atom or an alkyl group.
  • the alkyl group in R a preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably a methyl group or an ethyl group.
  • L 01 and L 02 are preferably -O-, -CO-, -OCO-, or -COO-.
  • k4 is an integer from 1 to 5. k4 is preferably an integer of 1 to 3, particularly preferably 1 or 2.
  • k5 is 0 or 1. k5 is preferably 0.
  • Ra 021 and Ra 022 each independently represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • the fluorinated alkyl group in Ra 021 and Ra 022 preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.
  • Ra 021 and Ra 022 are preferably a hydrogen atom, a fluorine atom, or a trifluoromethylene group.
  • Combinations of Ra 021 and Ra 022 include a combination in which Ra 021 and Ra 022 both have hydrogen atoms; a combination in which Ra 021 has a hydrogen atom and Ra 022 has a fluorine atom; a combination in which Ra 021 and Ra 022 both have fluorine atoms; Examples include a combination in which 021 is a hydrogen atom and Ra 022 is a trifluoromethylene group; a combination in which Ra 021 is a fluorine atom and Ra 022 is a trifluoromethylene group; and a combination in which both Ra 021 and Ra 022 are trifluoromethylene groups.
  • k6 is an integer from 0 to 5.
  • k6 is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • the plurality of Ra 021s may be the same or different.
  • the plurality of Ra 022s may be the same or different.
  • X 0 represents an iodine atom.
  • Rx 01 represents a substituent other than an iodine atom.
  • Rx 01 include an alkyl group, an alkoxy group, a fluorine atom, a chlorine atom, a halogenated alkyl group, and a hydroxyl group.
  • the halogenated alkyl group is preferably a fluorinated alkyl group.
  • Examples of the alkyl group, alkoxy group, and halogenated alkyl group in Rx 01 include those listed as the substituent for the aromatic hydrocarbon group in La 01 in the general formula (a0-1).
  • k1 and k2 each independently represent an integer from 0 to 4, and k1+k2 ⁇ 4.
  • k1 is preferably an integer of 1 to 4, more preferably 1 to 3, and even more preferably 2 or 3.
  • k2 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.
  • Rx 02 represents a substituent.
  • Rx 02 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
  • Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group in Rx 02 include those listed as the substituent for the aromatic hydrocarbon group in La 01 in the general formula (a0-1) above. It will be done.
  • k3 is an integer of 0 or more as long as the valence allows. k3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.
  • R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • M m+ is an m-valent cation.
  • m is an integer of 1 or more.
  • the structural unit (a0) is preferably a structural unit represented by any of the formulas (a01-an-1) to (a01-an-46), and -7) and any one of (a01-an-42) to (a01-an-45) are more preferred.
  • ⁇ Cation part ⁇ M m+ in the above formula represents an m-valent cation.
  • the cation is preferably a sulfonium cation or an iodonium cation.
  • m is an integer of 1 or more.
  • Preferred cation moieties ((M m+ ) 1/m ) include organic cations represented by the following general formulas (ca-1) to (ca-3), respectively.
  • R 201 to R 207 each independently represent an aryl group, an alkyl group, or an alkenyl group that may have a substituent.
  • R 201 to R 203 and R 206 to R 207 may be bonded to each other to form a ring together with the sulfur atom in the formula.
  • R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or -SO 2 - which may have a substituent. It is a containing cyclic group.
  • examples of the aryl group in R 201 to R 207 include unsubstituted aryl groups having 6 to 20 carbon atoms, such as phenyl group and naphthyl group. preferable.
  • the alkyl group in R 201 to R 207 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
  • the alkenyl group in R 201 to R 207 preferably has 2 to 10 carbon atoms.
  • R 201 to R 207 and R 210 may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the following general formula: Examples include groups represented by (car-r-1) to (car-r-7), respectively.
  • R' 201 is each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkyl group which may have a substituent. It is a good chain alkenyl group.
  • Cyclic group that may have a substituent The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
  • Aliphatic hydrocarbon group means a hydrocarbon group without aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
  • the aromatic hydrocarbon group in R' 201 is a hydrocarbon group having an aromatic ring.
  • the aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, Most preferably 6 to 10 carbon atoms.
  • the number of carbon atoms does not include the number of carbon atoms in the substituents.
  • the aromatic ring possessed by the aromatic hydrocarbon group in R' 201 is benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a ring in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms.
  • the aromatic hydrocarbon group in R' 201 includes a group in which one hydrogen atom is removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one of the hydrogen atoms in the aromatic ring is alkylene
  • arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group).
  • the alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
  • Examples of the cyclic aliphatic hydrocarbon group for R' 201 include aliphatic hydrocarbon groups containing a ring in the structure.
  • the aliphatic hydrocarbon group containing a ring in its structure includes an alicyclic hydrocarbon group (a group in which one hydrogen atom is removed from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.
  • the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
  • the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
  • the monocyclic alicyclic hydrocarbon group a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable.
  • the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
  • the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
  • the polycycloalkanes include polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane; steroids; More preferred are polycycloalkanes having a polycyclic skeleton of a condensed ring system such as a cyclic group having a skeleton.
  • cyclic aliphatic hydrocarbon group for R' 201 a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferable, and a group obtained by removing one hydrogen atom from a polycycloalkane is preferable. More preferred are adamantyl groups and norbornyl groups, and most preferred are adamantyl groups.
  • the linear or branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. , more preferably 1 to 4 carbon atoms, particularly preferably 1 to 3 carbon atoms.
  • a linear alkylene group is preferable, and specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [ -(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -], and the like.
  • a branched alkylene group is preferable, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2 -CH 2 -; -CH(CH 3 )CH 2 CH 2 -, alkyltrimethylene groups such as -CH 2 CH(CH 3 )CH 2 -; -CH(CH 3 ) Examples include alkylal
  • the cyclic hydrocarbon group in R' 201 may contain a heteroatom such as a heterocycle.
  • Examples of the substituent in the cyclic group of R' 201 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like.
  • the alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group.
  • the alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group. Most preferred are methoxy and ethoxy groups.
  • a fluorine atom is preferable.
  • halogenated alkyl group as a substituent examples include an alkyl group having 1 to 5 carbon atoms, such as a methyl group, ethyl group, propyl group, n-butyl group, and tert-butyl group, in which some or all of the hydrogen atoms are Examples include groups substituted with the aforementioned halogen atoms.
  • the carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) constituting a cyclic hydrocarbon group.
  • Chain-like alkyl group which may have a substituent The chain alkyl group of R' 201 may be either linear or branched.
  • the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
  • the branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms.
  • 1-methylethyl group 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group
  • Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.
  • Chain-like alkenyl group which may have a substituent The chain alkenyl group for R' 201 may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and The number of carbon atoms is more preferably 2 to 4, and the number of carbon atoms is particularly preferably 3.
  • Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group.
  • Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, and 2-methylpropenyl group.
  • a straight chain alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.
  • substituents on the chain alkyl group or alkenyl group of R' 201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a cyclic group in the above R' 201 . etc.
  • the cyclic group that may have a substituent, the chain alkyl group that may have a substituent, or the chain alkenyl group that may have a substituent for R'201 is other than those mentioned above.
  • a cyclic group that may have a substituent or a chain alkyl group that may have a substituent those similar to the acid-dissociable group represented by the above formula (a1-r-2) can also be mentioned.
  • R' 201 is preferably a cyclic group that may have a substituent, and more preferably a cyclic hydrocarbon group that may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; -SO 2 -containing cyclic groups represented by the general formulas (b5-r-1) to (b5-r-4), etc. are preferred.
  • R 201 to R 203 and R 206 to R 207 are sulfur atoms, when bonding with each other to form a ring with the sulfur atom in the formula; Heteroatoms such as oxygen atoms and nitrogen atoms, carbonyl groups, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )- (where R N is a carbon atom They may be bonded via a functional group such as an alkyl group of numbers 1 to 5.).
  • one ring in the formula containing a sulfur atom in its ring skeleton is preferably a 3- to 10-membered ring, particularly a 5- to 7-membered ring.
  • the ring formed include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiine ring, a tetrahydrothiophenium ring, a tetrahydrothio Examples include a pyranium ring.
  • R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are an alkyl group, they are bonded to each other. may be used to form a ring.
  • R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or -SO 2 - which may have a substituent. It is a containing cyclic group. Examples of the aryl group for R 210 include unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred.
  • the alkyl group for R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
  • the alkenyl group for R 210 preferably has 2 to 10 carbon atoms.
  • the -SO 2 --containing cyclic group which may have a substituent in R 210 is preferably a "-SO 2 --containing polycyclic group", which is represented by the above general formula (b5-r-1). More preferred are groups such as
  • Suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-75).
  • g1, g2, and g3 indicate the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20. ]
  • R'' 201 is a hydrogen atom or a substituent, and the substituent is the same as the substituent that R 201 to R 207 and R 210 to R 212 may have. ]
  • Suitable cations represented by formula (ca-2) include diphenyliodonium cations, bis(4-tert-butylphenyl)iodonium cations, and the like.
  • Suitable cations represented by the above formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).
  • a cation represented by the above formula (ca-1) is preferable.
  • an m-valent cation having a fluorine atom is preferable.
  • a cation represented by the following formula (ca-1-1) is preferable.
  • Rf 201 to Rf 203 each independently represent an aryl group, an alkyl group, or an alkenyl group that may have a substituent.
  • Rf 201 to Rf 203 may be bonded to each other to form a ring together with the sulfur atom in the formula.
  • at least one of Rf 201 to Rf 203 contains at least one fluorine atom.
  • Rf 201 to Rf 203 in the formula (ca-1-1) are the same as R 201 to R 203 in the formula (ca-1), respectively. However, at least one of Rf 201 to Rf 203 contains at least one fluorine atom.
  • the cation represented by formula (ca-1-1) preferably contains three or more fluorine atoms. Any one of Rf 201 to Rf 203 may have three or more fluorine atoms, and the total number of fluorine atoms contained in Rf 201 to Rf 203 may be three or more.
  • R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • the structural unit (a01) is preferably a structural unit represented by any of the above formulas (a01-1) to (a01-49), and the structural unit (a01) is preferably a structural unit represented by any of the above formulas (a01-1) to (a01-11), and (a01- 46) to (a01-49) are more preferred.
  • the number of structural units (a0) contained in the component (A1) may be one or more.
  • the proportion of the structural unit (a0) in the component (A1) is preferably 1 to 50 mol%, and 2 to 35 mol%, based on the total (100 mol%) of all the structural units constituting the component (A1). It is more preferably 5 to 30 mol%, even more preferably 10 to 25 mol%.
  • the proportion of the structural unit (a0) is at least the lower limit of the above-mentioned preferable range, sensitivity is further improved.
  • the proportion of the structural unit (a0) is less than or equal to the upper limit of the preferable range, roughness is further reduced.
  • Component (A1) may have other structural units in addition to the above-mentioned structural unit (a0).
  • Other structural units include, for example, a structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of an acid; a structural unit (a10) represented by the general formula (a10-1) described below; a lactone-containing unit Structural unit (a2) containing a cyclic group; Structural unit (a8) derived from a compound represented by the general formula (a8-1) described below, etc. are exemplified.
  • the structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity increases under the action of an acid.
  • Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups for base resins for chemically amplified resist compositions.
  • examples of acid-dissociable groups proposed as acid-dissociable groups for base resins for chemically amplified resist compositions include "acetal-type acid-dissociable groups” and "tertiary alkyl ester-type acid-dissociable groups” described below. group,””tertiary alkyloxycarbonylic acid dissociable group,” and “secondary alkyloxycarbonylic acid dissociable group.”
  • Acetal type acid dissociable group Among the polar groups, the acid-dissociable group that protects the carboxyl group or hydroxyl group is, for example, an acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as an "acetal-type acid-dissociable group"). ) can be mentioned.
  • Ra' 1 and Ra' 2 are hydrogen atoms or alkyl groups.
  • Ra' 3 is a hydrocarbon group, and Ra' 3 may be bonded to either Ra' 1 or Ra' 2 to form a ring.
  • At least one of Ra' 1 and Ra' 2 is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
  • the alkyl group may be one of the alkyl groups listed as substituents that may be bonded to the carbon atom at the ⁇ position in the explanation of the ⁇ -substituted acrylic ester above. Similar groups can be mentioned, and alkyl groups having 1 to 5 carbon atoms are preferred. Specifically, linear or branched alkyl groups are preferably mentioned.
  • examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. More preferred, and methyl group is particularly preferred.
  • the hydrocarbon group for Ra' 3 includes a linear or branched alkyl group, or a cyclic hydrocarbon group.
  • the linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms.
  • Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and the like. Among these, methyl group, ethyl group or n-butyl group are preferred, and methyl group or ethyl group is more preferred.
  • the branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specific examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, and isopropyl group is preferred.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
  • the aliphatic hydrocarbon group which is a monocyclic group a group obtained by removing one hydrogen atom from a monocycloalkane is preferable.
  • the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
  • the aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
  • the aromatic hydrocarbon group of Ra' 3 is an aromatic hydrocarbon group
  • the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
  • This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
  • the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms; Can be mentioned.
  • heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • aromatic heterocycle include a pyridine ring and a thiophene ring.
  • the aromatic hydrocarbon group in Ra' 3 is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); A group in which one hydrogen atom is removed from an aromatic compound (e.g.
  • biphenyl, fluorene, etc. a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., benzyl group , phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl group such as 2-naphthylethyl group, etc.).
  • the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and has 1 carbon atom. It is particularly preferable.
  • the cyclic hydrocarbon group at Ra' 3 may have a substituent.
  • this substituent include the above-mentioned Ra x5 .
  • the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring.
  • Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group, and the like.
  • Tertiary alkyl ester type acid dissociable group examples include acid-dissociable groups represented by the following general formula (a1-r-2). Note that among the acid-dissociable groups represented by the following formula (a1-r-2), those composed of an alkyl group may be hereinafter referred to as "tertiary alkyl ester type acid-dissociable groups" for convenience. .
  • Ra' 4 to Ra' 6 are each a hydrocarbon group, and Ra' 5 and Ra' 6 may be bonded to each other to form a ring.
  • Examples of the hydrocarbon group for Ra' 4 include a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group.
  • Straight chain or branched alkyl group, cyclic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, aromatic hydrocarbon group) in Ra' 4 ) is the same as Ra' 3 above.
  • the chain or cyclic alkenyl group for Ra' 4 is preferably an alkenyl group having 2 to 10 carbon atoms.
  • Examples of the hydrocarbon groups for Ra' 5 and Ra' 6 include the same ones as for Ra' 3 above.
  • Ra' 10 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with a halogen atom or a heteroatom-containing group; shows.
  • Ra' 11 represents a group forming an aliphatic cyclic group together with the carbon atom to which Ra' 10 is bonded.
  • Ya is a carbon atom.
  • Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms possessed by this cyclic hydrocarbon group may be substituted.
  • Ra 101 to Ra 103 are each independently a hydrogen atom, a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms; be. Some or all of the hydrogen atoms possessed by the chain saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra 101 to Ra 103 may be bonded to each other to form a cyclic structure.
  • Yaa is a carbon atom.
  • Xaa is a group that forms an aliphatic cyclic group together with Yaa.
  • Ra 104 is an aromatic hydrocarbon group which may have a substituent.
  • Ra' 12 and Ra' 13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms possessed by this chain saturated hydrocarbon group may be substituted.
  • Ra' 14 is a hydrocarbon group which may have a substituent. * indicates a bond (the same applies hereinafter). ]
  • Ra' 10 is a linear or branched alkyl group having 1 to 12 carbon atoms, which may be partially substituted with a halogen atom or a heteroatom-containing group. It is the basis.
  • the linear alkyl group for Ra' 10 has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
  • Examples of the branched alkyl group in Ra' 10 include the same ones as in Ra' 3 above.
  • the alkyl group at Ra' 10 may be partially substituted with a halogen atom or a heteroatom-containing group.
  • some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group.
  • some of the carbon atoms (methylene group, etc.) constituting the alkyl group may be substituted with a heteroatom-containing group.
  • the heteroatom here include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • Ra' 11 (the aliphatic cyclic group formed together with the carbon atom to which Ra' 10 is bonded) is the monocyclic group of Ra' 3 in formula (a1-r-1).
  • the groups listed as aliphatic hydrocarbon groups (alicyclic hydrocarbon groups) which are polycyclic groups are preferable. Among these, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl groups and cyclohexyl groups are more preferred.
  • the cyclic hydrocarbon group formed by Xa together with Ya is a cyclic monovalent hydrocarbon group (aliphatic Examples include groups obtained by further removing one or more hydrogen atoms from a hydrocarbon group.
  • the cyclic hydrocarbon group formed by Xa and Ya may have a substituent. Examples of this substituent include those similar to the substituents that the cyclic hydrocarbon group in Ra' 3 above may have.
  • the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra 101 to Ra 103 includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, Examples include pentyl group, hexyl group, heptyl group, octyl group, and decyl group.
  • Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra 101 to Ra 103 include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, Monocyclic aliphatic saturated hydrocarbon groups such as cyclodecyl group and cyclododecyl group; bicyclo[2.2.2]octanyl group, tricyclo[5.2.1.0 2,6 ]decanyl group, tricyclo[3.3 .1.1 3,7 ]decanyl group, tetracyclo[6.2.1.1 3,6 .
  • Ra 101 to Ra 103 are preferably a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, and among these, a hydrogen atom, a methyl group, or an ethyl group is preferable. More preferred is a hydrogen atom, particularly preferred.
  • Examples of the substituent of the chain saturated hydrocarbon group or aliphatic cyclic saturated hydrocarbon group represented by Ra 101 to Ra 103 include the same groups as Ra x5 described above.
  • Groups containing a carbon-carbon double bond formed by two or more of Ra 101 to Ra 103 bonding to each other to form a cyclic structure include, for example, a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methyl Examples include a cyclohexenyl group, a cyclopentylideneethenyl group, and a cyclohexylideneethenyl group. Among these, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylideneethenyl group are preferred from the viewpoint of ease of synthesis.
  • the aliphatic cyclic group formed by Xaa together with Yaa is a carbonized aliphatic group that is a monocyclic group or polycyclic group of Ra' 3 in formula (a1-r-1).
  • the groups listed as hydrogen groups are preferred.
  • the aromatic hydrocarbon group for Ra 104 includes a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms.
  • Ra 104 is preferably a group in which one or more hydrogen atoms are removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and more preferably a group in which one or more hydrogen atoms are removed from benzene, naphthalene, anthracene, or phenanthrene.
  • a group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene is more preferable
  • a group obtained by removing one or more hydrogen atoms from benzene or naphthalene is particularly preferable
  • a group obtained by removing one or more hydrogen atoms from benzene is more preferable.
  • a group obtained by removing one or more hydrogen atoms from benzene is more preferable.
  • Ra 104 in formula (a1-r2-3) may have include methyl group, ethyl group, propyl group, hydroxy group, carboxy group, halogen atom, alkoxy group (methoxy group, (ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc.
  • Ra' 12 and Ra' 13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms.
  • the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra' 12 and Ra' 13 the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in the above Ra 101 to Ra 103 can be used. Examples include those similar to hydrocarbon groups. Some or all of the hydrogen atoms possessed by this chain saturated hydrocarbon group may be substituted.
  • Ra' 12 and Ra' 13 are preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • examples of the substituent include the same groups as Ra x5 described above.
  • Ra' 14 is a hydrocarbon group that may have a substituent.
  • the hydrocarbon group for Ra' 14 includes a linear or branched alkyl group, or a cyclic hydrocarbon group.
  • the linear alkyl group in Ra' 14 preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms.
  • Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and the like. Among these, methyl group, ethyl group or n-butyl group are preferred, and methyl group or ethyl group is more preferred.
  • the branched alkyl group in Ra' 14 preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specific examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, and isopropyl group is preferred.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
  • the aliphatic hydrocarbon group which is a monocyclic group a group obtained by removing one hydrogen atom from a monocycloalkane is preferable.
  • the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
  • the aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
  • Ra' 14 examples include those similar to the aromatic hydrocarbon group in Ra 104 .
  • Ra' 14 is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene.
  • a group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene even more preferable is a group obtained by removing one or more hydrogen atoms from naphthalene or anthracene, and a group obtained by removing one or more hydrogen atoms from naphthalene. is most preferred.
  • substituents that Ra' 14 may have include the same substituents as those that Ra 104 may have.
  • Ra' 14 in formula (a1-r2-4) is a naphthyl group
  • the position bonded to the tertiary carbon atom in formula (a1-r2-4) is the 1st or 2nd position of the naphthyl group. It may be either.
  • the position bonded to the tertiary carbon atom in formula (a1-r2-4) is the 1st, 2nd or 2nd position of the anthryl group. It can be any of the 9th place.
  • the acid-dissociable group that protects the hydroxyl group is, for example, an acid-dissociable group represented by the following general formula (a1-r-3) (hereinafter referred to as a "tertiary alkyloxycarbonyl acid-dissociable group" for convenience). ”) can be mentioned.
  • Ra' 7 to Ra' 9 are each an alkyl group.
  • Ra' 7 to Ra' 9 are each preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Further, the total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.
  • Acid-dissociable groups that protect carboxy groups include acid-dissociable groups represented by the following general formula (a1-r-4).
  • Ra' 10 is a hydrocarbon group.
  • Ra' 11a and Ra' 11b are each independently a hydrogen atom, a halogen atom, or an alkyl group.
  • Ra' 12 is a hydrogen atom or a hydrocarbon group.
  • Ra' 10 and Ra' 11a or Ra' 11b may be bonded to each other to form a ring.
  • Ra' 11a or Ra' 11b and Ra' 12 may be bonded to each other to form a ring.
  • examples of the hydrocarbon group in Ra' 10 and Ra' 12 include those similar to those for Ra' 3 above.
  • the alkyl groups for Ra' 11a and Ra' 11b include the same alkyl groups as for Ra' 1 above.
  • the hydrocarbon group at Ra' 10 and Ra' 12 and the alkyl group at Ra' 11a and Ra' 11b may have a substituent. Examples of this substituent include the above-mentioned Ra x5 .
  • Ra' 10 and Ra' 11a or Ra' 11b may be bonded to each other to form a ring.
  • the ring may be polycyclic, monocyclic, alicyclic, or aromatic.
  • the alicyclic ring and aromatic ring may contain a heteroatom.
  • the ring formed by bonding Ra' 10 and Ra' 11a or Ra' 11b to each other is a monocycloalkene, a monocycloalkene in which some of the carbon atoms are heteroatoms (oxygen atom, sulfur atom, etc.). etc.), monocycloalkadienes are preferred, cycloalkenes having 3 to 6 carbon atoms are preferred, and cyclopentene or cyclohexene is preferred.
  • the ring formed by bonding Ra' 10 and Ra' 11a or Ra' 11b to each other may be a fused ring.
  • Specific examples of the condensed ring include indane and the like.
  • the ring formed by bonding Ra' 10 and Ra' 11a or Ra' 11b to each other may have a substituent.
  • this substituent include the above-mentioned Ra x5 .
  • Ra' 11a or Ra' 11b and Ra' 12 may be bonded to each other to form a ring, and as the ring, Ra' 10 and Ra' 11a or Ra' 11b may be bonded to each other to form a ring. Examples include those similar to the rings that are formed.
  • the structural unit (a1) is a structural unit derived from an acrylic ester in which the hydrogen atom bonded to the ⁇ -position carbon atom may be substituted with a substituent, a structural unit derived from acrylamide, hydroxystyrene or hydroxyl.
  • a structural unit in which at least a portion of the hydrogen atoms in the hydroxyl group of a structural unit derived from a styrene derivative is protected by a substituent containing the acid-decomposable group, a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative, - Examples include structural units in which at least a portion of the hydrogen atoms in C( O)-OH are protected by a substituent containing the acid-decomposable group.
  • structural units (a1) are preferably structural units derived from acrylic esters in which the hydrogen atom bonded to the ⁇ -position carbon atom may be substituted with a substituent.
  • Preferred specific examples of the structural unit (a1) include structural units represented by the following general formula (a1-1) or (a1-2).
  • R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • Va 1 is a divalent hydrocarbon group which may have an ether bond.
  • n a1 is an integer from 0 to 2.
  • Ra 1 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-2).
  • Wa 1 is n a2 + monovalent hydrocarbon group
  • n a2 is an integer of 1 to 3
  • Ra 2 is represented by the above general formula (a1-r-1) or (a1-r-3). It is an acid dissociable group.
  • R is the same as above.
  • R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred from the viewpoint of industrial availability.
  • the divalent hydrocarbon group in Va 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group as the divalent hydrocarbon group in Va 1 may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and the like.
  • the linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and has 1 to 4 carbon atoms. 3 is most preferred.
  • a linear alkylene group is preferable, and specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [ -(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -], and the like.
  • the branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and has 3 carbon atoms. Most preferred.
  • a branched alkylene group is preferable, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2 -CH 2
  • Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group in which the alicyclic hydrocarbon group is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those similar to the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
  • the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
  • the alicyclic hydrocarbon group may be polycyclic or monocyclic.
  • As the monocyclic alicyclic hydrocarbon group a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable.
  • the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
  • the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms.
  • Examples include adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
  • the aromatic hydrocarbon group as the divalent hydrocarbon group in Va 1 is a hydrocarbon group having an aromatic ring.
  • the aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 12 carbon atoms. preferable.
  • the number of carbon atoms does not include the number of carbon atoms in the substituents.
  • examples of the aromatic ring possessed by the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; Examples include aromatic heterocycles substituted with atoms.
  • the heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the aromatic hydrocarbon group includes a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group); ) in which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group) (a group obtained by removing one hydrogen atom from an aryl group in the group), and the like.
  • the number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
  • Ra 1 is an acid-dissociable group represented by the formula (a1-r-1) or (a1-r-2).
  • the n a2 +1-valent hydrocarbon group in Wa 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group means a hydrocarbon group without aromaticity, and may be saturated or unsaturated, and is usually preferably saturated.
  • the aliphatic hydrocarbon group is a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a linear or branched aliphatic hydrocarbon group. Examples include groups in which a ring-containing aliphatic hydrocarbon group is combined in the structure.
  • the n a2 +1 valence is preferably 2 to 4, more preferably 2 or 3.
  • Ra 2 is an acid dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).
  • R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • the number of structural units (a1) contained in the component (A1) may be one or more.
  • a structural unit represented by the above formula (a1-1) is more preferable because the characteristics (sensitivity, shape, etc.) in lithography using electron beams or EUV can be more easily improved.
  • the structural unit (a1) one containing a structural unit represented by the following general formula (a1-1-1) is particularly preferable.
  • Ra 1 '' is an acid dissociable group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4). show.]
  • R, Va 1 and n a1 are the same as R, Va 1 and n a1 in the formula (a1-1).
  • the acid dissociable group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4) is as described above. Among these, it is preferable to select a group in which the acid-dissociable group is a cyclic group, since it is suitable for enhancing reactivity in EB or EUV applications, and is represented by the general formula (a1-r2-1). Acid dissociable groups are more preferred.
  • the proportion of the structural unit (a1) in the component (A1) is preferably 5 to 95 mol%, and 10 to 90 mol%, based on the total (100 mol%) of all structural units constituting the component (A1). is more preferable, 30 to 70 mol% is even more preferable, and 40 to 60 mol% is particularly preferable.
  • lithography properties such as sensitivity, resolution, and roughness improvement are improved.
  • it is below the upper limit of the above-mentioned preferable range a balance with other structural units can be maintained, and various lithography properties will be improved.
  • the structural unit (a10) is a structural unit represented by the following general formula (a10-1).
  • R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • Ya x1 is a single bond or a divalent linking group.
  • Wa x1 is an aromatic hydrocarbon group which may have a substituent.
  • n ax1 is an integer of 1 or more.
  • R is the same as above.
  • R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred from the viewpoint of industrial availability.
  • Ya x1 is a single bond or a divalent linking group.
  • the divalent linking group in Ya It is mentioned as.
  • Wa x1 is an aromatic hydrocarbon group which may have a substituent.
  • the aromatic hydrocarbon group in Wa x1 include a group obtained by removing (na x1 +1) hydrogen atoms from an aromatic ring that may have a substituent.
  • the aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons.
  • the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
  • aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms; can be mentioned.
  • heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • aromatic heterocycle include a pyridine ring and a thiophene ring.
  • the aromatic hydrocarbon group in Wa x1 is an aromatic compound containing an aromatic ring that may have two or more substituents (e.g.
  • Wa x1 is preferably a group obtained by removing ( nax1 +1) hydrogen atoms from benzene, naphthalene, anthracene, or biphenyl, and a group obtained by removing ( nax1 +1) hydrogen atoms from benzene or naphthalene. is more preferred, and a group obtained by removing (n ax1 +1) hydrogen atoms from benzene is even more preferred.
  • the aromatic hydrocarbon group in Wa x1 may or may not have a substituent.
  • the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group.
  • Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include those listed as the substituent for the cyclic aliphatic hydrocarbon group in Ya x1 .
  • the substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and is preferably an ethyl group or a methyl group. A group is more preferred, and a methyl group is particularly preferred.
  • the aromatic hydrocarbon group in Wa x1 preferably has no substituent.
  • n ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably 1, 2 or 3, and 1 or 2 is Particularly preferred.
  • R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • the number of structural units (a10) contained in the component (A1) may be one or more.
  • the proportion of the structural unit (a10) in the component (A1) is as follows: It is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, even more preferably 25 to 60 mol%.
  • Component (A1) may have a structural unit (a2) containing a lactone-containing cyclic group (excluding the structural unit (a1)).
  • the lactone-containing cyclic group of the structural unit (a2) is effective in increasing the adhesion of the resist film to the substrate when the component (A1) is used to form the resist film.
  • the structural unit (a2) for example, the acid diffusion length can be appropriately adjusted, the adhesion of the resist film to the substrate can be increased, and the solubility during development can be appropriately adjusted, so that the lithography properties can be improved. etc. will be good.
  • the lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when it has other ring structures, it is called a polycyclic group regardless of the structure.
  • the lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
  • the lactone-containing cyclic group in the structural unit (a2) is not particularly limited and any arbitrary group can be used. Specifically, groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be mentioned.
  • R'' is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group
  • A'' has 1 to 1 carbon atoms, which may include an oxygen atom (-O-) or a sulfur atom (-S-); 5 alkylene group, oxygen atom or sulfur atom, n' is an integer of 0 to 2, and m' is 0 or 1.
  • * indicates a bond (the same applies hereinafter).
  • the alkyl group at Ra' 21 is preferably an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group is preferably linear or branched. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, and the like. Among these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.
  • the alkoxy group for Ra' 21 is preferably an alkoxy group having 1 to 6 carbon atoms.
  • the alkoxy group is preferably linear or branched. Specifically, a group in which the alkyl group mentioned above as the alkyl group in Ra' 21 and an oxygen atom (-O-) are connected can be mentioned.
  • the halogen atom at Ra' 21 is preferably a fluorine atom. Examples of the halogenated alkyl group at Ra' 21 include groups in which part or all of the hydrogen atoms of the alkyl group at Ra' 21 are substituted with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
  • R" is a hydrogen atom, an alkyl group, or a lactone-containing cyclic group.
  • the alkyl group in R'' may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms.
  • R'' is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is a methyl or ethyl group. is particularly preferred.
  • R'' is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms.
  • groups obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane and cyclohexane; adamantane, norbornane examples include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane.
  • Examples of the lactone-containing cyclic group in R'' include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7).
  • the hydroxyalkyl group in Ra' 21 preferably has 1 to 6 carbon atoms, and specifically includes a group in which at least one hydrogen atom of the alkyl group in Ra' 21 is substituted with a hydroxyl group. It will be done.
  • Ra' 21 is preferably each independently a hydrogen atom or a cyano group.
  • the alkylene group having 1 to 5 carbon atoms in A'' is linear or branched.
  • alkylene groups such as methylene group, ethylene group, n-propylene group, isopropylene group, etc.
  • specific examples include the terminal or sulfur atom of the alkylene group.
  • groups in which -O- or -S- is present between carbon atoms such as -O-CH 2 -, -CH 2 -O-CH 2 -, -S-CH 2 -, -CH 2 -S -CH 2 -, etc.
  • A'' is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.
  • the structural unit (a2) is preferably a structural unit derived from an acrylic ester in which the hydrogen atom bonded to the ⁇ -position carbon atom may be substituted with a substituent.
  • the structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).
  • R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • Ya 21 is a single bond or a divalent linking group.
  • La 21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group.
  • Ra 21 is a lactone-containing cyclic group.
  • R is the same as above.
  • R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or a methyl group is particularly preferred from the viewpoint of industrial availability.
  • the divalent linking group for Ya 21 is not particularly limited, but includes a divalent hydrocarbon group that may have a substituent, a divalent linking group containing a hetero atom, etc. are preferably mentioned.
  • Ya 21 is preferably a single bond, and La 21 is preferably -COO- or -OCO-.
  • Ra 21 is a lactone-containing cyclic group.
  • Preferable examples of the lactone-containing cyclic group in Ra 21 include groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7).
  • the number of structural units (a2) contained in the component (A1) may be one or more.
  • the proportion of the structural unit (a2) is 1 to 20 mol% with respect to the total (100 mol%) of all structural units constituting the component (A1). It is preferably 1 to 15 mol%, and even more preferably 1 to 10 mol%.
  • the proportion of the structural unit (a2) is at least the preferable lower limit value, the effect of containing the structural unit (a2) can be sufficiently obtained due to the above-mentioned effect, and when it is below the upper limit value, the ratio with other structural units is A balance can be achieved, and various lithography properties can be improved.
  • the structural unit (a8) is a structural unit derived from a compound represented by the following general formula (a8-1).
  • W 2 is a polymerizable group-containing group.
  • Ya x2 is a single bond or a (na x2 +1)-valent linking group. Ya x2 and W 2 may form a condensed ring.
  • R 1 is a fluorinated alkyl group having 1 to 12 carbon atoms.
  • R 2 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom, or a hydrogen atom.
  • R 2 and Ya x2 may be bonded to each other to form a ring structure.
  • n ax2 is an integer from 1 to 3.
  • the "polymerizable group" in the polymerizable group-containing group of W2 is a group that allows a compound having a polymerizable group to be polymerized by radical polymerization, etc. A group containing multiple bonds.
  • the polymerizable group-containing group may be a group consisting only of a polymerizable group, or a group consisting of a polymerizable group and another group other than the polymerizable group.
  • groups other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.
  • the fused ring formed by Ya x2 and W 2 includes a fused ring formed by the polymerizable group at the W 2 site and Ya x2 , and a fused ring formed by Ya x2 and a group other than the polymerizable group at the W 2 site. Examples include fused rings.
  • the condensed ring formed by Ya x2 and W 2 may have a substituent.
  • R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • the structural unit (a8) has the chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1- 09) and (a8-1-10), respectively, is preferable, and at least one type selected from the group consisting of structural units represented by chemical formulas (a8-1-01) to (a8-1-04), ( At least one type selected from the group consisting of structural units represented by a8-1-09) is more preferred.
  • the number of structural units (a8) contained in the component (A1) may be one or more.
  • the proportion of the structural unit (a8) in the component (A1) is preferably 0 to 50 mol%, and 0 to 30 mol%, based on the total (100 mol%) of all the structural units constituting the component (A1). % is more preferable.
  • the component (A1) contained in the resist composition may be used alone or in combination of two or more.
  • component (A1) for example, a polymer compound containing a repeating structure of a structural unit (a0) and a structural unit (a1); Examples include polymeric compounds containing repeating structures.
  • the component (A1) is prepared by dissolving monomers for inducing each structural unit in a polymerization solvent, and then initiating radical polymerization of, for example, azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (for example, V-601, etc.). It can be manufactured by adding an agent and polymerizing it.
  • the component (A1) can be obtained by dissolving a monomer inducing the structural unit (a0), a monomer inducing the structural unit (a1) and the structural unit (a10) in a polymerization solvent, and then adding the above-mentioned monomer to the polymerization solvent.
  • It can be produced by adding a radical polymerization initiator, polymerizing, and then performing a deprotection reaction.
  • a chain transfer agent such as HS-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 -OH in combination
  • -C(CF 3 ) is added to the terminal.
  • 2 -OH group may be introduced.
  • a copolymer into which a hydroxyalkyl group is introduced in which some of the hydrogen atoms of the alkyl group are replaced with fluorine atoms can reduce development defects and reduce LER (line edge roughness: unevenness of line sidewalls). It is effective in reducing
  • the weight average molecular weight (Mw) of the component (A1) is not particularly limited, and is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, and from 10,000 to 30,000 is more preferable.
  • Mw of component (A1) is below the preferable upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and when it is above the preferable lower limit of this range, it has good dry etching resistance.
  • the cross-sectional shape of the resist pattern is good.
  • the degree of dispersion (Mw/Mn) of component (A1) is not particularly limited, and is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, particularly preferably 1.0 to 2.0. .
  • Mn indicates a number average molecular weight.
  • the resist composition of the present embodiment contains, as the (A) component, a base material component (hereinafter referred to as "(A2) ) may be used in combination.
  • the component (A2) is not particularly limited, and may be arbitrarily selected from a large number of components conventionally known as base components for chemically amplified resist compositions.
  • As the component (A2) one type of high molecular compound or low molecular compound may be used alone, or two or more types may be used in combination.
  • the proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and 100% by mass, based on the total mass of component (A). It may be. When the proportion is 25% by mass or more, a resist pattern that is excellent in various lithography properties such as high sensitivity, resolution, and roughness improvement is easily formed.
  • the content of component (A) may be adjusted depending on the thickness of the resist film to be formed, etc.
  • the resist composition of this embodiment may further contain other components in addition to the component (A) described above.
  • Other components include, for example, the following components (B), (D), (E), (F), and (S).
  • the resist composition of this embodiment may further contain an acid generator component (B) that generates acid upon exposure.
  • Component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resist compositions can be used.
  • Such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts; oxime sulfonate acid generators; diazomethane-based acid generators such as bisalkyl or bisarylsulfonyl diazomethanes and poly(bissulfonyl)diazomethanes; Acid generators include a wide variety of acid generators such as nitrobenzylsulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators.
  • Examples of onium salt-based acid generators include compounds represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”), and compounds represented by the general formula (b-2). Examples include a compound (hereinafter also referred to as “component (b-2)”) or a compound represented by general formula (b-3) (hereinafter also referred to as “component (b-3)”).
  • R 101 and R 104 to R 108 each independently represent a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a substituent. It is a chain alkenyl group that may have.
  • R 104 and R 105 may be bonded to each other to form a ring structure.
  • R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom.
  • Y 101 is a divalent linking group or a single bond containing an oxygen atom.
  • V 101 to V 103 each independently represent a single bond, an alkylene group, or a fluorinated alkylene group.
  • L 101 to L 102 are each independently a single bond or an oxygen atom.
  • L 103 to L 105 are each independently a single bond, -CO- or -SO 2 -.
  • m is an integer of 1 or more, and M' m+ is an m-valent onium cation.
  • R 101 is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a substituent It is a chain alkenyl group which may have.
  • Cyclic group that may have a substituent The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
  • Aliphatic hydrocarbon group means a hydrocarbon group without aromaticity. Moreover, it is preferable that the aliphatic hydrocarbon group is saturated.
  • the aromatic hydrocarbon group in R 101 is a hydrocarbon group having an aromatic ring.
  • the number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. .
  • the number of carbon atoms does not include the number of carbon atoms in substituents.
  • the aromatic ring possessed by the aromatic hydrocarbon group in R 101 is benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples include aromatic heterocycles.
  • the heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • the aromatic hydrocarbon group in R 101 includes a group in which one hydrogen atom is removed from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), a group in which one hydrogen atom in the aromatic ring is alkylene Examples include groups substituted with groups (eg, benzyl group, phenethyl group, 1-naphthylmethyl group, etc.).
  • the number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
  • Examples of the cyclic aliphatic hydrocarbon group in R 101 include aliphatic hydrocarbon groups containing a ring in the structure.
  • the aliphatic hydrocarbon group containing a ring in its structure includes an alicyclic hydrocarbon group (a group in which one hydrogen atom is removed from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.
  • the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
  • the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
  • the monocyclic alicyclic hydrocarbon group a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable.
  • the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
  • the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
  • the polycycloalkanes include polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane; steroids; More preferred are polycycloalkanes having a polycyclic skeleton of a condensed ring system such as a cyclic group having a skeleton.
  • cyclic aliphatic hydrocarbon group for R 101 a group obtained by removing one or more hydrogen atoms from a monocycloalkane or polycycloalkane is preferable, and a group obtained by removing one hydrogen atom from a polycycloalkane is more preferable.
  • an adamantyl group and a norbornyl group are more preferable, and an adamantyl group is particularly preferable.
  • the linear aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. , 1 to 3 are most preferred.
  • a linear alkylene group is preferable, and specifically, a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [ -(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -], and the like.
  • the branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 or 4 carbon atoms. , 3 are most preferred.
  • a branched alkylene group is preferable, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2 -CH 2 -; -CH(CH 3 )CH 2 CH 2 -, alkyltrimethylene groups such as -CH 2 CH(CH 3 )CH 2 -; -CH(CH 3 ) Examples include alkylal
  • the cyclic hydrocarbon group in R 101 may contain a heteroatom such as a heterocycle.
  • * represents a bond bonded to Y 101 in formula (b-1).
  • R is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, or a -SO 2 --containing cyclic group;
  • B" has 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom is an alkylene group, an oxygen atom or a sulfur atom, and n' is an integer of 0 to 2. * indicates a bond.
  • B'' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom. It is. B'' is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.
  • Examples of the substituent in the cyclic group of R 101 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, and the like.
  • the alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms.
  • the alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, or tert-butoxy group. Most preferred are methoxy and ethoxy groups.
  • the halogen atom used as a substituent is preferably a fluorine atom, a bromine atom, or an iodine atom.
  • the halogenated alkyl group as a substituent include an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc., in which some or all of the hydrogen atoms are Examples include groups substituted with the aforementioned halogen atoms.
  • the carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) constituting a cyclic hydrocarbon group.
  • the cyclic hydrocarbon group in R 101 may be a fused cyclic group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused.
  • the fused ring include one in which one or more aromatic rings are fused to a polycycloalkane having a polycyclic skeleton of a bridged ring system.
  • Specific examples of the bridged ring polycycloalkanes include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane.
  • the fused ring type is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, and a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane. More preferred are groups containing fused rings.
  • Specific examples of the fused cyclic group for R 101 include those represented by the following formulas (r-br-1) to (r-br-2). In the formula, * represents a bond bonded to Y 101 in formula (b-1).
  • substituents that the fused cyclic group in R 101 may have include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, aromatic hydrocarbon groups, and aliphatic groups. Examples include cyclic hydrocarbon groups. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as a substituent for the fused cyclic group include those listed as the substituent for the cyclic group in R 101 above.
  • Examples of the aromatic hydrocarbon group as a substituent for the fused cyclic group include a group in which one hydrogen atom is removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom is removed from the aromatic ring, A group in which one of the groups is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), the above Examples include heterocyclic groups represented by formulas (r-hr-1) to (r-hr-6), respectively.
  • Examples of the alicyclic hydrocarbon group as a substituent for the fused cyclic group include groups obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, and tricy[5.2 .1.0 2,6 ] A group obtained by removing one hydrogen atom from a polycycloalkane such as clodecane or tetracyclododecane; lactone-containing cyclic group represented by the above general formulas (b5-r-1) to (b5-r-4); -SO 2 --containing cyclic group represented by the above formula (r-hr-7) to Examples include heterocyclic groups each represented by (r-hr-16).
  • the chain alkyl group for R 101 may be either linear or branched.
  • the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
  • the branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms.
  • 1-methylethyl group 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group
  • Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.
  • Chain-like alkenyl group which may have a substituent:
  • the chain alkenyl group for R 101 may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, and even more preferably 2 to 4 carbon atoms. 3 is particularly preferred.
  • Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group.
  • Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, and 2-methylpropenyl group.
  • a straight chain alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.
  • Examples of the substituent in the chain alkyl group or alkenyl group of R 101 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group in R 101 above. Can be mentioned.
  • R 101 is preferably a cyclic group that may have a substituent, and more preferably a cyclic hydrocarbon group that may have a substituent.
  • the cyclic hydrocarbon group includes a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; the general formulas (a2-r-1) to (a2-r- 7) Lactone-containing cyclic groups represented by formulas (b5-r-1) to (b5-r- 4 ) are preferred, and polycycloalkane-containing cyclic groups are preferred.
  • a group obtained by removing one or more hydrogen atoms from is more preferable, and an adamantyl group is even more preferable.
  • Y 101 is a single bond or a divalent linking group containing an oxygen atom.
  • Y 101 may contain atoms other than the oxygen atom.
  • atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.
  • the divalent linking group containing an oxygen atom include linking groups represented by the following general formulas (y-al-1) to (y-al-7), respectively.
  • the bond to R 101 in the above formula (b-1) is the following general formula (y-al-1) to It is V' 101 in (y-al-7).
  • V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms
  • V' 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.
  • the divalent saturated hydrocarbon group in V' 102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and preferably an alkylene group having 1 to 5 carbon atoms. More preferably, it is an alkylene group.
  • the alkylene group in V' 101 and V' 102 may be a linear alkylene group or a branched alkylene group, with a linear alkylene group being preferred.
  • the alkylene group in V' 101 and V' 102 is a methylene group [-CH 2 -]; -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc.
  • alkylmethylene groups ethylene; Group [-CH 2 CH 2 -]; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 ) Alkylethylene group such as CH 2 -; trimethylene group (n-propylene group) [-CH 2 CH 2 CH 2 -]; -CH (CH 3 ) CH 2 CH 2 -, -CH 2 CH (CH 3 ) Alkyltrimethylene group such as CH 2 -; tetramethylene group [-CH 2 CH 2 CH 2 CH 2 -]; -CH (CH 3 ) CH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 ) CH 2 Examples include alkyltetramethylene groups such as CH 2 -; pentamethylene groups [-CH 2 CH 2 CH 2 CH 2 CH 2 -], and the like.
  • a part of the methylene group in the alkylene group in V' 101 or V' 102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms.
  • the aliphatic cyclic group is a cyclic aliphatic hydrocarbon group (a monocyclic aliphatic hydrocarbon group, a polycyclic aliphatic hydrocarbon group) represented by Ra' 3 in the above formula (a1-r-1).
  • a divalent group obtained by removing one hydrogen atom from ) is preferred, and a cyclohexylene group, a 1,5-adamantylene group, or a 2,6-adamantylene group is more preferred.
  • Y 101 is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, each represented by the above formulas (y-al-1) to (y-al-5). A linking group is more preferred.
  • V 101 is a single bond, an alkylene group, or a fluorinated alkylene group.
  • the alkylene group and fluorinated alkylene group in V 101 preferably have 1 to 4 carbon atoms.
  • V 101 is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.
  • R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.
  • anion moiety represented by the formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anions and perfluorobutanesulfonate anions. ;
  • Y 101 is a divalent linking group containing an oxygen atom, examples thereof include anions represented by any of the following formulas (an-1) to (an-3).
  • R''101 is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), respectively.
  • R''102 is an aliphatic cyclic group which may have a substituent, and is represented by the above formula (r-br-1) or (r-br-2).
  • R''103 is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent.
  • V" 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms.
  • R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • v'' are each independently an integer from 0 to 3
  • q'' are each independently an integer from 0 to 20
  • n'' is 0 or 1.
  • the aliphatic cyclic group which may have a substituent for R'' 101 , R'' 102 and R'' 103 is the group exemplified as the cyclic aliphatic hydrocarbon group for R 101 in formula (b-1) above. It is preferable that the substituent is the same as the substituent that may substitute the cyclic aliphatic hydrocarbon group in R 101 in the formula (b-1).
  • the aromatic cyclic group which may have a substituent in R" 101 and R" 103 is the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R 101 in formula (b-1) above. It is preferable that Examples of the substituent include the same substituents that may substitute the aromatic hydrocarbon group in R 101 in formula (b-1).
  • the chain alkyl group which may have a substituent in R'' 101 is preferably the group exemplified as the chain alkyl group in R 101 in formula (b-1) above.
  • the chain alkenyl group which may have a substituent in R'' 103 is preferably the group exemplified as the chain alkenyl group in R 101 in formula (b-1) above.
  • the alkylene group and fluorinated alkylene group in V" 101 preferably have 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms.
  • V" 101 include -CH 2 -, -( Examples include CH 2 ) 2 -, -CFH-, -CH 2 CFH-, -CH(CF 3 )-, and the like.
  • the anion moiety represented by the formula (b-1) is preferably an anion moiety represented by the formula (an-1).
  • R''101 in (an-1) is an aromatic cyclic group which may have a substituent are preferable, and those which are a phenyl group which may have a substituent are more preferable.
  • the substituent include a hydroxy group, an alkyl group, or a halogen atom.
  • the halogen atom is preferably a bromine atom or an iodine atom, and more preferably an iodine atom.
  • R 104 and R 105 each independently represent a cyclic group that may have a substituent, or a chain group that may have a substituent. is an alkyl group or a chain alkenyl group which may have a substituent, and examples thereof include those similar to R 101 in formula (b-1). However, R 104 and R 105 may be bonded to each other to form a ring. R 104 and R 105 are preferably a chain alkyl group that may have a substituent, and are a linear or branched alkyl group or a linear or branched fluorinated alkyl group. is more preferable.
  • the chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the number of carbon atoms in the chain alkyl group of R 104 and R 105 is preferably as small as possible within the range of the number of carbon atoms mentioned above, for reasons such as good solubility in a resist solvent.
  • the greater the number of hydrogen atoms substituted with fluorine atoms the stronger the acid strength, and the higher the resistance to high energy light and electron beams of 250 nm or less. This is preferable because it improves transparency.
  • the proportion of fluorine atoms in the chain alkyl group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. It is a perfluoroalkyl group.
  • V 102 and V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each of them is the same as V 101 in formula (b-1). Can be mentioned.
  • L 101 and L 102 are each independently a single bond or an oxygen atom.
  • R 106 to R 108 each independently represent a cyclic group that may have a substituent, or a chain that may have a substituent. is an alkyl group or a chain alkenyl group which may have a substituent, and examples thereof include those similar to R 101 in formula (b-1).
  • L 103 to L 105 are each independently a single bond, -CO- or -SO 2 -.
  • the anion in component (b-1) is preferable.
  • M' m+ represents an m-valent onium cation.
  • sulfonium cations and iodonium cations are preferred.
  • m is an integer of 1 or more.
  • Preferred cation moieties include organic cations represented by the above general formulas (ca-1) to (ca-3), respectively.
  • cations represented by the general formula (ca-1) are more preferred, and cations represented by the formulas (ca-1-1) to (ca-1-75) are even more preferred.
  • the component (B) may be used alone or in combination of two or more.
  • the resist composition of this embodiment does not need to contain the component (B) because the component (A1) has the structural unit (a0).
  • the content of component (B) in the resist composition is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, and even more preferably 0 to 10 parts by mass, based on 100 parts by mass of component (A). Particularly preferred is 0 to 5 parts by weight.
  • the resist composition of this embodiment further contains a base component (hereinafter also referred to as “component (D)”) that traps the acid generated by exposure (that is, controls the diffusion of acid). It is preferable to contain.
  • Component (D) acts as a quencher (acid diffusion control agent) that traps acid generated by exposure in the resist composition.
  • Component (D) includes, for example, a photodegradable base (D1) that decomposes upon exposure and loses acid diffusion controllability (hereinafter referred to as “component (D1)”), and a nitrogen-containing organic compound that does not fall under the component (D1).
  • Compound (D2) (hereinafter referred to as "component (D2)") and the like can be mentioned.
  • component (D1) a photodegradable base
  • component (D1)) it becomes easier to improve both the characteristics of increasing sensitivity and suppressing the occurrence of coating defects.
  • Component (D1) By using a resist composition containing component (D1), it is possible to further improve the contrast between exposed areas and unexposed areas of the resist film when forming a resist pattern.
  • Component (D1) is not particularly limited as long as it decomposes upon exposure and loses acid diffusion control properties, and may be a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)"). ), a compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component”), and a compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-2) component”).
  • components (d1-1) to (d1-3) do not act as quenchers because they decompose in the exposed areas of the resist film and lose their acid diffusion control properties (basicity), but they do not act as quenchers in the unexposed areas of the resist film. Acts as a char.
  • Rd 1 to Rd 4 are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. It is. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom in Rd 2 in formula (d1-2).
  • Yd 1 is a single bond or a divalent linking group.
  • m is an integer of 1 or more, and M m+ are each independently an m-valent organic cation.
  • Rd 1 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkyl group which may have a substituent. It is a good chain alkenyl group, and the same groups as R' 201 above can be mentioned. Among these, Rd 1 is an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain type which may have a substituent. Alkyl groups are preferred.
  • substituents that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, and the above general formulas (a2-r-1) to (a2-r- Examples include a lactone-containing cyclic group represented by 7), an ether bond, an ester bond, or a combination thereof.
  • an ether bond or an ester bond is included as a substituent, it may be via an alkylene group, and the substituent in this case is represented by the above formulas (y-al-1) to (y-al-5), respectively.
  • a linking group is preferred.
  • an aromatic hydrocarbon group, an aliphatic cyclic group, or a chain alkyl group in Rd 1 is represented by the above general formulas (y-al-1) to (y-al-7), respectively, as a substituent.
  • an aromatic hydrocarbon group or an aliphatic cyclic group in Rd 1 in formula (d3-1) is bonded to a carbon atom constituting a chain alkyl group or a chain alkyl group.
  • Preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and other ring structures).
  • the aliphatic cyclic group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, and tetracyclododecane. It is more preferable that there be.
  • the chain alkyl group preferably has 1 to 10 carbon atoms, and specifically includes a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group.
  • nonyl group, decyl group, etc. 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1- Examples include branched alkyl groups such as ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.
  • the chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent
  • the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8. 1 to 4 are more preferred.
  • the fluorinated alkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.
  • M m+ is an m-valent organic cation.
  • organic cation of M m+ cations similar to the cations represented by the above general formulas (ca-1) to (ca-3), respectively, can be preferably mentioned, and the cations shown by the above general formula (ca-1) are preferably mentioned. Cations are more preferred, and cations represented by the formulas (ca-1-1) to (ca-1-75) are even more preferred.
  • Component (d1-1) may be used alone or in combination of two or more.
  • Rd 2 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkyl group which may have a substituent. It is a good chain alkenyl group, and examples include those similar to R' 201 above. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom in Rd 2 (not substituted with fluorine). As a result, the anion of the component (d1-2) becomes an appropriately weak acid anion, and the quenching ability of the component (D) is improved.
  • Rd 2 is preferably a chain alkyl group that may have a substituent or an aliphatic cyclic group that may have a substituent; More preferably, it is a formula group.
  • the chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms.
  • the aliphatic cyclic group includes a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, tetracyclododecane, etc. (with a substituent). ); More preferably, it is a group obtained by removing one or more hydrogen atoms from camphor.
  • the hydrocarbon group of Rd 2 may have a substituent, and examples of the substituent include the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group) of Rd 1 of the above formula (d1-1). , chain alkyl group) may be included.
  • M m+ is an m-valent organic cation, and is the same as M m+ in formula (d1-1) above.
  • Component (d1-2) may be used alone or in combination of two or more.
  • Rd 3 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group, and examples thereof include those similar to R' 201 above, and it is preferably a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. Among these, a fluorinated alkyl group is preferred, and the same fluorinated alkyl group as Rd 1 above is more preferred.
  • Rd 4 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkyl group which may have a substituent. It is an alkenyl group, and the same groups as R' 201 above can be mentioned. Among these, preferred are alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups that may have substituents.
  • the alkyl group in Rd 4 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group.
  • the alkoxy group in Rd 4 is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, Examples include n-butoxy group and tert-butoxy group. Among them, methoxy group and ethoxy group are preferred.
  • alkenyl group for Rd 4 examples include the same alkenyl groups as for R' 201 above, and vinyl group, propenyl group (allyl group), 1-methylpropenyl group, and 2-methylpropenyl group are preferable. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.
  • Examples of the cyclic group in Rd 4 include the same cyclic groups as in R' 201 , such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclo[5.2.1.0 2,6 ]decane, An alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as tetracyclododecane, or an aromatic group such as a phenyl group or a naphthyl group is preferable.
  • Rd 4 is an alicyclic group
  • the resist composition dissolves well in an organic solvent, resulting in good lithography properties.
  • Rd 4 is an aromatic group
  • the resist composition has excellent light absorption efficiency and good sensitivity and lithography properties in lithography using EUV or the like as an exposure light source.
  • Yd 1 is a single bond or a divalent linking group.
  • the divalent linking group in Yd 1 is not particularly limited, but includes divalent hydrocarbon groups that may have substituents (aliphatic hydrocarbon groups, aromatic hydrocarbon groups), divalent hydrocarbon groups containing heteroatoms, etc. Examples include linking groups such as These are the divalent hydrocarbon group which may have a substituent, and the divalent linking group containing a hetero atom, which are mentioned in the explanation of the divalent linking group in Ya 21 in the above formula (a2-1). Examples include those similar to the valent linking group.
  • Yd 1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof.
  • the alkylene group is more preferably a linear or branched alkylene group, and even more preferably a methylene group or an ethylene group.
  • M m+ is an m-valent organic cation, and is the same as M m+ in formula (d1-1) above.
  • Component (d1-3) may be used alone or in combination of two or more.
  • any one of the components (d1-1) to (d1-3) above may be used alone, or two or more thereof may be used in combination.
  • the content of component (D1) in the resist composition is preferably 0.5 to 15 parts by mass, and 1 to 15 parts by mass, based on 100 parts by mass of component (A). It is more preferably 10 parts by weight, and even more preferably 2 to 8 parts by weight.
  • the content of component (D1) is at least the preferable lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained. On the other hand, when it is below the upper limit, sensitivity can be maintained well and throughput is also excellent.
  • the component (D1) preferably contains the component (d1-1) described above.
  • the content of component (d1-1) is preferably 50% by mass or more, preferably 70% by mass or more, and 90% by mass or more. It is more preferable that the amount is % by mass or more, and the component (D) may consist only of the compound (d1-1) component.
  • (D1) Method for producing component The method for producing the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods. Furthermore, the method for producing component (d1-3) is not particularly limited, and is produced, for example, in the same manner as the method described in US2012-0149916.
  • Component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not correspond to component (D1) above.
  • component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not fall under the component (D1), and any known components may be used.
  • aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are particularly preferred.
  • Aliphatic amines are amines having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms.
  • aliphatic amines examples include amines (alkyl amines or alkyl alcohol amines) or cyclic amines in which at least one hydrogen atom of ammonia NH 3 is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms.
  • alkyl amines and alkyl alcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, tri- Examples include alkylamine
  • Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a heteroatom.
  • the heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
  • Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
  • the aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, specifically, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5 .4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, and the like.
  • aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris ⁇ 2-(2-methoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(2-methoxyethoxymethoxy)ethyl ⁇ amine, tris ⁇ 2 -(1-methoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(1-ethoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(1-ethoxypropoxy)ethyl ⁇ amine, tris[2- ⁇ 2-(2-hydroxy) Examples include ethoxy)ethoxy ⁇ ethyl]amine, triethanolamine triacetate, and triethanolamine triacetate is preferred.
  • an aromatic amine may be used as the component (D2).
  • aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert -butylpyridine, 2,6-di-tert-butylpyridine and the like.
  • component (D2) is preferably an alkylamine, more preferably a trialkylamine having 5 to 10 carbon atoms.
  • Component (D2) may be used alone or in combination of two or more.
  • the content of component (D2) in the resist composition is preferably 0.01 to 5 parts by mass, and 0.01 to 5 parts by mass, based on 100 parts by mass of component (A). It is more preferably 1 to 5 parts by weight, and even more preferably 0.5 to 5 parts by weight.
  • the content of the component (D2) is at least the preferable lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained. On the other hand, when it is below the upper limit, sensitivity can be maintained well and throughput is also excellent.
  • the resist composition of this embodiment contains organic carboxylic acids, phosphorus oxoacids, and derivatives thereof as optional components for the purpose of preventing sensitivity deterioration, improving resist pattern shape, storage stability over time, etc.
  • At least one compound (E) selected from the group consisting of (hereinafter referred to as "component (E)") can be contained.
  • the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, among which salicylic acid is preferred.
  • the phosphorus oxoacid include phosphoric acid, phosphonic acid, and phosphinic acid, and among these, phosphonic acid is particularly preferred.
  • one kind of component (E) may be used alone, or two or more kinds may be used in combination.
  • the content of component (E) is preferably 0.01 to 5 parts by mass, and 0.05 to 3 parts by mass, based on 100 parts by mass of component (A). is more preferable. By setting it within the above range, the lithography characteristics are further improved.
  • the resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") as a hydrophobic resin.
  • Component (F) is used to impart water repellency to the resist film, and can improve lithography properties by being used as a resin separate from component (A).
  • the component (F) is described, for example, in JP-A No. 2010-002870, JP-A No. 2010-032994, JP-A No. 2010-277043, JP-A No. 2011-13569, and JP-A No. 2011-128226.
  • the following fluorine-containing polymer compounds can be used.
  • component (F) includes a polymer having a structural unit (f1) represented by the following general formula (f1-1).
  • This polymer includes a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the above structural unit (a1); ; It is preferable that it is a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1), and the structural unit (f1) and the structural unit (a1) More preferably, it is a copolymer with.
  • the structural unit (a1) copolymerized with the structural unit (f1) is a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, 1-methyl-1-adamantyl ( A structural unit derived from meth)acrylate is preferred, and a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate is more preferred.
  • R is the same as above, and Rf 102 and Rf 103 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Rf 102 and Rf 103 may be the same or different. nf 1 is an integer from 0 to 5, and Rf 101 is an organic group containing a fluorine atom. ]
  • R bonded to the carbon atom at the ⁇ position is the same as described above.
  • R a hydrogen atom or a methyl group is preferable.
  • the halogen atoms of Rf 102 and Rf 103 are preferably fluorine atoms.
  • Examples of the alkyl group having 1 to 5 carbon atoms for Rf 102 and Rf 103 include those similar to the alkyl group having 1 to 5 carbon atoms for R above, and methyl group or ethyl group is preferable.
  • the halogenated alkyl group having 1 to 5 carbon atoms in Rf 102 and Rf 103 includes a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom.
  • the halogen atom is preferably a fluorine atom.
  • Rf 102 and Rf 103 are preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom.
  • nf 1 is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.
  • Rf 101 is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom.
  • the hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. More preferably, the number of carbon atoms is 1 to 10, particularly preferred. Further, in the hydrocarbon group containing a fluorine atom, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more are fluorinated, and 60% or more are fluorinated.
  • Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, such as trifluoromethyl group, -CH 2 -CF 3 , -CH 2 -CF 2 -CF 3 , -CH(CF 3 ) 2 , -CH 2 -CH 2 -CF 3 and -CH 2 -CH 2 -CF 2 -CF 2 -CF 3 are particularly preferred.
  • the weight average molecular weight (Mw) of the component (F) (based on polystyrene standards determined by gel permeation chromatography) is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, and most preferably from 10,000 to 30,000. When it is below the upper limit of this range, there is sufficient solubility in a resist solvent for use as a resist, and when it is above the lower limit of this range, the water repellency of the resist film is good.
  • the degree of dispersion (Mw/Mn) of component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.
  • one kind of component (F) may be used alone, or two or more kinds may be used in combination.
  • the content of component (F) is preferably 0.5 to 10 parts by mass, and preferably 1 to 10 parts by mass, based on 100 parts by mass of component (A). It is more preferable that it is part.
  • the resist composition of this embodiment can be manufactured by dissolving a resist material in an organic solvent component (hereinafter referred to as "component (S)").
  • component (S) organic solvent component
  • the (S) component may be used alone or as a mixed solvent of two or more.
  • PGMEA, PGME, ⁇ -butyrolactone, EL, and cyclohexanone are preferred.
  • component (S) a mixed solvent of PGMEA and a polar solvent is also preferable.
  • the blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent.
  • component (S) a mixed solvent of at least one selected from PGMEA and EL and ⁇ -butyrolactone is also preferred. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5.
  • the amount of component (S) to be used is not particularly limited, and is appropriately set at a concentration that allows coating on a substrate, etc., depending on the thickness of the coating film. Generally, component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by weight, preferably 0.2 to 15% by weight.
  • impurities and the like may be removed using a porous polyimide membrane, a porous polyamide-imide membrane, or the like.
  • the resist composition may be filtered using a filter made of a porous polyimide membrane, a filter made of a porous polyamide-imide membrane, a filter made of a porous polyimide membrane and a porous polyamide-imide membrane, or the like.
  • the polyimide porous membrane and the polyamideimide porous membrane include those described in JP-A No. 2016-155121.
  • the resist composition of the present embodiment described above contains the resin component (A1) having the structural unit (a0). This makes it possible to increase sensitivity and reduce roughness.
  • the reason for the above effects is presumed to be as follows.
  • the structural unit (a0) contains an acid-generating group that generates an acid upon exposure to light, and the anion moiety that is the acid-generating group is incorporated into the resin component (A1). This suppresses excessive diffusion of acid generated by exposure.
  • the anion part of the structural unit (a0) includes two cyclic groups connected by a divalent linking group, and has appropriate rigidity. Such structural features are also believed to contribute to suppressing excessive acid diffusion. It is presumed that roughness is reduced by suppressing excessive diffusion of acid in this way.
  • the anion part of the structural unit (a0) has an appropriate size and can be appropriately close to the acid-decomposable group contained in the resin component (A1). Therefore, the acid-decomposable group is easily deprotected. Therefore, it is presumed that the sensitivity is increased.
  • the resist pattern forming method according to the second aspect of the present invention includes a step of forming a resist film on a support using the resist composition according to the first aspect of the present invention, and exposing the resist film to light.
  • This method includes a step of developing the exposed resist film to form a resist pattern.
  • One embodiment of such a resist pattern forming method includes, for example, a resist pattern forming method performed as follows.
  • the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and a bake (post-apply bake (PAB)) treatment is performed, preferably for 40 to 120 seconds at a temperature of 80 to 150°C. is applied for 60 to 90 seconds to form a resist film.
  • a bake (post-apply bake (PAB)) treatment is performed, preferably for 40 to 120 seconds at a temperature of 80 to 150°C. is applied for 60 to 90 seconds to form a resist film.
  • the resist film is exposed to light through a mask (mask pattern) on which a predetermined pattern is formed, or with an electron beam without passing through the mask pattern, using an exposure device such as an electron beam lithography device or an ArF exposure device.
  • a bake (post-exposure bake (PEB)) treatment is performed, for example, at a temperature of 80 to 150° C.
  • the development process is performed using an alkaline developer in the case of an alkaline development process, and is performed using a developer containing an organic solvent (organic developer) in the case of a solvent development process.
  • a rinsing process is performed.
  • a rinsing treatment in the case of an alkaline development process, water rinsing using pure water is preferable, and in the case of a solvent development process, it is preferable to use a rinsing liquid containing an organic solvent.
  • a treatment may be performed to remove the developer or rinse agent adhering to the pattern using a supercritical fluid.
  • drying is performed. In some cases, a bake process (post-bake) may be performed after the development process.
  • the support is not particularly limited, and conventionally known supports can be used, such as substrates for electronic components and substrates on which predetermined wiring patterns are formed. More specifically, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. As the material for the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used.
  • the wavelength used for exposure is not particularly limited, and may include ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. It can be done using radiation.
  • the method of exposing the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or liquid immersion lithography.
  • immersion exposure the space between the resist film and the lowest lens of the exposure device is filled in advance with a solvent (immersion medium) that has a refractive index greater than that of air, and exposure (immersion exposure) is performed in that state.
  • the immersion medium is preferably a solvent having a refractive index greater than that of air and less than the refractive index of the resist film to be exposed, such as water, fluorine-based inert liquid, silicone-based solvent, carbonized Examples include hydrogen-based solvents. Water is preferably used as the immersion medium.
  • Examples of the alkaline developer used in the alkaline development process include a 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.
  • TMAH tetramethylammonium hydroxide
  • the organic solvent contained in the organic developer used for development in the solvent development process may be any organic solvent as long as it can dissolve component (A) (component (A) before exposure), and may be selected from known organic solvents. You can choose as appropriate. Specific examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, hydrocarbon solvents, and the like.
  • ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butane
  • Examples include butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
  • nitrile solvents examples include acetonitrile, propionitrile, valeronitrile, butyronitrile, and the like.
  • additives can be added to the organic developer as necessary.
  • additives include surfactants.
  • the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used.
  • the development process can be carried out by a known development method, such as a method in which the support is immersed in a developer for a certain period of time (dipping method), a method in which the support is heaped up on the surface of the support by surface tension, and then left for a certain period of time. (paddle method), spraying the developer onto the surface of the support (spray method), and applying the developer onto the rotating support while scanning the developer application nozzle at a constant speed. Examples include a continuous dispensing method (dynamic dispensing method), etc.
  • organic solvent contained in the rinsing liquid used for rinsing after development in the solvent development process for example, among the organic solvents listed as organic solvents used in the organic developer, those that do not easily dissolve the resist pattern are appropriately selected. It can be used as Generally, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Any one type of these organic solvents may be used alone, or two or more types may be used in combination. Further, it may be used in combination with an organic solvent other than those mentioned above or water.
  • the rinsing process (cleaning process) using a rinsing liquid can be performed by a known rinsing method.
  • the rinsing method include a method of continuously applying a rinsing liquid onto a support rotating at a constant speed (rotary coating method), a method of immersing the support in a rinsing liquid for a certain period of time (dipping method), Examples include a method of spraying a rinsing liquid onto the surface of the support (spray method).
  • the resist pattern forming method of the present embodiment described above since the above-described resist composition is used, it is possible to achieve high sensitivity and form a resist pattern with good roughness reduction properties.
  • the resist composition of the embodiment described above, and various materials used in the pattern forming method of the embodiment described above e.g., resist solvent, developer, rinse solution, composition for forming an antireflective film, composition for forming a top coat
  • the material does not contain impurities such as metals, metal salts containing halogens, acids, alkalis, components containing sulfur atoms, or phosphorus atoms.
  • impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. can.
  • the content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and substantially free of impurities (parts per trillion). most preferably below the detection limit).
  • the compound according to the third aspect of the present invention is a compound represented by the following general formula (m0-1) (hereinafter also referred to as “compound (M0)").
  • W 01 represents a polymerizable group-containing group.
  • La 01 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • La 02 represents a divalent linking group.
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 01 represents a divalent linking group or a single bond.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group. However, both Ya 01 and Va 01 do not form a single bond.
  • Ra 01 represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • M m+ is an m-valent cation.
  • W 01 , La 01 , La 02 , Ar 01 , Ya 01 , Va 01 , Ra 01 , and M m+ are W 01 , La 01 in the formula (a0-1) , La 02 , Ar 01 , Ya 01 , Va 01 , Ra 01 , and M m+ , respectively.
  • the compound (M0) is preferably a compound represented by the following general formula (m0-1-1).
  • R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
  • Yx 01 represents a divalent linking group or a single bond containing a heteroatom.
  • La 011 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • La 021 represents a divalent linking group.
  • Ar 011 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 011 represents a divalent linking group or a single bond.
  • Va 011 represents a single bond, an alkylene group or a fluorinated alkylene group. However, both Ya 011 and Va 011 do not form a single bond.
  • Ra 011 is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • M m+ is an m-valent cation.
  • R, Yx 01 , La 011 , La 021 , Ar 011 , Ya 011 , Va 011 , Ra 011 , and M m+ in the formula (m0-1-1) are the same as in the formula (a0-1-1).
  • R, Yx 01 , La 011 , La 021 , Ar 011 , Ya 011 , Va 011 , Ra 011 , and M m+ are the same as in the formula (a0-1-1).
  • R, Yx 01 , La 011 , La 021 , Ar 011 , Ya 011 , Va 011 , Ra 011 , and M m+ respectively.
  • the compound (M0) is more preferably a compound represented by the following general formula (m0-1-1-1).
  • R, Yx 01 , La 021 , and Ra 011 are the same as R, Yx 01 , La 021 , and Ra 011 in the general formula (a0-1-1), respectively.
  • La 0 represents an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring.
  • R a represents a hydrogen atom or an alkyl group.
  • Ra 021 and Ra 022 each independently represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • X 0 represents an iodine atom.
  • Rx 01 represents a substituent other than an iodine atom.
  • Rx 02 represents a substituent.
  • k1 and k2 each independently represent an integer from 0 to 4, and k1+k2 ⁇ 4.
  • k3 is an integer of 0 or more as long as the valence allows.
  • k4 represents an integer from 1 to 5
  • k5 represents 0 or 1
  • k6 represents an integer from 0 to 5.
  • the plurality of Ra 021s may be the same or different.
  • k6 is 2 or more, a plurality of Ra 022 may be the same or different.
  • L 01 is a single bond, k5 and k6 will never both be 0.
  • M m+ is an m-valent
  • R, Yx 01 , La 021 , Ra 011 , L 01 , L 02 , Ra 021 , Ra 022 , Rx 01 , Rx 02 , k1 to k6, and M m+ are , R in the formula (a0-1-1), Yx 01 , La 021 , Ra 011 , L 01 , L 02 , Ra 021 , Ra 022 , Rx 01 , Rx 02 , k1 to k6, and M m+ , respectively It's the same.
  • R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • M m+ is an m-valent cation.
  • m is an integer of 1 or more.
  • Compound (M0) is preferably a compound represented by any of the formulas (M01-an-1) to (M01-an-45), and is preferably a compound represented by any of the formulas (M01-an-1) to (M01-an-7). ), and (M01-an-42) to (M01-an-45) are more preferred.
  • the compound (M0) of this embodiment can be produced by combining known methods.
  • Compound (M0) can be obtained, for example, by reactions (I) to (III) described below.
  • reaction (I) for example, a compound represented by the following general formula (A) and a compound represented by the following general formula (B) are reacted to obtain a compound represented by the following general formula (C). .
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group.
  • Ra 01 represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • Ya 01 represents a divalent linking group or a single bond.
  • a and b are groups capable of forming a divalent linking group or a single bond through a condensation reaction between the two.
  • c is a group capable of forming a divalent linking group or a single bond through a condensation reaction with d described below.
  • Ar 01 , Va 01 , and Ra 01 in the above reaction formula are the same as Ar 01 , Va 01 , Ra 01 , and Ya 01 in the general formula (a0-1), respectively.
  • a and b are groups capable of forming a divalent linking group or a single bond through a condensation reaction between the two.
  • one of a and b is a hydroxy group and the other is a carboxy group.
  • c is, for example, a hydroxy group or a carboxy group.
  • reaction (II) a compound represented by general formula (C) and a compound represented by general formula (D) below are reacted to obtain a compound represented by general formula (E) below.
  • W 01 represents a polymerizable group-containing group.
  • La 01 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 01 represents a divalent linking group or a single bond.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group.
  • Ra 01 represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • La 02 represents a divalent linking group.
  • c and d are groups capable of forming a divalent linking group through a condensation reaction between them. ]
  • W 01 , La 01 , La 02 , Ar 01 , Ya 01 , Va 01 , and Ra 01 in the above reaction formula are W 01 , La 01 , La 02 , Ar 01 in the general formula (a0-1), They are the same as Ya 01 , Va 01 , and Ra 01 , respectively.
  • c and d are groups capable of forming a divalent linking group through a condensation reaction between them. For example, it is preferable that one of c and d is a hydroxy group and the other is a carboxy group.
  • reaction (III) compound (M0) is obtained by performing a salt exchange reaction between a compound represented by general formula (E) and a compound represented by general formula (F) below.
  • compound (E) is obtained by performing a salt exchange reaction between a compound represented by general formula (E) and a compound represented by general formula (F) below.
  • Each of the above-mentioned compounds may be a commercially available product or may be synthesized by a known method.
  • W 01 represents a polymerizable group-containing group.
  • La 01 represents an aromatic hydrocarbon group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent.
  • La 02 represents a divalent linking group.
  • Ar 01 represents an aromatic hydrocarbon group which may have a substituent.
  • Ya 01 represents a divalent linking group or a single bond.
  • Va 01 represents a single bond, an alkylene group or a fluorinated alkylene group.
  • Ra 01 represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms.
  • M m+ is an m-valent cation.
  • W 01 , La 01 , La 02 , Ar 01 , Ya 01 , Va 01 , Ra 01 , and M m+ in the above reaction formula are W 01 , La 01 , La 02 in the general formula (a0-1), Same as Ar 01 , Ya 01 , Va 01 , Ra 01 , and M m+ .
  • TfO ⁇ represents a triflate anion.
  • the temperature conditions for reaction (I) and reaction (II) are not particularly limited, and are, for example, about -10 to 120°C, preferably 0 to 100°C, and more preferably 10 to 70°C.
  • the reaction time of reaction (I) is not particularly limited, and is, for example, about 1 to 72 hours, preferably 1 to 24 hours.
  • reaction solvents used in the above reactions (I) and (II) include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, and dimethylsulfoxide. etc.
  • condensation reactions in reaction (I) and reaction (II) may be performed in the presence of a condensing agent.
  • condensing agents include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and carbonyldiimidazole (CDI). ) etc.
  • a basic catalyst may be used in reaction (I) and reaction (II).
  • Specific examples of the basic catalyst include tertiary amines such as trimethylamine, triethylamine, and tributylamine, aromatic amines such as pyridine, dimethylaminopyridine (DMAP), and pyrrolidinopyridine, and diazabicyclononene (DBN). , diazabicycloundecene (DBU), and the like.
  • the temperature conditions for reaction (III) are not particularly limited, and are, for example, about 0 to 50°C.
  • the reaction time of reaction (III) is not particularly limited, and is, for example, about 1 minute to 24 hours.
  • the reaction solvent for reaction (III) is preferably, for example, a mixed solvent of an organic solvent and water.
  • the organic solvent include ketone solvents such as cyclohexanone, methyl ethyl ketone, and diethyl ketone; ether solvents such as diethyl ether, t-butyl methyl ether, and diisopropyl ether; tetrahydrofuran, 1,3-dioxolane, dichloromethane (methylene chloride), 1 , 2-dichloroethane, ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, propionitrile, or a mixed solvent thereof.
  • compound (M0) in the reaction solution may be isolated and purified.
  • Conventionally known methods can be used for isolation and purification; for example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be used alone or in combination of two or more of these. can.
  • the structure of the compound obtained as described above can be determined by 1 H-nuclear magnetic resonance (NMR) spectroscopy, 13 C-NMR spectroscopy, 19 F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry ( It can be confirmed by general organic analysis methods such as MS) method, elemental analysis method, and X-ray crystal diffraction method.
  • the compound of this embodiment can be used for producing a polymer compound according to the fourth aspect described below.
  • a fourth aspect of the present invention is a polymer compound having a structural unit derived from the compound (M0) according to the third aspect.
  • the structural unit derived from the compound (M0) according to the third aspect is the same as the above structural unit (a0).
  • the polymer compound according to the fourth aspect is the same as the component (A1) above.
  • the polymer compound according to the fourth aspect can be used for manufacturing the resist composition according to the first aspect.
  • the weight average molecular weight (Mw) and molecular weight dispersity (Mw/Mn) of the polymer compounds (A1-1) to (A1-18) were determined by GPC measurement (standard polystyrene conversion).
  • the copolymerization composition ratio (ratio (mole ratio) of each structural unit in the structural formula) of the polymer compounds (A1-1) to (A1-18) was determined by carbon-13 nuclear magnetic resonance spectrum (600MHz_ 13 C-NMR). I asked for it.
  • Polymer compound (A1-6): weight average molecular weight (Mw) 10,000, molecular weight dispersity (Mw/Mn) 1.51, l/m/n 35/50/15.
  • Polymer compound (A1-13): Weight average molecular weight (Mw) 10,000, molecular weight dispersity (Mw/Mn) 1.54, l/m/n 35/50/15.
  • Polymer compound (A1-14): Weight average molecular weight (Mw) 13500, molecular weight dispersity (Mw/Mn) 1.53, l/m/n 35/50/15.
  • Polymer compound (A1-15): Weight average molecular weight (Mw) 9800, molecular weight dispersity (Mw/Mn) 1.58, l/m/n 35/50/15.
  • Polymer compound (A1-16): weight average molecular weight (Mw) 9500, molecular weight dispersity (Mw/Mn) 1.56, l/m/n 35/50/15.
  • Polymer compound (A1-17): Weight average molecular weight (Mw) 9700, molecular weight dispersity (Mw/Mn) 1.56, l/m/n 35/50/15.
  • Polymer compound (A1-18): Weight average molecular weight (Mw) 9900, molecular weight dispersity (Mw/Mn) 1.53, l/m/n 35/50/15.
  • (A1)-1 to (A1)-18 The polymer compounds (A1-1) to (A1-18).
  • the weight average molecular weight (Mw) is a standard polystyrene equivalent weight average molecular weight determined by GPC measurement.
  • the copolymerization composition ratio (ratio (mole ratio) of each structural unit in the structural formula) was determined by 13 C-NMR.
  • (D)-1 An acid diffusion control agent consisting of the following compound (D-1).
  • LS pattern space pattern
  • TMAH tetramethylammonium hydroxide
  • the resist compositions of Examples 1 to 18 had better sensitivity and LWR than the resist compositions of Comparative Examples 1 and 2.

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Abstract

La présente composition de réserve comprend un composant de résine (A1) dont la solubilité varie dans une solution de développement en raison de l'action d'un acide. Le composant de résine (A1) a un motif constitutif (a0) dérivé d'un composé représenté par la formule (a0-1). W01 représente un groupe contenant un groupe polymérisable ; La01 représente un groupe hydrocarboné aromatique ou un groupe hydrocarboné alicyclique ; La02 représente un groupe de liaison divalent ; Ar01 représente un groupe hydrocarboné aromatique ; Ya01 représente un groupe de liaison divalent ou une liaison simple ; Va01 représente une liaison simple, un groupe alkylène ou un groupe alkylène fluoré ; Ra01 représente un atome d'hydrogène, un atome de fluor ou un groupe alkyle fluoré ayant de 1 à 5 atomes de carbone ; et Mm+ représente un cation de valence m.
PCT/JP2023/025597 2022-07-15 2023-07-11 Composition de réserve, procédé de formation de motif de réserve, composé et composé polymère WO2024014462A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013133357A (ja) * 2011-12-26 2013-07-08 Sumitomo Chemical Co Ltd 樹脂及びレジスト組成物
JP2014001259A (ja) * 2012-06-15 2014-01-09 Shin Etsu Chem Co Ltd スルホニウム塩、高分子化合物、レジスト材料及びパターン形成方法
JP2021187909A (ja) * 2020-05-27 2021-12-13 住友化学株式会社 エポキシ樹脂組成物
JP2022059571A (ja) * 2020-10-01 2022-04-13 信越化学工業株式会社 ポジ型レジスト材料及びパターン形成方法
JP2022191163A (ja) * 2021-06-15 2022-12-27 信越化学工業株式会社 レジスト材料及びパターン形成方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013133357A (ja) * 2011-12-26 2013-07-08 Sumitomo Chemical Co Ltd 樹脂及びレジスト組成物
JP2014001259A (ja) * 2012-06-15 2014-01-09 Shin Etsu Chem Co Ltd スルホニウム塩、高分子化合物、レジスト材料及びパターン形成方法
JP2021187909A (ja) * 2020-05-27 2021-12-13 住友化学株式会社 エポキシ樹脂組成物
JP2022059571A (ja) * 2020-10-01 2022-04-13 信越化学工業株式会社 ポジ型レジスト材料及びパターン形成方法
JP2022191163A (ja) * 2021-06-15 2022-12-27 信越化学工業株式会社 レジスト材料及びパターン形成方法

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