WO2020129476A1 - Composition de résine sensible à la lumière active ou au rayonnement, film de résine photosensible, procédé de formation de motif et procédé de fabrication d'un dispositif électronique - Google Patents

Composition de résine sensible à la lumière active ou au rayonnement, film de résine photosensible, procédé de formation de motif et procédé de fabrication d'un dispositif électronique Download PDF

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Publication number
WO2020129476A1
WO2020129476A1 PCT/JP2019/044524 JP2019044524W WO2020129476A1 WO 2020129476 A1 WO2020129476 A1 WO 2020129476A1 JP 2019044524 W JP2019044524 W JP 2019044524W WO 2020129476 A1 WO2020129476 A1 WO 2020129476A1
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group
general formula
repeating unit
sensitive
atom
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PCT/JP2019/044524
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English (en)
Japanese (ja)
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大輔 浅川
敬史 川島
研由 後藤
慶 山本
三千紘 白川
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富士フイルム株式会社
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Priority to JP2020561217A priority Critical patent/JP7191981B2/ja
Publication of WO2020129476A1 publication Critical patent/WO2020129476A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C08F12/24—Phenols or alcohols
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • 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
    • C08F28/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F28/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method.
  • Patent Document 1 describes a negative resist composition containing an alkali-soluble resin containing a repeating unit containing a hydroxyl group, a photoacid generator, and a crosslinking agent.
  • the present invention is excellent in sensitivity and EL when forming an ultrafine pattern (for example, a line and space pattern having a line width of 45 nm or a hole pattern having a hole size of 45 nm or less), a small LWR and LER, and a feeling of being excellent in CDU.
  • An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition, a resist film using the above actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and an electronic device manufacturing method.
  • the present invention is as follows.
  • a resin P having a repeating unit represented by the following general formula (P1) is contained in an amount of 30% by mass or more based on the total solid content, and a crosslinking agent is included in an amount of 10% by mass or less based on the total solid content.
  • Ray- or radiation-sensitive resin composition is contained in an amount of 30% by mass or more based on the total solid content, and a crosslinking agent is included in an amount of 10% by mass or less based on the total solid content.
  • R p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • L p represents a single bond or a polyvalent linking group. R p and L p may combine to form a ring structure.
  • X p represents O, S, or NR N1 .
  • R N1 represents a hydrogen atom or a monovalent organic group.
  • Y p represents O, S, or NR N2 .
  • R N2 represents a hydrogen atom or a monovalent organic group.
  • Z p represents a hydrogen atom or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure.
  • R p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • L p represents a single bond or a polyvalent linking group. R p and L p may combine to form a ring structure.
  • Y p represents O, S, or NR N2 .
  • R N2 represents a hydrogen atom or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure.
  • R p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure.
  • the resin P further includes a repeating unit K1 having an acid-decomposable group, and the repeating unit K1 is a repeating unit different from the repeating unit represented by the general formula (P1), ⁇ 1> to ⁇ 3.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to any one of items>.
  • the resin P further includes a repeating unit K2 having a polar group, and the repeating unit K2 is a repeating unit different from the repeating unit represented by the general formula (P1).
  • the actinic ray-sensitive or radiation-sensitive resin composition according to any one of items.
  • the polar group contained in the repeating unit K2 is an ester group, a sulfonate group, a sulfonamide group, a carboxylic acid group, a sulfonic acid group, a carbonate group, a carbamate group, an alcoholic hydroxyl group, a sulfoxide group, a sulfonyl group, a ketone group or an imide group.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to ⁇ 5> which is at least one group selected from the group consisting of an amide group, a sulfonimide group, a cyano group, a nitro group, and an ether group.
  • the polar group contained in the repeating unit K2 is at least one group selected from the group consisting of a lactone group, a sultone group, a sultam group, a carboxylic acid group, an alcoholic hydroxyl group, and a cyclic carbonate group, ⁇ 5> or The actinic ray-sensitive or radiation-sensitive resin composition according to ⁇ 6>.
  • ⁇ 8> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, further containing a photo-acid generator A.
  • ⁇ 9> The actinic ray-sensitive or radiation-sensitive resin composition according to ⁇ 8>, wherein the photoacid generator A is a photoacid generator Aw having a generated acid pKa of ⁇ 1.40 or more.
  • DA basic compound
  • DB basic compound
  • X p represents O, S, or NR N1 .
  • R N1 represents a hydrogen atom or a monovalent organic group.
  • Z p represents a hydrogen atom or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure. * Indicates a binding position with Y p .
  • ⁇ 13> A pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 14> A method for manufacturing an electronic device, including the pattern forming method according to ⁇ 13>.
  • the repeating unit represented by the general formula (P1) is protected by a group (leaving group) in which the polar group represented by Y p (or Y p and L p ) is decomposed and eliminated by the action of an acid. It has a different structure. That is, the repeating unit represented by the general formula (P1) is a repeating unit containing a group that is decomposed by the action of an acid to increase its polarity (hereinafter, also referred to as “acid-decomposable group”).
  • the pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention typically, when an alkali developing solution is adopted as the developing solution, a positive pattern is favorably formed, and When an organic developer is used as the liquid, a negative pattern is preferably formed.
  • the general formula (P1) has a polar group represented by -X p -Z p , it is possible to appropriately suppress the diffusion of the acid generated from the photo-acid generator, and improve the EL performance. The present inventors speculate. Further, the group represented by —X p —Z p interacts with the anionic group in the photo-acid generator typically contained in the resist composition, whereby the resin P and the photo-acid generator are interacted with.
  • the repeating unit represented by the general formula (P1) has a structure in which Y p and X p are bonded via two carbon atoms, and a rearrangement reaction easily occurs, so that the reactivity is high ( It has high sensitivity).
  • the rearrangement reaction, Y p and X p are those specific to structure bonded via two carbon atoms, Y p and X p are bonded via three or four carbon atoms the structure So usually it's hard to happen.
  • the leaving group has a polar group represented by -X p -Z p , the solubility of the unexposed portion of the resist film in an organic solvent developer is appropriately lowered in the formation of a negative pattern. It is considered that in forming the mold pattern, the sensitivity is improved by appropriately improving the solubility of the unexposed portion in the alkali developing solution.
  • an ultrafine pattern for example, line width 45nm line and space pattern or a hole pattern whose hole size is 45 nm or less
  • it is excellent in sensitivity and EL, LWR and LER are small, and it is CDU.
  • An excellent actinic ray-sensitive or radiation-sensitive resin composition, a resist film using the above actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and an electronic device manufacturing method can be provided.
  • the “actinic ray” or “radiation” means, for example, a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV), X-rays, and electron beams (EB: Electron Beam) and the like.
  • the term "light” as used herein means actinic rays or radiation.
  • exposure in the present specification means not only exposure using a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV, etc., but also electron beams and ions. Includes drawing with particle beams such as beams.
  • “to” is used to mean that numerical values described before and after the “to” are included as a lower limit value and an upper limit value.
  • (meth)acrylate represents acrylate and methacrylate.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are GPC (Gel Permeation Chromatography) device (HLC manufactured by Tosoh Corporation).
  • GPC measurement by -8120 GPC (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL/min, detector: differential It is defined as a polystyrene conversion value by a refractive index detector (Refractive Index Detector).
  • pKa acid dissociation constant pKa
  • pKa acid dissociation constant pKa in an aqueous solution
  • the value of pKa can be calculated by using the following software package 1 to calculate a value based on a database of Hammett's substituent constants and known literature values. All pKa values given herein refer to values calculated using this software package.
  • notation that does not indicate substituted or unsubstituted includes a group having a substituent as well as a group having no 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).
  • the "organic group” in this specification means the group containing at least 1 carbon atom.
  • the kind of the substituent, the position of the substituent, and the number of the substituents when “may have a substituent” are not particularly limited.
  • the number of substituents may be, for example, 1, 2, 3, or more.
  • the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, which can be selected from the following substituents T, for example.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group
  • an aryloxy group such as a phenoxy group and a p-tolyloxy group
  • Alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group
  • Acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group
  • an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin having a repeating unit represented by the general formula (P1) in the total solid content.
  • the actinic ray-sensitive or radiation-sensitive resin composition contains 30% by mass or more and contains 10% by mass or less of the crosslinking agent based on the total solid content.
  • the composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.
  • the composition of the present invention is typically a chemically amplified resist composition.
  • the composition of the present invention contains a resin having a repeating unit represented by the following general formula (P1) (hereinafter, also referred to as “resin P”).
  • the repeating unit represented by the following general formula (P1) is a repeating unit containing an acid-decomposable group, and the resin P is an acid-decomposable resin.
  • R p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • L p represents a single bond or a polyvalent linking group. R p and L p may combine to form a ring structure.
  • X p represents O, S, or NR N1 .
  • R N1 represents a hydrogen atom or a monovalent organic group.
  • Y p represents O, S, or NR N2 .
  • R N2 represents a hydrogen atom or a monovalent organic group.
  • Z p represents a hydrogen atom or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure.
  • R p1 and R p2 may not represent a perfluoroalkyl group or a perfluorocycloalkyl group, respectively, and R p3 and R p4 may both represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • the resin P exhibits sufficient acid decomposition reactivity.
  • R p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • the halogen atom represented by R p include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the monovalent organic group represented by R p is not particularly limited, but an alkyl group is preferable.
  • R p represents an alkyl group
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.
  • the alkyl group may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
  • R p is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.
  • L p represents a single bond or a polyvalent linking group.
  • the polyvalent linking group represented by L p is not particularly limited and includes, for example, —C( ⁇ O)—, —O—, —S( ⁇ O) 2 —, an alkylene group (preferably having 1 to 10 carbon atoms).
  • the cycloalkylene group preferably a cycloalkylene group having 3 to 20 carbon atoms
  • a divalent heterocyclic group preferably a cycloalkylene group having 3 to 20 carbon atoms
  • L p is preferably a divalent or trivalent linking group, more preferably a divalent linking group, —C( ⁇ O)—, —O—, —S( ⁇ O) 2 — ,
  • An alkylene group preferably an alkylene group having 1 to 10 carbon atoms
  • R p and L p may combine to form a ring structure.
  • X p represents O, S, or NR N1 .
  • R N1 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group includes an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms). ), an aryl group (preferably an aryl group having 6 to 20 carbon atoms), and the like.
  • R N1 is preferably a hydrogen atom.
  • X p preferably represents O.
  • Y p represents O, S, or NR N2 .
  • R N2 represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group when R N2 represents a monovalent organic group include monovalent organic groups when R N1 represents a monovalent organic group.
  • R N2 is preferably a hydrogen atom.
  • Y p preferably represents O or NH, more preferably O.
  • Z p represents a hydrogen atom or a monovalent organic group.
  • examples of the monovalent organic group include an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 6 carbon atoms). These groups may have a substituent, and examples of the substituent include a halogen atom (preferably a fluorine atom) and the like.
  • Z p is O or S
  • Z p is preferably a hydrogen atom.
  • Z p is preferably an alkylsulfonyl group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the above
  • the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • the alkyl group represented by R p1 and R p2 is not particularly limited, but is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group or an ethyl group.
  • a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
  • the alkyl group represented by R p1 and R p2 may have a substituent.
  • the cycloalkyl group represented by R p1 and R p2 is not particularly limited, and may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group.
  • the monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 20, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the polycyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 6 to 20, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinene group, a tricyclodecanyl group, Examples thereof include a tetracyclododecyl group and an androstanyl group.
  • a cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group is still more preferable.
  • the cycloalkyl group represented by R p1 and R p2 may have a substituent.
  • the alkenyl group represented by R p1 and R p2 is not particularly limited, but an alkenyl group having 2 to 10 carbon atoms is preferable, an alkenyl group having 2 to 6 carbon atoms is more preferable, and examples thereof include a vinyl group, an allyl group and a butenyl group. Etc.
  • the alkenyl group represented by R p1 and R p2 may have a substituent.
  • the cycloalkenyl group represented by R p1 and R p2 is not particularly limited, and may be a monocyclic cycloalkenyl group or a polycyclic cycloalkenyl group.
  • the monocyclic cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms
  • the polycyclic cycloalkenyl group is preferably a cycloalkenyl group having 6 to 20 carbon atoms.
  • As the cycloalkenyl group a cycloalkenyl group having 4 to 10 carbon atoms is more preferable.
  • the cycloalkenyl group represented by R p1 and R p2 may have a substituent.
  • the alkynyl group represented by R p1 and R p2 is not particularly limited, but an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable.
  • the alkynyl group represented by R p1 and R p2 may have a substituent.
  • the cycloalkynyl group represented by R p1 and R p2 is not particularly limited, and may be a monocyclic cycloalkynyl group or a polycyclic cycloalkynyl group.
  • the monocyclic cycloalkynyl group is preferably a cycloalkynyl group having 3 to 20 carbon atoms
  • the polycyclic cycloalkynyl group is preferably a cycloalkynyl group having 6 to 20 carbon atoms.
  • As the cycloalkynyl group a cycloalkynyl group having 4 to 10 carbon atoms is more preferable.
  • the cycloalkynyl group represented by R p1 and R p2 may have a substituent.
  • the aryl group represented by R p1 and R p2 is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and specifically, a phenyl group or a naphthyl group. , And anthryl groups are more preferable, and a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
  • the aryl group represented by R p1 and R p2 may have a substituent.
  • the alkyl group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.
  • R p1 and R p2 may be bonded to each other to form a ring structure.
  • the ring structure formed is preferably a ring structure having 3 to 20 carbon atoms, more preferably a ring structure having 4 to 10 carbon atoms, and further preferably a ring structure having 4 to 8 carbon atoms. preferable.
  • R p1 and R p2 each independently represent a methyl group or an ethyl group, or it is preferable that R p1 and R p2 are bonded to each other to form a ring structure having 4 to 8 carbon atoms. More preferably, it is more preferably a methyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group,
  • the group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • the alkyl group represented by R p3 and R p4 is not particularly limited, but an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group or an ethyl group.
  • a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
  • the alkyl group represented by R p3 and R p4 may have a substituent.
  • the cycloalkyl group represented by R p3 and R p4 is not particularly limited, and may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group.
  • the monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 20, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the polycyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 6 to 20, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinene group, a tricyclodecanyl group, Examples thereof include a tetracyclododecyl group and an androstanyl group.
  • a cycloalkyl group having 4 to 10 carbon atoms is more preferable, and a cyclohexyl group is still more preferable.
  • the cycloalkyl group represented by R p3 and R p4 may have a substituent.
  • the alkenyl group represented by R p3 and R p4 is not particularly limited, but an alkenyl group having 2 to 10 carbon atoms is preferable, an alkenyl group having 2 to 6 carbon atoms is more preferable, and examples thereof include a vinyl group, an allyl group and a butenyl group. Etc.
  • the alkenyl group represented by R p3 and R p4 may have a substituent.
  • the cycloalkenyl group represented by R p3 and R p4 is not particularly limited, and may be a monocyclic cycloalkenyl group or a polycyclic cycloalkenyl group.
  • the monocyclic cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms
  • the polycyclic cycloalkenyl group is preferably a cycloalkenyl group having 6 to 20 carbon atoms.
  • As the cycloalkenyl group a cycloalkenyl group having 4 to 10 carbon atoms is more preferable.
  • the cycloalkenyl group represented by R p3 and R p4 may have a substituent.
  • the alkynyl group represented by R p3 and R p4 is not particularly limited, but an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable.
  • the alkynyl group represented by R p3 and R p4 may have a substituent.
  • the cycloalkynyl group represented by R p3 and R p4 is not particularly limited, and may be a monocyclic cycloalkynyl group or a polycyclic cycloalkynyl group.
  • the monocyclic cycloalkynyl group is preferably a cycloalkynyl group having 3 to 20 carbon atoms
  • the polycyclic cycloalkynyl group is preferably a cycloalkynyl group having 6 to 20 carbon atoms.
  • As the cycloalkynyl group a cycloalkynyl group having 4 to 10 carbon atoms is more preferable.
  • the cycloalkynyl group represented by R p3 and R p4 may have a substituent.
  • the aryl group represented by R p3 and R p4 is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and specifically, a phenyl group or a naphthyl group. , And anthryl groups are more preferable, and a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
  • the aryl group represented by R p3 and R p4 may have a substituent.
  • the alkyl group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.
  • R p3 and R p4 may be bonded to each other to form a ring structure.
  • the ring structure formed is preferably a ring structure having 3 to 20 carbon atoms, more preferably a ring structure having 4 to 10 carbon atoms, and further preferably a ring structure having 4 to 8 carbon atoms. preferable.
  • R p3 and R p4 each independently represent a methyl group or an ethyl group, or it is preferable that R p3 and R p4 are bonded to each other to form a ring structure having 4 to 8 carbon atoms. More preferably, it is more preferably a methyl group.
  • the size of the decomposed product generated when the repeating unit represented by the general formula (P1) is decomposed by the action of an acid the lower the remaining amount of the decomposed product in the resist film and the development variation. You can therefore, it is preferable that the size of the decomposed product is smaller from the viewpoint of LWR, LER and CDU. It is considered that the size of the decomposed product has a correlation with the total atomic weight of the sites (decomposition sites) desorbed by the acid decomposition reaction.
  • the formula weight (total atomic weight) of the site (group) represented by the following general formula (P1-D), which corresponds to the decomposition site in the general formula (P1), is preferably 300 or less, and 250 It is more preferably the following or less, still more preferably 200 or less, further preferably 150 or less, particularly preferably 120 or less, and most preferably 110 or less.
  • X p represents O, S, or NR N1 .
  • R N1 represents a hydrogen atom or a monovalent organic group.
  • Z p represents a hydrogen atom or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure. * Indicates a binding position with Y p .
  • X p , Z p, R p1 ⁇ R p4 is, X p, in the general formula (P1) have the same meanings as Z p, R p1 ⁇ R p4 , preferable examples are also the same is there.
  • the polar group represented by —X p —Z p is preferably a hydroxy group. That is, the repeating unit represented by the general formula (P1) is preferably the repeating unit represented by the following general formula (P2).
  • R p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • L p represents a single bond or a polyvalent linking group. R p and L p may combine to form a ring structure.
  • Y p represents O, S, or NR N2 .
  • R N2 represents a hydrogen atom or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure.
  • R p, L p, Y p, and R p1 ⁇ R p4 is, R p in the general formula (P1) L p, have the same meanings as Y p, and R p1 ⁇ R p4 The same applies to the preferred examples.
  • the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P3) from the viewpoint of having appropriate solubility in a developing solution and easy availability of raw materials. More preferably.
  • R p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • R p1 and R p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group
  • the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
  • R p3 and R p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group,
  • the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a hetero atom between carbon-carbon bonds.
  • R p3 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group
  • R p4 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. Any two of R p1 to R p4 may be bonded to each other to form a ring structure.
  • R p and R p1 ⁇ R p4 has the general formula (P1) in the same meaning as R p and R p1 ⁇ R p4 of, and preferred examples are also the same.
  • the resin P may contain one kind of the repeating unit represented by the general formula (P1), or may contain two or more kinds in combination.
  • the content of the repeating unit represented by the general formula (P1) contained in the resin P (the total content when there are a plurality of repeating units represented by the general formula (P1)) is equal to all the repeating units of the resin P. It is preferably from 5 to 80 mol%, more preferably from 10 to 70 mol%, even more preferably from 15 to 60 mol%, based on the unit.
  • the resin P has, in addition to the repeating unit represented by the general formula (P1), a repeating unit having an acid-decomposable group different from the repeating unit represented by the general formula (P1) (also referred to as “repeating unit K1”). It is preferable to further include).
  • the acid-decomposable group preferably includes a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid (leaving group).
  • polar group carboxy group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group , Bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, tris(alkylsulfonyl)methylene group, etc.
  • Acid groups groups that dissociate in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), alcoholic hydroxyl groups, and the like.
  • the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and is a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), and the ⁇ -position of the hydroxyl group is electron withdrawing such as a fluorine atom.
  • Aliphatic alcohol groups for example, hexafluoroisopropanol group and the like
  • the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20.
  • the polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
  • the preferred group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving by the action of an acid (leaving group).
  • Examples of the group capable of leaving by the action of an acid (leaving group) include, for example, —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), and — Examples thereof include C(R 01 )(R 02 )(OR 39 ).
  • R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
  • R 36 and R 37 may combine with each other to form a ring.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
  • the alkyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and hexyl. Group, octyl group and the like.
  • the cycloalkyl group of R 36 to R 39 , R 01 , and R 02 may be monocyclic or polycyclic.
  • a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • a cycloalkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an ⁇ -pinene group, a tricyclodecanyl group, and a tetracyclododecyl group. , And androstanyl group and the like.
  • one or more carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
  • the aryl group of R 36 to R 39 , R 01 , and R 02 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
  • the aralkyl group of R 36 to R 39 , R 01 , and R 02 is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the alkenyl group of R 36 to R 39 , R 01 , and R 02 is preferably an alkenyl group having a carbon number of 2 to 8, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
  • the ring formed by combining R 36 and R 37 with each other is preferably a cycloalkyl group (monocyclic or polycyclic).
  • the monocyclic cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group or the like, and the polycyclic cycloalkyl group is preferably a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.
  • a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or an acetal ester group is preferable, and an acetal group or a tertiary alkyl ester group is more preferable.
  • the resin P preferably contains a repeating unit represented by the following general formula (AI) as the repeating unit K1.
  • T represents a single bond or a divalent linking group.
  • the divalent linking group of T include an alkylene group, an arylene group, —COO—Rt—, and —O—Rt—.
  • Rt represents an alkylene group, a cycloalkylene group, or an arylene group.
  • T is preferably a single bond or -COO-Rt-.
  • Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably —CH 2 —, —(CH 2 ) 2 —, or —(CH 2 ) 3 —. More preferably, T is a single bond.
  • Xa 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • Xa 1 is preferably a hydrogen atom or an alkyl group.
  • the alkyl group of Xa 1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
  • the alkyl group of Xa 1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group.
  • the alkyl group of Xa 1 is preferably a methyl group.
  • Rx 1 to Rx 3 each independently represent an alkyl group or a cycloalkyl group. Any two of Rx 1 to Rx 3 may be combined to form a ring structure, or may not be formed.
  • the alkyl group of Rx 1 , Rx 2 , and Rx 3 may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group. , Isobutyl group, t-butyl group and the like are preferable.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • a part of carbon-carbon bonds may be a double bond.
  • the cycloalkyl group of Rx 1 , Rx 2 , and Rx 3 may be monocyclic or polycyclic. Examples of the monocyclic cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic cycloalkyl group include a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the ring formed by combining two of Rx 1 , Rx 2 , and Rx 3 may be a monocycle or a polycycle.
  • the monocyclic ring include monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring.
  • polycycles include polycyclic cycloalkyl rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring.
  • a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is preferable.
  • the ring formed by combining two of Rx 1 , Rx 2 , and Rx 3 the ring shown below is also preferable.
  • the resin P has, as the repeating unit K1, the repeating unit described in paragraphs ⁇ 0336> to ⁇ 0369> of the specification of US Patent Application Publication No. 2016/0070167A1.
  • the resin P has a repeating unit K1 containing a group that decomposes by the action of an acid to produce an alcoholic hydroxyl group as described in paragraphs ⁇ 0363> to ⁇ 0364> of US Patent Application Publication No. 2016/0070167A1. It may have a unit.
  • the type of the repeating unit K1 contained in the resin P may be one type or two or more types.
  • the content of the repeating unit K1 contained in the resin P (the total content when a plurality of repeating units K1 is present) is preferably 10 to 90 mol %, and preferably 20 to 80 mol% with respect to all the repeating units of the resin P. Mol% is more preferable, and 30 to 70 mol% is further preferable.
  • the resin P has, in addition to the repeating unit represented by the general formula (P1), a repeating unit having a polar group different from the repeating unit represented by the general formula (P1) (also referred to as “repeating unit K2”). It is preferable to further include).
  • the polar group contained in the repeating unit K2 includes an ester group, a sulfonate group, a sulfonamide group, a carboxylic acid group, a sulfonic acid group, a carbonate group, a carbamate group, an alcoholic hydroxyl group, a sulfoxide group, a sulfonyl group, a ketone group, an imide group, It is preferably at least one group selected from the group consisting of an amide group, a sulfonimide group, a cyano group, a nitro group, and an ether group, and a lactone group, a sultone group, a sultam group, a carboxylic acid group, an alcoholic hydroxyl group, And at least one group selected from the group consisting of cyclic carbonate groups, more preferably a lactone group or a sultone group, and particularly preferably a lactone group. That is, the repeating unit K2
  • the lactone structure or sultone structure may have a lactone ring or a sultone ring, and is preferably a lactone structure having a 5- to 7-membered lactone ring or a sultone structure having a 5- to 7-membered sultone ring.
  • a lactone structure in which another ring is condensed to the 5- to 7-membered lactone ring in the form of forming a bicyclo structure or a spiro structure is also preferable.
  • a sultone structure in which another ring is condensed to a 5- to 7-membered sultone ring so as to form a bicyclo structure or a spiro structure is also preferable.
  • the resin P has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-22) or one of the following general formulas (SL1-1) to (SL1-3). It is preferable to include a repeating unit having a sultone structure represented. Further, the lactone structure or the sultone structure may be directly bonded to the main chain.
  • a lactone structure represented by the general formula (LC1-22) or a sultone structure represented by the general formula (SL1-1) is preferable.
  • the lactone structure or sultone structure may or may not have a substituent (Rb 2 ).
  • a substituent (Rb 2 ) an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxy group, A halogen atom, a hydroxyl group, a cyano group or the like is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferable.
  • n 2 represents an integer of 0 to 4. When n 2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different. Further, a plurality of substituents (Rb 2 ) may be bonded to each other to form a ring.
  • the repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (LS1).
  • a LS represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
  • t is the repeating number of the structure represented by —R LS2 —R LS3 — and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0.
  • (-R LS2 -R LS3 -)t is a single bond.
  • R LS2 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R LS2 , the plurality of R LS2 may be the same or different.
  • the alkylene group or cycloalkylene group of R LS2 may have a substituent.
  • R LS3 represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When there are a plurality of R LS3 , the plurality of R LS3 may be the same or different. Of these, R LS3 is preferably an ether bond or an ester bond, and more preferably an ester bond.
  • R LS4 represents a monovalent organic group having a lactone structure or a sultone structure.
  • a lactone structure it is preferably a group obtained by removing one hydrogen atom from one carbon atom constituting the sultone structure.
  • the carbon atom from which one hydrogen atom is removed is preferably not the carbon atom constituting the substituent (Rb 2 ).
  • R LS1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • Examples of the monomer corresponding to the repeating unit having at least one selected from the group consisting of a lactone structure and a sultone structure are shown below.
  • the methyl group bonded to the vinyl group may be replaced with a hydrogen atom, a halogen atom, or a monovalent organic group.
  • the resin P may have a repeating unit having a carbonate structure.
  • a carbonate structure a cyclic carbonic acid ester (cyclic carbonate) structure is preferable.
  • the repeating unit having a cyclic carbonic acid ester structure is preferably a repeating unit represented by the following general formula (A-1).
  • R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • n represents an integer of 0 or more.
  • R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
  • A represents a single bond or a divalent linking group.
  • Z represents an atomic group forming a monocycle or polycycle with the group represented by —O—CO—O— in the formula.
  • the resin P may have a repeating unit having a polar group such as a hydroxyl group, a cyano group, a carboxy group, and a fluorinated alcohol group (for example, a hexafluoroisopropanol group).
  • the repeating unit having the polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with the polar group.
  • the alicyclic hydrocarbon structure substituted with a polar group is preferably a cyclohexyl group, an adamantyl group, or a norbornane group.
  • the resin P has, as the repeating unit K2, the repeating units described in paragraphs ⁇ 0370> to ⁇ 0433> of the specification of US Patent Application Publication No. 2016/0070167A1.
  • the type of the repeating unit K2 contained in the resin P may be one type or two or more types.
  • the content of the repeating unit K2 contained in the resin P (the total content when there are a plurality of repeating units K2) is 5 to 70 mol% is preferable, 10 to 65 mol% is more preferable, and 20 to 60 mol% is further preferable.
  • the resin P may further include a repeating unit having neither an acid-decomposable group nor a polar group (also referred to as “repeating unit K3”).
  • the repeating unit K3 preferably has an alicyclic hydrocarbon structure. Examples of the repeating unit K3 include the repeating units described in paragraphs [0236] to ⁇ 0237> of US Patent Application Publication No. 2016/0026083A1. Hereinafter, preferable examples of the monomer corresponding to the repeating unit K3 are shown below.
  • repeating unit K3 examples include the repeating unit disclosed in paragraph ⁇ 0433> of U.S. Patent Application Publication No. 2016/0070167A1.
  • the type of the repeating unit K3 contained in the resin P may be one type or two or more types.
  • the content of the repeating unit K3 (the total content when there are a plurality of repeating units K3) is 5 to 40 mol% based on all the repeating units in the resin P. Is preferred, 5 to 30 mol% is more preferred, and 5 to 25 mol% is even more preferred.
  • the resin P may be used as another repeating unit in addition to the above repeating structural unit, dry etching resistance, standard developing solution suitability, substrate adhesion, resist profile, or resolving power which is a general necessary property of resist, It may have various repeating units for the purpose of adjusting heat resistance, sensitivity and the like. Examples of such repeating units include, but are not limited to, repeating units corresponding to a predetermined monomer.
  • the predetermined monomer has, for example, one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. A compound etc. are mentioned.
  • addition-polymerizable unsaturated compounds copolymerizable with the monomers corresponding to the above various repeating structural units may be used.
  • the content molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.
  • the repeating unit having an aromatic group is 15 mol% or less with respect to all the repeating units in the resin P from the viewpoint of the transparency of ArF light. It is more preferably 10 mol% or less.
  • the resin P has all the repeating units (meta). It is preferably composed of an acrylate-based repeating unit. In this case, all of the repeating units are methacrylate repeating units, all the repeating units are acrylate repeating units, and all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol% or less based on all repeating units of the resin P.
  • the resin P preferably has a repeating unit having an aromatic hydrocarbon ring group, and the phenolic hydroxyl group is decomposed by the action of an acid. It is more preferable to include a repeating unit having a structure (acid-decomposable group) protected by a leaving group that is eliminated by Examples of the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit and a hydroxystyrene (meth)acrylate repeating unit.
  • the content of the repeating unit having an aromatic hydrocarbon ring group contained in the resin P is in all repeating units in the resin P.
  • 30 mol% or more is preferable.
  • the upper limit is not particularly limited, but is 100 mol% or less, for example. Among them, 30 to 100 mol% is preferable, 40 to 100 mol% is more preferable, and 50 to 100 mol% is further preferable.
  • the weight average molecular weight (Mw) of the resin P is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 20,000.
  • the dispersity (Mw/Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further 1.1 to 2.0. preferable.
  • the resin P may be used alone or in combination of two or more.
  • the content of the resin P is 30% by mass or more based on the total solid content.
  • the content of the resin P is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, based on the total solid content.
  • the upper limit of the content of the resin P in the composition of the present invention is not particularly limited, but is preferably 98% by mass or less, more preferably 95% by mass or less, and further preferably 92% by mass or less.
  • the solid content is intended to mean a component excluding the solvent in the composition, and a liquid component is regarded as a solid component as long as it is a component other than the solvent.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a crosslinking agent in an amount of 10% by mass or less based on the total solid content of the composition.
  • the content of the crosslinking agent is preferably 5% by mass or less, more preferably 1% by mass or less.
  • the composition of the present invention typically preferably contains a photoacid generator (also referred to as “photoacid generator A”).
  • the photo-acid generator A is a compound that generates an acid upon irradiation with actinic rays or radiation.
  • the photoacid generator A is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation. Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.
  • photo-acid generator A known compounds that generate an acid upon irradiation with actinic rays or radiation can be used alone or as a mixture thereof, appropriately selected and used.
  • photo-acid generator A a photo-acid generator that is commonly used for causing a deprotection reaction of an acid-decomposable resin can be used.
  • paragraph ⁇ 0125 of US Patent Application Publication No. 2016/0070167A1 can be used.
  • paragraph ⁇ ⁇ 0319> the public disclosure disclosed in paragraphs [0086] to ⁇ 0094> of US Patent Application Publication No. 2015/0004544A1 and paragraphs ⁇ 0323> to ⁇ 0402> of US Patent Application Publication 2016/0237190A1.
  • Compounds of are preferably used.
  • photoacid generator A for example, compounds represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) are preferable.
  • R 201 , R 202 and R 203 each independently represent an organic group.
  • the carbon number of the organic group as R 201 , R 202 and R 203 is generally 1 to 30, preferably 1 to 20.
  • Two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester 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) and —CH 2 —CH 2 —O—CH 2 —CH 2 —.
  • Z ⁇ represents an anion (preferably a non-nucleophilic anion).
  • the photoacid generator A may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R 201 to R 203 of the compound represented by general formula (ZI) and at least one of R 201 to R 203 of the other compound represented by general formula (ZI) are single bonds. Alternatively, it may be a compound having a structure bonded via a linking group.
  • the compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
  • the arylsulfonium compound all of 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.
  • R 201 to R 203 is an aryl group, and the remaining two of R 201 to R 203 may be bonded to each other to form a ring structure, and an oxygen atom, a sulfur atom, It may contain an ester group, an amide group, or a carbonyl group.
  • the group formed by combining two members out of R 201 to R 203 is, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and/or a carbonyl group.
  • an alkylene group eg, butylene group, pentylene group, or —CH 2 —CH 2 —O—CH 2 —CH 2 —) group.
  • arylsulfonium compound examples include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an aryldicycloalkylsulfonium compound.
  • the aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
  • the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group which the arylsulfonium compound optionally has is a straight chain alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. Is preferred, and examples thereof 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, and cycloalkyl group of R 201 to R 203 are each independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, carbon atoms). It may have a C 6-14), an alkoxy group (for example, a C 1-15), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.
  • the compound (ZI-2) is a compound in which R 201 to R 203 in formula (ZI) each independently represents an organic group having no aromatic ring.
  • the aromatic ring also includes an aromatic ring containing a hetero atom.
  • the organic group having no 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 or 2-oxocyclo group.
  • the alkyl group and cycloalkyl group of R 201 to R 203 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, A propyl group, a butyl group, and a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
  • M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure has an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon atom.
  • -It may contain at least one carbon double bond.
  • R 6c and R 7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
  • R 6c and R 7c may combine to form a ring.
  • R x and R y each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group.
  • R x and R y may combine to form a ring. Further, at least two selected from M, R 6c and R 7c may combine to form a ring structure, and the above ring structure may contain a carbon-carbon double bond. Z ⁇ represents an anion.
  • the alkyl group and cycloalkyl group represented by M include a straight-chain alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and 3 to 15 carbon atoms (A branched chain alkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms) is preferable, and specifically, methyl group, ethyl group, propyl group. , N-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, norbornyl group and the like.
  • the aryl group represented by M is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.
  • M may further have a substituent (for example, the substituent T).
  • M may be a benzyl group.
  • the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.
  • Examples of the alkyl group, cycloalkyl group, and aryl group represented by R 6c and R 7c include the same as those described above for M, and the preferred embodiments are also the same. R 6c and R 7c may combine with each other to form a ring. Examples of the halogen atom represented by R 6c and R 7c include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group and cycloalkyl group represented by R x and R y are the same as those of M described above, and the preferable aspects thereof are also the same.
  • the alkenyl group represented by R x and R y is preferably an allyl group or a vinyl group.
  • the above R x and R y may further have a substituent (for example, the substituent T). Examples of this aspect include a 2-oxoalkyl group or an alkoxycarbonylalkyl group as R x and R y .
  • Examples of the 2-oxoalkyl group represented by R x and R y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically, 2-oxopropyl group, And a 2-oxobutyl group.
  • Examples of the alkoxycarbonylalkyl group represented by R x and R y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms).
  • R x and R y may combine to form a ring.
  • the ring structure formed by connecting R x and R y to each other may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.
  • M and R 6c may combine to form a ring structure, and the ring structure formed may contain a carbon-carbon double bond.
  • the compound (ZI-3) is preferably the compound (ZI-3A).
  • the compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and having a phenacylsulfonium salt structure.
  • R 1c to R 5c are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group.
  • the R 6c and R 7c has the same meaning as R 6c and R 7c in the above-mentioned general formula (ZI-3), preferred embodiments thereof are also the same.
  • the R x and R y the same meaning as R x and R y in general formula described above (ZI-3), preferred embodiments thereof are also the same.
  • R 1c to R 5c , R x and R y may be bonded to each other to form a ring structure, and these ring structures are each independently an oxygen atom, a sulfur atom, an ester bond, It may contain an amide bond or a carbon-carbon double bond.
  • R 5c and R 6c , R 5c and R x may be bonded to each other to form a ring structure, and the ring structure may independently include a carbon-carbon double bond.
  • R 6c and R 7c may be bonded to each other to form a ring structure.
  • the ring structure examples include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring formed by combining two or more of these rings.
  • the ring structure includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
  • Examples of the group formed by combining any two or more members out of R 1c to R 5c , R 6c and R 7c , and R x and R y include a butylene group and a pentylene group.
  • the group formed by combining R 5c and R 6c or R 5c and R x is preferably a single bond or an alkylene group.
  • Examples of the alkylene group include a methylene group and an ethylene group.
  • Zc - represents an anion.
  • the compound (ZI-4) is represented by the following general formula (ZI-4).
  • l represents an integer of 0 to 2. It is particularly preferred that l is 0.
  • r represents an integer of 0 to 8.
  • R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.
  • R 14's each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl. It represents an alkoxy group having a skeleton. These groups may have a substituent.
  • R 15's each independently represent an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R 15's may combine with each other to form a ring.
  • the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom.
  • the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom.
  • it is preferable that two R 15's are alkylene groups and they are bonded to each other to form a ring structure.
  • Z ⁇ represents an anion.
  • the alkyl group for R 13 , R 14 and R 15 is linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms.
  • a methyl group, an ethyl group, an n-butyl group, a t-butyl group or the like is more preferable.
  • Two R 15's may combine with each other to form a ring, and when forming a ring, the number of ring members is preferably 5 to 6. When two R 15 s are bonded to each other to form a ring, the ring may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a hydroxyl group, a halogen atom, an alkyl group, and an alkoxy group.
  • the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group and the like.
  • the alkyl group may have a substituent, and the substituent is not particularly limited, and examples thereof include a halogen atom.
  • the alkoxy group may be linear or branched.
  • the alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group and a tert-butoxy group.
  • the above-mentioned alkoxy group may have a substituent, and the substituent is not particularly limited. And a cycloalkyl group).
  • R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like.
  • Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group of R 204 to R 207 include a straight chain alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, A butyl group and a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group and a norbornyl group).
  • the aryl group, alkyl group and cycloalkyl group of R 204 to R 207 may each independently have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 3 carbon atoms). 15), aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
  • Z ⁇ represents an anion.
  • Z in the general formula (ZI) -, Z in the general formula (ZII) -, Z in the general formula (ZI-3) -, Zc in formula (ZI-3A) -, and Z in the general formula (ZI-4) - the preferred embodiment is an anion represented by the following general formula (3).
  • o represents an integer of 1 to 3.
  • p represents an integer of 0 to 10.
  • q represents an integer of 0 to 10.
  • Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf's are fluorine atoms.
  • R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R 4 and R 5 are present, R 4 and R 5 may be the same or different.
  • the alkyl group represented by R 4 and R 5 may have a substituent and preferably has 1 to 4 carbon atoms.
  • R 4 and R 5 are preferably hydrogen atoms. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the general formula (3).
  • L represents a divalent linking group.
  • the Ls may be the same or different.
  • -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO 2 -, -COO-alkylene group-, -OCO-alkylene group-, -CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.
  • W represents an organic group containing a cyclic structure.
  • cyclic organic groups are preferable.
  • the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
  • the alicyclic group may be monocyclic or polycyclic.
  • the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
  • polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
  • alicyclic groups having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferable.
  • the aryl group may be monocyclic or polycyclic. Examples of this aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
  • the heterocyclic group may be monocyclic or polycyclic. Polycyclic compounds can suppress the diffusion of acid more. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • heterocycle having no aromaticity examples include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring.
  • lactone ring and the sultone ring examples include the lactone structure and the sultone structure exemplified in the above resin.
  • a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable as the heterocycle in the heterocyclic group.
  • the above cyclic organic group may have a substituent.
  • this substituent include an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms), a cycloalkyl group (monocyclic, polycyclic, or spirocyclic). It may be any, and preferably has 3 to 20 carbon atoms), an aryl group (preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, and a sulfonamide. And a sulfonate group.
  • the carbon constituting the cyclic organic group may be carbonyl carbon.
  • X B1 and X B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom.
  • X B1 and X B2 are preferably hydrogen atoms.
  • X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group.
  • At least one of X B3 and X B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both X B3 and X B4 are a fluorine atom or a monovalent organic group having a fluorine atom. Is more preferable.
  • both X B3 and X B4 are an alkyl group substituted with a fluorine atom.
  • L, q and W are the same as in the general formula (3).
  • an aromatic sulfonate anion represented by the following general formula (SA1) is also preferable.
  • Ar represents an aryl group, and may further have a substituent other than the sulfonate anion and the -(DB) group. Further, examples of the substituent which may be included include a fluorine atom and a hydroxyl group.
  • N represents an integer of 0 or more.
  • n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.
  • D represents a single bond or a divalent linking group.
  • the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group composed of a combination of two or more thereof.
  • B represents a hydrocarbon group
  • D is a single bond and B is an aliphatic hydrocarbon structure.
  • B is more preferably an isopropyl group or a cyclohexyl group.
  • Z ⁇ in general formula (ZI), anion Z ⁇ in general formula (ZII), Z ⁇ in general formula (ZI-3), Zc ⁇ in general formula (ZI-3A), and general formula (ZI-4).
  • Preferred examples of Z ⁇ are shown below, but the present invention is not limited thereto.
  • the above-mentioned cation and anion can be arbitrarily combined and used as the photo-acid generator A.
  • the strength of the acid generated by the photo-acid generator A is not particularly limited, but a pKa of ⁇ 1.40 or more is particularly preferable from the viewpoint of improving EL performance and the like. That is, in the composition of the present invention, it is preferable to use, as the photo-acid generator A, a photo-acid generator having a generated acid pKa of ⁇ 1.40 or more (also referred to as “photo-acid generator Aw”). ..
  • the upper limit value of pKa of the acid generated from the photo-acid generator Aw is not particularly limited and is, for example, 5.00 or less.
  • the pKa of the acid generated from the photo-acid generator Aw -1.38 or more is preferable in that LWR, LER and CDU of the formed pattern are more excellent and/or the film surface uniformity of the film is more excellent.
  • the upper limit value thereof is preferably 2.00 or less, more preferably 1.30 or less, from the viewpoint that the LWR, LER, and CDU of the formed pattern are more excellent.
  • the acid generated from the photo-acid generator Aw is not particularly limited as long as it satisfies the above pKa, but it is preferably sulfonic acid.
  • Z in formula (ZI) of the above - Z in the general formula (ZII) -, Z in the general formula (ZI-3) -, Zc in formula (ZI-3A) -, And Z ⁇ in the general formula (ZI-4) is preferably represented by the following general formula (1-1) or (1-2). That, Z in the above general formula (ZI) -, Z in the general formula (ZII) -, Z in the general formula (ZI-3) -, Zc in formula (ZI-3A) -, and the general formula (ZI- A particularly preferred embodiment of Z ⁇ in 4) is an anion represented by the following general formula (1-1) or (1-2).
  • R 11 represents a hydrogen atom or a monovalent organic group
  • R 12 represents a monovalent organic group
  • Rf 11 represents a hydrogen atom, a fluorine atom, or a monovalent organic group.
  • R 21 , R 22 , and R 23 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group
  • R 24 represents a monovalent organic group.
  • Rf 21 represents a fluorine atom or a monovalent organic group containing a fluorine atom.
  • R 11 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group represented by R 11 is not particularly limited, and is preferably a monovalent organic group having 1 to 20 carbon atoms, and examples thereof include an alkyl group and a cycloalkyl group. May be linear or branched.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms, and further preferably has 1 to 6 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 6 to 20 carbon atoms.
  • the alkyl group or cycloalkyl group may further have a substituent.
  • the monovalent organic group represented by R 11 preferably does not have a fluorine atom. Among them, R 11 is preferably a hydrogen atom.
  • R 12 represents a monovalent organic group.
  • the monovalent organic group represented by R 12 is not particularly limited and is preferably a monovalent organic group having 1 to 20 carbon atoms.
  • a group represented by *-L 11 -W 11 is Can be mentioned.
  • L 11 represents a divalent linking group
  • W 11 represents an organic group having a cyclic structure
  • * represents a bonding position.
  • the divalent linking group represented by L 11 is, for example, —COO—(—C( ⁇ O)—O—). , -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO 2 -, a linear or branched alkylene group (preferably having 1 carbon atom) To 6), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group obtained by combining a plurality of these.
  • the above AL represents a linear or branched alkylene group (preferably having 1 to 6 carbon atoms).
  • W 11 represents an organic group containing a cyclic structure.
  • a cyclic organic group is preferable.
  • the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
  • the alicyclic group may be monocyclic or polycyclic.
  • the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
  • polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
  • 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, and an adamantyl group is preferable.
  • the aryl group may be monocyclic or polycyclic. Examples of this aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
  • the heterocyclic group may be monocyclic or polycyclic. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • heterocycle having no aromaticity examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
  • lactone ring and the sultone ring examples include the lactone structure and the sultone structure exemplified in the above resin.
  • a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable as the heterocycle in the heterocyclic group.
  • the above cyclic organic group may have a substituent.
  • substituents include an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms), a cycloalkyl group (monocyclic, polycyclic, or spirocyclic). It may be any, and preferably has 3 to 20 carbon atoms), an aryl group (preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, Examples thereof include a sulfonamide group and a sulfonic acid ester group.
  • the carbon constituting the cyclic organic group may be carbonyl carbon.
  • Rf 11 represents a hydrogen atom, a fluorine atom, or a monovalent organic group.
  • the monovalent organic group represented by Rf 11 is not particularly limited, but a monovalent organic group containing a fluorine atom is preferable, and examples thereof include an alkyl group substituted with at least one fluorine atom (straight chain or branched chain). Form) or a cycloalkyl group.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms.
  • the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
  • the cycloalkyl group substituted with at least one fluorine atom is preferably a perfluorocycloalkyl group.
  • Rf 11 is preferably a fluorine atom or a monovalent organic group containing a fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and further preferably a fluorine atom or CF 3 .
  • R 21 , R 22 , and R 23 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group.
  • the monovalent organic group represented by R 21 , R 22 and R 23 is not particularly limited, and examples thereof include the groups exemplified as the above-mentioned substituent T, and among them, a fluorine atom, an alkyl group (direct It may be chain-like or branched-chain, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 1 to 6 carbon atoms, or a cycloalkyl group (having 3 to 20 carbon atoms). (Preferably 6 to 15 are more preferable).
  • the alkyl group or cycloalkyl group represented by R 21 , R 22 and R 23 may further have a substituent, for example, may be substituted with a fluorine atom.
  • R 21 , R 22 and R 23 are preferably hydrogen atom or fluorine atom.
  • At least one of R 21 and R 22 preferably represents a group other than a fluorine atom, and more preferably both are hydrogen atoms.
  • R 24 represents a monovalent organic group.
  • the monovalent organic group represented by R 24 is preferably a monovalent organic group having 1 to 20 carbon atoms, and examples thereof include a monovalent organic group having 1 to 20 carbon atoms and having no fluorine atom. Specific examples thereof include the same monovalent organic groups represented by R 12 in the general formula (1-1).
  • Rf 21 represents a fluorine atom or a monovalent organic group containing a fluorine atom.
  • Examples of the monovalent organic group containing a fluorine atom represented by Rf 21 include those exemplified as the monovalent organic group containing a fluorine atom represented by Rf 11 in the general formula (1-1).
  • photo-acid generator Aw The following are specific examples of the photo-acid generator Aw, but the photo-acid generator Aw is not limited thereto.
  • the photo-acid generator A may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Moreover, you may use together the form of a low molecular compound and the form incorporated in a part of polymer.
  • the photo-acid generator A is preferably in the form of a low molecular weight compound.
  • the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
  • the photo-acid generator A is incorporated in a part of the polymer, it may be incorporated in a part of the resin P described above or a resin different from the resin P.
  • the photo-acid generator A may be used alone or in combination of two or more.
  • the content of the photo-acid generator A (the total content of plural kinds when present) is 0.1 to 35% by mass based on the total solid content of the composition of the present invention. Is preferred, 0.5 to 25 mass% is more preferred, and 1 to 20 mass% is even more preferred.
  • the composition of the present invention preferably contains an acid diffusion controller.
  • the acid diffusion control agent acts as a quencher that traps the acid generated from the photo-acid generator A or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to excess generated acid.
  • a basic compound (DA) a basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation.
  • compound (DB) a compound (DC) that generates an acid that becomes a weak acid relative to the photoacid generator A
  • DC compound
  • a compound (DD) having a group capable of leaving by the action of an acid also referred to as “compound (DD)”
  • an onium salt compound (DE) having a nitrogen atom in the cation portion also referred to as “compound (DE)”
  • Etc an acid diffusion control agent
  • a known acid diffusion control agent can be appropriately used.
  • Base compound (DA) As the basic compound (DA), compounds having a structure represented by the following formulas (A) to (E) are preferable.
  • R 200 , R 201 and R 202 may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or aryl. Represents a group (having 6 to 20 carbon atoms).
  • R 201 and R 202 may be bonded to each other to form a ring.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
  • the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
  • the alkyl group in general formulas (A) and (E) is more preferably unsubstituted.
  • guanidine As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine or the like is preferable, and an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, or an aniline derivative having a hydroxyl group and/or an ether bond is more preferable.
  • the value obtained by subtracting the pKa of the acid generated from the acid generator A (preferably the photoacid generator Aw) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13. 00 is more preferable.
  • the pKa of the conjugate acid of the basic compound (DA) varies depending on the kind of the photo-acid generator A (preferably the photo-acid generator Aw) used, but is preferably 0.00 to 14.00, 3.00 to 13.00 are more preferable, and 3.50 to 12.50 are still more preferable.
  • the basic compound (DB) (Basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation)
  • the basic compound (DB) has a proton acceptor functional group, and is decomposed by irradiation with actinic rays or radiation to reduce or disappear the proton acceptor property, or change from the proton acceptor property to acidic. It is a compound.
  • the proton acceptor functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as cyclic polyether, or ⁇ -conjugated Means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to.
  • 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 formula.
  • Examples of preferable partial structure of the proton acceptor functional group include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
  • the compound (DB) decomposes upon irradiation with actinic rays or radiation to reduce or disappear the proton acceptor property, or generate a compound in which the proton acceptor property is changed to acidic.
  • the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to acidic is a change in the proton acceptor property due to the addition of a proton to the proton acceptor functional group, and Means that when a proton adduct is produced from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.
  • the proton acceptor property can be confirmed by measuring pH.
  • the pKa of the compound generated by decomposition of the compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa ⁇ -1, more preferably -13 ⁇ pKa ⁇ -1, and -13 ⁇ pKa. It is more preferable to satisfy ⁇ -3.
  • the compound (DB) is preferably a compound represented by the general formula (bd-1).
  • General formula (bd-1) R b1 -B b1 -X b1 -A b1 -W 1 -N - -W 2 -Rf b1 [C b1 +]
  • W 1 and W 2 each independently represent —SO 2 — or —CO—.
  • Rf b1 represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.
  • a b1 represents a single bond or a divalent linking group.
  • X b1 represents a single bond, —SO 2 —, or —CO—.
  • B b1 represents a single bond, an oxygen atom, or —N(R b1x )R b1y —.
  • R b1x represents a hydrogen atom or an organic group.
  • R b1y represents a single bond or a divalent organic group.
  • R b1 represents a monovalent organic group having a proton acceptor functional group.
  • R b1x may be bonded to R b1y to form a ring, or may be bonded to R b1 to form a ring.
  • [C b1 + ] represents a counter cation.
  • At least one of -SO 2 - is preferably, both -SO 2 - is more preferable.
  • Rf b1 is preferably an alkyl group having 1 to 6 carbon atoms and optionally having a fluorine atom, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and a perfluoroalkyl group having 1 to 3 carbon atoms. More preferably, it is a fluoroalkyl group.
  • the divalent linking group for A b1 is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. Among them, an alkylene group having at least one fluorine atom is preferable, the number of carbon atoms is preferably 2 to 6, and more preferably 2 to 4.
  • the alkylene chain may have a connecting group such as an oxygen atom or a sulfur atom.
  • the alkylene group is preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom, and more preferably the carbon atom bonded to X b1 or W 1 has a fluorine atom.
  • the divalent linking group for A b1 is preferably a perfluoroalkylene group, more preferably a perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group.
  • the monovalent organic group for R b1x preferably has 2 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group which may have an oxygen atom in the ring, an aryl group, an aralkyl group, an alkenyl group and the like. Are listed.
  • the alkyl group for R b1x may have a substituent and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, and/or a nitrogen atom is contained in the alkyl chain. May have.
  • alkyl group having a substituent a group in which a cycloalkyl group is substituted on a linear or branched alkyl group (for example, adamantylmethyl group, adamantylethyl group, cyclohexylethyl group, camphor residue, etc.) Can be mentioned.
  • the cycloalkyl group for R b1x may have a substituent and is preferably a cycloalkyl group having 3 to 20 carbon atoms. Moreover, you may have an oxygen atom in the ring of a cycloalkyl group.
  • the aryl group for R b1x may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
  • the aralkyl group for R b1x may have a substituent and is preferably an aralkyl group having 7 to 20 carbon atoms.
  • the alkenyl group for R b1x may have a substituent, and examples thereof include a group having a double bond at any position of the alkyl group mentioned for R b1x .
  • the divalent organic group for R b1y is preferably an alkylene group.
  • the ring which R b1x and R b1y may be bonded to each other to form for example, a 5- to 8-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring may be mentioned.
  • the nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X b1 in —N(R b1x )R b1y —.
  • R b1 and R b1x are bonded to each other to form a ring.
  • the number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and the ring may contain an oxygen atom, a sulfur atom, and/or a nitrogen atom.
  • the nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X b1 in —N(R b1x )R b1y —.
  • Examples of the monocycle include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring and an 8-membered ring containing a nitrogen atom.
  • Examples of such a ring structure include a piperazine ring and a piperidine ring.
  • the polycycle includes a structure composed of a combination of 2 or 3 or more monocyclic structures.
  • Each of the monocycle and polycycle may have a substituent, and examples thereof include a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group.
  • alkoxy group preferably having 1 to 10 carbon atoms
  • acyl group preferably having 2 to 15 carbon atoms
  • acyloxy group preferably having 2 to 15 carbon atoms
  • alkoxycarbonyl group Preferred is a C2-15) or aminoacyl group (preferably a C2-20).
  • substituents may have a substituent, if possible. Examples of the case where the aryl group and the cycloalkyl group further have a substituent include an alkyl group (preferably having a carbon number of 1 to 15). Examples of the substituent which the aminoacyl group further has include an alkyl group (preferably having a carbon number of 1 to 15).
  • the proton-accepting functional group for R b1 is as described above, and examples of the partial structure include a structure of a crown ether, a primary to tertiary amine, and a nitrogen-containing heterocycle (pyridine, imidazole, pyrazine, etc.). It is preferable to have.
  • a functional group having a nitrogen atom is preferable, and a group having a primary to tertiary amino group or a nitrogen-containing heterocyclic group is more preferable.
  • all of the atoms adjacent to the nitrogen atom contained in the structure are preferably carbon atoms or hydrogen atoms.
  • an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom, etc.) is not directly bonded to the nitrogen atom.
  • the monovalent organic group in the monovalent organic group (group R b1 ) containing a proton acceptor functional group preferably has 2 to 30 carbon atoms, and is an alkyl group, a cycloalkyl group, an aryl group, Examples thereof include an aralkyl group and an alkenyl group, and each group may have a substituent.
  • the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group containing a proton acceptor functional group in R b1 are each an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, Examples thereof include the same groups as the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group mentioned as R b1x .
  • substituents which each of the above groups may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a cycloalkyl group (preferably having a carbon number of 3 to 10. A part is a hetero atom or a hetero atom).
  • a group having a such as an ester group
  • an aryl group preferably having a carbon number of 6 to 14
  • an alkoxy group preferably having a carbon number of 1 to 10
  • an acyl group preferably having a carbon number of 2 to 20
  • an acyloxy group preferably having 2 to 10 carbon atoms
  • an alkoxycarbonyl group preferably having 2 to 20 carbon atoms
  • an aminoacyl group preferably having 2 to 20 carbon atoms
  • substituent that the cyclic group in the aryl group and the cycloalkyl group have include an alkyl group (preferably having 1 to 20 carbon atoms).
  • the substituent of the aminoacyl group include 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).
  • the counter cation of [C b1 + ] is preferably a sulfonium cation or an iodonium cation.
  • the sulfonium cation and the iodonium cation include, for example, a sulfonium cation and an iodonium cation in the cation that the photoacid generator A may have (more specifically, a cation in the compound represented by the general formula (ZI), and The cation in the compound represented by the formula (ZII) and the like can be similarly used.
  • Difference between pKa of conjugate acid of basic compound (DB) and pKa of acid generated from photo-acid generator A (preferably photo-acid generator Aw) (photo from pKa of conjugate acid of basic compound (DB))
  • the value obtained by subtracting the pKa of the acid generated from the acid generator A is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13. 00 is more preferable.
  • the pKa of the conjugate acid of the basic compound (DB) varies depending on the kind of the photo-acid generator A (preferably the photo-acid generator Aw) used, but is preferably 0.00 to 14.00, 3.00 to 13.00 are more preferable, and 3.50 to 12.50 are still more preferable.
  • the compound (DC) that generates an acid that becomes a weak acid relative to the photoacid generator A
  • the compound (DC) is preferably a compound which generates an acid upon irradiation with actinic rays or radiation.
  • the compound that generates an acid upon irradiation with actinic rays or radiation is also referred to as “photoacid generator B”.
  • the photo-acid generator B is preferably a compound that generates an acid having a pKa of 1.00 or more higher than that of the acid generated from the photo-acid generator A (preferably the photo-acid generator Aw).
  • the value obtained by subtracting the pKa of the acid generated from the acid generator A (preferably the photo-acid generator Aw) is 1.00 or more, preferably 1.00 to 10.00, and 1.00 to 5.00. Is more preferable, and 1.00 to 3.00 is even more preferable.
  • the pKa of the acid generated from the photo-acid generator B varies depending on the type of the photo-acid generator A (preferably the photo-acid generator Aw) used, but is preferably 0.00 to 10.00, 0.50 to 5.00 is more preferable, and 1.00 to 5.00 is further preferable.
  • the photoacid generator B is preferably an onium salt compound composed of an anion and a cation.
  • onium salt compounds compounds represented by general formulas (d1-1) to (d1-3) are preferable.
  • R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).
  • Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon atom adjacent to S is not substituted with a fluorine atom).
  • the hydrocarbon group for Z 2c may be linear or branched, and may have a cyclic structure.
  • the carbon atom in the hydrocarbon group (preferably, the carbon atom forming the cyclic structure in the case where the hydrocarbon group has a cyclic structure) may be carbonyl carbon (—CO—).
  • hydrocarbon group examples include a group having a norbornyl group which may have a substituent.
  • the carbon atom forming the norbornyl group may be a carbonyl carbon.
  • R 52 represents an organic group
  • Y 3 represents a linear or branched alkylene group, a cycloalkylene group, or an arylene group
  • Rf represents a hydrocarbon group containing a fluorine atom.
  • Z 2c —SO 3 ⁇ ”in the general formula (d1-2) is an anion (preferably the above general formula (1-1) in the photo-acid generator A (preferably the photo-acid generator Aw). It is preferably different from the group represented or the group represented by the above general formula (1-2)).
  • M + is independently an ammonium cation, a sulfonium cation, or an iodonium cation.
  • the sulfonium cation and the iodonium cation include, for example, a sulfonium cation and an iodonium cation in the cation that the photoacid generator A may have (more specifically, a compound represented by the general formula (ZI), and a general formula (ZI).
  • the cations in the compounds represented by ZII) can likewise be used.
  • the photo-acid generator B may be a compound having a cation site and an anion site in the same molecule and having the cation site and the anion site linked by a covalent bond.
  • a compound represented by the general formula (C-1) or a compound represented by the general formula (C-2) is preferable.
  • R 1 , R 2 , and R 3 each independently represent a substituent having 1 or more carbon atoms.
  • L 1 represents a divalent linking group or a single bond that links a cationic group (S + , I + , or N + ) and —X ⁇ .
  • —X ⁇ represents —COO ⁇ , —SO 3 ⁇ , —SO 2 ⁇ , or —N ⁇ —R 4 .
  • R 4 has at least one of a carbonyl group (—CO—), a sulfonyl group (—SO 2 —), and a sulfinyl group (—S( ⁇ O)—) at a linking site with an adjacent N atom. It represents a monovalent substituent.
  • R 1 , R 2 , R 3 , R 4 , and L 1 may combine with each other to form a ring.
  • two of R 1 to R 3 may be combined to represent one divalent substituent, which may be bonded to the N atom by a double bond.
  • the substituent having 1 or more carbon atoms in R 1 to R 3 is an alkyl group, a cycloalkyl group, an aryl group (preferably having 6 to 15 carbon atoms), an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group , An alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group and the like. Of these, an alkyl group, a cycloalkyl group, or an aryl group is preferable.
  • L 1 as the divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group (preferably having 6 to 15 carbon atoms), a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane Examples thereof include a bond, a urea bond, and a group formed by combining two or more of these. Of these, an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these is preferable.
  • the photo-acid generator B is a compound that generates an acid having a pKa of 1.00 or more larger than that of the acid generated from the photo-acid generator A (preferably the photo-acid generator Aw), and has a nitrogen atom in the cation part. It may be an onium salt compound.
  • the onium salt compound having a nitrogen atom in the cation part preferably has a basic site containing a nitrogen atom in the cation part.
  • the basic moiety is preferably an amino group, and more preferably an aliphatic amino group. Further, it is preferable that all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms.
  • an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom or the like) is not directly bonded to a nitrogen atom.
  • the photo-acid generator B may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Moreover, you may use together the form of a low molecular compound and the form incorporated in a part of polymer.
  • the photo-acid generator B is preferably in the form of a low molecular compound.
  • the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
  • the compound (DD) is preferably an amine derivative having a group leaving on the nitrogen atom that is removed by the action of an acid.
  • the group capable of leaving by the action of an acid 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 more preferably a carbamate group or a hemiaminal ether group. ..
  • the compound (DD) is preferably a low molecular weight compound.
  • the molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and further preferably 100 to 500.
  • the compound (DD) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protective group constituting the carbamate group is represented by general formula (d-1) shown below.
  • Rb is independently a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), an aryl group (preferably having a carbon number of 3 to 30), an aralkyl group ( It preferably represents 1 to 10 carbon atoms or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb's may combine with each other to form a ring.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, or It may be substituted with a halogen atom.
  • Rb a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, an alkoxy group, or It may be substituted with a halogen atom.
  • Rb a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group,
  • Rb a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
  • the ring formed by connecting two Rb's to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
  • Specific structures of the group represented by formula (d-1) include, but are not limited to, the structures disclosed in paragraph ⁇ 0466> of US Patent Publication US2012/0135348A1.
  • the compound (DD) preferably has a structure represented by the following general formula (6).
  • l represents an integer of 0 to 2
  • m represents an integer of 1 to 3
  • Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • two Ras may be the same or different, and the two Ras may be connected to each other to form a heterocycle with the nitrogen atom in the formula.
  • This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
  • Rb has the same meaning as Rb in the general formula (d-1), and the preferred examples are also the same.
  • the alkyl group as Ra, the cycloalkyl group, the aryl group, and the aralkyl group may be each independently substituted with the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group as Rb. As a good group, it may be substituted with the same groups as those mentioned above.
  • alkyl group, cycloalkyl group, aryl group, and aralkyl group for Ra include the same groups as the specific examples described above for Rb.
  • particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph ⁇ 0475> of U.S. Patent Application Publication 2012/0135348A1.
  • Difference between pKa of conjugate acid of compound (DD) and pKa of acid generated from photoacid generator A (preferably photoacid generator Aw) (from pKa of conjugate acid of compound (DD) to photoacid generator A) is preferably 1.00 or more, more preferably 1.00 to 14.00, still more preferably 2.00 to 13.00. ..
  • the pKa of the conjugate acid of the compound (DD) varies depending on the kind of the photo-acid generator A (preferably the photo-acid generator Aw) used, but is preferably 0.00 to 14.00, and 3. 00 to 13.00 is more preferable, and 3.50 to 12.50 is further preferable.
  • the compound (DE) is preferably a compound having a basic site containing a nitrogen atom in the cation part.
  • the basic moiety is preferably an amino group, and more preferably an aliphatic amino group. It is further preferred that all of the atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom or the like) is not directly bonded to a nitrogen atom.
  • Specific preferred examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph ⁇ 0203> of US Patent Application Publication No. 2015/0309408A1.
  • the pKa of the conjugate acid of the compound (DE) varies depending on the kind of the photo-acid generator A (preferably the photo-acid generator Aw) used, but is preferably 0.00 to 14.00, and 3. 00 to 13.00 is more preferable, and 3.50 to 12.50 is further preferable.
  • the composition of the present invention comprises the above-mentioned photoacid generator Aw, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, and a photoacid generator Aw.
  • the acid diffusion controlling agent may be used alone or in combination of two or more.
  • the content of the acid diffusion controlling agent in the composition of the present invention (when a plurality of kinds are present, the total thereof) is preferably 0.05 to 10% by mass, based on the total solid content of the composition, and 0.05 to 5% by mass is more preferable.
  • the composition of the present invention may include a hydrophobic resin.
  • the hydrophobic resin is a resin different from the resin P, and has a repeating unit having a group (acid-decomposable group) that is decomposed by the action of an acid to increase the polarity because it is superior in film thickness uniformity. It is preferably substantially free.
  • substantially free of the repeating unit having an acid-decomposable group means that the content of the repeating unit containing the acid-decomposable group in the hydrophobic resin is based on all repeating units of the hydrophobic resin.
  • composition of the present invention contains the hydrophobic resin, it is easy to control the static and/or dynamic contact angle on the surface of the resist film (actinic ray-sensitive or radiation-sensitive film). This makes it possible to improve the developing characteristics, suppress outgassing, improve the immersion liquid following property in the immersion exposure, and reduce the immersion defects.
  • the hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and a polar substance and a non-polar substance can be uniformly dispersed. It may not contribute to mixing.
  • the hydrophobic resin is a fluorine atom, a group having a fluorine atom, a group having a silicon atom, a linear or branched alkyl group having 6 or more carbon atoms or a cycloalkyl group, from the viewpoint of uneven distribution on the film surface layer.
  • a resin having one or more groups (hereinafter also referred to as “hydrophobic groups”) selected from the group consisting of aryl groups substituted with several 5 or more cycloalkyl groups is preferable. Further, the hydrophobic resin preferably contains a repeating unit containing the above-mentioned hydrophobic group.
  • the hydrophobic resin contains a fluorine atom and/or a silicon atom
  • the fluorine atom and/or the silicon atom in the hydrophobic resin may be contained in the main chain of the resin and may be contained in the side chain. It may be.
  • a linear or branched alkyl group having a fluorine atom, a cycloalkyl group, or an aryl group having a fluorine atom is preferable.
  • a linear or branched alkyl group having a fluorine atom a perfluoroalkyl group having 1 to 4 carbon atoms is preferable, and CF 3 is more preferable.
  • a perfluorocycloalkyl group having 3 to 20 carbon atoms is preferable.
  • the aryl group having a fluorine atom include a phenyl group substituted with a fluorine atom.
  • Examples of the group having a silicon atom include an alkylsilyl group.
  • Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.
  • Examples of the linear or branched alkyl group having 6 or more carbon atoms or the cycloalkyl group include a linear or branched alkyl group having 6 to 20 carbon atoms or a cycloalkyl group. Examples thereof include a 2-ethylhexyl group, a norbornyl group, and an adamantyl group.
  • aryl group having 9 or more carbon atoms examples include an aryl group having a polycyclic structure formed by combining two or more 5- or 6-membered monocyclic aromatic hydrocarbon rings.
  • an aralkyl group having 10 or more carbon atoms for example, an aralkyl group having 10 to 20 carbon atoms is preferable, and specifically, 1-naphthylmethyl group, 1-(1-naphthyl)ethyl group, triphenylmethyl group. , And a pyrenylmethyl group.
  • Examples of the aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms include, for example, a linear alkyl group having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) or Examples thereof include a phenyl group substituted with a branched alkyl group.
  • Examples of the aryl group substituted with at least one cycloalkyl group having 5 or more carbon atoms include a phenyl group substituted with a cycloalkyl group having 5 to 20 carbon atoms (preferably 5 to 10 carbon atoms).
  • the hydrophobic resin preferably contains a repeating unit containing a fluorine atom or a group having a fluorine atom.
  • the number of fluorine atoms contained in the hydrophobic resin is preferably larger than the number of fluorine atoms contained in the above photoacid generator A, from the viewpoint that the film thickness uniformity is more excellent.
  • the number of fluorine atoms contained in the hydrophobic resin is calculated by the following formula (1) when the hydrophobic resin contains only one type of repeating unit containing a fluorine atom.
  • the hydrophobic resin contains two or more kinds of repeating units containing a fluorine atom, it is calculated as the sum of the values calculated by the following formula (1) for each repeating unit containing a fluorine atom.
  • Formula (1): Y A a ⁇ b ⁇ 100 Y A: the number of fluorine atoms contained in the hydrophobic resin a: the number of fluorine atoms in the repeating unit containing a fluorine atom b: content of repeating unit containing a fluorine atom with respect to all repeating units in the hydrophobic resin (mole %)
  • the hydrophobic resin preferably contains at least one group selected from (x) and (y) shown below, and more preferably contains a repeating unit containing a group selected from (y). Moreover, (x) and (y) shown below may contain the above-mentioned hydrophobic group.
  • Examples of the acid group (x) include phenolic hydroxyl group, carboxy group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl) ) Imido group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and tris(alkylsulfonyl) Examples thereof include a methylene group.
  • a fluorinated alcohol group preferably a hexafluoroisopropanol group
  • a sulfonimide group or a bis(alkylcarbonyl)m
  • Examples of the group (y) that is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer include a lactone group, a carboxyester group (—COO— or —OCO—), an acid anhydride group (—CO).
  • Examples of the repeating unit containing a group selected from the above (y) include (1) repeating units in which the group selected from the above (y) is directly bonded to the main chain of the resin (for example, acrylic acid ester and methacrylic acid). (Repeating unit by ester) and (2) a repeating unit in which the group selected from the above (y) is bonded to the main chain of the resin via a linking group.
  • Examples of the repeating unit having a lactone group include the same repeating unit as the repeating unit having a lactone structure described above in the section of Resin P.
  • the repeating unit containing a group selected from the above (y) is preferable, and the repeating unit represented by the following general formula (7) is more preferable.
  • Z 1 represents a halogen atom, a hydrogen atom, an alkyl group, or a cycloalkyl group.
  • the halogen atom represented by Z 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom is preferable.
  • the alkyl group represented by Z 1 include an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group may be linear or branched.
  • the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, and more preferably has 5 to 15 carbon atoms.
  • L 1 represents a (n+1)-valent linking group.
  • the (n+1)-valent linking group represented by L 1 is not particularly limited, and examples thereof include a divalent or higher valent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.
  • the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the hetero atom may be contained in the form of, for example, —O—, —S—, —SO 2 —, —NR A —, —CO—, or a combination group of two or more thereof.
  • R A represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the divalent or higher valent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom includes, for example, a straight chain having 1 to 20 carbon atoms which may contain a hetero atom, or a branched chain. Examples thereof include an alkylene group and a cycloalkylene group, and a linear or branched alkylene group having 1 to 10 carbon atoms is preferable.
  • X 1 represents a group represented by *-Y 1 -R 1 .
  • the above Y 1 represents —CO—O— or —O—CO—.
  • the above * represents the bonding position.
  • R 1 represents an electron-withdrawing group.
  • the electron-withdrawing group is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms (which may be linear or branched) substituted with at least one fluorine atom, or cyclo. Examples thereof include an alkyl group, and specific examples thereof include —CF 3 , —CF 2 CF 3 , —CH 2 CF 3 , —CHFCF 3 , and —CH(CF 3 ) 2 . Of these, —CH(CF 3 ) 2 is preferable as the electron-withdrawing group, because the uniformity of the film thickness is more excellent.
  • n represents a positive integer. n is not particularly limited as long as it is 1 or more, and its upper limit value is 10, for example. When n is 2 or more, the plurality of X 1 may be the same as or different from each other.
  • the hydrophobic resin contains a repeating unit containing a group selected from the above (y), the content thereof is preferably 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin, and 3 to 98 mol% Is more preferable and 5 to 95 mol% is even more preferable.
  • the hydrophobic resin contains a repeating unit containing a fluorine atom
  • the content thereof is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and more preferably 30 to 100 mol% based on all the repeating units in the hydrophobic resin. 95 mol% is more preferable.
  • the hydrophobic resin contains a repeating unit containing a silicon atom
  • the content thereof is preferably 10 to 100 mol% and more preferably 20 to 100 mol% based on all repeating units in the hydrophobic resin.
  • the hydrophobic resin contains a repeating unit represented by the above general formula (7) and another repeating unit other than the repeating unit represented by the general formula (7) in terms of being more excellent in film surface uniformity. It is preferable.
  • Other repeating units other than the repeating unit represented by the general formula (7) include a repeating unit containing a group selected from the above (y) and containing the above-mentioned hydrophobic group (in other words, the above-mentioned alkali
  • a repeating unit having a group that is decomposed by the action of a developing solution to increase its solubility in an alkaline developing solution and is preferably a repeating unit containing the above-mentioned hydrophobic group, and contains a group selected from the above (y).
  • the repeating unit represented by the general formula (7) contains the repeating unit represented by the general formula (7) and another repeating unit other than the repeating unit represented by the general formula (7), the repeating unit represented by the general formula (7)
  • the content of the unit is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, based on all repeating units of the hydrophobic resin.
  • the lower limit is not particularly limited and is, for example, 10 mol% or more, more preferably 30 mol% or more.
  • the standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.
  • the total content of the residual monomer and/or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
  • the dispersity (Mw/Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.
  • hydrophobic resin known resins can be used alone or as a mixture thereof, appropriately selected and used.
  • known resins disclosed in paragraphs [0451] to ⁇ 0704> of U.S. Patent Publication No. 2015/0168830A1 and paragraphs ⁇ 0340> to ⁇ 0356> of U.S. Patent Publication No. 2016/0274458A1 are described. It can be suitably used as a hydrophobic resin.
  • the repeating units disclosed in paragraphs [0177] to ⁇ 0258> of US Patent Application Publication No. 2016/0237190A1 are also preferable as the repeating units constituting the hydrophobic resin.
  • the hydrophobic resins may be used alone or in combination of two or more. It is also preferable to mix and use two or more kinds of hydrophobic resins having different surface energies from the viewpoint of achieving both the immersion liquid following property in the immersion exposure and the developing property.
  • the content of the hydrophobic resin in the composition of the present invention (when more than one is contained, the total content thereof) is the total solid content in the composition of the present invention.
  • 0.1 to 12.0 mass% is preferable, 0.2 to 10.0 mass% is more preferable, and 0.3 to 10.0 mass% is more preferable.
  • the composition of the present invention may contain a solvent.
  • a known resist solvent can be appropriately used.
  • paragraphs ⁇ 0665> to ⁇ 0670> of the specification of US Patent Application Publication No. 2016/0070167A1 paragraphs ⁇ 0210> to ⁇ 0235> of the specification of US Patent Application Publication 2015/0004544A1
  • Known solvents disclosed in paragraphs ⁇ 0424> to [0426] of the specification and paragraphs [0357] to ⁇ 0366> of US Patent Application Publication No. 2016/0274458A1 can be preferably used.
  • Examples of the solvent that can be used when preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms),
  • Examples of the organic solvent include a monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
  • a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure with a solvent having no hydroxyl group may be used.
  • the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-exemplified compounds can be appropriately selected, but the solvent having a hydroxyl group is preferably alkylene glycol monoalkyl ether or alkyl lactate, and propylene glycol monomethyl ether (PGME). ), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred.
  • the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether acetate, an alkylalkoxypropionate, a monoketone compound which may have a ring, a cyclic lactone, an alkyl acetate or the like, and among these, propylene.
  • Glycol monomethyl ether acetate (PGMEA) ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, ethyl ethoxypropionate.
  • the mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and 20/80 to 60/40. More preferable.
  • a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable from the viewpoint of coating uniformity.
  • the solvent preferably comprises propylene glycol monomethyl ether acetate.
  • the solvent may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.
  • the solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and further preferably 2.0 to 5.3% by mass. That is, when the composition contains a solvent, the content of the solvent in the composition is preferably adjusted so as to satisfy the preferable range of the solid content concentration.
  • the solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
  • the solid content concentration in the composition is set in an appropriate range to give an appropriate viscosity to improve the coatability or film-forming property, and the resist film (actinic ray-sensitive or radiation-sensitive) composed of the composition of the present invention. The thickness of the film can be adjusted.
  • the composition of the present invention may include a surfactant.
  • the surfactant is preferably a fluorine-based and/or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom). ..
  • composition of the present invention contains a surfactant
  • a surfactant when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is easy to obtain a pattern with good sensitivity and resolution and less adhesiveness and development defects.
  • the fluorine-based and/or silicon-based surfactants include the surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425. Further, a surfactant other than the fluorine-based and/or silicon-based surfactant described in paragraph ⁇ 0280> of US Patent Application Publication No. 2008/0248425 may be used.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant (when a plurality of them are contained, the total content thereof) is 0.0001 to 2% by mass based on the total solid content of the composition. Is preferred, and 0.0005 to 1 mass% is more preferred.
  • the content of the surfactant is 10 mass ppm (parts per million) or more with respect to the total solid content of the composition, the uneven distribution of the surface of the hydrophobic resin increases. As a result, the surface of the resist film can be made more hydrophobic, and the water following property during immersion exposure is improved.
  • composition of the present invention further contains a resin other than the above, an acid proliferating agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, or a dissolution accelerator. Good.
  • the composition of the present invention is preferably used by dissolving the above-mentioned components in a predetermined organic solvent (preferably the above-mentioned mixed solvent), filtering this, and then coating the solution on a predetermined support (substrate).
  • a predetermined organic solvent preferably the above-mentioned 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, still more preferably 0.03 ⁇ m or less.
  • the pore size of the filter used for filter filtration is preferably 3 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.3 ⁇ m or less.
  • This filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon.
  • cyclic filtration may be performed, and a plurality of types of filters are connected in series or in parallel. It may be connected to and filtered.
  • the composition may be filtered multiple times. Further, the composition may be subjected to deaeration treatment or the like before and after filtration with a filter.
  • the composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition that changes properties by reacting upon irradiation with actinic rays or radiation. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, a mold structure for imprinting, other photofabrication process, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition.
  • the pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems) and the like.
  • the present invention also relates to a pattern forming method using the above actinic ray-sensitive or radiation-sensitive resin composition.
  • the pattern forming method of the present invention will be described below. Further, the resist film (actinic ray-sensitive or radiation-sensitive film) of the present invention will be described together with the description of the pattern forming method.
  • the pattern forming method of the present invention is (I) A step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) on a support using the above actinic ray-sensitive or radiation-sensitive resin composition (resist film forming step (film forming step) ) , (Ii) a step of exposing (irradiating with actinic rays or radiation) the resist film (exposure step); and (Iii) a step of developing the exposed resist film with a developing solution (developing step).
  • the pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii), and may further include the following steps.
  • the exposure method in the (ii) exposure step may be immersion exposure.
  • the pattern forming method of the present invention preferably includes (iv) pre-heating (PB: PreBake) step before the (ii) exposure step.
  • the pattern forming method of the present invention preferably includes (v) post exposure bake (PEB: Post Exposure Bake) step after (ii) exposure step and before (iii) development step.
  • the pattern forming method of the present invention may include (ii) the exposure step a plurality of times.
  • the pattern forming method of the present invention may include (iv) the preheating step a plurality of times.
  • the pattern forming method of the present invention may include (v) the post-exposure heating step a plurality of times.
  • the above-mentioned (i) resist film forming step (film forming step) , (Ii) exposure step, and (iii) development step can be performed by a generally known method.
  • the film thickness of the resist film is preferably 110 nm or less, more preferably 95 nm or less.
  • a resist underlayer film for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film
  • SOG Spin On Glass
  • SOC Spin On Carbon
  • antireflection film As a material for forming the resist underlayer film, a known organic or inorganic material can be appropriately used.
  • a protective film top coat may be formed on the upper layer of the resist film. Known materials can be appropriately used for the protective film. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No.
  • the protective film forming composition disclosed in U.S. Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A can be preferably used.
  • the composition for forming a protective film preferably contains the above-mentioned acid diffusion controlling agent. You may form a protective film on the upper layer of the resist film containing the hydrophobic resin mentioned above.
  • the support is not particularly limited, and a substrate that is generally used in the manufacturing process of semiconductors such as IC or the manufacturing process of circuit boards such as liquid crystal or thermal head, and other lithography process of photofabrication is used. it can.
  • Specific examples of the support include inorganic substrates such as silicon, SiO 2 , and SiN.
  • the heating temperature is preferably 70 to 130° C., and more preferably 80 to 120° C. in both the (iv) preheating step and (v) post-exposure heating step.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds in both the (iv) preheating step and (v) post-exposure heating step. Heating can be performed by means provided in the exposure device and the developing device, and may be performed using a hot plate or the like.
  • the wavelength of the light source used in the exposure step is not limited, but examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray, and electron beam.
  • far-ultraviolet light is preferable, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, still more preferably 1 to 200 nm.
  • KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), electron beam or the like is preferable, and KrF excimer laser, ArF excimer laser, EUV or electron beam is more preferable.
  • an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer) may be used.
  • the alkali developing solution a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. It can be used.
  • the alkaline developer may contain an appropriate amount of alcohols and/or surfactants.
  • the alkali concentration of the alkali developer is usually 0.1 to 20% by mass.
  • the pH of the alkaline developer is usually 10 to 15.
  • the time for developing with an alkaline developer is usually 10 to 300 seconds.
  • the alkali concentration, pH, and development time of the alkali developing solution can be appropriately adjusted according to the pattern to be formed.
  • the organic developer is a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. It is preferable.
  • ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
  • ester solvent examples include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl acetate.
  • examples thereof include butyl acid salt, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
  • the solvents disclosed in paragraphs ⁇ 0715> to ⁇ 0718> of US Patent Application Publication No. 2016/0070167A1 can be used.
  • a plurality of the above solvents may be mixed, or a solvent other than the above or water may be mixed.
  • the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of water.
  • the content of the organic solvent in the organic developing solution is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass based on the total amount of the developing solution. % Is particularly preferred.
  • the developer may contain an appropriate amount of a known surfactant if necessary.
  • the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.
  • the organic developer may contain an acid diffusion controller.
  • the developing method for example, a method of dipping the substrate in a tank filled with the developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and leaving it standing for a certain period of time (paddle method), The method of spraying the developing solution on the substrate surface (spray method), the method of continuously discharging the developing solution while scanning the developing solution discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing method), etc.
  • dip method a method of dipping the substrate in a tank filled with the developing solution for a certain period of time
  • paddle method a method of raising the developing solution on the surface of the substrate by surface tension and leaving it standing for a certain period of time
  • spray method The method of spraying the developing solution on the substrate surface
  • spray method the method of continuously discharging the developing solution while scanning the developing solution discharge nozzle at a constant speed on the substrate rotating at a constant speed
  • the step of developing with an alkaline aqueous solution (alkali developing step) and the step of developing with a developing solution containing an organic solvent (organic solvent developing step) may be combined.
  • alkali developing step an alkaline aqueous solution
  • organic solvent developing step an organic solvent developing step
  • pure water can be used, for example. Pure water may contain an appropriate amount of a surfactant.
  • a treatment of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be added.
  • a heat treatment may be performed to remove the water remaining in the pattern.
  • the rinse solution used in the rinse step after the development step using the developer containing the organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used.
  • a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. It is preferable. Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amide-based solvent, and the ether-based solvent include the same solvents as those described for the developer containing an organic solvent.
  • a rinse liquid containing a monohydric alcohol is more preferable.
  • Examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methylisobutylcarbinol.
  • the monohydric alcohol preferably has 5 or more carbon atoms, and examples thereof include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol and 3-methyl-1-butanol. , And methyl isobutyl carbinol.
  • a plurality of each component may be mixed, or may be mixed with an organic solvent other than the above and used.
  • the water content in the rinse solution used in the rinse step after the development step using the developer containing the organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. When the water content is 10% by mass or less, good developing characteristics can be obtained.
  • the rinse solution after the development step using the developer containing the organic solvent may contain an appropriate amount of the surfactant.
  • the developed substrate is washed with a rinse solution.
  • the method of cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (spin coating method), or immersing the substrate in a bath filled with the rinse liquid for a certain period of time Examples include a method (dip method), a method of spraying a rinse liquid on the substrate surface (spray method), and the like. Among them, a method in which the cleaning treatment is performed by the spin coating method, and after the cleaning, the substrate is rotated at a rotation number of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate is preferable. It is also preferable to include a heating step (Post Bake) after the rinse step.
  • Post Bake a heating step after the rinse step.
  • the heating temperature is usually 40 to 160° C., preferably 70 to 95° C.
  • the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention for example, a resist solvent, a developing solution, a rinsing liquid, a composition for forming an antireflection film, or a top. It is preferable that the coating forming composition) does not contain impurities such as metal components, isomers, and residual monomers.
  • the content of these impurities contained in the above-mentioned various materials is preferably 1 mass ppm or less, more preferably 100 mass ppt (parts per trillion) or less, further preferably 10 mass ppt or less, and substantially not containing (It is below the detection limit of the measuring device) is particularly preferable.
  • Examples of methods for removing impurities such as metals from the above various materials include filtration using a filter.
  • the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, still more preferably 3 nm or less.
  • a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
  • a filter previously washed with an organic solvent may be used.
  • plural kinds of filters may be connected in series or in parallel and used. When using a plurality of types of filters, filters having different pore sizes and/or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step.
  • the filter is preferably a filter with reduced eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (JP-A-2016-201426).
  • an adsorbent may be used to remove impurities, and filter filtration and an adsorbent may be used in combination.
  • a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.
  • Examples of the metal adsorbent include materials disclosed in Japanese Patent Application Publication No. 2016-206500 (JP-A-2016-206500). Further, as a method of reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material forming various materials, a filter for the raw materials forming various materials is filtered, Alternatively, there may be mentioned a method such as lining the inside of the apparatus with Teflon (registered trademark) and performing distillation under conditions in which contamination is suppressed as much as possible.
  • Teflon registered trademark
  • the glass lining treatment in all steps of the manufacturing facility for synthesizing various materials (binder, photo-acid generator, etc.) of the resist component in order to reduce the metal to the ppt order.
  • Preferable conditions for the filter filtration performed on the raw materials constituting various materials are the same as the above-mentioned conditions.
  • a method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention.
  • a method of improving the surface roughness of the pattern for example, a method of treating the pattern with a plasma of a gas containing hydrogen, which is disclosed in US Patent Application Publication No. 2015/0104957, can be mentioned.
  • Japanese Patent Application Publication No. 2004-235468 JP 2004-235468 A
  • US Patent Application Publication No. 2010/0020297 and Proc. of SPIE Vol.
  • a known method as described in 8328 83280N-1 “EUV Resist Curing Technology for LWR Reduction and Etch Selectivity Enhancement” may be applied.
  • the pattern formed by the above method is a spacer disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (JP-A-3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as the core material of the process.
  • the present invention also relates to a method for manufacturing an electronic device, including the pattern forming method described above.
  • the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric/electronic device (for example, a home electric appliance, an OA (Office Automation) related device, a media related device, an optical device, a communication device, or the like). To be done.
  • an electric/electronic device for example, a home electric appliance, an OA (Office Automation) related device, a media related device, an optical device, a communication device, or the like.
  • methacrylic acid chloride (36.8 g) and tetrahydrofuran (400 mL) were stirred at 0° C., and a pinacol-tetrahydrofuran solution was added dropwise so that the internal temperature was maintained at 15° C. or lower.
  • the reaction solution was heated to room temperature and then stirred for 30 minutes. Then, the reaction solution was poured into 400 mL of saturated aqueous sodium hydrogen carbonate solution, and tetrahydrofuran was distilled off under reduced pressure. The resulting aqueous solution was extracted 3 times with 250 mL of ethyl acetate and dried over sodium sulfate.
  • reaction solution was allowed to cool, then reprecipitated with a large amount of methanol/water (mass ratio 9:1) and filtered, and the obtained solid was vacuum dried to give acid-decomposable resin A-1 of 29.33. A mass part was obtained.
  • the composition ratio (molar ratio; corresponding in order from the left) measured by 13 C-NMR (nuclear magnetic resonance method) was 40/30/30 (mol %).
  • Acid-decomposable resin The structures of the acid-decomposable resins (A-1 to A-22, B-1 and B-2) used are shown below.
  • the weight average molecular weight (Mw) and dispersity (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (polystyrene conversion amount).
  • the composition ratio (mol% ratio) of the resin was measured by 13 C-NMR (nuclear magnetic resonance).
  • the unit of the content ratio of each repeating unit of the above resin is mol %.
  • a site of the repeating unit represented by the general formula (P1) in A-1 to A-22 that is eliminated by an acid decomposition reaction (a decomposition site (a site represented by the above general formula (P1-D)))
  • Table 1 below shows the sum of the atomic weights of
  • the pKa of the acid (generated acid) generated from PAG-1 to PAG-12, N-5 and N-6 is shown below.
  • ⁇ Hydrophobic resin> The structures of the hydrophobic resins (1b, 2b) used are shown below.
  • the weight average molecular weight (Mw) and dispersity (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (polystyrene conversion amount).
  • the composition ratio (mol% ratio) of the resin was measured by 13 C-NMR.
  • the unit of the content ratio of each repeating unit of the above resin is mol %.
  • SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
  • PGME Propylene glycol monomethyl ether
  • SL-3 cyclohexanone
  • SL-4 ⁇ -butyrolactone
  • resist composition The components shown in Tables 4 and 5 were mixed so that the solid content concentration was 3% by mass.
  • the actinic ray-sensitive or radiation-sensitive resin composition was prepared by filtering the obtained mixed solution with a polyethylene filter having a pore size of 0.03 ⁇ m.
  • the solid content means all components other than the solvent.
  • the obtained wafer was subjected to an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) with a line width of 44 nm of 1:. It was exposed through a 6% halftone mask with a 1-line and space pattern. Ultrapure water was used as the immersion liquid. Then, it heated at 100 degreeC for 60 second (PEB:Post Exposure Bake).
  • PEB Post Exposure Bake
  • TMAH tetramethylammonium hydroxide
  • resist composition Each component shown in Table 6 was dissolved in a solvent to prepare a solution having a solid content concentration of 1.6% by mass. Next, the actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was prepared by filtering the obtained solution through a polyethylene filter having a pore size of 0.03 ⁇ m.
  • PEB Post Exposure Bake
  • EL Exposure amount at which the line width of the line was ⁇ 10% of the target value of 20 nm (that is, 18 nm and 22 nm) was determined.
  • EL (%) [[(exposure amount for line width of 22 nm)-(exposure amount for line width of 18 nm)]/E opt ] ⁇ 100
  • the composition of the present invention was excellent in sensitivity and EL in forming an ultrafine pattern, small in LWR and LER, and excellent in CDU.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Emergency Medicine (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne : une composition de résine sensible à la lumière active ou sensible au rayonnement présentant une sensibilité et une électroluminescence (EL) exceptionnelles lorsqu'un motif ultrafin (par exemple, un motif à lignes et espaces présentant une largeur de ligne de 45 nm ou un motif à trous présentant une dimension de trou de 45 nm ou moins) est formé, une faible rugosité de largeur de ligne (LWR) et une faible rugosité de bord de ligne (LER) et une excellente uniformité de dimension critique (CDU) ; et un film de résine photosensible, un procédé de formation de motif et un procédé de fabrication d'un dispositif électronique à l'aide de la composition. La composition de résine sensible à la lumière active ou sensible au rayonnement contient une résine présentant un motif récurrent représenté par la formule générale (P1) dans un rapport de teneur de 30 % en masse par rapport à la totalité de la teneur en solides et un agent de réticulation dans un rapport de teneur de 10 % en masse par rapport à la totalité de la teneur en solides. L'invention concerne également le film de résine photosensible, le procédé de formation de motif et le procédé de fabrication d'un dispositif électronique qui utilisent la composition de résine sensible à la lumière active ou au rayonnement.
PCT/JP2019/044524 2018-12-21 2019-11-13 Composition de résine sensible à la lumière active ou au rayonnement, film de résine photosensible, procédé de formation de motif et procédé de fabrication d'un dispositif électronique WO2020129476A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023195255A1 (fr) * 2022-04-07 2023-10-12 Jsr株式会社 Composition de résine sensible au rayonnement et procédé de formation de motif de réserve

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000267287A (ja) * 1998-09-17 2000-09-29 Fuji Photo Film Co Ltd ポジ型感光性樹脂組成物
JP2004280049A (ja) * 2002-10-03 2004-10-07 E I Du Pont De Nemours & Co 水酸化され、光酸で切断可能な基を有するフォトレジスト
JP2009192784A (ja) * 2008-02-14 2009-08-27 Shin Etsu Chem Co Ltd レジスト材料、レジスト保護膜材料、及びパターン形成方法
JP2015087644A (ja) * 2013-10-31 2015-05-07 Jsr株式会社 感放射線性樹脂組成物及びネガ型レジストパターン形成方法
JP2016206459A (ja) * 2015-04-23 2016-12-08 Jsr株式会社 レジストパターン形成方法及び感放射線性樹脂組成物
JP2016218202A (ja) * 2015-05-19 2016-12-22 信越化学工業株式会社 高分子化合物及び単量体並びにレジスト材料及びパターン形成方法
JP2017119678A (ja) * 2015-12-28 2017-07-06 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000267287A (ja) * 1998-09-17 2000-09-29 Fuji Photo Film Co Ltd ポジ型感光性樹脂組成物
JP2004280049A (ja) * 2002-10-03 2004-10-07 E I Du Pont De Nemours & Co 水酸化され、光酸で切断可能な基を有するフォトレジスト
JP2009192784A (ja) * 2008-02-14 2009-08-27 Shin Etsu Chem Co Ltd レジスト材料、レジスト保護膜材料、及びパターン形成方法
JP2015087644A (ja) * 2013-10-31 2015-05-07 Jsr株式会社 感放射線性樹脂組成物及びネガ型レジストパターン形成方法
JP2016206459A (ja) * 2015-04-23 2016-12-08 Jsr株式会社 レジストパターン形成方法及び感放射線性樹脂組成物
JP2016218202A (ja) * 2015-05-19 2016-12-22 信越化学工業株式会社 高分子化合物及び単量体並びにレジスト材料及びパターン形成方法
JP2017119678A (ja) * 2015-12-28 2017-07-06 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023195255A1 (fr) * 2022-04-07 2023-10-12 Jsr株式会社 Composition de résine sensible au rayonnement et procédé de formation de motif de réserve

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