WO2014132934A1 - Composition de résine sensible aux rayons actifs ou sensible à un rayonnement, film sensible aux rayons actifs ou sensible à un rayonnement, procédé de formation de motifs, dispositif électronique et procédé permettant de fabriquer un dispositif électronique - Google Patents

Composition de résine sensible aux rayons actifs ou sensible à un rayonnement, film sensible aux rayons actifs ou sensible à un rayonnement, procédé de formation de motifs, dispositif électronique et procédé permettant de fabriquer un dispositif électronique Download PDF

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Publication number
WO2014132934A1
WO2014132934A1 PCT/JP2014/054380 JP2014054380W WO2014132934A1 WO 2014132934 A1 WO2014132934 A1 WO 2014132934A1 JP 2014054380 W JP2014054380 W JP 2014054380W WO 2014132934 A1 WO2014132934 A1 WO 2014132934A1
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group
carbon atoms
sensitive
atom
radiation
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PCT/JP2014/054380
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English (en)
Japanese (ja)
Inventor
修史 平野
滝沢　裕雄
英明 椿
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富士フイルム株式会社
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Publication of WO2014132934A1 publication Critical patent/WO2014132934A1/fr

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    • 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
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern formation method, an electronic device, and an electronic device manufacturing method. More specifically, the present invention relates to an ultra-microlithographic process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a process for producing a mold for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication.
  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a process, an actinic ray-sensitive or radiation-sensitive film using the same, a pattern formation method, an electronic device, and a method for manufacturing an electronic device.
  • immersion liquid a high refractive index liquid
  • Documents 1 to 3 disclose chemically amplified resist compositions having hydrophobicity suitable for immersion exposure.
  • the resist composition is hydrophobized in order to improve the problem of pattern collapse due to ultrafine patterning, there is a case where an adverse effect on lithography properties may be observed depending on the hydrophobizing method. It has been found by the present inventors that the affinity and penetrability are lowered, the sensitivity is lowered and roughness characteristics are deteriorated, and development defects are sometimes caused.
  • the present invention is excellent in sensitivity, resolution, pattern shape, and development defect suppressing ability, and particularly for EUV exposure, it has excellent ability to suppress pattern shape deterioration (film slippage) due to out-of-band light.
  • An object is to provide a light-sensitive or radiation-sensitive resin composition, an actinic light-sensitive or radiation-sensitive film, a pattern forming method, an electronic device, and a method for manufacturing the electronic device.
  • R ′ represents a hydrogen atom or an alkyl group.
  • L represents a single bond or a divalent linking group.
  • R 1 represents a hydrogen atom or a monovalent substituent.
  • R 2 represents a monovalent substituent not containing a fluorine atom.
  • R 1 and R 2 may be bonded to each other to form a ring together with the oxygen atom in the formula.
  • R 3 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
  • Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • R 1 and R 2 each independently represents an alkyl group. However, at least one alkyl group has 2 or more carbon atoms.
  • R 11 and R 12 each independently represents an alkyl group, and R 13 represents a hydrogen atom or an alkyl group.
  • R 11 and R 12 may be connected to each other to form a ring, and R 11 and R 13 may be connected to each other to form a ring.
  • the resin (Aa) is further a fluorine atom, a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, or 6 or more carbon atoms.
  • Rb represents a hydrogen atom, an alkyl group or a halogen atom.
  • S 1a represents a substituent, and when a plurality of S 1a are present, each is independent.
  • p represents an integer of 0 to 5.
  • Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
  • Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
  • ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5.
  • L ky represents an alkylene group, an oxygen atom or a sulfur atom.
  • Z ka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group. If Z ka there are a plurality, the plurality of Z ka may be the same or different, may be connected to form a ring Z ka each other.
  • nka represents an integer of 0 to 10.
  • R kb1 and R kb2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R kb1 , R kb2, and R ky5 are connected to each other.
  • a ring may be formed.
  • nkb represents 0 or 1.
  • R ky5 represents an electron withdrawing group.
  • actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], further comprising a compound that generates an acid upon irradiation with actinic rays or radiation.
  • the content of the resin (Aa) is in the range of 0.01 to 30% by mass based on the total solid content in the composition, according to any one of [1] to [7] An actinic ray-sensitive or radiation-sensitive resin composition.
  • the content of the resin (Aa) is in the range of 0.01 to 20% by mass based on the total solid content in the composition, according to any one of [1] to [7] An actinic ray-sensitive or radiation-sensitive resin composition.
  • the content of the resin (Aa) is in the range of 0.01 to 10% by mass based on the total solid content in the composition, according to any one of [1] to [7] An actinic ray-sensitive or radiation-sensitive resin composition.
  • the actinic ray A pattern forming method comprising exposing a light-sensitive or radiation-sensitive film by irradiating with actinic light or radiation and developing the exposed light-sensitive or radiation-sensitive film.
  • [15] A semiconductor device manufactured through a process including the pattern forming method according to [13] or [14].
  • the present invention is excellent in sensitivity, resolution, pattern shape and ability to suppress development defects, and particularly sensitive to EUV exposure, which has excellent ability to suppress pattern shape deterioration (film slippage) due to out-of-band light. It has become possible to provide a light-sensitive or radiation-sensitive resin composition, an actinic light-sensitive or radiation-sensitive film and a pattern forming method, an electronic device manufacturing method, and an electronic device.
  • the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • active light refers to, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet (EUV) rays, X rays, soft X rays, electron rays (EB). Etc.
  • light means actinic rays or radiation.
  • the term “exposure” as used herein refers to not only exposure with far ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. Include in exposure.
  • the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “the composition of the present invention”) according to the present invention is represented by the general formula (Aa1) or (Aa2) described later as a repeating unit that decomposes by the action of an acid.
  • the resin (Aa) that contains a repeating unit represented by the following formula is unevenly distributed on the surface of the film and forms a protective film, and the solubility in the developer changes due to the action of an acid, which is different from the resin (Aa).
  • Resin (Ab) is contained.
  • the composition of the present invention comprises at least one selected from a compound that generates an acid upon irradiation with an actinic ray or radiation, an acid proliferating agent, a solvent, a basic compound, a surfactant, and other additives. Furthermore, it contains.
  • Resin (Aa) is a resin that contains a repeating unit represented by the following general formula (Aa1) or (Aa2) as a repeating unit that is decomposed by the action of an acid, is unevenly distributed on the film surface by film formation, and forms a protective film. is there.
  • a repeating unit represented by the following general formula (Aa1) or (Aa2) as a repeating unit that is decomposed by the action of an acid, is unevenly distributed on the film surface by film formation, and forms a protective film. is there.
  • the protective film is formed unevenly distributed on the film surface by the film formation is, for example, the surface static contact angle (contact angle by pure water) of the composition film not added with the resin (Aa) and the resin (Aa).
  • the surface static contact angle of the composition film to which () is added is compared, and when the contact angle increases, it can be considered that a protective layer has been formed.
  • a resin containing a repeating unit represented by the general formula (Aa1) or (Aa2) having a high reaction rate (sensitivity) to the action of an acid as a compound that is unevenly distributed on the film surface by film formation to form a protective film As a result of the development of Aa), as one of the effects, it has become possible to achieve high sensitivity while improving pattern shape deterioration (film slippage) due to out-band light in EUV lithography.
  • R ′ represents a hydrogen atom or an alkyl group.
  • L represents a single bond or a divalent linking group.
  • R 1 represents a hydrogen atom or a monovalent substituent.
  • R 2 represents a monovalent substituent not containing a fluorine atom.
  • R 1 and R 2 may be bonded to each other to form a ring together with the oxygen atom in the formula.
  • R 3 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
  • Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
  • L 1 represents a single bond or a divalent linking group.
  • R 1 and R 2 each independently represents an alkyl group. However, at least one alkyl group has 2 or more carbon atoms.
  • R 11 and R 12 each independently represents an alkyl group, and R 13 represents a hydrogen atom or an alkyl group. Any two of R 11 , R 12 and R 13 may be connected to each other to form a ring.
  • a repeating unit represented by the general formula (Aa1) (hereinafter also referred to as “repeating unit (Aa1)”) and a repeating unit represented by the general formula (Aa2) (hereinafter also referred to as “repeating unit (Aa2)”). )
  • the resin (Aa) more preferably includes a repeating unit (Aa1).
  • the repeating unit (Aa1) and the repeating unit (Aa2) will be described in detail.
  • the alkyl group of R ′ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms.
  • An alkyl group is more preferable, and an alkyl group having 1 or 2 carbon atoms (that is, a methyl group or an ethyl group) is preferable.
  • Specific examples of the alkyl group for R ′ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. Can do.
  • R ′ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, a methyl group or ethyl It is more preferably a group, and particularly preferably a hydrogen atom.
  • Examples of the divalent linking group represented by L include an alkylene group, an aromatic ring group, a cycloalkylene group, —COO—L 1 ′ —, —OL 1 ′ —, —CONH—, and two or more thereof.
  • Examples include groups formed in combination.
  • L 1 ′ is an alkylene group (preferably having 1 to 20 carbon atoms), a cycloalkylene group (preferably having 3 to 20 carbon atoms), a group having a lactone structure, an aromatic ring group, or a combination of an alkylene group and an aromatic ring group Represents a group.
  • the alkylene group as the divalent linking group represented by L is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group.
  • An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 or 2 carbon atoms is particularly preferable.
  • the cycloalkylene group as the divalent linking group represented by L is preferably a cycloalkylene group having 3 to 20 carbon atoms, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group. , Cycloheptylene group, cyclooctylene group, norbornylene group or adamantylene group.
  • the aromatic ring group as the divalent linking group represented by L is an aromatic ring group having 6 to 18 carbon atoms (more preferably 6 to 10 carbon atoms) such as a benzene ring or a naphthalene ring group, or, for example, thiophene
  • Preferred examples include aromatic ring groups including hetero rings such as rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings.
  • a benzene ring group is particularly preferable.
  • alkylene group, cycloalkylene group and aromatic ring group represented by L 1 ′ are the same as those in the alkylene group, cycloalkylene group and aromatic ring group as the divalent linking group represented by L. .
  • any group having a lactone structure can be used.
  • a 5- to 7-membered ring lactone structure is preferable, and a bicyclic lactone structure is included in the 5- to 7-membered ring lactone structure.
  • a structure in which another ring structure is condensed to form a structure or a spiro structure is preferable.
  • KA-1-1 to KA-1-17 described later can be mentioned, and KA-1-1, KA-1-4, KA-1-5, and KA-1-17 are preferable.
  • alkylene group and aromatic group in the group in which the alkylene group and the aromatic ring group represented by L 1 ′ are combined are those in the alkylene group and aromatic ring group as the divalent linking group represented by L It is the same.
  • L is preferably a single bond, aromatic ring group, norbornane ring group or adamantane ring group, more preferably a single bond, norbornane ring group or adamantane ring group, more preferably a single bond or norbornane ring group, and a single bond Particularly preferred.
  • the monovalent substituent for R 1 is preferably a group represented by * —C (R 111 ) (R 112 ) (R 113 ).
  • * represents a bond linked to a carbon atom in the repeating unit represented by the general formula (Aa1).
  • R 111 to R 113 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group.
  • the alkyl group of R 111 to R 113 is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Is more preferable.
  • alkyl group of R 111 to R 113 include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, neopentyl group, hexyl group, 2 -Ethylhexyl group, octyl group, dodecyl group and the like can be mentioned, and the alkyl group of R 111 to R 113 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group or a t-butyl group.
  • At least two of R 111 to R 113 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, and all of R 111 to R 113 are an alkyl group, a cycloalkyl group, It preferably represents an aryl group, an aralkyl group or a heterocyclic group.
  • the cycloalkyl group of R 111 to R 113 may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 15 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms.
  • An alkyl group is more preferable, and a cycloalkyl group having 3 to 6 carbon atoms is still more preferable.
  • cycloalkyl group represented by R 111 to R 113 include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, a cyclodecyl group, and a 1-adamantyl group. , 2-adamantyl group, 1-norbornyl group, 2-norbornyl group and the like.
  • the cycloalkyl group of R 111 to R 113 is preferably a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.
  • the aryl group of R 111 to R 113 is preferably an aryl group having 6 to 15 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and a plurality of aromatic rings are bonded to each other via a single bond. It also includes linked structures (eg, biphenyl group, terphenyl group). Specific examples of the aryl group of R 111 to R 113 include a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a terphenyl group, and the like. The aryl group of R 111 to R 113 is preferably a phenyl group, a naphthyl group, or a biphenyl group.
  • the aralkyl group of R 111 to R 113 is preferably an aralkyl group having 6 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 12 carbon atoms.
  • Specific examples of the aralkyl group of R 111 to R 113 include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and the like.
  • the heterocyclic group of R 111 to R 113 is preferably a heterocyclic group having 6 to 20 carbon atoms, and more preferably a heterocyclic group having 6 to 12 carbon atoms.
  • Specific examples of the heterocyclic group represented by R 111 to R 113 include, for example, pyridyl group, pyrazyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydrothiophene group, piperidyl group, piperazyl group, furanyl group, pyranyl group, chromanyl group. Etc.
  • the alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group as R 111 to R 113 may further have a substituent.
  • alkyl group as R 111 to R 113 may further have include a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxy group, a carboxy group, a halogen atom, and an alkoxy group.
  • the above substituents may be bonded to each other to form a ring, and examples of the ring when the above substituents are bonded to each other to form a ring include a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group. .
  • the carbon number of the substituent that the cycloalkyl group may further have is preferably 1-8.
  • Examples of the substituent that the aryl group, aralkyl group and heterocyclic group as R 111 to R 113 may further have include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, and an alkyl group.
  • Group preferably 1 to 15 carbon atoms
  • alkoxy group preferably 1 to 15 carbon atoms
  • cycloalkyl group preferably 3 to 15 carbon atoms
  • aryl group preferably 6 to 14 carbon atoms
  • alkoxycarbonyl examples thereof include a group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and the like.
  • At least two of R 111 to R 113 may form a ring with each other.
  • examples of the ring formed include a tetrahydropyran ring, a cyclopentane ring, a cyclohexane ring, an adamantane ring, a norbornene ring, and a norbornane ring.
  • These rings may have a substituent, and examples of the substituent that may be included include the alkyl group and the groups described above as specific examples of the substituent that the alkyl group as R 111 to R 113 may further have. Is mentioned.
  • examples of the ring formed include an adamantane ring, norbornane ring, norbornene ring, bicyclo [2,2,2] octane ring, bicyclo [3, 1,1] heptane ring.
  • an adamantane ring is particularly preferred.
  • substituents may be included include the alkyl groups and the groups described above as specific examples of the substituent that the alkyl groups as R 111 to R 113 may further have. It is done.
  • the monovalent substituent of R 2 does not contain a fluorine atom. If an electron withdrawing group such as a fluorine atom is included, the reaction rate (sensitivity) to the action of the acid is slow, so the desired performance cannot be achieved, while oxygen and nitrogen also act as electron withdrawing groups. It has been found by the present inventors that the desired performance is obtained even if atoms are included.
  • the monovalent substituent of R 2 may be a group consisting of two or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom.
  • it is a group consisting of two or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom, more preferably from two or more atoms selected from a carbon atom, a hydrogen atom and an oxygen atom.
  • a group consisting of a carbon atom and a hydrogen atom is particularly preferable.
  • the monovalent substituent of R 2 is preferably a group represented by * -MQ.
  • * Represents a bond connected to an oxygen atom in the general formula (Aa1).
  • M represents a single bond or a divalent linking group.
  • Q represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group (not including a fluorine atom).
  • the divalent linking group as M is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene group.
  • an alkylene group preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group
  • a cycloalkylene group preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group
  • a cycloalkylene group having 3 to 15 carbon atoms such as a cyclopentylene group or a cyclohexylene group
  • R 0 is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, Hexyl group and octyl group).
  • M is preferably a single bond, an alkylene group, or a divalent linking group comprising a combination of an alkylene group and at least one of —O—, —CO—, —CS— and —N (R 0 ) —.
  • a divalent linking group comprising a bond, an alkylene group, or a combination of an alkylene group and —O— is more preferable.
  • R 0 has the same meaning as R 0 described above.
  • M may further have a substituent, and the substituent that M may further have is the same as the substituent that the alkyl group of R 111 to R 113 described above may have.
  • alkyl group as Q are the same as those described for the alkyl group as R 111 to R 113 described above, for example.
  • the cycloalkyl group as Q may be monocyclic or polycyclic.
  • the cycloalkyl group preferably has 3 to 10 carbon atoms.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, a 2-norbornyl group, Bornyl group, isobornyl group, 4-tetracyclo [6.2.1.1 3,6 .
  • a 0 2,7 ] dodecyl group, an 8-tricyclo [5.2.1.0 2,6 ] decyl group, and a 2-bicyclo [2.2.1] heptyl group are preferable.
  • a cyclopentyl group, a cyclohexyl group, a 2-adamantyl group, an 8-tricyclo [5.2.1.0 2,6 ] decyl group, and a 2-bicyclo [2.2.1] heptyl group are preferable.
  • aryl group as Q are the same as those described for the aryl group as R 111 to R 113 described above, for example.
  • heterocyclic group as Q are the same as those described for the heterocyclic group as R 111 to R 113 described above, for example.
  • the alkyl group, cycloalkyl group, aryl group and heterocyclic group (not including a fluorine atom) as Q may have a substituent, for example, an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, Examples thereof include a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.
  • R 2 is preferably an alkyl group, an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, an aralkyl group, an aryloxyalkyl group or a heterocyclic group (not including a fluorine atom), and an alkyl group or a cycloalkyl group More preferably, it is a group.
  • alkyl group substituted by a cycloalkyl group “aralkyl group (arylalkyl group)” and “aryloxyalkyl group” as R 2 are the alkylene group as M, respectively. This is the same as that described in.
  • heterocyclic group not including a fluorine atom
  • R 2 Specific examples and preferred examples of the heterocyclic group (not including a fluorine atom) as R 2 are the same as those described for the heterocyclic group (not including a fluorine atom) as Q.
  • substituent represented by R 2 include a methyl group, an ethyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylethyl group, a 2-adamantyl group, and 8-tricyclo [5.2.1. 0 2,6 ] decyl group, 2-bicyclo [2.2.1] heptyl group, benzyl group, 2-phenethyl group, 2-phenoxyethylene group and the like.
  • R 1 and R 2 may be bonded to each other to form a ring (oxygen-containing heterocycle) together with the oxygen atom in the formula.
  • the oxygen-containing heterocyclic structure may be any of a monocyclic, polycyclic or spiro ring, and is preferably a monocyclic oxygen-containing heterocyclic structure, preferably having 3 to 10 carbon atoms, more preferably Is 4 or 5.
  • M when M is a divalent linking group, Q may be bonded to M via a single bond or another linking group to form a ring.
  • the other linking group include an alkylene group (preferably an alkylene group having 1 to 3 carbon atoms), and the ring formed is preferably a 5- or 6-membered ring.
  • R 3 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, a methyl group or ethyl It is more preferably a group, and particularly preferably a hydrogen atom.
  • one of R 1 and R 3 is preferably a group containing 2 or more carbon atoms.
  • the repeating unit represented by the general formula (Aa1) is preferably a repeating unit represented by any one of the following general formulas (Aa1-1) to (Aa1-4).
  • R ′ 1 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 11 , R 12 and R 13 has the same meaning as R 1 , R 2 and R 3 in the general formula (Aa1).
  • R ′ 2 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 21 , R 22 and R 23 has the same meaning as R 1 , R 2 and R 3 in the general formula (Aa1).
  • R ′ 3 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 31 , R 32 and R 33 has the same meaning as R 1 , R 2 and R 3 in the general formula (Aa1).
  • L ′ represents a single bond or a divalent linking group.
  • the divalent linking group for L ′ include an alkylene group, an aromatic ring group, a cycloalkylene group, —COO-L 1 ′ —, —OL 1 ′ —, —CONH—, and two or more thereof. Examples include groups formed in combination.
  • L 1 ′ represents an alkylene group (preferably having a carbon number of 1 to 20), a cycloalkylene group (preferably having a carbon number of 3 to 20), an aromatic ring group, or a combination of an alkylene group and an aromatic ring group.
  • L ′ is preferably a single bond.
  • R 41 , R 42 and R 43 has the same meaning as R 1 , R 2 and R 3 in the general formula (Aa1).
  • the repeating unit represented by the general formula (Aa1) is preferably a repeating unit represented by any one of the general formulas (Aa1-1) to (Aa1-4).
  • the repeating unit represented by any one of (Aa1-1) to (Aa1-3) is more preferred, and the repeating unit represented by the general formula (Aa1-1) or (Aa1-3). More preferred is a repeating unit represented by formula (Aa1-1).
  • the repeating unit represented by the general formula (Aa1) is also preferably a repeating unit represented by any of the following (Aa1-a) to (Aa1-f).
  • R a ′, L a , R 2a and R 1a is the same as R ′, L, R 2 and R 1 in formula (Aa1), and the preferred ranges are also the same.
  • R b ′, L b , R 2b and R 3b is the same as R ′, L, R 2 and R 3 in the general formula (Aa1), and preferred ranges are also the same.
  • R c ′, L c , R 2c and R 3c is the same as R ′, L, R 2 and R 3 in formula (Aa1), and the preferred ranges are also the same.
  • R 1a ′ is the same as R 111 in formula (Aa1), and the preferred range is also the same.
  • R d ′, L d , R 2d and R 3d is the same as R ′, L, R 2 and R 3 in the general formula (Aa1), and preferred ranges are also the same.
  • R 2a ′ and R 2b ′ is the same as R 111 and R 112 in General Formula (Aa1), and the preferred range is also the same.
  • R e ′, L e , R 2e and R 3e is the same as R ′, L, R 2 and R 3 in formula (Aa1), and the preferred range is also the same.
  • R 3a ′, R 3b ′ and R 3c ′ is the same as R 111 , R 112 and R 113 in General Formula (Aa1), and the preferred range is also the same.
  • R f ′ and L f are the same as R ′ and L in the general formula (Aa1), and preferred ranges are also the same.
  • R 3f is the same as R 3 in formula (Aa1), and the preferred range is also the same.
  • R 4f represents an atomic group necessary for forming an oxygen-containing heterocyclic ring together with the carbon atom and the oxygen atom in the formula.
  • the oxygen-containing heterocyclic structure formed by R 4f together with the carbon atom and the oxygen atom is preferably a monocyclic oxygen-containing heterocyclic structure, and the oxygen-containing heterocyclic ring preferably has 3 to 10 carbon atoms, more preferably 4 or 5.
  • the repeating unit represented by the general formula (Aa1) is more preferably a repeating unit represented by any one of the general formulas (Aa1-c) to (Aa1-f).
  • a repeating unit represented by formula (Aa1-e) or (Aa1-f) is more preferable.
  • Preferred specific examples of each partial structure and each group in the general formula (Aa1) are shown below.
  • Preferred specific examples of the partial structure represented by the following general formula (Aa1 ′) in the above general formula (Aa1) are as follows.
  • * represents a bond connected to the carbon atom to which R1 and R3 in the general formula (Aa1) are bonded
  • R ′ and L are each in the general formula (Aa1).
  • R ′ and L are represented.
  • R 2 in the general formula (Aa1) Specific examples of R 2 in the general formula (Aa1) are shown below.
  • * represents a bond bonded to an oxygen atom in the general formula (Aa1).
  • R 4f forms an oxygen-containing group together with the carbon atom and the oxygen atom in the formula
  • R 4f forms an oxygen-containing group together with the carbon atom and the oxygen atom in the formula
  • * Represents a bond linked to an oxygen atom in the general formula (Aa1-f).
  • R 3f is the same as that in formula (Aa1-f).
  • repeating unit represented by the general formula (Aa1) Specific examples of the repeating unit represented by the general formula (Aa1) are shown below, but the present invention is not limited thereto.
  • the content of the repeating unit represented by the general formula (Aa1) in the resin (Aa) (the total when there are a plurality of types) is 5 to 80 mol% with respect to all the repeating units in the resin (Aa). It is preferably 5 to 60 mol%, more preferably 10 to 40 mol%.
  • R 1 and R 2 represent an alkyl group as described above. However, at least one alkyl group has 2 or more carbon atoms. From the viewpoint of more reliably achieving the effects of the present invention, both R 1 and R 2 are preferably alkyl groups having 2 or more carbon atoms, more preferably alkyl groups having 2 to 10 carbon atoms, More preferably, both 1 and R 2 are ethyl groups.
  • R 11 and R 12 each independently represent an alkyl group
  • R 13 represents a hydrogen atom or an alkyl group.
  • the alkyl group as R 11 to R 13 is preferably an alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t -Butyl group, neopentyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like.
  • the alkyl group for R 11 and R 12 is more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • R 13 is more preferably a hydrogen atom or a methyl group.
  • R 11 and R 12 may be connected to each other to form a ring, and R 11 and R 13 may be connected to each other to form a ring.
  • a monocyclic or polycyclic alicyclic hydrocarbon group is preferable, and in particular, R 11 and R 12 are bonded to each other to form a monocyclic or polycyclic alicyclic hydrocarbon group. It is preferable.
  • the ring formed by connecting R 11 and R 12 is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • the ring formed by connecting R 11 and R 13 is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • the ring formed by connecting R 11 and R 12 or R 11 and R 13 is more preferably an alicyclic group described later as X in formula (Aa2-1).
  • the alkyl group as R 1 , R 2 and R 11 to R 13 may further have a substituent.
  • substituents include cycloalkyl groups, aryl groups, amino groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, aralkyloxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups. Groups and nitro groups.
  • the ring formed by connecting R 11 and R 12 and the ring formed by connecting R 11 and R 13 may further have a substituent, and as such a substituent, Alkyl groups (methyl group, ethyl group, propyl group, butyl group, perfluoroalkyl group (for example, trifluoromethyl group) etc.) and alkyl groups as R 1 , R 2 and R 11 to R 13 Specific examples of substituents that can be used include the groups described above.
  • the above substituents may be bonded to each other to form a ring, and examples of the ring when the above substituents are bonded to each other to form a ring include a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group. .
  • Ra represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom as described above.
  • the alkyl group for Ra is preferably an alkyl group having 1 to 4 carbon atoms and may have a substituent.
  • Preferable substituents that the alkyl group of Ra may have include, for example, a hydroxyl group and a halogen atom.
  • halogen atom for Ra examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms (for example, a trifluoromethyl group), and the glass transition point (Tg) of the resin (A).
  • Tg glass transition point
  • a methyl group is particularly preferable from the viewpoint of improving resolution and space width roughness.
  • Ra is preferably a hydrogen atom.
  • L 1 represents a single bond or a divalent linking group as described above.
  • L 11 represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
  • alkylene group for L 1 and L 11 examples include alkylene groups having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.
  • An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 or 2 carbon atoms is particularly preferable.
  • the cycloalkylene group for L 11 is preferably a cycloalkylene group having 3 to 20 carbon atoms, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group. , Norbornylene group or adamantylene group.
  • the carbon constituting the ring may be a carbonyl carbon, a heteroatom such as an oxygen atom, an ester bond, and a lactone A ring may be formed.
  • a phenylene group such as 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, and 1,4-naphthylene group are preferable, A 1,4-phenylene group is more preferred.
  • L 1 is preferably a single bond, a divalent aromatic ring group, a divalent group having a norbornylene group or a divalent group having an adamantylene group, and particularly preferably a single bond.
  • the repeating unit represented by the general formula (Aa2) is preferably a repeating unit represented by the following general formula (Aa2-1).
  • X represents an alicyclic group.
  • R 1, R 2, Ra and L 1 respectively, have the same meaning as R 1, R 2, Ra and L 1 in the general formula (Aa2), specific examples, R 1 also in the general formula (Aa2) for preferred embodiments , R 2 , Ra and L 1 are the same.
  • the alicyclic group as X may be monocyclic, polycyclic or bridged, and preferably represents an alicyclic group having 3 to 25 carbon atoms.
  • the alicyclic group may have a substituent, and examples of the substituent are the same as the substituents described above as the substituent that the ring formed by connecting R 11 and R 12 may have. Can be mentioned.
  • X preferably represents an alicyclic group having 3 to 25 carbon atoms, more preferably an alicyclic group having 5 to 20 carbon atoms, and particularly preferably a cycloalkyl group having 5 to 15 carbon atoms.
  • X is preferably a 3- to 8-membered alicyclic group or a condensed ring group thereof, and more preferably a 5- or 6-membered ring or a condensed ring group thereof. Below, the structural example of the alicyclic group as X is shown.
  • Preferred examples of the alicyclic group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, A cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group can be exemplified.
  • a cyclohexyl group, a cyclopentyl group, an adamantyl group and a norbornyl group are more preferred, a cyclohexyl group and a cyclopentyl group are more preferred, and a cyclohexyl group is particularly preferred.
  • repeating unit represented by the general formula (Aa2) or (Aa2-1) are shown below, but the present invention is not limited thereto.
  • the content of the repeating unit represented by the general formula (Aa2) in the resin (Aa) is 5 to 80 mol% with respect to all the repeating units in the resin (Aa). Preferably, it is 5 to 60 mol%, more preferably 10 to 40 mol%.
  • the resin (Aa) includes a fluorine atom, a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, and a carbon number It may further include a repeating unit (Aa3) having one or more groups selected from the group consisting of 6 or more aryl groups and an aralkyl group having 7 or more carbon atoms.
  • This repeating unit (Aa3) is a repeating unit different from the above-described repeating units (Aa1) and (Aa2).
  • the repeating unit (Aa3) preferably has a fluorine atom or a group having a fluorine atom. Since the resin (Aa) has a fluorine atom or a group having a fluorine atom, the absorption coefficient of the resin (Aa) with respect to extreme ultraviolet rays is improved, and the resin (Aa) has a property of being unevenly distributed on the resist film surface. Therefore, it is considered that the energy of the extreme ultraviolet light can be efficiently absorbed on the film surface to which the extreme ultraviolet light is more strongly irradiated at the time of exposure, and as a result, the sensitivity is considered to be improved.
  • Examples of the group having a fluorine atom include an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, and an aryl group having a fluorine atom.
  • the alkyl group having a fluorine atom preferably includes an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and a straight chain in which at least one hydrogen atom is substituted with a fluorine atom. Or it is a branched alkyl group and may have substituents other than a fluorine atom.
  • the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
  • aryl group having a fluorine atom examples include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .
  • alkyl group having a fluorine atom examples include groups represented by the following general formulas (F2) to (F4).
  • the invention is not limited to this.
  • R 57 to R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R 57 to R 61, at least one of R 62 to R 64 , and at least one of R 65 to R 68 are each independently a fluorine atom or at least one hydrogen atom substituted with a fluorine atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms).
  • R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms.
  • R 62 , R 63 and R 68 are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R 62 and R 63 may be connected to each other to form a ring.
  • Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
  • Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like.
  • Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
  • Specific examples of the group represented by the general formula (F4) include, for example, —C (CF 3 ) 2 OH, —C (C 2 F 5 ) 2 OH, —C (CF 3 ) (CH 3 ) OH, —CH (CF 3 ) OH and the like can be mentioned, and —C (CF 3 ) 2 OH is preferable.
  • Examples of the group having a silicon atom include an alkylsilyl structure (preferably a trialkylsilyl group) and a cyclic siloxane structure.
  • alkylsilyl structure or cyclic siloxane structure for W 3 to W 6 include groups represented by the following general formulas (CS-1) to (CS-3).
  • R 12 to R 26 each independently represents a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
  • L 3 to L 5 each represents a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).
  • N represents an integer of 1 to 5.
  • n is preferably an integer of 2 to 4.
  • the alkyl group having 6 or more carbon atoms is preferably a linear or branched alkyl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and a substituent (however, a fluorine atom, a fluorine atom) And does not correspond to a group having a silicon atom).
  • the cycloalkyl group having 5 or more carbon atoms is preferably a cycloalkyl group having 5 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and a substituent (provided that a fluorine atom or a fluorine atom is substituted). Or a group having a silicon atom).
  • the aryl group having 6 or more carbon atoms is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further a substituent (provided that it has a fluorine atom or a fluorine atom). Or a group having a silicon atom).
  • the aryl group may be substituted with at least one alkyl group having 3 or more carbon atoms, or at least one cycloalkyl group having 5 or more carbon atoms, and may be substituted with other substituents (however, a fluorine atom). Or a group having a fluorine atom or a group having a silicon atom).
  • the alkyl group having 3 or more carbon atoms is preferably a linear or branched alkyl group having 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms.
  • the aryl group substituted with at least one alkyl group having 3 or more carbon atoms the aryl group is preferably substituted with 1 to 9 alkyl groups having 3 or more carbon atoms, and preferably 1 to 7 carbon atoms. It is more preferably substituted with 3 or more alkyl groups, and further preferably substituted with 1 to 5 alkyl groups having 3 or more carbon atoms.
  • the cycloalkyl group having 5 or more carbon atoms is preferably a cycloalkyl group having 5 to 20 carbon atoms, more preferably 5 to 15 carbon atoms.
  • the aryl group substituted with at least one cycloalkyl group having 5 or more carbon atoms the aryl group is preferably substituted with 1 to 5 cycloalkyl groups having 5 or more carbon atoms. It is more preferably substituted with a cycloalkyl group having 5 or more carbon atoms, and further preferably substituted with 1 to 3 cycloalkyl groups having 5 or more carbon atoms.
  • the aralkyl group having 7 or more carbon atoms is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and a substituent (however, a fluorine atom or a group having a fluorine atom). And a group having a silicon atom).
  • the resin (Aa) preferably has at least one repeating unit represented by any one of the following general formulas (C-Ia) to (C-Id) as the repeating unit (Aa3).
  • R 10 and R 11 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group.
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.
  • R 10 and R 11 are preferably each independently a hydrogen atom or a methyl group.
  • W 3 , W 5 and W 6 are each independently a group having a fluorine atom, a group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, or an aryl having 6 or more carbon atoms. And an organic group having at least one selected from the group consisting of a group and an aralkyl group having 7 or more carbon atoms.
  • W 4 represents an organic group having one or more selected from the group consisting of a group having a fluorine atom, a group having a silicon atom, an alkyl group having 3 or more carbon atoms, and a cycloalkyl group having 5 or more carbon atoms. .
  • Ar 11 represents an (r + 1) -valent aromatic ring group.
  • R represents an integer of 1 to 10.
  • the divalent aromatic ring group when r is 1 may have a substituent, for example, a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group And arylene groups having 6 to 18 carbon atoms.
  • Specific examples of the (r + 1) -valent aromatic ring group in the case where r is an integer of 2 or more include (r-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
  • the group formed can be preferably mentioned.
  • Examples of the group having a fluorine atom for W 3 to W 6 are the same as those described above for the group having a fluorine atom.
  • the group having a fluorine atom for W 3 to W 6 may be directly bonded to the repeating units represented by the general formulas (C-Ia) to (C-Id), and further includes an alkylene group, a phenylene group, Via the group selected from the group consisting of an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond, or a combination of two or more thereof, the above general formula (C-Ia) It may be bonded to a repeating unit represented by (C-Id).
  • Examples of the group having a silicon atom for W 3 to W 6 are the same as those described above for the group having a silicon atom.
  • the alkyl group having 6 or more carbon atoms, the cycloalkyl group having 5 or more carbon atoms, the aryl group having 6 or more carbon atoms, and the aralkyl group having 7 or more carbon atoms for W 3 , W 5 , and W 6 are described above. It is the same as that.
  • the alkyl group having 3 or more carbon atoms and the cycloalkyl group having 5 or more carbon atoms for W 4 are each represented by “the number of carbon atoms in the aromatic ring group substituted with at least one alkyl group having 3 or more carbon atoms”. This is the same as that described for the “3 or more alkyl group” and the “cycloalkyl group having 5 or more carbon atoms” in the aromatic ring group substituted with at least one cycloalkyl group having 5 or more carbon atoms.
  • W 3 , W 5 and W 6 are each independently a group having a silicon atom, an alkyl group having 6 or more carbon atoms, or a carbon number. It is also preferable to represent an organic group having one or more selected from the group consisting of a cycloalkyl group having 5 or more, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms, and W 4 represents a silicon atom It is also preferable to represent an organic group having one or more selected from the group consisting of a group having an alkyl group, an alkyl group having 3 or more carbon atoms, and a cycloalkyl group having 5 or more carbon atoms.
  • EUV light extreme ultraviolet
  • W 3 , W 5 and W 6 are each independently an organic group having a fluorine atom, an organic group having a silicon atom, an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms, or a carbon number having 6 or more.
  • the exposure source is extreme ultraviolet light (EUV light)
  • EUV light an organic group having a silicon atom, 6 carbon atoms or more is preferable. It is also preferably an alkyl group, a cycloalkyl group having 5 or more carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
  • W 4 is preferably an organic group having a fluorine atom, an organic group having a silicon atom, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 5 or more carbon atoms, and the exposure source is extreme ultraviolet light (EUV light).
  • EUV light extreme ultraviolet light
  • X 1 represents a hydrogen atom, —CH 3 , —F or —CF 3 .
  • the resin (Aa) preferably has an aryl group, and more preferably has a repeating unit having an aryl group. Since the resin (Aa) has an aryl group, the aryl group absorbs the out-of-band light of EUV light, and only the surface of the exposed portion is exposed to the out-of-band light, and the surface of the pattern becomes rough ( In particular, in the case of EUV exposure), it is possible to further suppress problems that the cross-sectional shape of the pattern becomes a T-top shape or a reverse taper shape, or the surface of the pattern to be separated does not separate from each other and a bridge portion is generated.
  • the repeating unit (Aa3) may have an aryl group, or the resin (Aa) further has a repeating unit other than the repeating unit (Aa3), and the repeating unit has an aryl group. It may be.
  • the repeating unit (Aa3) is preferably a repeating unit represented by the following general formula (C-II).
  • R 12 represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a fluorine atom.
  • W 7 represents an organic group having one or more selected from the group consisting of a group having a fluorine atom, a group having a silicon atom, an alkyl group having 3 or more carbon atoms, and a cycloalkyl group having 5 or more carbon atoms.
  • L 1 represents a single bond or a —COOL 2 — group.
  • L 2 represents a single bond or an alkylene group.
  • n an integer of 1 to 5.
  • the group having a fluorine atom and the group having a silicon atom for W 7 are the same as those described above for the group having a fluorine atom and the group having a silicon atom, respectively.
  • the alkyl group having 3 or more carbon atoms and the cycloalkyl group having 5 or more carbon atoms for W 7 are each represented by “the number of carbon atoms in the aromatic ring group substituted with at least one alkyl group having 3 or more carbon atoms”.
  • W 7 is a trialkylsilyl group, a trialkoxysilyl group, an alkyl group having a trialkylsilyl group, an alkyl group having a trialkoxysilyl group, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 5 or more carbon atoms. Preferably there is.
  • the carbon number of the alkyl group or alkoxy group bonded to the silicon atom is It is preferably 1 to 5, and more preferably 1 to 3.
  • the alkyl group bonded to the trialkylsilyl group or trialkoxysilyl group has 1 to 5 carbon atoms. Preferably, it is preferably 1 to 3.
  • R 12 is preferably a hydrogen atom or a methyl group.
  • the alkylene group as L 2 is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. L 2 is preferably a single bond.
  • W 7 is preferably an organic group having a fluorine atom, an organic group having a silicon atom, an alkyl group having 3 or more carbon atoms, or a cycloalkyl group having 5 or more carbon atoms.
  • Specific examples of the repeating unit represented by formula (C-II) are shown below, but are not limited thereto.
  • the content of the repeating unit (Aa3) with respect to all the repeating units of the resin (Aa) is preferably 1 to 95 mol%, and 3 to 65 mol%. More preferred is 5 to 35 mol%.
  • the resin (Aa) may further contain a repeating unit represented by the following general formula (Aa4) (hereinafter also referred to as “repeating unit (Aa4)”).
  • Aa4 a repeating unit represented by the following general formula (Aa4)
  • the hydrophobicity can be improved and the uneven distribution can be further improved, and the absorption of the out-band light can be improved.
  • Rb represents a hydrogen atom, an alkyl group or a halogen atom.
  • S 1a represents a substituent, and when a plurality of S 1a are present, each is independent.
  • p represents an integer of 0 to 5.
  • Rb in the formula represents a hydrogen atom, an alkyl group or a halogen atom as described above, and the alkyl group may have a substituent.
  • Rb is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a fluorine atom, more preferably a hydrogen atom.
  • S 1a represents a substituent as described above.
  • substituent represented by S 1a include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, a halogen atom, a cyano group, an organic group containing a silicon atom, an aryl group, an aryloxy group, and an aralkyl.
  • the substituent represented by S 1a may be a group in which the above-described group is bonded to a divalent linking group.
  • the divalent linking group include a substituted or unsubstituted alkylene group, Examples thereof include a substituted or unsubstituted cycloalkylene group, —O—, or a divalent linking group obtained by combining a plurality of these.
  • the alkyl group represented by S 1a is preferably, for example, an alkyl group having 1 to 20 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group. Group, t-butyl group, pentyl group, hexyl group and the like.
  • the alkyl group may further have a substituent.
  • substituents that may have, for example, halogen atom, alkoxy group, cycloalkyl group, hydroxyl group, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, Examples thereof include heterocyclic residues such as a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group, and a pyrrolidone residue, and a substituent having 12 or less carbon atoms is preferable.
  • the cycloalkyl group represented by S 1a is preferably, for example, a cycloalkyl group having 3 to 10 carbon atoms, and specifically includes a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornel group, an adamantyl group, and the like. Can be mentioned.
  • the cycloalkyl group may further have a substituent.
  • an alkyl group is mentioned.
  • an alkoxy group having 1 to 10 carbon atoms is preferable, and specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • the alkoxy group may have a further substituent, and examples of such a substituent include the same groups as the preferred substituent that the alkyl group as S 1a described above may have.
  • acyl group represented by S 1a for example, those having 2 to 10 carbon atoms are preferable, and specific examples include acetyl group, propionyl group, butyryl group, isobutyryl group and the like.
  • the acyl group may have a further substituent, and examples of such a substituent include the same groups as the preferable substituent that the alkyl group as S 1a described above may have.
  • the acyloxy group represented by S 1a is preferably, for example, one having 2 to 10 carbon atoms.
  • Examples of the acyl group in the acyloxy group include the same specific examples as those of the acyl group described above, and the substituents that can be included are also the same.
  • aryl group represented by S 1a for example, those having 6 to 10 carbon atoms are preferable, and specific examples include phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, anthracenyl group and the like. It is done.
  • the aryl group may have a further substituent, and examples of such a substituent include a group similar to the preferable substituent that the alkyl group or cycloalkyl group as S 1a described above may have. Can be mentioned.
  • aryloxy group and arylthio group represented by S 1a for example, those having 2 to 10 carbon atoms are preferable.
  • Examples of the aryl group in the aryloxy group and the arylthio group include specific examples similar to the above-described aryl group, and the substituents that can be included are also the same.
  • aralkyl group represented by S 1a for example, those having 7 to 15 carbon atoms are preferable, and specific examples include a benzyl group. These groups may further have a substituent. Examples of such a substituent include the same groups as the preferable substituents that the alkyl group or cycloalkyl group as S 1a described above may have. Is mentioned.
  • aralkyloxy group and aralkylthio group represented by S 1a for example, those having 7 to 15 carbon atoms are preferable.
  • examples of the aralkyl group in the aralkyloxy group and the aralkylthio group include specific examples similar to the above-described aralkyl, and the substituents that may be included are also the same.
  • the alkylthio group represented by S 1a is preferably, for example, one having 1 to 10 carbon atoms.
  • Examples of the alkyl group in the alkylthio group include the same specific examples as the alkyl described above, and the substituents that can be included are also the same.
  • Examples of the halogen atom represented by S 1a include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom and a chlorine atom are preferable, and a fluorine atom is most preferable.
  • the organic group in the organic group containing a silicon atom represented by S 1a is a group containing at least one carbon atom, and an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a halogen atom (for example, a fluorine atom, a chlorine atom) A hetero atom such as an atom or a bromine atom).
  • This organic group preferably has 1 to 30 carbon atoms.
  • the organic group containing a silicon atom is preferably represented by the following general formula (S).
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group or a halogen atom.
  • L represents a single bond or a divalent linking group.
  • alkyl group for R 1 , R 2 and R 3 for example, an alkyl group having 1 to 20 carbon atoms is preferable and may have a substituent.
  • alkenyl group for R 1 , R 2 and R 3 for example, an alkenyl group having 2 to 10 carbon atoms is preferable and may have a substituent.
  • cycloalkyl group in R 1 , R 2 and R 3 for example, a cycloalkyl group having 3 to 10 carbon atoms is preferable and may have a substituent.
  • alkoxy group for R 1 , R 2 and R 3 for example, an alkoxy group having 1 to 10 carbon atoms is preferable and may have a substituent.
  • aryl group for R 1 , R 2 and R 3 for example, an aryl group having 6 to 10 carbon atoms is preferable and may have a substituent.
  • aralkyl group in R 1 , R 2 and R 3 for example, an aralkyl group having 7 to 15 carbon atoms is preferable and may have a substituent.
  • the divalent linking group represented by L include, for example, a substituted or unsubstituted alkylene group, —O—, —S—, — (C ⁇ O) —, or a combination of two or more thereof. Groups.
  • S 1a is preferably an alkyl group which may have a substituent, an organic group containing a halogen atom or a silicon atom, and an alkyl group, an alkyl group substituted with a halogen atom, or a silicon atom.
  • an alkyl group or a group represented by the following general formula (S-1) is more preferable.
  • R 11 , R 21 and R 31 each independently represents an alkyl group.
  • L 1 represents a single bond or a divalent linking group.
  • the alkyl group as R 11 , R 21 and R 31 has the same definition as the alkyl group as R 1 , R 2 and R 3 in the general formula (S) described above, and a divalent linking group as L 1. Is synonymous with the divalent linking group as L in formula (S).
  • p represents an integer of 0 to 5, as described above. p is preferably an integer of 1 to 5.
  • repeating unit (Aa4) Specific examples of the repeating unit (Aa4) are shown below, but the present invention is not limited thereto, and the position of the substituent on the benzene ring (corresponding to the S 1a group) is also limited to the following specific examples. It is not what is done.
  • the content of the repeating unit (Aa4) is preferably 1 to 99 mol%, more preferably 1 to 70 mol% with respect to all the repeating units in the resin (Aa). %, More preferably 1 to 50 mol%, particularly preferably 1 to 30 mol%.
  • the resin (Aa) may further contain a repeating unit (Aa5) having at least two or more polar conversion groups.
  • the repeating unit (Aa5) is preferably a repeating unit (Aa5-1) having at least two or more polar conversion groups and at least one of a fluorine atom and a silicon atom on one side chain. That is, it is a repeating unit having a structure having at least one of a fluorine atom and a silicon atom on a side chain having a plurality of polarity converting groups.
  • the fluorine atom may be a fluorine atom as an electron withdrawing group in a polarity conversion group described later, or may be a fluorine atom different from the fluorine atom as the electron withdrawing group.
  • the repeating unit (Aa5) is a repeating unit (Aa5-2) having at least two or more polar conversion groups and having no fluorine atom and no silicon atom, and the resin (Aa) has a fluorine atom and It is also preferable to further have the above repeating unit (Aa3) having at least one of silicon atoms.
  • the repeating unit (Aa5) has at least two or more polar conversion groups on one side chain, and a fluorine atom and a silicon atom on a side chain different from the side chain in the same repeating unit.
  • a repeating unit (Aa5-3) having at least one of them is also preferred.
  • the side chain having a polarity converting group and the side chain having at least one of a fluorine atom and a silicon atom are in the ⁇ -position via the main chain carbon atom, that is, as shown in the following formula (4): It is preferable that they are in a positional relationship.
  • B1 represents a partial structure having a polarity converting group
  • B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.
  • the polar conversion group is a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer, and has a structure represented by the general formula (KA-1) or (KB-1). This is a partial structure represented by COO-.
  • the lactone structure represented by the general formula (KA-1) can be any group as long as it has a lactone ring, but is preferably a group having a 5- to 7-membered ring lactone structure, and has a 5- to 7-membered structure. Those in which other ring structures are condensed so as to form a bicyclo structure or a spiro structure in the ring lactone structure are preferred.
  • ester group for example, —COO— in acrylate
  • —COO— in acrylate directly bonded to the main chain of the resin in the repeating unit is not included in the polar conversion group in this case because the function as the polar conversion group is inferior.
  • repeating unit (Aa5) may not have two separate entire structures represented by (KA-1) or (KB-1). It is understood that the attractive group includes two polar conversion groups, even if the two ester structures are sandwiched or the form of formula (KY-1) described later.
  • the polarity conversion group is more preferably a partial structure represented by —COO— in the structure represented by the general formula (KA-1). preferable.
  • Z ka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group, if Z ka there are a plurality, the plurality of Z ka same But it can be different.
  • Z ka may be linked together to form a ring.
  • the ring formed by linking Z ka together include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).
  • Nka represents an integer from 0 to 10.
  • it is an integer of 0 to 8, more preferably an integer of 0 to 5, still more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.
  • the lactone ring is not particularly limited as long as it is a group having a lactone structure, but is preferably a group having a 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in a form to form are preferable.
  • X kb1 and X kb2 are each independently an electron withdrawing group.
  • nkb and nkb ′ each independently represents 0 or 1.
  • X kb1 and X kb2 are directly connected to an ester group (—COO—).
  • R kb1 to R kb4 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R kb1 , R kb2 and X kb1 are connected to each other to form a ring And at least two of R kb3 , R kb4 and X kb2 may be connected to each other to form a ring.
  • the ring that may be formed by linking at least two of R kb3 , R kb4, and X kb2 is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group.
  • the lactone ring include structures represented by formulas (KA-1-1) to (KA-1-17) described later.
  • the structure represented by the general formula (KA-1) or (KB-1) is a structure represented by the general formula (KA-1) ( KB- ) when X kb1 and X kb2 are monovalent.
  • it does not have a bond as in the structure represented by 1), it is a monovalent or higher-valent partial structure obtained by removing at least one arbitrary hydrogen atom in the structure.
  • X kb1 , X kb2 , R kb1 to R kb4 a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group And a sulfinyl group, a halo (cyclo) alkyl group or a haloaryl group represented by —C (R f1 ) (R f2 ) —R f3 , and combinations thereof.
  • halo (cyclo) alkyl group represents an alkyl group or a cycloalkyl group that is at least partially halogenated.
  • the electron-withdrawing group is a divalent or higher valent group, the remaining bond forms a bond with an arbitrary atom or substituent, and the main chain of the resin (Aa) through a further substituent It may be connected to.
  • R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group.
  • R f2 and R f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R f2 and R f3 may be linked to form a ring.
  • the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group.
  • At least two of R f1 to R f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.
  • Examples of the (halo) alkyl group in R f1 to R f3 include an alkyl group in Z ka and a structure in which this is halogenated.
  • Examples of the (per) halocycloalkyl group and the (per) haloaryl group in the ring formed by R f1 to R f3 or the combination of R f2 and R f3 include, for example, the cycloalkyl group in Z ka is halogenated. More preferably, a fluorocycloalkyl group represented by -C (n) F (2n-2) H and a perfluoroaryl group represented by -C (n) F (n-1). It is done.
  • the number n of carbon atoms is not particularly limited, but preferably 5 to 13 and more preferably 6.
  • R f2 represents the same group as R f1 or is linked to R f3 to form a ring.
  • the electron withdrawing group is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R f1 ) (R f2 ) —R f3 , more preferably —C ( CF 3 ) 2 H or —C (CF 3 ) 2 CH 3 .
  • a part of fluorine atoms may be substituted with another electron withdrawing group.
  • Z ka is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron withdrawing group, more preferably an alkyl group, a cycloalkyl group or an electron withdrawing group.
  • an ether group the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable.
  • the electron withdrawing group has the same meaning as described above.
  • halogen atom as Z ka examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group as Z ka may have a substituent and may be linear or branched.
  • the linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
  • the branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.
  • i-propyl group, i-butyl group, sec-butyl group, t-butyl group, i-pentyl group examples thereof include t-pentyl group, i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like.
  • Those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group are preferred.
  • the cycloalkyl group of Z ka may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. Note that some of the carbon atoms in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
  • the monocyclic cycloalkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms.
  • the polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms.
  • an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, ⁇ -pinel group, tricyclodecanyl group , Tetocyclododecyl group and androstanyl group examples of these cycloalkyl groups include those represented by the following formula.
  • Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group.
  • Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.
  • the alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group.
  • alkoxy group examples include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • substituent that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).
  • Examples of the Z ka aryl group include a phenyl group and a naphthyl group.
  • substituent that the alkyl group, cycloalkyl group, and aryl group of Z ka may further include, for example, a hydroxyl group; a halogen atom; a nitro group; a cyano group; the above alkyl group; a methoxy group, an ethoxy group, a hydroxyethoxy group, Alkoxy groups such as propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; benzyl group, phenethyl group and cumyl group Aralkyloxy group; Aralkyloxy group; Aralkyloxy group; Acyl group such as formyl group, acetyl group, butyryl group, benzoy
  • the receding contact angle with water of the resin composition film after alkali development can be lowered.
  • the receding contact angle with water of the resin composition film after alkali development is preferably 50 ° or less, more preferably 40 ° or less at the temperature at the time of exposure, usually room temperature 23 ⁇ 3 ° C. and humidity 45 ⁇ 5%. More preferably, it is 35 ° or less, and most preferably 30 ° or less.
  • the receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
  • the hydrolysis rate of the resin (Aa) with respect to the alkaline developer is preferably 0.001 nm / sec or more, more preferably 0.01 nm / sec or more, and further preferably 0.1 nm / sec or more. Most preferably, it is 1 nm / sec or more.
  • the hydrolysis rate of the resin (Aa) with respect to the alkaline developer was 23.degree. C. TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%), and the resin film was formed only with the resin (Aa). This is the rate at which the film thickness decreases.
  • TMAH tetramethylammonium hydroxide aqueous solution
  • lactone ring structure in formula (KA-1) a group having a lactone structure represented by any of the following (KA-1-1) to (KA-1-17) is more preferable. Further, a group having a lactone structure may be directly bonded to the main chain.
  • Preferred lactone structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1 ⁇ 14) and (KA-1-17). Specific examples of the skeleton having a lactone structure are shown below, but are not limited thereto.
  • the lactone structure portion may or may not have a substituent.
  • Preferred substituents include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, Examples include a hydroxyl group, a cyano group, and an acid-decomposable group.
  • alkyl group having 1 to 4 carbon atoms More preferred are an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 4 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, and an acid-decomposable group.
  • substituents When a plurality of substituents are present, they may be the same or different, and the substituents may be bonded to form a ring.
  • Some lactone structures have an optically active substance, but any optically active substance may be used.
  • One optically active substance may be used alone or a plurality of optically active substances may be mixed and used.
  • its optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.
  • the structure represented by (KB-1) has a structure in which an electron withdrawing group is present at a position close to the ester structure, and thus has a high polarity conversion ability.
  • X kb2 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by the aforementioned —C (R f1 ) (R f2 ) —R f3 .
  • the at least two polarity conversion groups contained in the repeating unit (Aa5) are more preferably a partial structure having two polarity conversion groups represented by the following general formula (KY-1).
  • the structure represented by the general formula (KY-1) is a group having a monovalent or higher group in which at least one arbitrary hydrogen atom in the structure is removed.
  • R ky1 and R ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents.
  • R ky1 and R ky4 may be bonded to the same atom to form a double bond.
  • R ky1 and R ky4 are bonded to the same oxygen atom to form a part of a carbonyl group ( ⁇ O). May be formed.
  • R ky2 and R ky3 are each independently an electron withdrawing group, or R ky1 and R ky3 are linked to form a lactone ring, and R ky2 is an electron withdrawing group.
  • the lactone ring to be formed the structures (KA-1-1) to (KA-1-17) are preferable.
  • the electron withdrawing group include the same groups as those of X kb1 in the formula (KB-1), and are preferably a halogen atom or the group represented by —C (R f1 ) (R f2 ) —R f3.
  • At least two of R ky1 , R ky3 and R ky4 may be linked to each other to form a monocyclic or polycyclic structure.
  • R kb1 to R kb4 , nkb, and nkb ′ are respectively synonymous with those in the formula (KB-1).
  • R ky1 and R ky4 include the same groups as Z ka in formula (KA-1).
  • the lactone ring formed by linking R ky1 and R ky3 the structures (KA-1-1) to (KA-1-17) are preferable.
  • the electron withdrawing group include those similar to X kb1 in formula (KB-1).
  • the structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2).
  • the structure represented by the general formula (KY-2) is a group having a monovalent or higher group in which at least one arbitrary hydrogen atom in the structure is removed.
  • R ky6 to R ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group. Two or more of R ky6 to R ky10 may be connected to each other to form a monocyclic or polycyclic structure.
  • R ky5 represents an electron withdrawing group.
  • the electron withdrawing group include the same groups as those described above for X kb1 in the formula (KB-1), and are preferably a halogen atom or the group represented by —C (R f1 ) (R f2 ) —R f3.
  • R kb1 , R kb2 , and nkb have the same meanings as those in formula (KB-1).
  • Specific examples of R ky5 to R ky10 include the same groups as Z ka in formula (KA-1).
  • the structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).
  • Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
  • Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
  • ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5.
  • L ky represents an alkylene group, an oxygen atom or a sulfur atom.
  • Z ka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group. If Z ka there are a plurality, the plurality of Z ka may be the same or different, may be connected to form a ring Z ka each other.
  • nka represents an integer of 0 to 10.
  • R kb1 and R kb2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group, and at least two of R kb1 , R kb2, and R ky5 are connected to each other.
  • a ring may be formed.
  • nkb represents 0 or 1.
  • R ky5 represents an electron withdrawing group. * Represents a binding site with the remainder of the repeating unit.
  • L ky represents an alkylene group, an oxygen atom, or a sulfur atom as described above.
  • Examples of the alkylene group for L ky include a methylene group and an ethylene group.
  • L ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.
  • Rs represents a chain or cyclic alkylene group, and when there are a plurality of Rs, they may be the same or different.
  • Ls represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.
  • ns represents the number of repeating linking groups represented by-(Rs-Ls)-, and represents an integer of 0 to 5. ns is preferably 0 or 1.
  • the repeating unit (Aa5) preferably has a structure represented by the formula (K0).
  • R k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group having a polarity converting group.
  • R k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group having a polarity converting group.
  • R k1 and R k2 as a whole have two or more polarity conversion groups.
  • the ester group directly connected to the main chain of the repeating unit represented by the general formula (K0) is not included in the polar conversion group in the present invention.
  • the repeating unit (Aa5) is not limited as long as it is a repeating unit obtained by polymerization, such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is.
  • Examples include acrylate-based repeating units (including those having substituents at the ⁇ -position and ⁇ -position), styrene-based repeating units (including those having substituents at the ⁇ -position and ⁇ -position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.
  • the resin (Aa) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a repeating unit having at least one of a fluorine atom and a silicon atom.
  • the resin (Aa) is unevenly distributed on the surface layer of the actinic ray-sensitive or radiation-sensitive resin film and the immersion medium is water, the resist film surface with respect to water when the actinic ray-sensitive or radiation-sensitive resin film is used
  • the receding contact angle can be improved, and the immersion water followability can be improved.
  • the receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film is preferably 60 ° to 90 °, more preferably 65 ° or more, even more preferably at the temperature at the time of exposure, usually room temperature 23 ⁇ 3 ° C. and humidity 45 ⁇ 5%. Is 70 ° or more.
  • the content of the resin (Aa) in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray-sensitive or radiation-sensitive resin film falls within the above range, Based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, it is preferably 0.01 to 30% by mass, more preferably 0.01 to 20% by mass, and 0.01 to The content is more preferably 10% by mass, particularly preferably 0.1 to 5% by mass.
  • the resin (Aa) is ubiquitous at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute.
  • the immersion head In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern.
  • the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
  • the resin (Aa) contains at least one of a fluorine atom and a silicon atom, thereby improving the hydrophobicity (water followability) of the resist surface and reducing the development residue (scum).
  • the resin (Aa) may be a resin having a plurality of polarity conversion groups and at least one of a fluorine atom and a silicon atom, and the fluorine atom has the general formula (KB) It may be an electron withdrawing group of X kb1 and X kb2 in -1).
  • the fluorine atom or silicon atom in the resin (Aa) may be present in the main chain of the resin or may be substituted with a side chain.
  • Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the content of the repeating unit (Aa5) is preferably 10 to 90 mol%, more preferably 30 to 85 mol% with respect to all the repeating units in the resin (Aa). %, More preferably 50 to 80 mol%.
  • the content of the repeating unit (Aa5-1) is preferably 10 to 90 mol%, more preferably 30 to 85 mol%, still more preferably 50 to 80 mol% with respect to all the repeating units in the resin (Aa).
  • the content of the repeating unit (Aa5-2) is preferably 10 to 90 mol%, more preferably 30 to 85 mol%, still more preferably 50 to 80 mol%, based on all repeating units in the resin (Aa).
  • the content of the repeating unit (Aa5-3) is preferably 10 to 90 mol%, more preferably 30 to 85 mol%, still more preferably 50 to 80 mol%, based on all repeating units in the resin (Aa).
  • the resin (Aa) may further contain a repeating unit corresponding to the polymerizable compound represented by the following general formula (ca-1) or (cb-1).
  • A may have a methacryl group which may have a substituent, an acryl group which may have a substituent, or a substituent. Represents a good norbornene group.
  • Z 1 each independently represents a single bond, an ether bond (—O—), an ester bond, an amide bond, a urethane bond or a urea bond.
  • q is 2 or more, the plurality of groups represented by Z 1 may be the same or different.
  • Z 2 each independently represents a single bond or a chain or cyclic alkylene group which may have a substituent.
  • q is 2 or more, the plurality of groups represented by Z 2 may be the same or different.
  • Ta and Tb are each independently a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, a substituent
  • An acyl group which may have a group, an alkyloxycarbonyl group which may have a substituent, a carboxy group, a nitrile group, a hydroxyl group, an amide group which may have a substituent or a substituent. Represents an optionally substituted aryl group.
  • Tas When there are a plurality of Tas, Tas may be bonded to form a ring.
  • Tb When there are a plurality of Tb, Tb may be bonded together to form a condensed ring which may contain a hetero atom together with the benzene ring substituted by Tb.
  • Tc is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, a nitrile group, a hydroxyl group or an amide which may have a substituent.
  • L represents a carbonyl group, a carbonyloxy group or an ether bond (—O—).
  • (L) r represents a group formed by combining L with r, and a plurality of L may be the same or different.
  • n represents an integer of 1 to 28.
  • n represents an integer of 0 to 11.
  • p represents an integer of 0 to 5.
  • q represents an integer of 0 to 5.
  • r represents an integer of 0 to 5.
  • JP-A No. 2010-159413 describe preferred forms, production methods, and specific examples of the polymerizable compounds represented by the general formulas (ca-1) and (cb-1). Can be referred to.
  • the content of the repeating unit (Aa6) is preferably 10 to 90 mol% with respect to all the repeating units in the resin (Aa), The amount is preferably 30 to 85 mol%, more preferably 50 to 80 mol%.
  • the resin (Aa) may further contain at least one repeating unit (Aa7) derived from a monomer represented by the following general formula (aa1-1).
  • Q 1 represents an organic group containing a polymerizable group.
  • L 1 and L 2 each independently represents a single bond or a divalent linking group.
  • Rf represents an organic group having a fluorine atom.
  • the organic group containing a polymerizable group represented by Q 1 in the formula is not particularly limited as long as it is a group containing a polymerizable group.
  • the polymerizable group include an acryl group, a methacryl group, a styryl group, a norbornenyl group, a maleimide group, and a vinyl ether group, and an acryl group, a methacryl group, and a styryl group are particularly preferable.
  • Examples of the divalent linking group represented by L 1 and L 2 include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, —O—, —CO -Or a divalent linking group obtained by combining a plurality of these.
  • arylene group for example, those having 6 to 14 carbon atoms are preferable, and specific examples include phenylene group, naphthylene group, anthrylene group, phenanthrylene group, biphenylene group, terphenylene group and the like.
  • alkylene group and cycloalkylene group for example, those having 1 to 15 carbon atoms are preferable, and specific examples include one hydrogen atom in a linear, branched or cyclic alkyl group described below.
  • examples include: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group N-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group
  • Examples of the substituent that the arylene group, alkylene group, and cycloalkylene group may have include an alkyl group, an aralkyl group, an alkoxy group, and a fluorine atom.
  • L 1 is more preferably a single bond, a phenylene group, an ether group, a carbonyl group, or a carbonyloxy group
  • L 2 is more preferably an alkylene group, an ether group, a carbonyl group, or a carbonyloxy group.
  • the organic group in the organic group having a fluorine atom as Rf is a group containing at least one carbon atom, and an organic group containing a carbon-hydrogen bond portion is preferable.
  • Rf is, for example, an alkyl group substituted with a fluorine atom or a cycloalkyl group substituted with a fluorine atom.
  • the repeating unit (Aa7) is preferably a repeating unit represented by the following general formula (aa1-2-1) or (aa1-3-1).
  • Ra 1 and Ra 2 each independently represents a hydrogen atom or an alkyl group. Ra 1 and Ra 2 are preferably a hydrogen atom or a methyl group.
  • L 21 and L 22 each independently represent a single bond or a divalent linking group, and have the same meaning as L 2 in formula (aa1-1) described above.
  • Rf 1 and Rf 2 each independently represents an organic group having a fluorine atom, and have the same meaning as Rf in formula (aa1-1).
  • the repeating unit (Aa7) is preferably a repeating unit represented by the following general formula (aa1-2-2) or (aa1-3-2).
  • Ra 1 and Ra 2 each independently represents a hydrogen atom or an alkyl group.
  • R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group.
  • m 1 and m 2 each independently represents an integer of 0 to 5.
  • Rf 1 and Rf 2 each independently represents an organic group having a fluorine atom.
  • Ra 1 and Ra 2 are preferably a hydrogen atom or a methyl group.
  • the alkyl group represented by R 1 , R 2 , R 3 and R 4 for example, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and specific examples include a methyl group, an ethyl group, Examples include propyl group, isopropyl group, butyl group, t-butyl group and the like.
  • This alkyl group may have a substituent, and examples of the substituent include an alkoxy group, an aryl group, and a halogen atom.
  • n 1 and m 2 are preferably integers of 0 to 3, more preferably 0 or 1, and most preferably 1.
  • the organic group having a fluorine atom as Rf 1 and Rf 2 has the same meaning as Rf in formula (aa1-1).
  • the repeating unit (Aa7) is preferably a repeating unit represented by the following general formula (aa1-2-3) or (aa1-3-3).
  • Ra 1 represents a hydrogen atom or a methyl group.
  • Rf 1 and Rf 2 each independently represents an organic group having a fluorine atom, and have the same meaning as Rf in formula (aa1-1).
  • repeating unit (Aa7) Specific examples of the repeating unit (Aa7) are shown below, but the present invention is not limited thereto.
  • the content of the repeating unit (Aa7) is preferably 10 to 90 mol% with respect to all the repeating units in the resin (Aa), The amount is preferably 30 to 85 mol%, more preferably 50 to 80 mol%.
  • the resin (Aa) may further have at least one group selected from the following groups (x) to (z).
  • the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the resin (Aa).
  • the repeating unit containing a fluorine atom is preferably 10 to 100% by mass, more preferably 30 to 100% by mass with respect to all the repeating units in the resin (Aa).
  • the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the molecular weight of the resin (Aa).
  • the repeating unit containing a silicon atom is preferably 10 to 90% by mass, more preferably 20 to 80% by mass with respect to all the repeating units of the resin (Aa).
  • the standard polystyrene equivalent weight average molecular weight of the resin (Aa) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 20,000.
  • the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.
  • the resin (Aa) various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization or anionic polymerization). For example, it can be synthesized by the same method as the general synthesis method of the resin (Ab) described in the resin (Ab) described later.
  • a conventional method for example, radical polymerization or anionic polymerization.
  • it can be synthesized by the same method as the general synthesis method of the resin (Ab) described in the resin (Ab) described later.
  • resin (Aa) Although the specific example of resin (Aa) is shown below, this invention is not limited to this.
  • Resin (Ab) whose solubility in a developing solution is changed by the action of an acid
  • the composition according to the present invention contains a resin (Ab) whose solubility in a developer is changed by the action of an acid.
  • Resin (Ab) is a resin whose solubility in a developer changes due to the action of an acid. Specifically, the solubility in an alkali developer increases due to the action of an acid, or an organic solvent as a main component. Solubility in developer decreases.
  • the resin (Ab) is preferably insoluble or hardly soluble in an alkaline developer.
  • the resin (Ab) preferably has a repeating unit having an acid-decomposable group.
  • Examples of the acid-decomposable group include a group in which a hydrogen atom of an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group is protected with a group capable of leaving by the action of an acid. .
  • Examples of the group capable of leaving by the action of an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), —C ( ⁇ O) — OC (R 36 ) (R 37 ) (R 38 ), —C (R 01 ) (R 02 ) (OR 39 ), —C (R 01 ) (R 02 ) —C ( ⁇ O) —O— C (R 36 ) (R 37 ) (R 38 ) and the like can be mentioned.
  • R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be bonded to each other to form a ring.
  • R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the resin (Ab) preferably contains at least one repeating unit represented by the following general formulas (A1) and (A2).
  • n represents an integer of 1 to 5
  • m represents an integer of 0 to 4 that satisfies the relationship 1 ⁇ m + n ⁇ 5.
  • S 1 represents a substituent (excluding a hydrogen atom), and when m is 2 or more, the plurality of S 1 may be the same as or different from each other.
  • a 1 represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one A 1 represents a group capable of leaving by the action of an acid.
  • n ⁇ 2 the plurality of A 1 may be the same as or different from each other.
  • X is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group; T represents a single bond or a divalent linking group.
  • a 2 represents a group capable of leaving by the action of an acid.
  • n represents an integer of 1 to 5, preferably 1 or 2, and particularly preferably 1.
  • m represents an integer of 0 to 4 that satisfies the relationship of 1 ⁇ m + n ⁇ 5, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
  • S 1 represents a substituent (excluding a hydrogen atom) as described above. Examples of the substituent include those similar to the substituents described for S 1 in the general formula (Ab3) to be described later.
  • a 1 represents a hydrogen atom or a group capable of leaving by the action of an acid, and at least one A 1 is a group capable of leaving by the action of an acid.
  • Examples of the group capable of leaving by the action of an acid include tertiary alkyl groups such as t-butyl group and t-amyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, and formula —C (L 1 ) (L 2 ) —O—Z 2 represents an acetal group.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl group.
  • Z 2 represents an alkyl group, a cycloalkyl group, or an aralkyl group.
  • Z 2 and L 1 may be bonded to each other to form a 5-membered or 6-membered ring.
  • the alkyl group may be a linear alkyl group or a branched alkyl group.
  • the linear alkyl group those having 1 to 30 carbon atoms are preferable, and those having 1 to 20 carbon atoms are more preferable.
  • Examples of such linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n- Examples include heptyl group, n-octyl group, n-nonyl group and n-decanyl group.
  • the branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.
  • Examples of such branched alkyl groups include i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i-hexyl group, t-hexyl group, i-heptyl group. , T-heptyl group, i-octyl group, t-octyl group, inonyl group and t-decanoyl group.
  • alkyl groups may further have a substituent.
  • substituents include a hydroxyl group; a halogen atom such as a fluorine, chlorine, bromine and iodine atom; a nitro group; a cyano group; an amide group; a sulfonamide group; a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Alkyl groups such as butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; Examples include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group
  • an ethyl group, an isopropyl group, an isobutyl group, a cyclohexylethyl group, a phenylmethyl group, or a phenylethyl group is particularly preferable.
  • the cycloalkyl group may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
  • the monocyclic cycloalkyl group preferably has 3 to 8 carbon atoms.
  • Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.
  • Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo or tetracyclo structure.
  • the polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms.
  • Examples of such a cycloalkyl group include an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, ⁇ ⁇ ⁇ -pinanyl group, tricyclodecanyl group, tetocyclododecyl group and androstanyl group.
  • Examples of the aralkyl group in L 1 , L 2 and Z 2 include those having 7 to 15 carbon atoms such as benzyl group and phenethyl group.
  • aralkyl groups may further have a substituent.
  • substituents include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, and an aralkylthio group.
  • the aralkyl group having a substituent include an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthiophenethyl group.
  • carbon number of the substituent which these aralkyl groups may have is preferably 12 or less.
  • Examples of the 5-membered or 6-membered ring that can be formed by bonding Z 2 and L 1 to each other include a tetrahydropyran ring and a tetrahydrofuran ring. Of these, a tetrahydropyran ring is particularly preferred.
  • Z 2 is preferably a linear or branched alkyl group. Thereby, the effect of the present invention becomes more remarkable.
  • the specific example of the repeating unit represented by general formula (A1) below is given, it is not limited to these.
  • X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyl as described above.
  • An oxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group is represented.
  • the alkyl group as X may have a substituent and may be linear or branched.
  • the straight chain alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.
  • the branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, such as i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like.
  • the alkoxy group as X may have a substituent, for example, the above alkoxy group having 1 to 8 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group And a cyclohexyloxy group.
  • halogen atom as X examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.
  • the acyl group as X may have a substituent, for example, an acyl group having 2 to 8 carbon atoms, specifically, a formyl group, acetyl group, propanoyl group, butanoyl group, pivaloyl group Preferred examples include benzoyl group.
  • the acyloxy group as X may have a substituent, and is preferably an acyloxy group having 2 to 8 carbon atoms.
  • An oxy group, an octanoyloxy group, a benzoyloxy group, etc. can be mentioned.
  • the cycloalkyl group as X may have a substituent, may be monocyclic, polycyclic, or bridged.
  • the cycloalkyl group may have a bridged structure.
  • the monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.
  • Examples of the polycyclic type include groups having a bicyclo, tricyclo or tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable.
  • an adamantyl group, norbornyl group, isobornyl group examples thereof include a camphanyl group, a dicyclopentyl group, an ⁇ -pinanyl group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group.
  • a part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
  • the aryl group as X may have a substituent and preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, and an anthracenyl group. .
  • the alkyloxycarbonyl group as X may have a substituent and preferably has 2 to 8 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.
  • the alkylcarbonyloxy group as X may have a substituent and preferably has 2 to 8 carbon atoms, and examples thereof include a methylcarbonyloxy group and an ethylcarbonyloxy group.
  • the aralkyl group as X may have a substituent, and is preferably an aralkyl group having 7 to 16 carbon atoms, for example, a benzyl group.
  • alkyl group, alkoxy group, acyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, alkylcarbonyloxy group, aralkyl group as X may further have include a hydroxyl group, a fluorine atom, chlorine Atom, bromine atom, iodine atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, aryl group, carboxyl group, alkyloxycarbonyl group, alkylcarbonyloxy group Or an aralkyl group etc. are mentioned.
  • T represents a single bond or a divalent linking group as described above.
  • the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a —COO—Rt— group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group or a — (CH 2 ) 3 — group.
  • a 2 represents a group capable of leaving by the action of an acid as described above. That is, the repeating unit represented by the general formula (A2) has a group represented by “—COOA 2 ” as an acid-decomposable group.
  • the A 2 for example, those previously described for A 1 in the general formula (A1) similar to the.
  • a 2 is preferably a hydrocarbon group (preferably having a carbon number of 20 or less, more preferably 4 to 12), and a t-butyl group, a t-amyl group, or a hydrocarbon group having an alicyclic structure (for example, an alicyclic group).
  • the group itself and a group in which an alicyclic group is substituted on the alkyl group) are more preferable.
  • a 2 is preferably a tertiary alkyl group or a tertiary cycloalkyl group.
  • the alicyclic structure may be monocyclic or polycyclic. Specific examples include monocyclo, bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms. The number of carbon atoms is preferably 6-30, and particularly preferably 7-25. These hydrocarbon groups having an alicyclic structure may have a substituent. Examples of the alicyclic structure include the alicyclic structures (1) to (50) given as examples of the cycloalkyl group of Z ka in the general formula (KA-1) in the above resin (Aa). . Further, specific examples of preferred alicyclic structures and specific examples of substituents that the alicyclic structure may have are the same as the specific examples described in the alicyclic structure as Z ka in the general formula (KA-1). Examples are given.
  • R 11 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group
  • Z represents an alicyclic hydrocarbon group together with a carbon atom. Represents the necessary atomic group.
  • R 12 to R 16 each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R 12 to R 14 , or Either R 15 or R 16 represents an alicyclic hydrocarbon group.
  • R 17 to R 21 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R 17 to R 21 Represents an alicyclic hydrocarbon group.
  • R 19 or R 21 represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
  • R 22 to R 25 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R 22 to R 25 Represents an alicyclic hydrocarbon group.
  • R 23 and R 24 may be bonded to each other to form a ring.
  • the alkyl group for R 12 to R 25 may be either substituted or unsubstituted, and is a linear or branched alkyl group having 1 to 4 carbon atoms Represents.
  • the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
  • the further substituent of the alkyl group includes an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.
  • Examples of the alicyclic hydrocarbon group in R 11 to R 25 or the alicyclic hydrocarbon group formed by Z and a carbon atom include those described above as the alicyclic structure.
  • the repeating unit represented by the general formula (A2) is preferably a repeating unit represented by the following formula.
  • repeating unit represented by the general formula (A2) is preferably a repeating unit represented by the following general formula (A3) in another embodiment.
  • AR represents an aryl group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
  • R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
  • the repeating unit represented by formula (A3) will be described in detail.
  • AR represents an aryl group as described above.
  • the aryl group for AR is preferably a group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, or a fluorene group, and more preferably a group having 6 to 15 carbon atoms.
  • AR is a naphthyl group, anthryl group or fluorene group
  • this carbon atom may be bonded to the ⁇ -position of the naphthyl group or may be bonded to the ⁇ -position.
  • AR is an anthryl group
  • this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.
  • the aryl group as AR may have one or more substituents.
  • substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group.
  • a linear or branched alkyl group having 1 to 5 carbon atoms and an alkoxy group containing the alkyl group moiety are preferable, and a paramethyl group
  • the aryl group as AR has a plurality of substituents
  • at least two of the plurality of substituents may be bonded to each other to form a ring.
  • the ring is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • this ring may be a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
  • this ring may have a substituent.
  • this substituent the thing similar to what is mentioned later about the further substituent which Rn may have is mentioned.
  • the repeating unit represented by the general formula (A3) preferably contains two or more aromatic rings from the viewpoint of roughness performance.
  • the number of aromatic rings contained in this repeating unit is usually preferably 5 or less, and more preferably 3 or less.
  • AR preferably contains two or more aromatic rings, and AR is more preferably a naphthyl group or a biphenyl group.
  • the number of aromatic rings possessed by AR is usually preferably 5 or less, and more preferably 3 or less.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • the alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group.
  • the alkyl group is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. Examples thereof include those having 1 to 20 carbon atoms.
  • the alkyl group of Rn preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.
  • Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
  • aryl group of Rn for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.
  • Each of the alkyl group, cycloalkyl group and aryl group as Rn may further have a substituent.
  • substituents include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and a thiophenecarbonyloxy group.
  • Thiophenemethylcarbonyloxy group and heterocyclic residues such as pyrrolidone residues.
  • an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group are particularly preferable.
  • R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group as described above.
  • alkyl group and cycloalkyl group of R include the same as those described above for Rn.
  • Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.
  • R is an alkyl group or a cycloalkyl group having a substituent
  • particularly preferable R is, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group.
  • R is, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group.
  • halogen atom for R examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom is particularly preferable.
  • alkyl group moiety contained in the alkyloxycarbonyl group of R for example, the configuration described above as the alkyl group of R can be employed.
  • Rn and AR are preferably bonded to each other to form a non-aromatic ring, and in particular, roughness performance can be further improved.
  • the non-aromatic ring that may be formed by bonding Rn and AR is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • the non-aromatic ring may be an aliphatic ring or a heterocycle containing a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
  • the non-aromatic ring may have a substituent.
  • this substituent the thing similar to having demonstrated previously about the further substituent which Rn may have is mentioned, for example.
  • the specific example of the monomer corresponding to the repeating unit represented by general formula (A2) and the specific example of this repeating unit are given to the following, it is not limited to these.
  • the repeating unit shown below is more preferable.
  • the repeating unit represented by the general formula (A2) is preferably a repeating unit of t-butyl methacrylate or ethylcyclopentyl methacrylate.
  • the monomer corresponding to the repeating unit represented by the general formula (A2) includes (meth) acrylic acid chloride and an alcohol compound in a solvent such as THF, acetone and methylene chloride, and a basic catalyst such as triethylamine, pyridine and DBU. It can be synthesized by esterification below. A commercially available product may be used.
  • the resin (Ab) may further contain a repeating unit represented by the following general formula (A5).
  • X is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, aryl group, carboxyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, or Represents an aralkyl group and is the same as X in formula (A2b).
  • a 4 represents a hydrocarbon group that is not eliminated by the action of an acid.
  • examples of the hydrocarbon group that is not eliminated by the action of the acid A 4 include hydrocarbon groups other than the acid-decomposable groups, such as an alkyl that is not eliminated by the action of the acid.
  • a group preferably having 1 to 15 carbon atoms
  • a cycloalkyl group preferably having 3 to 15 carbon atoms
  • an aryl group preferably having 6 to 15 carbon atoms which is not eliminated by the action of an acid, etc.
  • the hydrocarbon group that is not eliminated by the action of the acid of A 4 may be further substituted with a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or the like.
  • the resin (Ab) further has a repeating unit represented by the general formula (A6).
  • R 2 represents a hydrogen atom, a methyl group, a cyano group, a halogen atom, or a perfluoro group having 1 to 4 carbon atoms.
  • R 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, an alkoxy group or an acyl group.
  • q represents an integer of 0 to 4.
  • Ar represents a q + 2 valent aromatic ring.
  • W represents a group or a hydrogen atom that is not decomposed by the action of an acid.
  • a benzene ring, a naphthalene ring and an anthracene ring are preferable, and a benzene ring is more preferable.
  • W represents a group that is not decomposed by the action of an acid (also referred to as an acid-stable group), and examples include groups other than the above-mentioned acid-decomposable groups. Specifically, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, An aryl group, an acyl group, an alkylamide group, an arylamidomethyl group, an arylamide group, etc. are mentioned.
  • the acid stabilizing group is preferably an acyl group or an alkylamide group, more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, or an aryloxy group.
  • the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group.
  • the alkyl group those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferable.
  • alkenyl groups carbon numbers such as vinyl group, propenyl group, allyl group and butenyl group are preferred.
  • W may be at any position on the benzene ring, but is preferably a meta position or a para position of the styrene skeleton, particularly preferably a para position. Specific examples of the repeating unit represented by formula (A6) are shown below, but are not limited thereto.
  • the resin (Ab) preferably further has a repeating unit composed of a (meth) acrylic acid derivative that is not decomposed by the action of an acid.
  • a repeating unit composed of a (meth) acrylic acid derivative that is not decomposed by the action of an acid.
  • the content of the repeating unit having an acid-decomposable group in the resin (Ab) is preferably from 5 to 95 mol%, more preferably from 10 to 60 mol%, particularly preferably from 15 to 50 mol%, based on all repeating units. It is.
  • the content of the repeating unit represented by the general formula (A1) in the resin (Ab) is preferably 0 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 20 to 20 mol% in all repeating units. 50 mol%.
  • the content of the repeating unit represented by the general formula (A2) in the resin (Ab) is preferably 0 to 90 mol%, more preferably 5 to 75 mol%, and particularly preferably 10 to 60 mol%.
  • the content of the repeating unit represented by the general formula (A3) in the resin (Ab) is preferably from 0 to 90 mol%, more preferably from 5 to 75 mol%, particularly preferably from 10 to 10 in all repeating units. 60 mol%.
  • the content of the repeating unit represented by the general formula (A5) in the resin (Ab) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, particularly preferably 0 to 30 mol%.
  • the resin (Ab) may further have a repeating unit represented by the general formula (A6), which is preferable from the viewpoints of improving the film quality and suppressing the decrease in the film thickness of the unexposed area.
  • the content of the repeating unit represented by the general formula (A5) is preferably 0 to 50% by mole, more preferably 0 to 40% by mole, and particularly preferably 0 to 40% by mole in each of all the repeating units. 30 mol%.
  • the resin (Ab) is copolymerized with other polymerizable monomers suitable so that an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group can be introduced in order to maintain good developability for an alkali developer.
  • an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group
  • other hydrophobic polymerizable monomers such as alkyl acrylate and alkyl methacrylate may be copolymerized.
  • the monomer corresponding to the repeating unit represented by the general formula (A2) includes (meth) acrylic acid chloride and an alcohol compound in a solvent such as THF, acetone and methylene chloride, and a basic catalyst such as triethylamine, pyridine and DBU. It can be synthesized by esterification below. A commercially available product may be used.
  • the monomer corresponding to the repeating unit represented by the general formula (A1) is a hydroxy-substituted styrene monomer and a vinyl ether compound in a solvent such as THF and methylene chloride, such as p-toluenesulfonic acid and p-toluenesulfonic acid pyridine salt. It can be synthesized by acetalization in the presence of an acidic catalyst or by t-Boc protection using t-butyl dicarbonate in the presence of a basic catalyst such as triethylamine, pyridine, DBU or the like. A commercially available product may be used.
  • the resin (Ab) preferably has a repeating unit represented by the following general formula (A).
  • R 21 , R 22 and R 23 each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 22 may be bonded to Ar 2 to form a ring, in which case R 22 represents a single bond or an alkylene group.
  • X 2 represents a single bond, —COO—, or —CONR 30 —
  • R 30 represents a hydrogen atom or an alkyl group.
  • L 2 represents a single bond or an alkylene group.
  • Ar 2 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 22 to form a ring.
  • N represents an integer of 1 to 4.
  • the alkyl group of R 21 , R 22 and R 23 in the general formula (A) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec which may have a substituent.
  • -Alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms Is mentioned.
  • alkyl group contained in the alkoxycarbonyl group the same alkyl groups as those described above for R 21 , R 22 and R 23 are preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
  • Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.
  • Ar 2 represents an (n + 1) -valent aromatic ring group.
  • the divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or the like.
  • Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.
  • n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
  • the group formed can be preferably mentioned.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • R 30 represents a hydrogen atom, an alkyl group
  • the alkyl group for R 30 in, the same as the alkyl group of R 21 ⁇ R 23.
  • X 2 is preferably a single bond, —COO— or —CONH—, more preferably a single bond or —COO—.
  • the alkylene group for L 2 is preferably an alkylene group having 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.
  • Ar 2 is more preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, particularly preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.
  • This repeating unit preferably has a hydroxystyrene structure. That is, Ar 2 is preferably a benzene ring group.
  • repeating unit represented by formula (A) is shown below, but the present invention is not limited thereto.
  • a represents 1 or 2.
  • the repeating unit represented by the general formula (A) is preferably a repeating unit represented by the following formula (Ab1) or Ab2), and more preferably a repeating unit represented by the formula (A1). .
  • R 23 has the same meaning as R 23 in the general formula (A).
  • the resin (Ab) may contain two or more types of repeating units represented by the general formula (A).
  • the resin (Ab) preferably contains a repeating unit represented by the following general formula (Ab3).
  • n represents an integer of 1 to 5
  • m represents an integer of 0 to 4 that satisfies the relationship 1 ⁇ m + n ⁇ 5.
  • n is preferably 1 or 2, more preferably 1.
  • m is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
  • S 1 represents a substituent.
  • the plurality of S 1 may be the same as or different from each other.
  • the substituent represented by S 1 include an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxy group, a halogen atom, a cyano group, and a nitro group.
  • alkyl group and a cycloalkyl group a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group
  • a linear or branched alkyl group having 1 to 20 carbon atoms such as a dodecyl group or a cycloalkyl group is preferable. These groups may further have a substituent.
  • substituents that may be included are alkyl group, alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy Group, a thiophenemethylcarbonyloxy group, a heterocyclic residue such as a pyrrolidone residue, and the like, and a substituent having 12 or less carbon atoms is preferable.
  • alkyl group having a substituent examples include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, a cycloalkylcarbonyloxymethyl group, a cycloalkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, and an aralkylcarbonyloxyethyl group.
  • alkyl group and cycloalkyl group in these groups are not particularly limited, and may further have a substituent such as the aforementioned alkyl group, cycloalkyl group, or alkoxy group.
  • alkylcarbonyloxyethyl group and cycloalkylcarbonyloxyethyl group examples include a cyclohexylcarbonyloxyethyl group, a t-butylcyclohexylcarbonyloxyethyl group, and an n-butylcyclohexylcarbonyloxyethyl group.
  • the aryl group is not particularly limited, but generally includes those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, anthracenyl group and the like, and further the above-mentioned alkyl group and cycloalkyl group. And may have a substituent such as an alkoxy group.
  • the aryloxyethyl group include a phenyloxyethyl group, a cyclohexylphenyloxyethyl group, and the like. These groups may further have a substituent.
  • Aralkyl is not particularly limited, and examples thereof include a benzyl group.
  • examples of the aralkylcarbonyloxyethyl group include a benzylcarbonyloxyethyl group. These groups may further have a substituent.
  • Examples of the repeating unit represented by the general formula (Ab3) include the following.
  • the resin (Ab) contains at least a repeating unit represented by the following formula as the repeating unit represented by the general formula (Ab3).
  • the content of the repeating unit represented by the general formula (A) in the resin (Ab) is high resolution, sensitivity, PEB temperature dependency and dry etching resistance, and good pattern shape. Is more preferably from 10 mol% to 75 mol%, and more preferably from 15 mol% to 70 mol%, based on all the repeating units in the resin (Ab). More preferably, it is 20 mol% or more and 65 mol% or less.
  • the content of the repeating unit represented by the general formula (Ab3) in the resin (Ab) is preferably 0 to 90 mol%, more preferably 5 to 80 mol%, based on all repeating units in the resin (Ab). More preferably, it is 10 to 70 mol%, and particularly preferably 20 to 60 mol%.
  • the resin (Ab) preferably has a repeating unit represented by the following general formula.
  • j represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1.
  • repeating unit represented by these general formulas include the following.
  • the resin (Ab) is a repeating unit (B) (hereinafter referred to as “acid generating repeating unit (B)” or “repeating” having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid.
  • This structural site may be, for example, a structural site that generates an acid anion in the repeating unit (B) by being decomposed by irradiation with an actinic ray or radiation, or the repeating unit (B ) May be a structural site that generates a cation structure.
  • this structural part is preferably an ionic structural part having a sulfonium salt structure or an iodonium salt structure, for example.
  • This structural part may be, for example, the same structural part as the structural part represented by A in the general formulas (B1), (B2), and (B3) described below.
  • the repeating unit (B) is preferably at least one selected from the group consisting of repeating units represented by the following general formulas (B1), (B2), and (B3).
  • the repeating unit represented by the following general formula (B1) or (B3) is more preferable, and the repeating unit represented by the following general formula (B1) is particularly preferable.
  • A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
  • R 04 , R 05 and R 07 to R 09 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 06 represents a cyano group, a carboxy group, —CO—OR 25 or —CO—N (R 26 ) (R 27 ).
  • R 25 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.
  • R 26 and R 27 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.
  • R 26 and R 27 may be bonded to each other to form a ring together with the nitrogen atom.
  • X 1 , X 2 and X 3 are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO 2 —, —CO—, —N (R 33 ) —, or these Represents a divalent linking group in combination of a plurality.
  • R 33 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.
  • the alkyl group for R 04 , R 05 and R 07 to R 09 is preferably those having 20 or less carbon atoms, and more preferably those having 8 or less carbon atoms.
  • Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. These alkyl groups may further have a substituent.
  • the cycloalkyl group of R 04 , R 05 and R 07 to R 09 may be monocyclic or polycyclic. This cycloalkyl group preferably has 3 to 8 carbon atoms. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
  • Examples of the halogen atom for R 04 , R 05 and R 07 to R 09 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a fluorine atom is particularly preferable.
  • alkyl group contained in the alkoxycarbonyl group of R 04, R 05 and R 07 ⁇ R 09 for example, those previously mentioned as the alkyl group of R 04, R 05 and R 07 ⁇ R 09 are preferred.
  • alkyl groups for R 25 to R 27 and R 33 for example, those previously mentioned as the alkyl groups for R 04 , R 05 and R 07 to R 09 are preferable.
  • cycloalkyl group represented by R 25 to R 27 and R 33 for example, those listed above as the cycloalkyl groups represented by R 04 , R 05 and R 07 to R 09 are preferable.
  • alkenyl group for R 25 to R 27 and R 33 those having 2 to 6 carbon atoms are preferable.
  • alkenyl group examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
  • the cycloalkenyl group for R 25 to R 27 and R 33 is preferably one having 3 to 6 carbon atoms.
  • Examples of such a cycloalkenyl group include a cyclohexenyl group.
  • the aryl group of R 25 to R 27 and R 33 may be a monocyclic aromatic group or a polycyclic aromatic group. This aryl group is preferably one having 6 to 14 carbon atoms. This aryl group may further have a substituent. In addition, aryl groups may be bonded to each other to form a multicycle. Examples of the aryl group of R 25 to R 27 and R 33 include a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, and a naphthyl group.
  • the aralkyl group for R 25 to R 27 and R 33 is preferably one having 7 to 15 carbon atoms. This aralkyl group may further have a substituent. Examples of the aralkyl group of R 25 to R 27 and R 33 include a benzyl group, a phenethyl group, and a cumyl group.
  • the ring formed by combining R 26 and R 27 together with the nitrogen atom is preferably a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine.
  • the arylene group of X 1 to X 3 is preferably an arylene group having 6 to 14 carbon atoms.
  • Examples of such an arylene group include a phenylene group, a tolylene group, and a naphthylene group. These arylene groups may further have a substituent.
  • the alkylene group for X 1 to X 3 is preferably an alkylene group having 1 to 8 carbon atoms.
  • Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. These alkylene groups may further have a substituent.
  • the cycloalkylene group represented by X 1 to X 3 is preferably one having 5 to 8 carbon atoms.
  • Examples of such a cycloalkylene group include a cyclopentylene group and a cyclohexylene group. These cycloalkylene groups may further have a substituent.
  • Preferred substituents that each group in the general formulas (B1) to (B3) may have include, for example, a hydroxyl group; a halogen atom (fluorine, chlorine, bromine, iodine); a nitro group; a cyano group; an amide group; Groups; alkyl groups previously mentioned as R04, R05 and R07 to R09; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; methoxycarbonyl, ethoxycarbonyl, etc.
  • alkoxy group such as a formyl group, an acetyl group and a benzoyl group; an acyloxy group such as an acetoxy group and a butyryloxy group; and a carboxy group.
  • substituents preferably have 8 or less carbon atoms.
  • A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
  • photoinitiator of photocationic polymerization, photoinitiator of photoradical polymerization, photodecoloration of pigments examples thereof include structural sites possessed by compounds that generate acid by known light used in agents, photochromic agents, and microresists.
  • part provided with the sulfonium salt structure or the iodonium salt structure is more preferable. More specifically, A is preferably a group represented by the following general formula (ZI) or (ZII).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two of R 201 to R 203 include alkylene groups such as a butylene group and a pentylene group.
  • Z ⁇ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation.
  • Z ⁇ is preferably a non-nucleophilic anion.
  • the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.
  • the non-nucleophilic anion means an anion having a very low ability to cause a nucleophilic reaction.
  • a non-nucleophilic anion is used, degradation with time due to intramolecular nucleophilic reaction can be suppressed. This makes it possible to improve the temporal stability of the resin and the composition.
  • Examples of the organic group for R 201 , R 202 and R 203 include corresponding groups in the groups represented by (ZI-1), (ZI-2) and (ZI-3) described later.
  • More preferred examples of the group represented by (ZI) include the (ZI-1) group, (ZI-2) group, (ZI-3) group and (ZI-4) group described below.
  • the (ZI-1) group is a group having arylsulfonium as a cation, wherein at least one of R 201 to R 203 in the general formula (ZI) is an aryl group.
  • R 201 to R 203 may be an aryl group, or a part of R 201 to R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
  • Examples of the (ZI-1) group include groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, and aryldicycloalkylsulfonium.
  • the aryl group in arylsulfonium is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group may have a heterocyclic structure containing a hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom. Examples of this heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene.
  • these aryl groups may be the same as or different from each other.
  • the alkyl group or cycloalkyl group that arylsulfonium has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.
  • Examples of such an alkyl group or cycloalkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
  • the aryl group, alkyl group or cycloalkyl group of R 201 to R 203 is an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), an aryl group (eg, having 6 to 14 carbon atoms).
  • An alkoxy group for example, having 1 to 15 carbon atoms
  • a halogen atom, a hydroxyl group or a phenylthio group may be used as a substituent.
  • Preferred examples of the substituent include a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. It is done. More preferable substituents include, for example, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
  • the substituent may be substituted with any one of three R 201 to R 203 , or may be substituted with two or more of these.
  • R 201 to R 203 are a phenyl group, these substituents are preferably substituted at the p-position of the phenyl group.
  • the (ZI-2) group is a group in which R 201 to R 203 in the general formula (ZI) each independently represents an organic group having no aromatic ring.
  • the aromatic ring includes a heterocycle containing a hetero atom.
  • the organic group not containing an aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
  • R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocyclo group.
  • the alkyl group and cycloalkyl group represented by R 201 to R 203 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), and And a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group). More preferable examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group.
  • the cycloalkyl group is more preferably a 2-oxocycloalkyl group.
  • the 2-oxoalkyl group may be linear or branched.
  • the 2-oxoalkyl group is preferably a group having> C ⁇ O at the 2-position of the above alkyl group.
  • the 2-oxocycloalkyl group is preferably a group having> C ⁇ O at the 2-position of the above cycloalkyl group.
  • the alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentoxy group).
  • R 201 to R 203 may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
  • the (ZI-3) group is a group represented by the following general formula (ZI-3), which is a group having a phenacylsulfonium salt structure.
  • R 1c to R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
  • R 6c and R 7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
  • R x and R y each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
  • R 1c to R 5c , R 6c and R 7c , and R x and R y may be bonded to each other to form a ring structure.
  • This ring structure may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond. Examples of the group formed by bonding these to each other include a butylene group and a pentylene group.
  • Zc ⁇ represents a non-nucleophilic anion, and examples thereof include the same as Z ⁇ in general formula (ZI).
  • the (ZI-4) group is a group represented by the following general formula (ZI-4). This group is effective for suppressing outgas.
  • R 1 to R 13 each independently represents a hydrogen atom or a substituent. At least one of R 1 to R 13 is preferably a substituent containing an alcoholic hydroxyl group.
  • alcoholic hydroxyl group means a hydroxyl group bonded to a carbon atom of an alkyl group.
  • Z is a single bond or a divalent linking group.
  • Z c - represents a non-nucleophilic anion, for example, Z in formula (ZI) - include the same one.
  • R 1 to R 13 are substituents containing an alcoholic hydroxyl group
  • R 1 to R 13 are preferably groups represented by — (WY).
  • Y is an alkyl group substituted with a hydroxyl group
  • W is a single bond or a divalent linking group.
  • Preferred examples of the alkyl group represented by Y include an ethyl group, a propyl group, and an isopropyl group.
  • Y particularly preferably includes a structure represented by —CH 2 CH 2 OH.
  • the divalent linking group represented by W is not particularly limited, but preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, A divalent group in which an arbitrary hydrogen atom in an alkoxycarbonyl group or a carbamoyl group is replaced by a single bond, and more preferably an arbitrary hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group or an alkoxycarbonyl group. It is a divalent group replaced by a single bond.
  • R 1 to R 13 are substituents containing an alcoholic hydroxyl group
  • the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.
  • the substituent containing an alcoholic hydroxyl group as R 1 to R 13 may have two or more alcoholic hydroxyl groups.
  • the number of alcoholic hydroxyl groups having a substituent containing an alcoholic hydroxyl group as R 1 to R 13 is 1 to 6, preferably 1 to 3, and more preferably 1.
  • the number of alcoholic hydroxyl groups contained in the (ZI-4) group is preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 3 in total for all of R 1 to R 13. .
  • R 1 to R 13 are, for example, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a complex Ring group, cyano group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (anilino group) ), Ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkyl
  • R 1 to R 13 are preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a cyano group, an alkoxy group, an acyloxy group, an acylamino group, an amino group.
  • R 1 to R 13 do not contain an alcoholic hydroxyl group
  • R 1 to R 13 are particularly preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or an alkoxy group.
  • R 1 to R 13 may be bonded to each other to form a ring structure.
  • This ring structure includes aromatic and non-aromatic hydrocarbon rings and heterocycles. These ring structures may be further combined to form a condensed ring.
  • the (ZI-4) group preferably has a structure in which at least one of R 1 to R 13 contains an alcoholic hydroxyl group, and more preferably at least one of R 9 to R 13 is an alcoholic group. It has a structure containing a hydroxyl group.
  • Z represents a single bond or a divalent linking group as described above.
  • the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, an acyl group, Examples thereof include an alkylsulfonyl group, —CH ⁇ CH—, an aminocarbonylamino group, and an aminosulfonylamino group.
  • This divalent linking group may have a substituent.
  • substituents include those similar to those listed above for R 1 to R 13 .
  • Z is preferably a single bond, an ether bond or a thioether bond, and particularly preferably a single bond.
  • R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. Specific examples and preferred embodiments of the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 are the same as those described for R 201 to R 203 in the aforementioned compound (ZI-1).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have a substituent.
  • this substituent include the same as those described for R 201 to R 203 in the aforementioned compound (ZI-1).
  • Z ⁇ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁇ in formula (ZI).
  • Preferred examples of A also include groups represented by the following general formula (ZCI) or (ZCII).
  • R 301 and R 302 each independently represents an organic group.
  • the organic group generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • R 301 and R 302 may be bonded to each other to form a ring structure.
  • This ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond and a carbonyl group in the ring.
  • Examples of the group that can be formed by bonding R 301 and R 302 to each other include alkylene groups such as a butylene group and a pentylene group.
  • Examples of the organic group for R 301 and R 302 include an aryl group, an alkyl group, and a cycloalkyl group that are mentioned as examples of R 201 to R 203 in General Formula (ZI).
  • M represents an atomic group that forms an acid by addition of a proton. More specifically, a structure represented by any one of the general formulas AN1 to AN3 described later can be given. Of these, the structure represented by the general formula AN1 is particularly preferable.
  • R 303 represents an organic group.
  • the organic group as R 303 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Specific examples of the organic group for R 303 include an aryl group, an alkyl group, a cycloalkyl group, and the like given as specific examples of R 204 and R 205 in the general formula (ZII).
  • examples of the structural site that generates an acid upon irradiation with actinic rays or radiation include a structural site that becomes a sulfonic acid precursor contained in the following photoacid generator.
  • examples of the photoacid generator include the following compounds (1) to (3).
  • the repeating unit (B) has a structural portion that is converted into an acid anion by irradiation with actinic rays or radiation.
  • a in the general formulas (B1) to (B3) is preferably a structural site that is converted to an acid anion by irradiation with actinic rays or radiation.
  • the repeating unit (B) has a structure in which an acid anion is generated in the side chain of the resin by irradiation with actinic rays or radiation.
  • X 11 represents —O—, —S—, —CO—, —SO 2 —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.
  • X 12 and X 13 each independently represent a single bond, —O—, —S—, —CO—, —SO 2 —, —NR— (R represents a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.
  • the alkyl group of R may be linear or branched. Moreover, the alkyl group of R may further have a substituent.
  • the alkyl group preferably has 20 or less carbon atoms, more preferably 8 or less carbon atoms, and still more preferably 3 or less carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.
  • the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members.
  • X 11 is more preferably —O—, —CO—, —NR— (R is a hydrogen atom or an alkyl group) or a combination thereof, and —COO— or —CONR— (R is hydrogen) Particularly preferred is an atom or an alkyl group.
  • L 11 represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a group obtained by combining two or more thereof.
  • two or more groups to be combined may be the same as each other or different from each other.
  • These groups include O—, —S—, —CO—, —SO 2 —, —NR— (where R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent They may be linked via an aromatic ring group or a group obtained by combining these.
  • the alkylene group for L 11 may be linear or branched.
  • the alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • alkenylene group for L 11 for example, a group having a double bond at any position of the above alkylene group can be mentioned.
  • the divalent aliphatic hydrocarbon ring group as L 11 may be monocyclic or polycyclic.
  • the divalent aliphatic hydrocarbon ring group preferably has 5 to 12 carbon atoms, and more preferably has 6 to 10 carbon atoms.
  • the divalent aromatic ring group as the linking group may be an arylene group or a heteroarylene group.
  • the aromatic ring group preferably has 6 to 14 carbon atoms. This aromatic ring group may further have a substituent.
  • —NR— as a linking group and a divalent nitrogen-containing non-aromatic heterocyclic group are the same as those in X 11 described above, for example.
  • L 11 is an alkylene group, a divalent aliphatic hydrocarbon ring group, or a combination of an alkylene group and a divalent aliphatic hydrocarbon ring group via —OCO—, —O— or —CONH—.
  • Groups for example, -alkylene group-O-alkylene group-, -alkylene group-OCO-alkylene group- or -divalent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group- Is particularly preferred.
  • —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X 12 and X 13 are the same as those in X 11 described above, and preferred examples are also the same.
  • X 12 is more preferably a single bond, —S—, —O—, —CO—, —SO 2 — or a combination thereof, and is a single bond, —S—, —OCO— or —OSO 2 —. Is particularly preferred.
  • X 13 is more preferably —O—, —CO—, —SO 2 —, or a combination of these, and —OSO 2 — is particularly preferred.
  • Ar 1 represents a divalent aromatic ring group.
  • the divalent aromatic ring group may be an arylene group or a heteroarylene group.
  • This divalent aromatic ring group may further have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an aryl group.
  • Ar 1 is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, or an aralkylene group in which an arylene group having 6 to 18 carbon atoms and an alkylene having 1 to 4 carbon atoms are combined.
  • a phenylene group, a naphthylene group, a biphenylene group, or a phenylene group substituted with a phenyl group is particularly preferable.
  • L 12 represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All are substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group.
  • two or more groups to be combined may be the same as each other or different from each other.
  • These groups include —O—, —S—, —CO—, —SO 2 —, —NR— (where R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, divalent May be connected via a group of aromatic rings or a combination thereof.
  • L 12 an alkylene group, a divalent aromatic ring group, or a combination thereof, in which some or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group) A group is more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.
  • L 12 is particularly preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.
  • the alkylene group for L 12 may be linear or branched.
  • the alkylene group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • Examples of the alkenylene group for L 12 include a group having a double bond at an arbitrary position of the alkylene group.
  • the divalent aliphatic hydrocarbon ring group represented by L 12 may be monocyclic or polycyclic.
  • the divalent aliphatic hydrocarbon ring group preferably has 3 to 17 carbon atoms.
  • Examples of the divalent aromatic ring group for L 12 include the same groups as those described above as the linking group for L 11 .
  • linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L 12 include the same specific examples as in X 11 described above, and preferred examples are also the same.
  • Z 1 represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation, and specifically includes, for example, a structure represented by the above formula (ZI).
  • Ar 2 represents a divalent aromatic ring group.
  • the divalent aromatic ring group may be an arylene group or a heteroarylene group. These divalent aromatic ring groups preferably have 6 to 18 carbon atoms. These divalent aromatic ring groups may further have a substituent.
  • X 21 represents —O—, —S—, —CO—, —SO 2 —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.
  • R represents a hydrogen atom or an alkyl group
  • a divalent nitrogen-containing non-aromatic heterocyclic group or these Represents a combined group.
  • Examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group in X 21 include the same as those described above for X 11 .
  • X 22 represents a single bond, —O—, —S—, —CO—, —SO 2 —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or And represents a combination of these.
  • R represents a hydrogen atom or an alkyl group
  • a divalent nitrogen-containing non-aromatic heterocyclic group or And represents a combination of these.
  • Examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group in X 22 include the same as those described above for X 11 .
  • X 22 is more preferably —O—, —S—, —CO—, —SO 2 —, or a combination thereof, and particularly preferably —O—, —OCO—, or —OSO 2 —.
  • L 21 represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
  • two or more groups to be combined may be the same as each other or different from each other. These groups include —O—, —S—, —CO—, —SO 2 —, —NR— (where R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, divalent May be connected via a group of aromatic rings or a combination thereof.
  • Examples of the alkylene group, alkenylene group, and divalent aliphatic hydrocarbon ring group for L 21 include the same groups as those described above for L 11 .
  • the divalent aromatic ring group of L 21 may be an arylene group or a heteroarylene group.
  • the divalent aromatic ring group preferably has 6 to 14 carbon atoms.
  • Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in L 21 include the same as those described above for X 11 .
  • L 21 represents a single bond, an alkylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group in which two or more of these are combined (for example, -alkylene group-divalent aromatic ring group- Or a divalent aliphatic hydrocarbon ring group-alkylene group-), or a group in which two or more of these are combined through a linking group such as —OCO—, —COO—, —O— and —S— ( For example, -alkylene group-OCO-2 valent aromatic ring group-, -alkylene group-S-2 valent aromatic ring group-, or -alkylene group-O-alkylene group-2 valent aromatic ring group-) Particularly preferred.
  • L 22 represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All may be substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group.
  • two or more groups to be combined may be the same as each other or different from each other.
  • These groups include —O—, S—, —CO—, —SO 2 —, —NR— (where R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent They may be linked via an aromatic ring group or a group obtained by combining these.
  • L 22 is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group).
  • a fluorine atom or a fluorinated alkyl group more preferably a perfluoroalkyl group.
  • an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.
  • alkylene group examples include L 12 in the general formula (L1). The same group as the specific example illustrated previously is mentioned.
  • linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L 22 include the same specific examples as in X 11 described above, and preferred examples are also the same.
  • Z 2 represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation. Specific examples of Z 2 are the same as those described above for Z 1.
  • X 31 and X 32 each independently represent a single bond, —O—, —S—, —CO—, —SO 2 —, —NR— (R represents a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.
  • Examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group in each of X 31 and X 32 include the same as those described above for X 11 .
  • X 31 is preferably a single bond, —O—, —CO—, —NR— (where R is a hydrogen atom or an alkyl group), or a combination thereof, and more preferably a single bond, —COO— or —CONR— (R is a hydrogen atom or an alkyl group) is particularly preferred.
  • X 32 is more preferably —O—, —S—, —CO—, —SO 2 —, a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof, —O—, — OCO— or —OSO 2 — is particularly preferred.
  • L 31 represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof.
  • two or more groups to be combined may be the same or different from each other.
  • these groups include —O—, —S—, —CO—, —SO 2 —, —NR— (where R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, divalent May be linked via a group of these aromatic rings or a combination thereof.
  • alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, and divalent aromatic ring group of L 31 include the same as those described above for L 21 .
  • linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L 31 include the same specific examples as those in X 11 described above, and preferred examples are also the same.
  • L 32 represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these.
  • two or more groups to be combined may be the same as each other or different from each other.
  • These groups include —O—, —S—, —CO—, —SO 2 —, —NR— (where R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, divalent May be connected via a group of aromatic rings or a combination thereof.
  • L 32 is an alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, or a combination of two or more thereof, wherein a part or all of the hydrogen atoms are fluorine atoms, It is preferably substituted with a substituent selected from a fluorinated alkyl group, a nitro group, and a cyano group.
  • L 32 is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group).
  • a fluorine atom or a fluorinated alkyl group more preferably a perfluoroalkyl group.
  • an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.
  • L 32 alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, and a group obtained by combining two or more of these include L 12 described above. The same thing is mentioned.
  • Specific examples of the linking group —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in L 32 include the same specific examples as those described above for X 11 , and preferred examples are also the same.
  • the alkylene group represented by R 32 has 1 carbon atom Is preferably 1 to 8, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 2 carbon atoms.
  • Z 3 represents an onium salt that becomes an imido acid group or a methide acid group by irradiation with actinic rays or radiation.
  • the onium salt represented by Z 3 is preferably a sulfonium salt or an iodonium salt, and a structure represented by the following general formula (ZIII) or (ZIV) is preferred.
  • Z 1 , Z 2 , Z 3 , Z 4 , and Z 5 each independently represent —CO— or —SO 2 —, and more preferably —SO 2 —. It is.
  • Rz 1 , Rz 2 and Rz 3 each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group.
  • the alkyl groups of Rz 1 , Rz 2 and Rz 3 may be linear or branched.
  • the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the monovalent aliphatic hydrocarbon ring group represented by Rz 1 , Rz 2 and Rz 3 preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms.
  • the aryl group of Rz 1 , Rz 2 and Rz 3 preferably has 6 to 18 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.
  • a phenyl group is particularly preferable.
  • Preferable examples of the aralkyl group of Rz 1 , Rz 2 and Rz 3 include those in which an alkylene group having 1 to 8 carbon atoms and the aryl group are bonded.
  • An aralkyl group formed by bonding an alkylene group having 1 to 6 carbon atoms and the aryl group is more preferable, and an aralkyl group formed by bonding an alkylene group having 1 to 4 carbon atoms and the aryl group is particularly preferable.
  • a + represents a sulfonium cation or an iodonium cation.
  • Preferable examples of A + include a sulfonium cation in the general formula (ZI) or an iodonium cation structure in the general formula (ZII).
  • repeating unit (B) Specific examples of the repeating unit (B) are shown below, but the scope of the present invention is not limited thereto.
  • the content of the repeating unit (B) in the resin (Ab) is 0.1 to 80 mol% with respect to all the repeating units in the resin (Ab). Preferably, it is 0.5 to 60 mol%, and more preferably 1 to 40 mol%.
  • the weight average molecular weight (Mw) of the resin (Ab) is preferably in the range of 1000 to 200,000, respectively. 200,000 or less is preferable from the viewpoint of the dissolution rate and sensitivity of the resin itself with respect to alkali.
  • the dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0.
  • the weight average molecular weight (Mw) of the resin is preferably in the range of 1,000 to 200,000, more preferably in the range of 1,000 to 100,000, and particularly preferably 1,000. It is in the range of ⁇ 50,000, and most preferably in the range of 1,000 to 25,000.
  • the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (Ab) are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSK gel Multipore HXL-M (Tosoh Corporation) 7.8 mm ID ⁇ 30.0 cm can be obtained by using THF (tetrahydrofuran) as an eluent.
  • (Ab) can use various commercially available products, and can be synthesized according to a conventional method (for example, radical polymerization or anionic polymerization method).
  • a conventional method for example, radical polymerization or anionic polymerization method.
  • a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
  • the dropping polymerization method is added, and the dropping polymerization method is preferable.
  • reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Further, the composition of the present invention such as propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), and cyclohexanone described later is used. Solvents that dissolve are mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, the generation of particles during storage can be suppressed.
  • ethers such as tetrahydrofuran
  • the resin (Ab) is preferably polymerized by a known anionic polymerization method or radical polymerization method.
  • the anionic polymerization method is usually performed at a temperature of ⁇ 100 to 90 ° C. in an organic solvent under an inert gas atmosphere such as nitrogen or argon using an alkali metal or an organic alkali metal as a polymerization initiator.
  • a block copolymer is obtained by sequentially adding monomers to the reaction system for polymerization, and a random copolymer is obtained by adding a mixture of monomers to the reaction system for polymerization. can get.
  • alkali metal of the polymerization initiator examples include lithium, sodium, potassium, cesium and the like
  • organic alkali metal examples include alkylated products, allylated products and arylated products of the alkali metals, specifically Is ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, lithium triphenyl, sodium naphthalene, ⁇ -methylstyrene sodium dianion, 1,1-diphenylhexyl lithium 1,1-diphenyl-3-methylpentyl lithium and the like.
  • the radical polymerization method is a known radical polymerization start such as azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and organic oxides such as benzoyl peroxide, methyl ethyl ketone peroxide and cumene hydroperoxide.
  • a known chain transfer agent such as 1-dodecanethiol is used in combination with an inert gas atmosphere such as nitrogen or argon in an organic solvent at a temperature of 50 to 200 ° C. .
  • organic solvent examples include aliphatic hydrocarbons such as n-hexane and n-heptane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene and toluene, and ketones such as methyl ethyl ketone and cyclohexanone.
  • Polyhydric alcohol derivatives, ethers such as diethyl ether, tetrahydrofuran and dioxane, anisole, It can be mentioned organic solvents which are usually used in anionic polymerization such as methylated phosphoramide, which are used as a single solvent or two or more kinds of mixed solvents. More preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone.
  • an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
  • Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like.
  • the concentration of the reaction is usually 5 to 50% by mass, preferably 30 to 50% by mass.
  • the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
  • Resin (Ab) having a dispersity of 2.0 or less can be synthesized by performing radical polymerization using an azo polymerization initiator. Further preferred resin (Ab) having a dispersity of 1.0 to 1.5 can be synthesized by living radical polymerization, for example.
  • Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
  • Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent
  • a normal method such as a method can be applied.
  • the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.
  • the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer.
  • a compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use.
  • a precipitation or reprecipitation solvent a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
  • the amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally, 100 to 10,000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300 to 1000 parts by mass.
  • the temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.).
  • the precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
  • Precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
  • the resin may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
  • a resin having no aromatic ring as the resin (Ab) from the viewpoint of transparency to the ArF excimer laser.
  • a resin (Ab) suitable for ArF excimer laser exposure for example, a resin (A ′) described in paragraphs 0446 to 0477 of JP2013-15590A can be used.
  • the total content of the resin (Ab) is usually 10 to 99% by mass, preferably 20 to 99% by mass, particularly preferably 30 to 99% by mass, based on the total solid content of the composition of the present invention. %. Although the specific example of resin (Ab) is shown below, it is not limited to these.
  • the content of the repeating unit containing a fluorine atom is preferably 1 mol% or less, and more preferably no fluorine atom is contained.
  • the content of the repeating unit other than the repeating unit (B) and containing a fluorine atom is more preferably 1 mol% or less. Most preferably, no atoms are contained.
  • the composition of the present invention includes a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”). May be contained.
  • the acid generator is not particularly limited as long as it is a publicly known acid generator, but upon irradiation with actinic rays or radiation, at least any of organic acids such as sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide. Compounds that generate such are preferred.
  • More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
  • Z ⁇ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
  • Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
  • the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
  • the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
  • the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms).
  • an alkylthio group preferably 1 to 15 carbon atoms
  • an alkylsulfonyl group preferably 1 to 15 carbon atoms
  • an alkyliminosulfonyl group preferably 2 to 15 carbon atoms
  • an aryloxysulfonyl group preferably a carbon atom Number 6 to 20
  • alkylaryloxysulfonyl group preferably having 7 to 20 carbon atoms
  • cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.
  • examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
  • aralkyl group in the aralkyl carboxylate anion preferably an aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be mentioned.
  • Examples of the sulfonylimide anion include saccharin anion.
  • the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
  • a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
  • alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
  • non-nucleophilic anions examples include fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), fluorinated antimony (eg, SbF 6 ⁇ ), and the like. .
  • non-nucleophilic anion examples include an aliphatic sulfonate anion in which at least ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom.
  • the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
  • the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
  • anion represented with the following general formula (AN1) is also mentioned as a preferable aspect.
  • Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • A represents a cyclic organic group.
  • x represents an integer of 1 to 20
  • y represents an integer of 0 to 10
  • z represents an integer of 0 to 10.
  • the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Specific examples of Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , CH 2 CH 2 C 4 F 9 may be mentioned, among which a fluorine atom and CF 3 are preferable.
  • both Xf are fluorine atoms.
  • the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
  • R 1 and R 2 are preferably a fluorine atom or CF 3 .
  • x is preferably from 1 to 10, and more preferably from 1 to 5.
  • y is preferably 0 to 4, more preferably 0.
  • z is preferably 0 to 5, and more preferably 0 to 3.
  • the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred.
  • —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
  • the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
  • the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group.
  • a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred.
  • an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
  • Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
  • Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.
  • examples of the cyclic organic group may include a lactone structure, and specific examples include those represented by the general formulas (LC1-1) to (LC1-17) that the above-described resin (P) may have. Can be mentioned.
  • the cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like.
  • the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
  • Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
  • R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
  • aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
  • Preferred examples of the alkyl group and cycloalkyl group represented by R 201 to R 203 include a straight-chain or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms.
  • alkyl group More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent.
  • substituents examples include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.
  • halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms).
  • An aryl group preferably 6 to 14 carbon atoms
  • an alkoxycarbonyl group preferably 2
  • R 1a to R 13a each independently represents a hydrogen atom or a substituent.
  • R 1a to R 13a are preferably not hydrogen atoms, and more preferably any one of R 9a to R 13a is not a hydrogen atom.
  • Za is a single bond or a divalent linking group.
  • X ⁇ has the same meaning as Z ⁇ in formula (ZI).
  • R 1a to R 13a are not a hydrogen atom include halogen atoms, linear, branched, and cyclic alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, nitro groups, and carboxyl groups.
  • R 1a to R 13a are not a hydrogen atom, it is preferably a linear, branched or cyclic alkyl group substituted with a hydroxyl group.
  • Examples of the divalent linking group for Za include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether bond, a thioether bond, an amino group, a disulfide group, and — (CH 2 ) N —CO—, — (CH 2 ) n —SO 2 —, —CH ⁇ CH—, aminocarbonylamino group, aminosulfonylamino group and the like (n is an integer of 1 to 3).
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent.
  • this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
  • Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁇ in formula (ZI).
  • Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).
  • Ar 3 and Ar 4 each independently represents an aryl group.
  • R 208 , R 209 and R 210 each independently represents an alkyl group, a cycloalkyl group or an aryl group.
  • A represents an alkylene group, an alkenylene group or an arylene group.
  • Specific examples of the aryl group represented by Ar 3 , Ar 4 , R 208 , R 209, and R 210 are the same as the specific examples of the aryl group represented by R 201 , R 202, and R 203 in the general formula (ZI). Can be mentioned.
  • alkyl group and cycloalkyl group represented by R 208 , R 209 and R 210 include specific examples of the alkyl group and cycloalkyl group represented by R 201 , R 202 and R 203 in the general formula (ZI), respectively. The same can be mentioned.
  • the alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms.
  • To 12 alkenylene groups for example, ethenylene group, propenylene group, butenylene group, etc.
  • the arylene group of A is an arylene group having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.)
  • acid generators particularly preferred examples are given below.
  • An acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the photoacid generator is preferably 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, and still more preferably 1 based on the total solid content of the composition. ⁇ 40% by weight.
  • the actinic ray-sensitive or radiation-sensitive composition of the present invention further comprises a compound that decomposes by the action of an acid to generate an acid (hereinafter referred to as an acid proliferating agent). 1 type or 2 types or more).
  • the acid generated by the acid proliferating agent is preferably sulfonic acid, methide acid or imide acid.
  • the content of the acid proliferating agent is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total solid content of the composition, and 1.0 to More preferably, it is 20 mass%.
  • solvent that can be used in preparing the composition of the present invention is not particularly limited as long as it dissolves each component.
  • alkylene glycol monoalkyl ether carboxylate propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane
  • alkylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), etc.
  • lactate alkyl ester ethyl lactate, methyl lactate, etc.
  • a cyclic lactone ⁇ -butyrolactone, preferably 4 to 10 carbon atoms
  • a chain or cyclic ketone (2-heptanone, cyclohexanone, etc. preferably 4 to 10 carbon atoms
  • an alkylene carbonate ethylene carbonate
  • alkyl acetate such as carboxylic acid alkyl (butyl acetate is preferred), and the like alkoxy alkyl acetates (ethyl ethoxypropionate).
  • Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].
  • alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.
  • solvents may be used alone or in combination of two or more.
  • the mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.
  • the solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a basic compound.
  • the basic compound is preferably a compound having a stronger basicity than phenol.
  • this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.
  • nitrogen-containing basic compound that can be used is not particularly limited, for example, compounds classified into the following (1) to (7) can be used.
  • Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.
  • the carbon number of the alkyl group as R is not particularly limited, but is usually 1 to 20, preferably 1 to 12.
  • the carbon number of the cycloalkyl group as R is not particularly limited, but is usually 3 to 20, and preferably 5 to 15.
  • the number of carbon atoms of the aryl group as R is not particularly limited, but is usually 6 to 20, and preferably 6 to 10. Specific examples include a phenyl group and a naphthyl group.
  • the carbon number of the aralkyl group as R is not particularly limited, but is usually 7 to 20, preferably 7 to 11. Specific examples include a benzyl group.
  • a hydrogen atom may be substituted with a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
  • Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl.
  • preferred basic compounds represented by the general formula (BS-1) include those in which at least one R is an alkyl group substituted with a hydroxy group. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.
  • the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed.
  • an oxyalkylene chain As the oxyalkylene chain, —CH 2 CH 2 O— is preferable.
  • tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.
  • Examples of the basic compound represented by the general formula (BS-1) include the following.
  • This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).
  • a compound having two or more ring structures is also preferably used.
  • Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.
  • An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound.
  • the phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.
  • This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene chains in one molecule is preferably 3 to 9, and more preferably 4 to 6.
  • —CH 2 CH 2 O— is particularly preferable.
  • the amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform.
  • the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.
  • ammonium salt As the basic compound, an ammonium salt can also be used as appropriate.
  • the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are particularly preferred.
  • halide chloride, bromide and iodide are particularly preferable.
  • sulfonate an organic sulfonate having 1 to 20 carbon atoms is particularly preferable.
  • examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
  • the alkyl group contained in the alkyl sulfonate may have a substituent.
  • substituents include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group.
  • alkyl sulfonate examples include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
  • aryl group contained in the aryl sulfonate examples include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent.
  • this substituent for example, a linear or branched alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms are preferable. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferred.
  • the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
  • the ammonium salt may be hydroxide or carboxylate.
  • the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred.
  • Preferred basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. . These may further have a substituent.
  • Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.
  • Particularly preferable basic compounds include, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2 -Phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- Diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4-aminoethylpyridine, 3-a Nopyrrolidine, piperazine, N- (2-aminoethyl) piperazine,
  • a compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity PA
  • the composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to an acid [hereinafter also referred to as compound (PA)].
  • the proton acceptor functional group is a functional group having electrons or a group capable of electrostatically interacting with protons.
  • a functional group having a macrocyclic structure such as a cyclic polyether or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
  • Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.
  • the compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity.
  • the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
  • a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
  • a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected.
  • an ionic compound that has a proton acceptor moiety in the cation moiety may be used.
  • a compound represented by the following general formula (7) is exemplified.
  • A represents a sulfur atom or an iodine atom.
  • M represents 1 or 2
  • n 1 or 2.
  • A is a sulfur atom
  • m + n 3
  • A is an iodine atom
  • m + n 2.
  • R represents an aryl group
  • R N represents an aryl group substituted with a proton acceptor functional group.
  • X ⁇ represents a counter anion
  • X ⁇ include those similar to X— in the general formula (ZI) described above.
  • aryl group of R and R N is a phenyl group are preferably exemplified.
  • proton acceptor functional group possessed by RN are the same as the proton acceptor functional group described in the above formula (PA-1).
  • the compounding ratio of the compound (PA) in the whole composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in the total solid content.
  • composition of the present invention may further contain a guanidine compound having a structure represented by the following formula.
  • the guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by three nitrogens.
  • the basicity of the guanidine compound (A) of the present invention is preferably such that the pKa of the conjugate acid is 6.0 or more, and 7.0 to 20.0 is high in neutralization reactivity with the acid, It is preferable because of excellent roughness characteristics, and more preferably 8.0 to 16.0.
  • pKa means pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the higher the acid strength. Specifically, pKa in an aqueous solution can be actually measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the software package 1 below, A value based on a database of constants and known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.
  • log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds.
  • P n-octanol / water partition coefficient
  • the distribution coefficient is obtained by calculation without experimentation.
  • CSChemDrawUltraVer The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.
  • logP of the guanidine compound (A) is 10 or less. By being below the above value, it can be contained uniformly in the resist film.
  • the log P of the guanidine compound (A) is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, and still more preferably in the range of 4 to 8.
  • the guanidine compound (A) in the present invention preferably has no nitrogen atom other than the guanidine structure.
  • Low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid comprises a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter referred to as “low molecular compound”
  • low molecular compound it is possible to contain “low molecular compound (D)” or “compound (D)”.
  • the low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.
  • the group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
  • the molecular weight of the low molecular compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
  • the compound (D) is preferably an amine derivative having a group on the nitrogen atom that is eliminated by the action of an acid.
  • Compound (D) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protecting group constituting the carbamate group can be represented by the following general formula (d-1).
  • R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
  • R ′ is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
  • the compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).
  • the compound (D) has a structure represented by the following general formula (D).
  • the compound (D) may correspond to the basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.
  • Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • n 2
  • the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.
  • Rb each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxyalkyl group.
  • Rb when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.
  • At least two Rb may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
  • N represents an integer of 0 to 2
  • m represents an integer of 1 to 3
  • n + m 3.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Ra and Rb are functional groups such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, and oxo group.
  • An alkoxy group and a halogen atom may be substituted. The same applies to the alkoxyalkyl group represented by Rb.
  • alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra and / or Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group are substituted with the above functional group, alkoxy group, or halogen atom).
  • a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc.
  • a group derived from these alkanes for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group
  • a group derived from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, a group derived from these cycloalkanes, for example, a methyl group, an ethyl group, an cycloalkyl
  • Examples of the divalent heterocyclic hydrocarbon group (preferably having a carbon number of 1 to 20) or a derivative thereof formed by bonding of Ra to each other include, for example, pyrrolidine, piperidine, morpholine, 1, 4, 5 , 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1, 2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2 , 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-e Derived from heterocyclic compounds such as, indole, indoline
  • a particularly preferred compound (D) in the present invention is specifically shown, but the present invention is not limited thereto.
  • the compound represented by the general formula (D) can be synthesized based on JP-A 2007-298569, JP-A 2009-199021 and the like.
  • the low molecular compound (D) can be used singly or in combination of two or more.
  • the composition of the present invention may or may not contain the low molecular compound (D), but when it is contained, the content of the compound (D) is the total solid of the composition combined with the basic compound described above.
  • the amount is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the minute.
  • the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment.
  • the acid generator / [compound (D) + basic compound] (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.
  • examples of compounds that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in Paragraph 0108 of JP-A No. 2007-298569, and the like. It is done.
  • a photosensitive basic compound may be used as the basic compound.
  • the photosensitive basic compound include JP-T-2003-524799 and J. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) and the like can be used.
  • the molecular weight of the basic compound is usually 100 to 1500, preferably 150 to 1300, and more preferably 200 to 1000.
  • composition according to the present invention contains a basic compound
  • its content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, preferably 0.1 to The content is more preferably 5.0% by mass, and particularly preferably 0.2 to 4.0% by mass.
  • the molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, and still more preferably 0.1-3.
  • the photoacid generator at the molar ratio is based on the total amount of the repeating unit (B) of the resin and the photoacid generator that the resin may further contain.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a surfactant.
  • a surfactant fluorine-based and / or silicon-based surfactants are particularly preferable.
  • fluorine-based and / or silicon-based surfactant examples include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656 and PF6320 manufactured by OMNOVA, and Troisol S manufactured by Troy Chemical Co., Ltd. -366, Fluorard FC430 manufactured by Sumitomo 3M Limited, and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Surfactants other than fluorine and / or silicon may be used.
  • examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.
  • surfactants can be used as appropriate.
  • surfactant that can be used include surfactants described in [0273] and after in US 2008 / 0248425A1.
  • One type of surfactant may be used alone, or two or more types may be used in combination.
  • the amount used is preferably from 0.0001 to 2% by mass, more preferably from 0.001 to 2%, based on the total solid content of the composition. 1% by mass.
  • composition of the present invention has a molecular weight of 3000 or less as described in carboxylic acids, carboxylic acid onium salts, Proceeding of SPIE, 2724, 355 (1996), etc.
  • a blocking compound, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant, and the like can be appropriately contained.
  • carboxylic acid is preferably used for improving the performance.
  • aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.
  • the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass in the total solid content of the composition.
  • the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used in a film thickness of 10 to 250 nm, more preferably in a film thickness of 20 to 200 nm, from the viewpoint of improving resolution. Preferably, it is preferably used at 30 to 100 nm.
  • Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
  • the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0. Is 5.3 mass%.
  • the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.
  • the solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.
  • the above components are dissolved in a predetermined organic solvent, preferably the mixed solvent, filtered, and then applied onto a predetermined support (substrate).
  • a predetermined organic solvent preferably the mixed solvent
  • the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less made of polytetrafluoroethylene, polyethylene, or nylon.
  • filter filtration for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel.
  • the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.
  • the present invention relates to an actinic ray-sensitive or radiation-sensitive film formed using the above-described composition of the present invention. Moreover, the pattern formation method of this invention has the process of exposing and developing the said actinic-light sensitive or radiation sensitive film
  • composition according to the present invention is typically used as follows. That is, the composition according to the present invention is typically applied on a support such as a substrate to form a film.
  • the thickness of this film is preferably 0.02 to 0.1 ⁇ m.
  • spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
  • This composition can be used, for example, on a substrate used in the manufacture of precision integrated circuit elements, imprint molds, etc. (eg, silicon / silicon dioxide coating, silicon nitride and chromium deposited quartz substrates, etc.) It is applied using a coater or the like. Thereafter, this is dried to form an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a resist film).
  • a known antireflection film can be applied in advance.
  • the actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation, and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C.), followed by development. By performing baking, a more favorable pattern can be obtained.
  • actinic rays or radiation examples include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams.
  • actinic rays or radiation for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable.
  • actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-rays, and electron beams.
  • Preferable actinic rays or radiations include, for example, KrF excimer laser, electron beam, X-ray and EUV light. More preferred are electron beam, X-ray and EUV light.
  • the present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition for KrF excimer laser, electron beam, X-ray or EUV light (more preferably for electron beam, X-ray or EUV light).
  • an alkali developer is usually used.
  • the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.
  • examples include alkaline aqueous solutions containing a quaternary ammonium salt or cyclic amines such as pyrrole and pihelidine.
  • An appropriate amount of alcohols and / or surfactant may be added to the alkaline developer.
  • concentration of the alkali developer is usually from 0.1 to 20% by mass.
  • PH of alkaline developer Is usually 10.0 to 15.0.
  • composition of the present invention can also be used in a process of obtaining a negative pattern by coating, forming a film, and exposing, and then developing using a developer containing an organic solvent as a main component.
  • a process described in JP 2010-217884 A can be used.
  • Organic solvents include polar solvents such as ester solvents (eg, butyl acetate, ethyl acetate, etc.), ketone solvents (eg, 2-heptanone, cyclohexanone, etc.), alcohol solvents, amide solvents, ether solvents, etc.
  • polar solvents such as ester solvents (eg, butyl acetate, ethyl acetate, etc.), ketone solvents (eg, 2-heptanone, cyclohexanone, etc.), alcohol solvents, amide solvents, ether solvents, etc.
  • hydrocarbon solvents can be used.
  • the water content of the organic developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
  • the organic developer may have a basic compound, and specific examples include compounds described as basic compounds that can be included in the resin composition of the present invention. “A double development process combining organic solvent development and alkali development may be performed.
  • an imprint mold may be produced using the composition according to the present invention.
  • Japanese Patent No. 4109085 Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology”. See “Development and Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Editing: Yoshihiko Hirai (Frontier Publishing)”.
  • Resin (Aa-22) was synthesized according to the following scheme. 0.43 g of compound (1), 13.32 g of compound (2), 0.94 g of compound (3), and 0.55 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Were dissolved in 66.60 g of cyclohexanone. 16.65 g of cyclohexanone was placed in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.
  • the photoacid generator was appropriately selected from the acid generators z1 to z143 listed above.
  • the compound (N-7) corresponds to the compound (PA) described above, and was synthesized based on the description in [0354] of JP-A-2006-330098.
  • W-1 Megafuck R08 (Dainippon Ink & Chemicals, Inc .; fluorine and silicon)
  • W-2 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
  • W-3 Troisol S-366 (manufactured by Troy Chemical Co., Ltd .; fluorine-based)
  • W-4 PF6320 (manufactured by OMNOVA; fluorine-based) ⁇ Electron Beam (EB) Exposure>
  • Examples 1A to 41A, Comparative Examples 1A to 5A (1) Preparation and application of coating solution of actinic ray-sensitive or radiation-sensitive resin composition
  • a coating solution composition having a solid content concentration of 3% by mass having the composition shown in the table below is precisely filtered with a membrane filter having a pore size of 0.1 ⁇ m. Filtration gave an actin
  • This actinic ray-sensitive or radiation-sensitive resin composition is applied onto a 6-inch Si wafer that has been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and heated at 100 ° C. for 60 seconds. It dried on the plate and obtained the resist film with a film thickness of 100 nm.
  • HMDS hexamethyldisilazane
  • Film verification rate (%) (applied film thickness 100 nm ⁇ pattern height) / applied film thickness 100 nm ⁇ 100 A: Less than 5.0% B: 5.0% or more and less than 10.0% C: 10.0% or more and less than 15.0% D: 15.0% or more and less than 20.0% E: 20.0% or more ⁇ Extreme Ultraviolet (EUV) Exposure> (Examples 1B to 41B, Comparative Examples 1B to 5B) (1) Preparation and application of actinic ray-sensitive or radiation-sensitive resin composition coating liquid composition having a composition shown in the table below and having a solid content concentration of 1.5% by mass, a membrane filter having a pore size of 0.05 ⁇ m Was subjected to microfiltration to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution.
  • EUV Ultraviolet
  • This actinic ray-sensitive or radiation-sensitive resin composition is applied onto a 6-inch Si wafer that has been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and hot at 100 ° C. for 60 seconds. It dried on the plate and obtained the resist film with a film thickness of 50 nm.
  • HMDS hexamethyldisilazane
  • Film verification rate (%) (applied film thickness 50 nm ⁇ pattern height) / applied film thickness 50 nm ⁇ 100 A: Less than 5.0% B: 5.0% or more and less than 10.0% C: 10.0% or more and less than 15.0% D: 15.0% or more and less than 20.0% E: 20.0% or more ⁇ Development defects> (Examples 1C to 41C, Comparative Examples 1C to 5C)
  • the positive resist solution prepared as described above was applied uniformly onto a substrate coated with a 60 nm antireflection film (DUV44 manufactured by Brewer Sciences) using a spin coater Mark8 manufactured by Tokyo Electron, and was applied at 130 ° C. for 60 seconds.

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Abstract

La présente invention se rapporte à une composition de résine sensible aux rayons actifs ou sensible à un rayonnement qui contient : une résine (Aa) qui comprend une unité répétitive représentée par la formule générale (Aa1) ou (Aa2) sous la forme d'une unité répétitive décomposée par l'action d'un acide, la résine (Aa) formant un film de protection et étant répartie de manière irrégulière sur une surface de film au moyen d'une production de film ; et une résine (Ab) différente de la résine (Aa), la solubilité de la résine (Ab) par rapport à une solution de développement étant changée par l'action d'un acide.
PCT/JP2014/054380 2013-02-28 2014-02-24 Composition de résine sensible aux rayons actifs ou sensible à un rayonnement, film sensible aux rayons actifs ou sensible à un rayonnement, procédé de formation de motifs, dispositif électronique et procédé permettant de fabriquer un dispositif électronique WO2014132934A1 (fr)

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US20170299963A1 (en) * 2016-04-14 2017-10-19 Shin-Etsu Chemical Co., Ltd. Monomer, polymer, resist composition, and patterning process

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JP6520490B2 (ja) * 2015-07-08 2019-05-29 信越化学工業株式会社 パターン形成方法
KR20180042313A (ko) * 2015-09-30 2018-04-25 후지필름 가부시키가이샤 수지막, 착색 감광성 조성물, 수지막의 제조 방법, 컬러 필터, 차광막, 고체 촬상 소자, 및 화상 표시 장치
JP6688811B2 (ja) * 2015-12-25 2020-04-28 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜の生産方法、パターン形成方法、及び、電子デバイスの製造方法
JP7058217B2 (ja) * 2016-06-30 2022-04-21 富士フイルム株式会社 パターン形成方法、電子デバイスの製造方法、感活性光線性又は感放射線性樹脂組成物、及び、レジスト膜
KR102323057B1 (ko) * 2016-12-22 2021-11-08 후지필름 가부시키가이샤 감활성광선성 또는 감방사선성 수지 조성물, 감활성광선성 또는 감방사선성막, 패턴 형성 방법, 전자 디바이스의 제조 방법 및 광산발생제

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JP2012137686A (ja) * 2010-12-27 2012-07-19 Fujifilm Corp 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜及びパターン形成方法
JP2013015590A (ja) * 2011-06-30 2013-01-24 Fujifilm Corp 感活性光線性又は感放射線性樹脂組成物、並びに、それを用いた感活性光線性又は感放射線性膜及びパターン形成方法
JP2013083966A (ja) * 2011-09-30 2013-05-09 Fujifilm Corp 感活性光線性又は感放射線性樹脂組成物、並びに、それを用いた感活性光線性又は感放射線性膜及びパターン形成方法

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JP2017043662A (ja) * 2015-08-24 2017-03-02 信越化学工業株式会社 導電性ポリマー複合体及び基板
US20170299963A1 (en) * 2016-04-14 2017-10-19 Shin-Etsu Chemical Co., Ltd. Monomer, polymer, resist composition, and patterning process
US10054853B2 (en) * 2016-04-14 2018-08-21 Shin-Etsu Chemical Co., Ltd. Monomer, polymer, resist composition, and patterning process

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