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WO2024024669A1 - Composition de résine sensible aux rayons actiniques ou à un rayonnement, film sensible aux rayons actiniques ou à un rayonnement, procédé de formation de motif, et procédé de fabrication de dispositif électronique - Google Patents

Composition de résine sensible aux rayons actiniques ou à un rayonnement, film sensible aux rayons actiniques ou à un rayonnement, procédé de formation de motif, et procédé de fabrication de dispositif électronique Download PDF

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Publication number
WO2024024669A1
WO2024024669A1 PCT/JP2023/026778 JP2023026778W WO2024024669A1 WO 2024024669 A1 WO2024024669 A1 WO 2024024669A1 JP 2023026778 W JP2023026778 W JP 2023026778W WO 2024024669 A1 WO2024024669 A1 WO 2024024669A1
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Prior art keywords
group
sensitive
radiation
actinic ray
ring
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English (en)
Japanese (ja)
Inventor
修平 山口
太朗 三好
孝太郎 高橋
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Fujifilm Corp
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Fujifilm Corp
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Priority to KR1020257002930A priority Critical patent/KR20250029198A/ko
Priority to JP2024537672A priority patent/JPWO2024024669A1/ja
Publication of WO2024024669A1 publication Critical patent/WO2024024669A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • 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
    • C08F20/12—Esters of monohydric alcohols or phenols
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method. More specifically, the present invention relates to an ultra-microlithography process applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the manufacturing process of nanoimprint molds, the manufacturing process of high-density information recording media, etc. The present invention relates to actinic ray-sensitive or radiation-sensitive resin compositions, actinic ray-sensitive or radiation-sensitive films, pattern forming methods, and electronic device manufacturing methods that can be suitably used in other photofabrication processes.
  • ultra-microlithography process applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the manufacturing process of nanoimprint molds, the manufacturing process of high-density information recording media, etc.
  • the present invention relates to actinic ray-sensitive or radiation
  • Patent Document 1 describes a chemically amplified resist material that includes a radiation-sensitive sensitizer and a specific component that generates acid upon exposure and has excellent sensitivity and roughness performance.
  • Patent Document 2 describes a resist composition containing a compound represented by a specific formula (I), a resin having an acid-labile group, and an acid generator.
  • density dependence refers to the case where when forming a certain pattern (for example, a 1:1 line and space pattern with a line width of 50 nm), the exposure amount around the area where the pattern is formed is small (sparse density dependence).
  • Poor density dependence refers to a large D/B (for example, D/B is 2.05 or more), which is the ratio of the above sensitivity, and excellent density dependence refers to a small D/B. (For example, D/B is less than 2.05).
  • the present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that has excellent density dependence in forming ultrafine patterns (for example, line-and-space patterns with line widths of 50 nm or less, hole patterns with pore diameters of 50 nm or less, etc.). The task is to do so.
  • Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.
  • An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) whose polarity increases by the action of an acid and a compound (B) represented by the following general formula (B-1).
  • X represents a cyclic group having 4 to 20 carbon atoms and having an unsaturated bond.
  • Each of the plurality of Rb 1 's independently represents -OH, -ORb 3 , -NRb 4 Rb 5 , -SH, or -SRb 6 .
  • at least one Rb 1 represents -OH, -NHRb 4 ', or -SH bonded to a carbon atom forming an unsaturated bond.
  • Rb 3 represents an alkyl group, an aryl group, an acyl group, an acyloxy group, or a combination thereof.
  • Rb 4 and Rb 5 each independently represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, -CHO, or a group bonded to each other to form a nitrogen-containing heterocycle.
  • Rb 4 ' represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or -CHO.
  • Rb 6 represents an alkyl group, an aryl group, or an acyl group.
  • a plurality of Rb 1 may be bonded to each other to form a ring.
  • Rb 2 represents a substituent.
  • the plurality of Rb 2s may be the same or different, and the plurality of Rb 2s may be bonded to each other to form a ring.
  • Rb 1 and Rb 2 may be bonded to each other to form a ring.
  • m represents an integer from 0 to 6
  • n represents an integer from 2 to 4.
  • the compound represented by the above general formula (B-1) does not have a halogen atom.
  • R 101 , R 102 and R 103 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group.
  • R 102 may be combined with Ar A to form a ring, and in this case R 102 represents a single bond or an alkylene group.
  • L A represents a single bond or a divalent linking group.
  • Ar A represents an aromatic ring group.
  • k represents an integer from 1 to 5.
  • Ra 1 to Ra 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • La 1 represents a divalent linking group having an aromatic group.
  • Ra 4 to Ra 6 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, or an alkenyl group. Note that two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
  • Ra 7 to Ra 9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • La 2 represents a single bond or a divalent linking group.
  • Ara represents an aromatic ring group.
  • Ra 10 to Ra 12 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, an alkoxy group, or an alkenyl group. Note that Ra 10 to Ra 12 may be bonded to each other to form a ring. Furthermore, Ra 9 to Ra 12 may be combined with Ara.
  • L represents a single bond or a divalent linking group.
  • A represents a group that decomposes under the action of an acid.
  • nc represents an integer from 1 to 5.
  • Xc represents a (nc+1)-valent linking group.
  • Mc + represents a sulfonium ion or an iodonium ion.
  • L represents a single bond or a divalent linking group.
  • A represents a group that decomposes under the action of an acid.
  • nc represents an integer from 1 to 5.
  • Mc + represents a sulfonium ion or an iodonium ion.
  • a pattern forming method comprising: an exposure step of exposing the actinic ray-sensitive or radiation-sensitive film; and a developing step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
  • a method for manufacturing an electronic device including the pattern forming method according to [10].
  • the present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that exhibits excellent density dependence in the formation of ultra-fine patterns (for example, line-and-space patterns with line widths of 50 nm or less, hole patterns with pore diameters of 50 nm or less, etc.). can do. Further, the present invention can provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.
  • ultra-fine patterns for example, line-and-space patterns with line widths of 50 nm or less, hole patterns with pore diameters of 50 nm or less, etc.
  • FIG. 7 is a schematic diagram showing an exposure area when determining sensitivity D when the exposure amount around a pattern forming area is small (sparse) in evaluation of density dependence.
  • FIG. 7 is a schematic diagram showing an exposure area when determining sensitivity B when the exposure amount around a region forming a pattern is large (in a dense case) in evaluation of density dependence.
  • active rays or “radiation” include, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV), X-rays, soft X-rays, and electron It means a line (EB: Electron Beam) or the like.
  • light means actinic rays or radiation.
  • exposure refers not only to exposure to the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also to electron beams and ion beams, unless otherwise specified. It also includes drawing using particle beams such as beams.
  • " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • (meth)acrylate represents at least one of acrylate and methacrylate.
  • (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin are determined using a GPC (Gel Permeation Chromatography) apparatus (HLC manufactured by Tosoh Corporation).
  • GPC Gel Permeation Chromatography
  • the notation that does not indicate substituted or unsubstituted includes a group containing a substituent as well as a group having no substituent.
  • alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • organic group refers to a group containing at least one carbon atom.
  • monovalent substituents are preferred. Examples of the substituent include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.
  • substituent T examples include halogen atoms such as fluorine, chlorine, bromine and iodine; alkoxy groups such as methoxy, ethoxy and tert-butoxy; cycloalkyloxy; phenoxy and p-tolyloxy groups; Aryloxy groups; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl groups; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy groups; acetyl Acyl groups such as benzoyl, isobutyryl, acryloyl, methacryloyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; phenylsulfanyl groups; alkyls
  • substituent T when these substituents can further have one or more substituents, the further substituent is a group having one or more substituents selected from the above-mentioned substituents (for example, a monoalkylamino group). , dialkylamino group, arylamino group, trifluoromethyl group, etc.) are also included as examples of the substituent T.
  • the direction of bonding of the divalent groups described is not limited unless otherwise specified.
  • Y in the compound represented by the formula "X-Y-Z" is -COO-
  • Y may be -CO-O- or -O-CO- Good too.
  • the above compound may be "X-CO-O-Z" or "X-O-CO-Z”.
  • acid dissociation constant refers to pKa in an aqueous solution, and specifically, it is a value based on Hammett's substituent constant and a database of known literature values using the following software package 1. is the value obtained by calculation. All pKa values described herein are values calculated using this software package.
  • Software package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
  • pKa can also be determined by molecular orbital calculation method.
  • a specific method for this includes a method of calculating H 2 + dissociation free energy in an aqueous solution based on a thermodynamic cycle.
  • the H + dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to this. .
  • DFT density functional theory
  • there is a plurality of software that can perform DFT and one example is Gaussian 16.
  • pKa refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using software package 1, as described above. If calculation is not possible, a value obtained by Gaussian 16 based on DFT (density functional theory) is used.
  • pKa refers to "pKa in aqueous solution” as described above, but if pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is adopted. shall be.
  • solid content means a component that forms an actinic ray-sensitive or radiation-sensitive film, and does not include a solvent. Furthermore, if the component forms an actinic ray-sensitive or radiation-sensitive film, it is considered to be a solid content even if the component is liquid.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as the "composition of the present invention") comprises at least a resin (A) whose polarity increases due to the action of an acid, and the following general formula (B- This is an actinic ray-sensitive or radiation-sensitive resin composition containing the compound (B) represented by 1).
  • X represents a cyclic group having 4 to 20 carbon atoms and having an unsaturated bond.
  • Each of the plurality of Rb 1 's independently represents -OH, -ORb 3 , -NRb 4 Rb 5 , -SH, or -SRb 6 .
  • at least one Rb 1 represents -OH, -NHRb 4 ', or -SH bonded to a carbon atom forming an unsaturated bond.
  • Rb 3 represents an alkyl group, an aryl group, an acyl group, an acyloxy group, or a combination thereof.
  • Rb 4 and Rb 5 each independently represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, -CHO, or a group bonded to each other to form a nitrogen-containing heterocycle.
  • Rb 4 ' represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or -CHO.
  • Rb 6 represents an alkyl group, an aryl group, or an acyl group.
  • a plurality of Rb 1 may be bonded to each other to form a ring.
  • Rb 2 represents a substituent.
  • the plurality of Rb 2s may be the same or different, and the plurality of Rb 2s may be bonded to each other to form a ring.
  • Rb 1 and Rb 2 may be combined with each other to form a ring.
  • m represents an integer from 0 to 6
  • n represents an integer from 2 to 4.
  • the compound represented by the above general formula (B-1) does not have a halogen atom.
  • the composition of the present invention has excellent density dependence in forming extremely fine patterns (for example, line-and-space patterns with a line width of 50 nm or less, hole patterns with a hole diameter of 50 nm or less, etc.), the present invention They estimate as follows.
  • the compound (B) contained in the composition of the present invention has a cyclic group having an unsaturated bond. Furthermore, the above cyclic group is substituted with at least two specific electron-donating groups, at least one of which is -OH, -NHRb 3 , -SH bonded to a carbon atom forming an unsaturated bond. It is a group with strong electron-donating properties.
  • the cyclic group possessed by compound (B) becomes electron-rich and easily releases secondary electrons when irradiated with actinic light or radiation such as EUV or EB, and the pattern obtained by a composition containing this group becomes electron-rich. It is estimated that it will be easier to obtain the desired pattern regardless of the situation.
  • the compound (B) contained in the composition of the present invention does not have a halogen atom. Therefore, the reduction in the amount of secondary electron emission due to electron withdrawal from the cyclic group by the halogen atom, and the absence of side reactions due to the reaction between the secondary electrons and the halogen atom, also contribute to the formation of the desired pattern. I believe.
  • the composition of the present invention is considered to have excellent density dependence in the formation of extremely fine patterns (for example, line-and-space patterns with a line width of 50 nm or less, hole patterns with a hole diameter of 50 nm or less, etc.). .
  • the composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition.
  • the composition of the present invention may be a resist composition for alkaline development or an organic solvent development resist composition.
  • the composition of the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition.
  • the composition of the present invention is typically a chemically amplified resist composition.
  • Actinic ray-sensitive or radiation-sensitive films can be formed using the composition of the present invention.
  • the actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film.
  • composition of the present invention contains a compound (B) represented by the above general formula (B-1). Note that compound (B) is a nonionic compound.
  • X represents a cyclic group having 4 to 20 carbon atoms and having an unsaturated bond.
  • the number of carbon atoms here refers to the number of carbon atoms as ring members constituting a ring, and does not include carbon atoms contained in a substituent when the cyclic group as X has a substituent.
  • the cyclic group may or may not have aromaticity.
  • non-aromatic cyclic group examples include an alicyclic group having an unsaturated bond and a non-aromatic heterocyclic group having an unsaturated bond.
  • the alicyclic group having an unsaturated bond may be monocyclic or polycyclic.
  • Examples of the alicyclic group having a monocyclic unsaturated bond include cycloalkenyl groups such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • As alicyclic groups having polycyclic unsaturated bonds for example, some carbon-carbon bonds in polycyclic cycloalkyl groups such as norbornyl groups, tricyclodecanyl groups, and adamantyl groups are unsaturated bonds (carbon - a cycloalkenyl group forming a carbon double bond).
  • the non-aromatic heterocyclic group having an unsaturated bond may be monocyclic or polycyclic.
  • non-aromatic heterocycles having unsaturated bonds include those in which some carbon-carbon bonds form unsaturated bonds, such as tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. Examples include heterocycles with
  • aromatic cyclic group examples include an aryl group and an aromatic heterocyclic group.
  • the aryl group may be monocyclic or polycyclic.
  • Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
  • the aromatic heterocyclic group may be monocyclic or polycyclic.
  • the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, an indole ring, a benzodiazole ring, and a carbazole ring.
  • a furan ring a thiophene ring
  • a benzofuran ring a benzothiophene ring
  • a dibenzofuran ring a dibenzothiophene ring
  • a pyridine ring an indole ring
  • a benzodiazole ring a carbazole ring
  • X is preferably a group having aromaticity, more preferably an aryl group, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
  • a plurality of Rb 1 each independently represent -OH, -ORb 3 , -NRb 4 Rb 5 , -SH, or -SRb 6 .
  • at least one Rb 1 represents -OH, -NHRb 4 ', or -SH bonded to a carbon atom forming an unsaturated bond.
  • Rb 3 represents an alkyl group, an aryl group, an acyl group, an acyloxy group, or a combination thereof.
  • Rb 4 and Rb 5 each independently represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, -CHO, or a group bonded to each other to form a nitrogen-containing heterocycle.
  • Rb 4 ' represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or -CHO.
  • Rb 6 represents an alkyl group, an aryl group, or an acyl group.
  • Examples of the alkyl group represented by Rb 3 include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, and an n-propyl group.
  • the aryl group represented by Rb 3 includes aryl groups having 6 to 14 carbon atoms such as phenyl group and naphthyl group.
  • Examples of the acyl group represented by Rb 3 include a group in which the above-mentioned alkyl group or aryl group as Rb 3 is bonded to a carbonyl group.
  • Examples of the acyloxy group represented by Rb 3 include a group in which the above-mentioned acyl group as Rb 3 is bonded to an oxy group.
  • Examples of the alkyl group, aryl group, and acyl group represented by Rb 4 and Rb 5 include the alkyl group, aryl group, and acyl group represented by Rb 3 described above.
  • Rb 4 and Rb 5 may be bonded to each other to form a nitrogen-containing heterocyclic group.
  • the nitrogen-containing heterocycle formed by bonding Rb 4 and Rb 5 may be monocyclic or polycyclic, and includes a pyrazole ring, an imidazole ring, a triazole ring, a benzotriazole ring, and the like.
  • Examples of the alkyl group, aryl group, or acyl group represented by Rb 4 ' include the alkyl group, aryl group, and acyl group represented by Rb 3 described above.
  • Examples of the alkyl group, aryl group, and acyl group represented by Rb 6 include the alkyl group, aryl group, and acyl group represented by Rb 3 described above.
  • Each of Rb 3 to Rb 6 may further have a substituent.
  • substituents include an alkyl group (e.g., linear or branched having 1 to 12 carbon atoms), an aryl group (e.g., 6 to 14 carbon atoms), an acyl group (e.g., 2 to 12 carbon atoms), - Examples include OH, -COOH, and groups formed by combining these.
  • a plurality of Rb 1 may be bonded to each other to form a ring.
  • the ring formed by combining a plurality of Rb 1s is not particularly limited, but includes, for example, a monocyclic ring or a polycyclic ring containing a 5- or 6-membered ring.
  • At least one Rb 1 represents -OH, -NHRb 4 ', or -SH bonded to a carbon atom forming an unsaturated bond. It is preferable that two or more of Rb 1 represents -OH, -NHRb 4 ', or -SH bonded to a carbon atom forming an unsaturated bond, and two or three of Rb 1 bond to a carbon atom forming an unsaturated bond. More preferably, it represents -OH, -NHRb 4 ', or -SH.
  • Rb 1 is -OH bonded to a carbon atom forming an unsaturated bond, and more preferably two or more are -OH bonded to carbon atoms forming an unsaturated bond.
  • two or three Rb 1 are -OH bonded to carbon atoms forming an unsaturated bond.
  • Rb 2 represents a substituent.
  • Substituents represented by Rb 2 include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxycarbonyl groups, acyl groups, and heterocyclic groups (however, X in general formula (B-1) is a heterocyclic group). ), -COOH group, -SO 3 H group, etc.
  • Examples of the alkyl group represented by Rb 2 include straight-chain or branched alkyl groups having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, and an n-propyl group.
  • Examples of the alkenyl group represented by Rb 2 include alkenyl groups having 2 to 12 carbon atoms such as vinyl group and 2-propenyl group.
  • Examples of the cycloalkyl group represented by Rb 2 include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group.
  • Examples of the aryl group represented by Rb 2 include aryl groups having 6 to 14 carbon atoms such as phenyl group and naphthyl group.
  • Examples of the alkyl group in the alkoxycarbonyl group represented by Rb 2 include the alkyl groups described above as Rb 2 .
  • Examples of the acyl group represented by Rb 2 include a group in which the above-mentioned alkyl group or aryl group as Rb 2 is bonded to a carbonyl group.
  • heterocycles in the heterocyclic group represented by Rb 2 include heterocycles having 3 to 14 carbon atoms, such as aromatic heterocycles such as furan ring, thiophene ring, benzofuran ring, and benzothiophene ring, and tetrahydropyran ring.
  • aromatic heterocycles such as furan ring, thiophene ring, benzofuran ring, and benzothiophene ring, and tetrahydropyran ring.
  • Non-aromatic heterocycles such as
  • the substituent represented by Rb 2 may further have a substituent.
  • Further substituents include, for example, the above-mentioned substituents as Rb 2 , alkoxy groups (for example, having 1 to 12 carbon atoms), acyloxy groups (for example, having 2 to 12 carbon atoms), -OH, and combinations thereof. The following groups are mentioned.
  • the plurality of Rb 2s may be the same or different, and the plurality of Rb 2s may be bonded to each other to form a ring.
  • Rb 1 and Rb 2 may be bonded to each other to form a ring.
  • the ring formed by combining a plurality of Rb 1 or the ring formed by combining Rb 1 and Rb 2 is not particularly limited, but includes, for example, a monocyclic ring or a polycyclic ring containing a 5- or 6-membered ring. It will be done.
  • n represents an integer of 2 to 4. n is preferably 2 or 3.
  • the compound represented by the general formula (B-1) is preferably a compound represented by the following general formula (B-b).
  • Each of the plurality of Rb 1b independently represents -OH, -ORb 3 , -NRb 4 Rb 5 , -SH, or -SRb 6 .
  • at least one Rb 1b represents -OH.
  • Rb 3 represents an alkyl group, an aryl group, an acyl group, an acyloxy group, or a combination thereof.
  • Rb 4 and Rb 5 each independently represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, -CHO, or a group bonded to each other to form a nitrogen-containing heterocycle.
  • Rb 6 represents an alkyl group, an aryl group, or an acyl group.
  • a plurality of Rb 1b may be bonded to each other to form a ring.
  • Rb 2 represents a substituent. When a plurality of Rb 2s exist, the plurality of Rb 2s may be the same or different, and the plurality of Rb 2s may be bonded to each other to form a ring. Rb 1b and Rb 2 may be bonded to each other to form a ring.
  • m represents an integer from 0 to 6
  • n represents an integer from 2 to 4.
  • p represents 0 or 1.
  • m, n, and Rb 2 have the same meanings as m, n, and Rb 2 in general formula (B-1), respectively, and preferred examples are also the same.
  • Each substituent represented by Rb 1b in general formula (B-b) has the same meaning as each substituent represented by Rb 1 in general formula (B-1).
  • at least one Rb 1b represents -OH.
  • two or more Rb 1b are -OH, and more preferably two or three Rb 1b are -OH.
  • the compound represented by the above general formula (B-1) does not have a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Since the above compound does not have a halogen atom, the amount of secondary electron emission decreases due to the halogen atom withdrawing electrons from the cyclic group, and side reactions due to the reaction between the secondary electron and the halogen atom occur. It doesn't happen.
  • each group in the above general formula (B-1) does not have a halogen atom.
  • compound (B) may or may not have a group that decomposes under the action of an acid, but preferably does not have a group that decomposes under the action of an acid.
  • the group decomposed by the action of an acid is the same as the group decomposed by the action of an acid as A in general formula (c1) described below.
  • the molecular weight of compound (B) is preferably 1500 or less, more preferably 1000 or less, from the viewpoint of solubility in a developer.
  • the lower limit is not particularly limited, but may be, for example, 100 or more.
  • Compound (B) can be synthesized by a known method and is also available as a commercial product.
  • composition of the present invention may contain one type of compound (B) or two or more types.
  • the content of compound (B) is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the total solid content of the composition of the present invention.
  • the composition of the present invention may contain a compound (impurity) produced by oxidation of compound (B).
  • a compound (impurity) produced by oxidation of compound (B) include compounds having a quinone structure.
  • the above-mentioned impurities are preferably 1.0% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less, based on the total solid content of the composition of the present invention.
  • the composition of the present invention includes a resin whose polarity increases under the action of an acid (hereinafter also referred to as "resin (A)").
  • the resin (A) usually contains a group that is decomposed by the action of an acid to increase its polarity (hereinafter also referred to as an "acid-decomposable group”), and preferably contains a repeating unit having an acid-decomposable group.
  • an acid-decomposable group when an alkaline developer is typically employed as the developer in the pattern forming method of the present specification, a positive pattern is suitably formed, and development When an organic developer is used as the liquid, a negative pattern is suitably formed.
  • a repeating unit having an acid-decomposable group containing an unsaturated bond is preferable.
  • An acid-decomposable group refers to a group that is decomposed by the action of an acid to produce a polar group.
  • the acid-decomposable group preferably has a structure in which a polar group is protected by a group that leaves by the action of an acid (leaving group). That is, the resin (A) has a repeating unit having a group that is decomposed by the action of an acid to produce a polar group.
  • a resin having this repeating unit has increased polarity due to the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.
  • the polar group is preferably an alkali-soluble group, such as carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric 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) Examples include acidic groups such as methylene group and tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.
  • alkali-soluble group such as carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulf
  • a carboxyl group a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.
  • Examples of groups that are eliminated by the action of acids include groups represented by formulas (Y1) to (Y4).
  • Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
  • Formula (Y3) -C(R 36 )(R 37 )(OR 38 )
  • Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight chain) or branched chain), or an aryl group (monocyclic or polycyclic). Note that when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups. Among these, it is preferable that Rx 1 to Rx 3 each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferable.
  • Rx 1 to Rx 3 may be combined to form a monocyclic ring or a polycyclic ring.
  • alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. preferable.
  • Examples of the cycloalkyl group for Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • a polycyclic cycloalkyl group is preferred.
  • the aryl group for Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, and an anthryl group.
  • the alkenyl group for Rx 1 to Rx 3 a vinyl group is preferred.
  • the ring formed by bonding two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
  • the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group.
  • a polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is a group in which one of the methylene groups constituting the ring contains a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinylidene group. It may be replaced with .
  • one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
  • the group represented by formula (Y1) or formula (Y2) is, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group. is preferred.
  • the composition of the present invention is, for example, an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group represented by Rx 1 to Rx 3 , and It is also preferable that the ring formed by bonding two of Rx 1 to Rx 3 further has a fluorine atom or an iodine atom as a substituent.
  • R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may be combined with each other to form a ring.
  • the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
  • R 36 is a hydrogen atom.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group containing a heteroatom such as an oxygen atom and/or a heteroatom such as a carbonyl group.
  • one or more methylene groups may be replaced with a group containing a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group.
  • R 38 may be bonded to another substituent in the main chain of the repeating unit to form a ring.
  • the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
  • composition of the present invention is, for example, an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, monovalent organic groups represented by R 36 to R 38 and R 37 and R 38 It is also preferable that the ring formed by bonding with each other further has a fluorine atom or an iodine atom as a substituent.
  • formula (Y3) a group represented by the following formula (Y3-1) is preferable.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group).
  • M represents a single bond or a divalent linking group.
  • Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde represents a group or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
  • one of the methylene groups may be replaced with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group.
  • L 1 and L 2 are a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L 1 may be combined to form a ring (preferably a 5-membered or 6-membered ring).
  • L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
  • Examples of the secondary alkyl group include isopropyl group, cyclohexyl group, and norbornyl group, and examples of the tertiary alkyl group include tert-butyl group and adamantane group.
  • Tg glass transition temperature
  • activation energy are increased, film strength can be ensured and fogging can be suppressed.
  • composition of the present invention is, for example, an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, an alkyl group, a cycloalkyl group, an aryl group represented by L 1 and L 2 ; It is also preferable that the group combining these further has a fluorine atom or an iodine atom as a substituent. It is also preferable that the alkyl group, cycloalkyl group, aryl group, and aralkyl group contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group one of the methylene groups is replaced with a hetero atom such as an oxygen atom, or a group containing a hetero atom such as a carbonyl group. You can leave it there.
  • the composition of the present invention is, for example, an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it may contain an alkyl group represented by Q that may contain a hetero atom, or a hetero atom.
  • an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, and a group combining these
  • the hetero atom include a fluorine atom and an iodine atom. It is also preferred that it is a heteroatom selected from the group consisting of and oxygen atoms.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and Ar may be bonded to each other to form a non-aromatic ring.
  • an aryl group is preferable.
  • the composition of the present invention is, for example, an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, an aromatic ring group represented by Ar, and an alkyl group or cycloalkyl group represented by Rn, It is also preferable that the aryl group has a fluorine atom or an iodine atom as a substituent.
  • the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have a halogen atom such as a fluorine atom as a substituent.
  • Groups that are eliminated by the action of acids include 2-cyclopentenyl groups having substituents (alkyl groups, etc.) such as 3-methyl-2-cyclopentenyl groups, and 1,1,4,4 A cyclohexyl group having a substituent (alkyl group, etc.) such as -tetramethylcyclohexyl group may be used.
  • the resin (A) has a repeating unit represented by the following general formula (A-1) or (A-2) as a repeating unit having an acid-decomposable group from the viewpoint of improving roughness performance.
  • Ra 1 to Ra 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • La 1 represents a divalent linking group having an aromatic group.
  • Ra 4 to Ra 6 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, or an alkenyl group. Note that two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
  • Ra 7 to Ra 9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • La 2 represents a single bond or a divalent linking group.
  • Ara represents an aromatic ring group.
  • Ra 10 to Ra 12 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, an alkoxy group, or an alkenyl group. Note that Ra 10 to Ra 12 may be bonded to each other to form a ring. Furthermore, Ra 9 to Ra 12 may be combined with Ara.
  • Ra 1 to Ra 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • the alkyl groups of Ra 1 to Ra 3 may be either linear or branched.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3.
  • the number of carbon atoms in the cycloalkyl group of Ra 1 to Ra 3 is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15.
  • Examples of the cycloalkyl group for Ra 1 to Ra 3 include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • a cycloalkyl group is preferred.
  • Examples of the halogen atom of Ra 1 to Ra 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or an iodine atom being preferred.
  • the alkyl group contained in the alkoxycarbonyl group of Ra 1 to Ra 3 may be either linear or branched.
  • the number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3.
  • Ra 1 to Ra 3 are preferably each independently a hydrogen atom or an alkyl group, more preferably Ra 1 and Ra 3 are hydrogen atoms, and Ra 2 is a hydrogen atom or a methyl group.
  • La 1 represents a divalent linking group having an aromatic group. It is preferable that La 1 contains an arylene group. La 1 preferably represents an arylene group or a divalent linking group containing an arylene group and a divalent linking group other than the arylene group. Examples of divalent linking groups other than arylene groups include carbonyl group (-CO-), -O-, -S-, -SO-, -SO 2 -, amide group (-CONR-), and sulfonamide group (- SO 2 NR-), an alkylene group, a cycloalkylene group, an alkenylene group, and a linking group in which a plurality of these are linked.
  • Each of the above R represents a hydrogen atom or an organic group, and the organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.
  • the divalent linking group other than the arylene group is preferably at least one of a carbonyl group and -O-, and more preferably a carbonyl group.
  • La 1 represents an arylene group or a divalent linking group consisting of an arylene group and a carbonyl group.
  • the arylene group contained in La 1 is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and particularly preferably a phenylene group.
  • Ra 3 and La 1 in general formula (A-1) may be connected to form a ring.
  • the aromatic group contained in La 1 may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, an acyloxy group, and an alkoxy group. Examples include carbonyl group, halogen atom, and cyano group.
  • Ra 4 to Ra 6 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, or an alkenyl group.
  • the alkyl groups of Ra 4 to Ra 6 may be either linear or branched.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6.
  • the methylene group contained in the alkyl group of Ra 4 to Ra 6 may be replaced with at least one of -CO- and -O-.
  • the number of carbon atoms in the cycloalkyl group of Ra 4 to Ra 6 is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15.
  • Examples of the cycloalkyl group for Ra 4 to Ra 6 include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • a cycloalkyl group is preferred.
  • the number of carbon atoms in the aryl group of Ra 4 to Ra 6 is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10.
  • the most preferred aryl group for Ra 4 to Ra 6 is a phenyl group.
  • the aralkyl group of Ra 4 to Ra 6 is preferably a group in which one hydrogen atom in the alkyl group of Ra 4 to Ra 6 described above is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), For example, a benzyl group and the like can be mentioned.
  • the number of carbon atoms in the alkenyl group of Ra 4 to Ra 6 is not particularly limited, but is preferably 2 to 5, more preferably 2 to 4.
  • a vinyl group is preferred.
  • the aromatic heterocyclic group of Ra 4 to Ra 6 preferably contains at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom, and more preferably a sulfur atom.
  • the number of heteroatoms contained in the aromatic heterocyclic group is preferably 1 to 5, more preferably 1 to 3.
  • the number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably from 2 to 20, more preferably from 3 to 15.
  • the aromatic heterocyclic group may be monocyclic or polycyclic.
  • Examples of the aromatic heterocyclic group of Ra 4 to Ra 6 include thienyl group, furanyl group, benzothienyl group, dibenzothienyl group, benzofuranyl group, pyrrole group, oxazolyl group, thiazolyl group, pyridyl group, isothiazolyl group, thiadiazolyl group. Examples include groups. Each group represented by Ra 4 to Ra 6 may have a substituent. Examples of the substituent include the above substituent T, and preferred are an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, and an alkoxy group. Furthermore, two or more substituents may be bonded to each other to form a ring.
  • Two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
  • the repeating unit represented by general formula (A-1) is preferably a repeating unit represented by general formula (A-11) below.
  • Ra 1 to Ra 3 and Ra 4 to Ra 6 in general formula (A-11) are respectively synonymous with Ra 1 to Ra 3 and Ra 4 to Ra 6 in general formula (A-1) above, and are preferable.
  • the example is similar.
  • La 11 represents a single bond or a divalent linking group.
  • the linking group include carbonyl group (-CO-), -O-, -S-, -SO-, -SO 2 -, amide group (-CONR-), Examples include a sulfonamide group (-SO 2 NR-), an alkylene group, a cycloalkylene group, an alkenylene group, and a linking group in which a plurality of these are linked.
  • Each of the above R represents a hydrogen atom or an organic group, and the organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.
  • La 11 is preferably a single bond or *-CO-O-**. * represents a bond with the carbon atom of the main chain, and ** represents a bond with an aromatic ring group.
  • Ra 0 represents an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, a halogen atom, or a cyano group.
  • the plurality of Ra 0s may be the same or different.
  • na represents an integer of 0 to 4.
  • ma represents an integer from 0 to 2.
  • na is preferably 0 or 1.
  • Ma is preferably 0 or 1.
  • repeating unit represented by general formula (A-1) Specific examples of the repeating unit represented by general formula (A-1) are shown below, but the present invention is not limited thereto.
  • Ra 7 to Ra 9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • the alkyl group, cycloalkyl group, halogen atom, cyano group, and alkoxycarbonyl group represented by Ra 7 to Ra 9 include the alkyl group, cycloalkyl group, and cycloalkyl group represented by Ra 1 to Ra 3 in the above general formula (A-1). group, a halogen atom, a cyano group, and an alkoxycarbonyl group.
  • Ra 7 to Ra 9 are preferably each independently a hydrogen atom or an alkyl group, more preferably Ra 7 and Ra 9 are hydrogen atoms, and Ra 8 is a hydrogen atom or a methyl group.
  • La 2 represents a single bond or a divalent linking group.
  • the linking group include carbonyl group (-CO-), -O-, -S-, -SO-, -SO 2 -, amide group (-CONR-), Examples include a sulfonamide group (-SO 2 NR-), an alkylene group, a cycloalkylene group, an alkenylene group, and a linking group in which a plurality of these are linked.
  • Each of the above R represents a hydrogen atom or an organic group, and the organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof.
  • La 2 is preferably a single bond.
  • Ara represents an aromatic ring group.
  • Ara preferably represents an arylene group, preferably represents an arylene group having 6 to 20 carbon atoms, more preferably represents an arylene group having 6 to 10 carbon atoms, and particularly preferably represents a phenylene group.
  • Ra 10 to Ra 12 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, an aralkyl group, an alkoxy group, or an alkenyl group. represents.
  • the alkyl group, cycloalkyl group, aryl group, aromatic heterocyclic group, aralkyl group, and alkenyl group represented by Ra 10 to Ra 12 include Ra 4 to Ra 6 in the above general formula (A-1). Examples include alkyl groups, cycloalkyl groups, aryl groups, aromatic heterocyclic groups, aralkyl groups, and alkenyl groups, and preferred examples are also the same.
  • Examples of the alkyl group possessed by the alkoxy group represented by Ra 10 to Ra 12 include the alkyl groups represented by Ra 4 to Ra 6 in the above-mentioned general formula (A-1), and preferred examples are also the same.
  • Each group represented by Ra 10 to Ra 12 may have a substituent.
  • Ra 10 to Ra 12 may be bonded to each other to form a ring. Furthermore, Ra 9 to Ra 12 may be combined with Ara.
  • repeating unit represented by general formula (A-2) Specific examples of the repeating unit represented by general formula (A-2) are shown below, but the present invention is not limited thereto.
  • the number of repeating units represented by general formula (A-1) or (A-2) contained in the resin (A) may be one or two or more.
  • the content of the repeating unit represented by general formula (A-1) or (A-2) is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total repeating units in the resin (A). Preferably, 15 mol% or more is more preferable. Further, the content of the repeating unit represented by general formula (A-1) or (A-2) is preferably 70 mol% or less, and 60 mol% or less, based on all repeating units in the resin (A). is more preferable, and even more preferably 50 mol% or less.
  • the resin (A) further contains another acid-decomposable repeating unit (a repeating unit having an acid-decomposable group). May contain.
  • the resin (A) contains a repeating unit having a polar group from the viewpoint of improving roughness performance.
  • polar groups include hydroxyl group, lactone structure, saltone structure, lactam structure, imide structure, amide structure, sulfonamide structure, carbonate structure, urethane structure, urea structure, nitrile structure, sulfoxide structure, and sulfone structure.
  • a repeating unit having an aromatic hydroxyl group is preferable, and a repeating unit having an aromatic hydroxyl group is particularly preferable.
  • the repeating unit containing an aromatic hydroxyl group is preferably a repeating unit represented by the following general formula (A-3).
  • the resin (A) preferably has a repeating unit represented by the following general formula (A-3).
  • R 101 , R 102 and R 103 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group.
  • R 102 may be combined with Ar A to form a ring, and in that case R 102 represents a single bond or an alkylene group.
  • L A represents a single bond or a divalent linking group.
  • Ar A represents an aromatic ring group.
  • k represents an integer from 1 to 5.
  • R 101 , R 102 and R 103 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group.
  • Examples of the alkyl group represented by R 101 to R 103 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group.
  • An alkyl group having 20 or less carbon atoms is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is still more preferable.
  • the cycloalkyl group represented by R 101 to R 103 may be monocyclic or polycyclic. Among these, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group are preferred.
  • the alkyl group contained in the alkoxycarbonyl group represented by R 101 to R 103 is preferably the same as the alkyl group in R 101 to R 103 above.
  • the alkylene group for R 102 is preferably a group obtained by removing one arbitrary hydrogen atom from the alkyl group in R 101 to R 103 above.
  • Examples of the halogen atom represented by R 101 to R 103 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
  • Preferred substituents for each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. , an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group.
  • the number of carbon atoms in the substituent is preferably 8 or less.
  • Ar A represents a (k+1)-valent aromatic ring group.
  • R 102 When R 102 is combined with Ar A to form a ring, it represents a (k+2)-valent aromatic ring group.
  • the divalent aromatic ring group when k is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, and anthracenylene group.
  • a hetero ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring.
  • a ring group is preferred.
  • (k+1)-valent aromatic ring groups when k is an integer of 2 or more include (k-1) arbitrary hydrogen atoms removed from the above-mentioned specific examples of divalent aromatic ring groups. The following groups are mentioned.
  • the (k+1)-valent aromatic ring group may further have a substituent.
  • substituents that the (k+1)-valent aromatic ring group may have include a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, and an alkylsulfonyloxy group. , an alkyloxycarbonyl group, an aryloxycarbonyl group, and the like. A plurality of substituents may be combined to form a ring.
  • Ar A is preferably an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group.
  • the repeating unit represented by general formula (A-3) preferably has a hydroxystyrene structure. That is, Ar A is preferably a benzene ring group, more preferably a phenylene group (a divalent benzene ring group).
  • L A represents a single bond or a divalent linking group.
  • the divalent linking group represented by L A includes *-X 4 -L 4 -**.
  • X 4 represents a single bond, -COO-, or -CONR 64 -
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 4 represents a single bond or an alkylene group. * is a bond with the carbon atom of the main chain in general formula (A-3), and ** is a bond with Ar A.
  • the alkyl group of R 64 in -CONR 64 - (R 64 represents a hydrogen atom or an alkyl group) represented by X 4 includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec Examples include alkyl groups having 20 or less carbon atoms such as -butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or less carbon atoms being preferred.
  • X 4 is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond or -COO-.
  • the alkylene group for L 4 is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.
  • L A is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond.
  • k represents an integer of 1 to 5.
  • k is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • the repeating unit represented by general formula (A-3) is preferably a repeating unit represented by general formula (1) below.
  • A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
  • R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and there are a plurality of them. They may be the same or different depending on the case. When a plurality of R's are present, they may cooperate with each other to form a ring.
  • R is preferably a hydrogen atom.
  • a represents an integer from 1 to 3.
  • b represents an integer from 0 to (3-a).
  • repeating unit represented by general formula (A-3) are shown below, but the present invention is not limited thereto.
  • a represents an integer of 1 to 3.
  • R represents a hydrogen atom or a methyl group
  • a represents an integer of 1 to 3.
  • examples of polar groups include acid groups.
  • examples of the acid group include acid groups in the "repeating unit having an acid group" described below.
  • the content of the repeating unit having a polar group is preferably 5 mol% or more with respect to all repeating units in the resin (A), and 10 It is more preferably mol % or more, and even more preferably 20 mol % or more. Further, the content of repeating units having polar groups is preferably 90 mol% or less, more preferably 85 mol% or less, and 80 mol% or less, based on all repeating units in the resin (A). It is more preferable that it is the following.
  • the resin (A) may contain at least one repeating unit selected from the group consisting of the following group A, and/or at least one repeating unit selected from the group consisting of the following group B. good.
  • Group A A group consisting of the following repeating units (20) to (25).
  • (20) A repeating unit having an acid group, as described below.
  • a repeating unit having a photoacid generating group described below A repeating unit having a photoacid generating group described later (25)
  • Group B A group consisting of the following repeating units (30) to (32).
  • a preferred embodiment of the resin (A) includes an embodiment in which the resin (A) contains at least one of a repeating unit having a phenolic hydroxyl group and a repeating unit having a lactone group. This improves the adhesion of the resist film formed from the composition of the present invention to the substrate.
  • the resin (A) preferably has an acid group, and as described below, preferably contains a repeating unit having an acid group.
  • the resin (A) has an acid group, the interaction between the resin (A) and the acid generated from the photoacid generator is more excellent. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can be made more rectangular.
  • the resin (A) may have at least one repeating unit selected from the group consisting of the above group A.
  • the resin (A) should have at least one repeating unit selected from the group consisting of the above group A. is preferred.
  • the resin (A) may contain at least one of a fluorine atom and an iodine atom.
  • the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
  • the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom; It may contain two types: a repeating unit having a fluorine atom and a repeating unit containing an iodine atom.
  • the resin (A) may have at least one repeating unit selected from the group consisting of Group B above.
  • the resin (A) may have at least one repeating unit selected from the group consisting of the above group B. preferable.
  • the resin (A) contains neither a fluorine atom nor a silicon atom.
  • the resin (A) may have a repeating unit having an acid group.
  • an acid group having a pKa of 13 or less is preferable.
  • the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10.
  • the content of acid groups in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among these, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and even more preferably 1.6 to 4.0 mmol/g.
  • the content of acid groups is within the above range, development proceeds well, the formed pattern shape is excellent, and the resolution is also excellent.
  • the acid group for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group is preferable.
  • hexafluoroisopropanol group one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group).
  • the repeating unit having an acid group is different from the above-mentioned repeating unit having a structure in which the polar group is protected with a group that is eliminated by the action of an acid, and the repeating unit having a lactone group, sultone group, or carbonate group described below. Preferably it is a repeating unit.
  • the repeating unit having an acid group may have a fluorine atom or an iodine atom.
  • repeating unit having an acid group in addition to specific examples of the repeating unit represented by the above-mentioned general formula (A-3), the following repeating units may be mentioned.
  • the content of the repeating unit having an acid group is preferably 5 mol% or more, and 10 mol% or more, based on all the repeating units in the resin (A). is more preferable.
  • the upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on all repeating units in the resin (A).
  • Resin (A) is a repeating unit that does not have either an acid-decomposable group or an acid group and has a fluorine atom, a bromine atom, or an iodine atom, in addition to the above-mentioned acid-decomposable repeating units and repeating units having an acid group. (hereinafter also referred to as unit X).
  • the ⁇ repeat unit having neither an acid-decomposable group nor an acid group but a fluorine atom, a bromine atom, or an iodine atom> referred to herein means the ⁇ repeat unit having a lactone group, sultone group, or carbonate group> described below. It is preferable that the repeating unit is different from other types of repeating units belonging to Group A, such as , and ⁇ repeat unit having a photoacid generating group>.
  • a repeating unit represented by formula (C) is preferable.
  • L 5 represents a single bond or an ester group.
  • R 9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.
  • R10 may have a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, a fluorine atom or an iodine atom. Represents an aryl group or a group combining these.
  • repeating units having a fluorine atom or an iodine atom are shown below.
  • the content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in the resin (A).
  • the total content of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom is preferably 10 mol% or more based on all repeating units of the resin (A). , more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 40 mol% or more.
  • the upper limit is not particularly limited, but is, for example, 100 mol% or less based on all repeating units of the resin (A).
  • the repeating unit containing at least one of a fluorine atom, a bromine atom, and an iodine atom includes, for example, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and an acid-decomposable group, a fluorine atom, a bromine atom, and a repeating unit having an acid-decomposable group.
  • Examples include repeating units having an atom or an iodine atom and an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.
  • the resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one type selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferable that the unit Y does not have an acid group such as a hydroxyl group or a hexafluoropropanol group.
  • the unit Y also corresponds to the above-mentioned repeating unit having a polar group.
  • the lactone group or sultone group may have a lactone structure or a sultone structure.
  • the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
  • 5- to 7-membered ring lactone structures are fused with other ring structures to form a bicyclo or spiro structure, or 5- to 7-membered sultone structures to form a bicyclo or spiro structure. More preferred is a structure in which another ring structure is condensed.
  • the resin (A) has a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or a lactone structure represented by any of the following formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or sultone group formed by abstracting one or more hydrogen atoms from a ring member atom of a sultone structure, and the lactone group or sultone group may be directly bonded to the main chain.
  • ring member atoms of a lactone group or a sultone group may constitute the main chain of the resin (A).
  • the lactone structure or sultone structure may have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include 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 1 to 8 carbon atoms, and a carboxyl group. , a halogen atom, a cyano group, and an acid-decomposable group.
  • n2 represents an integer from 0 to 4. When n2 is 2 or more, a plurality of Rb 2s may be different, or a plurality of Rb 2s may be bonded to each other to form a ring.
  • Examples of the unit include a repeating unit represented by the following formula (AI).
  • Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group.
  • Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linkage of a combination thereof. represents a group.
  • Ab is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -.
  • Ab 1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group.
  • V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-21), or Represents a group formed by abstracting one hydrogen atom from a ring member atom of a sultone structure represented by any of 3).
  • any optical isomer may be used. Further, one type of optical isomer may be used alone or a plurality of optical isomers may be used in combination. When one type of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
  • a cyclic carbonate group is preferable.
  • a repeating unit having a cyclic carbonate group a repeating unit represented by the following formula (A-1) is preferable.
  • R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
  • n represents an integer of 0 or more.
  • R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 's may be the same or different.
  • A represents a single bond or a divalent linking group.
  • the divalent linking group mentioned above is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these.
  • a valent linking group is preferred.
  • Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.
  • Rx represents a hydrogen atom, -CH 3 , -CH 2 OH, or -CF 3 .
  • the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in the resin (A).
  • the upper limit thereof is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, particularly 60 mol% or less, based on all repeating units in the resin (A). preferable.
  • the resin (A) is a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (preferably an electron beam or extreme ultraviolet rays) (hereinafter also referred to as a "photoacid generating group") as a repeating unit other than the above. It may have.
  • actinic rays or radiation preferably an electron beam or extreme ultraviolet rays
  • photoacid generating group a repeating unit having a group that generates an acid when decomposed by irradiation with an electron beam or extreme ultraviolet rays.
  • the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).
  • R 41 represents a hydrogen atom or a methyl group.
  • L 41 represents a single bond or a divalent linking group.
  • L 42 represents a divalent linking group.
  • R 40 represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain. Examples of repeating units having a photoacid generating group are shown below.
  • examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs [0094] to [0105] of JP2014-041327A and WO2018/193954A. Examples include the repeating units described in paragraph [0094].
  • the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more with respect to all repeating units in the resin (A), More preferably 5 mol% or more. Further, the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on all repeating units in the resin (A).
  • the resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
  • the repeating units represented by the following formulas (V-1) and (V-2) are preferably repeating units different from the above-mentioned repeating units.
  • R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is the number of carbon atoms 1 to 6 alkyl groups or fluorinated alkyl groups), or carboxyl groups.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • n 3 represents an integer from 0 to 6.
  • n 4 represents an integer from 0 to 4.
  • X 4 is a methylene group, an oxygen atom, or a sulfur atom.
  • Examples of the repeating unit represented by formula (V-1) or (V-2) are shown below.
  • Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating unit described in paragraph [0100] of International Publication No. 2018/193954.
  • the resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development.
  • Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C.
  • Tg is preferably 400°C or less, more preferably 350°C or less.
  • Tg of a repeating unit the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of a repeating unit" is calculated by the following method.
  • the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method.
  • the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated.
  • the Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed to determine the Tg (° C.) of the polymer.
  • the Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
  • the resin (A) In order to increase the Tg of the resin (A) (preferably to make the Tg higher than 90° C.), it is preferable to reduce the mobility of the main chain of the resin (A).
  • methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e). (a) Introduction of a bulky substituent to the main chain (b) Introduction of multiple substituents to the main chain (c) Introduction of a substituent that induces interaction between the resins (A) near the main chain ( d) Main chain formation with a cyclic structure (e) Connection of the cyclic structure to the main chain It is preferable that the resin (A) has a repeating unit whose homopolymer Tg is 130° C. or higher.
  • the resin (A) may have a repeating unit having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
  • Examples of the repeating unit having a lactone group, sultone group, or carbonate group that the resin (A) has include the repeating units described in ⁇ Repeating unit having a lactone group, sultone group, or carbonate group> described above.
  • the preferable content is also as explained above in ⁇ Repeating unit having lactone group, sultone group, or carbonate group>.
  • the resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity.
  • the repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
  • the repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A No. 2014-098921.
  • the resin (A) may have a repeating unit having an alkali-soluble group.
  • the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the ⁇ position (for example, a hexafluoroisopropanol group). , carboxyl group is preferred.
  • the resin (A) contains a repeating unit having an alkali-soluble group, resolution in contact hole applications increases. Examples of the repeating unit having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.
  • the resin (A) has an alicyclic hydrocarbon structure and may have repeating units that are not acid-decomposable. This can reduce the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure.
  • repeating units having an alicyclic hydrocarbon structure and not showing acid decomposability include 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate. Examples include repeating units derived from acrylates.
  • the resin (A) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.
  • R 5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
  • Ra represents a hydrogen atom, an alkyl group, or two groups of -CH 2 -O-Ra.
  • Ra 2 represents a hydrogen atom, an alkyl group or an acyl group. Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A No. 2014-098921.
  • the resin (A) may have repeating units other than the above-mentioned repeating units.
  • the resin (A) has a repeating unit selected from the group consisting of a repeating unit having an oxathian ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. You may do so.
  • the resin (A) contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. It may have.
  • the repeating unit is composed of repeating units.
  • all of the repeating units are composed of (meth)acrylate repeating units.
  • all of the repeating units are methacrylate repeating units
  • all of the repeating units are acrylate repeating units
  • all of the repeating units are methacrylate.
  • Either a type repeating unit or an acrylate type repeating unit can be used, and it is preferable that the acrylate type repeating unit accounts for 50 mol% or less of the total repeating units.
  • Resin (A) can be synthesized according to conventional methods (eg, radical polymerization).
  • the weight average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, and even more preferably 3,000 to 30,000, as a polystyrene equivalent value determined by GPC method. Particularly preferred is 5,000 to 15,000.
  • the degree of dispersion (molecular weight distribution, Pd, Mw/Mn) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and 1.2 to 2.0. is particularly preferred. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
  • composition of the present invention may contain one type of resin (A) or two or more types.
  • the content of the resin (A) is preferably 40.0 to 99.9% by mass, and 60.0 to 90.0% by mass, based on the total solid content of the composition of the present invention. is more preferable.
  • the resin (A) may be used alone or in combination.
  • the composition of the present invention preferably contains a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation.
  • the photoacid generator may be in the form of a low molecular compound or may be incorporated into a part of the polymer. Further, a form of a low molecular compound and a form incorporated into a part of a polymer may be used together.
  • the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
  • the lower limit is not particularly limited, but is preferably 100 or more.
  • the photoacid generator When the photoacid generator is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A).
  • the photoacid generator is preferably in the form of a low molecular weight compound.
  • the photoacid generator is preferably a compound that generates an acid with a pKa of -2.0 or more when irradiated with actinic rays or radiation, and a compound that generates an acid with a pKa of -2.0 or more and 1.0 or less. It is more preferable that
  • Examples of the photoacid generator include a compound represented by "M + X - " (onium salt), and preferably a compound that generates an organic acid upon exposure to light.
  • Examples of the organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.), carbonylsulfonylimide acid, bis(alkylsulfonyl)imidic acid, and tris(alkylsulfonyl)methide acid.
  • sulfonic acids aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.
  • carboxylic acids aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.
  • carbonylsulfonylimide acid bis(al
  • M + represents an organic cation.
  • the organic cation is not particularly limited.
  • the valence of the organic cation may be one or more than two.
  • the organic cations include a cation represented by formula (ZaI) (hereinafter also referred to as “cation (ZaI)”), or a cation represented by formula (ZaII) (hereinafter referred to as “cation (ZaII)”).
  • ZaI cation represented by formula (ZaI)
  • ZaII cation (ZaII)
  • R 201 , R 202 , and R 203 each independently represent an organic group.
  • the number of carbon atoms in the organic group as R 201 , R 202 , and R 203 is preferably 1 to 30, more preferably 1 to 20.
  • Two of R 201 to R 203 may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
  • Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (for example, a butylene group and a pentylene group), and -CH 2 -CH 2 -O-CH 2 -CH 2 -. Can be mentioned.
  • Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.
  • the cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in the above formula (ZaI) is an aryl group.
  • the arylsulfonium cation all of R 201 to R 203 may be an aryl group, or some of R 201 to R 203 may be an aryl group, and the remainder 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 combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, or an ester group. , an amide group, or a carbonyl group.
  • the group formed by combining two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and/or a carbonyl group. and alkylene groups such as butylene, pentylene, and -CH 2 -CH 2 -O-CH 2 -CH 2 -.
  • Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
  • the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and 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 arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group that the arylsulfonium cation has as necessary is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms.
  • a cycloalkyl group is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group is more preferred.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may have include an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, having 3 to 15 carbon atoms).
  • aryl group for example, 6 to 14 carbon atoms
  • alkoxy group for example, 1 to 15 carbon atoms
  • cycloalkylalkoxy group for example, 1 to 15 carbon atoms
  • halogen atom for example, fluorine and iodine
  • a hydroxyl group for example, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group.
  • the above-mentioned substituent may further have a substituent if possible, and it is also preferable that the above-mentioned alkyl group has a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group. It is also preferable that the above substituents form an acid-decomposable group by any combination.
  • the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to produce a polar group, and preferably has a structure in which the polar group is protected with a group that is eliminated by the action of an acid.
  • the above polar group and leaving group are as described above.
  • the cation (ZaI-2) is a cation in which R 201 to R 203 in the formula (ZaI) each independently represent an organic group having no aromatic ring.
  • the aromatic ring also includes an aromatic ring containing a heteroatom.
  • the carbon number of the organic group having no aromatic ring as R 201 to R 203 is preferably 1 to 30, more preferably 1 to 20.
  • R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or An alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
  • the alkyl group and cycloalkyl group of R 201 to R 203 are, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group). , butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. It is also preferable that the substituents R 201 to R 203 each independently form an acid-decomposable group by any combination of substituents.
  • the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
  • R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkyl group.
  • R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
  • R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. It is also preferable that the substituents of R 1c to R 7c and R x and R y each independently form an acid-decomposable group by any combination of substituents.
  • R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring.
  • the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • the above-mentioned ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings.
  • the ring include 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 of R 1c to R 5c , R 6c and R 7c , and R x and R y include alkylene groups such as a butylene group and a pentylene group.
  • the methylene group in this alkylene group may be substituted with a hetero atom such as an oxygen atom.
  • the group formed by bonding R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
  • Alkylene groups include methylene and ethylene groups.
  • R 1c to R 5c , R 6c , R 7c , R x , R y , and any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by bonding R x and R y to each other may have a substituent.
  • the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
  • R13 is a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (cycloalkyl It may be a group itself or a group partially containing a cycloalkyl group). These groups may have substituents.
  • a halogen atom e.g., a fluorine atom, an iodine atom, etc.
  • R14 is a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group.
  • each R 14 independently represents the above group such as a hydroxyl group.
  • R 15 each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group.
  • Two R 15s may be bonded to each other to form a ring.
  • the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
  • two R 15s are alkylene groups and are preferably bonded to each other to form a ring structure.
  • the ring formed by bonding the alkyl group, cycloalkyl group, naphthyl group, and two R 15s to each other may have a substituent.
  • the alkyl groups of R 13 , R 14 and R 15 may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10.
  • the alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. It is also preferable that each substituent of R 13 to R 15 and R x and R y each independently form an acid-decomposable group by any combination of substituents.
  • R 204 and R 205 each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group of R 204 and R 205 may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
  • Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group of R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, butyl group, pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (e.g., carbon number 1 to 15), a cycloalkyl group (e.g., carbon number 3 to 15), an aryl group (eg, carbon number 6 to 15), an alkoxy group (eg, carbon number 1 to 15), a halogen atom, a hydroxyl group, and a phenylthio group.
  • the substituents of R 204 and R 205 each independently form an acid-decomposable group using any combination of substituents.
  • X - represents an organic anion.
  • the organic anion is not particularly limited, and includes mono- or divalent or higher-valent organic anions.
  • an anion having a significantly low ability to cause a nucleophilic reaction is preferable, and a non-nucleophilic anion is more preferable.
  • non-nucleophilic anions examples include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkylcarboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
  • sulfonic acid anions aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.
  • carboxylic acid anions aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkylcarboxylic acid anions
  • sulfonylimide anions bis(alkylsulfonyl)imi
  • the aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be a linear or branched alkyl group, or a cycloalkyl group, and may be a linear or branched alkyl group having 1 to 30 carbon atoms. Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferable.
  • the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom and may be a perfluoroalkyl group).
  • the aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
  • alkyl group, cycloalkyl group, and aryl group listed above may have a substituent.
  • Substituents are not particularly limited, but include, for example, nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups ( (preferably has 1 to 10 carbon atoms), cycloalkyl group (preferably has 3 to 15 carbon atoms), aryl group (preferably has 6 to 14 carbon atoms), alkoxycarbonyl group (preferably has 2 to 7 carbon atoms), acyl group (preferably has 2 to 7 carbon atoms), (preferably has 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably has 2 to 7 carbon atoms), alkylthio group (preferably has 1 to 15 carbon atoms), alkylsulfonyl group (preferably has 1 to 15 carbon atoms), al
  • the aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 7 to 14 carbon atoms.
  • Examples of the aralkyl group having 7 to 14 carbon atoms include benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.
  • Examples of the sulfonylimide anion include saccharin anion.
  • the alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
  • the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
  • non-nucleophilic anions include, for example, fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), and fluorinated antimony (eg, SbF 6 ⁇ ).
  • non-nucleophilic anions include aliphatic sulfonic acid anions in which at least the ⁇ -position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom.
  • a bis(alkylsulfonyl)imide anion substituted with , or a tris(alkylsulfonyl)methide anion whose alkyl group is substituted with a fluorine atom is preferred.
  • perfluoroaliphatic sulfonate anions preferably having 4 to 8 carbon atoms
  • benzenesulfonate anions having a fluorine atom are more preferable, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobutanesulfonate anions, etc.
  • More preferred is benzenesulfonic acid anion or 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.
  • an anion represented by the following formula (AN1) is also preferable.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent.
  • the substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred.
  • groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.
  • groups that are not electron-withdrawing groups -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR', or -NHCOR' are preferable, each independently. .
  • R' is a monovalent hydrocarbon group.
  • Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; ethynyl Monovalent linear or branched hydrocarbon groups such as alkynyl groups, propynyl groups, butynyl groups; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, adamantyl groups, etc.
  • Cycloalkyl group monovalent alicyclic hydrocarbon group such as cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl Aryl groups such as naphthyl group, anthryl group, and methylanthryl group; monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and anthrylmethyl group; Can be mentioned.
  • R 1 and R 2 are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.
  • L represents a divalent linking group.
  • each L may be the same or different.
  • the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene group ( (preferably having 1 to 6 carbon atoms), 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 that is a combination of a plurality of these. .
  • divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 - , or -COO-alkylene group- is more preferred.
  • a group represented by the following formula (AN1-1) is preferable. * a -(CR 2a 2 ) X -Q-(CR 2b 2 ) Y -* b (AN1-1)
  • * a represents the bonding position with R 3 in formula (AN1).
  • * b represents the bonding position with -C(R 1 )(R 2 )- in formula (AN1).
  • X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3.
  • R 2a and R 2b each independently represent a hydrogen atom or a substituent. When a plurality of R 2a and R 2b exist, the plurality of R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 directly bonded to -C(R 1 )(R 2 )- in formula (AN1) is other than a fluorine atom.
  • Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2- * B .
  • R 3 represents an organic group.
  • the above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group) or a branched group (e.g., t-butyl group, etc.). (branched alkyl group) or a cyclic group.
  • the above organic group may or may not have a substituent.
  • the above organic group may or may not have a hetero atom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).
  • R 3 is preferably an organic group having a cyclic structure.
  • the above-mentioned cyclic structure may be monocyclic or polycyclic, and may have a substituent.
  • the ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1).
  • the organic group having a cyclic structure may or may not have a hetero atom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), for example. Heteroatoms may be substituted for one or more of the carbon atoms forming the cyclic structure.
  • the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group.
  • the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
  • the hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
  • the above cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and preferably has 5 to 12 carbon atoms.
  • lactone group and sultone group examples include structures represented by the above-mentioned formulas (LC1-1) to (LC1-21) and structures represented by the formulas (SL1-1) to (SL1-3). In either of these, a group formed by removing one hydrogen atom from the ring atoms constituting the lactone structure or sultone structure is preferable.
  • the non-nucleophilic anion may be a benzenesulfonic acid anion, and is preferably a benzenesulfonic acid anion substituted with a branched alkyl group or a cycloalkyl group.
  • an anion represented by the following formula (AN2) is also preferable.
  • o represents an integer from 1 to 3.
  • p represents an integer from 0 to 10.
  • q represents an integer from 0 to 10.
  • Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
  • the number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4.
  • 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, more preferably a fluorine atom or CF 3 , and even more preferably both Xfs 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 exist, each of R 4 and R 5 may be the same or different.
  • the alkyl group represented by R 4 and R 5 preferably has 1 to 4 carbon atoms. The above alkyl group may have a substituent.
  • R 4 and R 5 are preferably hydrogen atoms.
  • L represents a divalent linking group.
  • the definition of L is synonymous with L in formula (AN1).
  • W represents an organic group containing a cyclic structure.
  • a cyclic organic group is preferred.
  • 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.
  • Aryl groups may be monocyclic or polycyclic.
  • the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
  • the heterocyclic group may be monocyclic or polycyclic. Among these, when it is a polycyclic heterocyclic group, acid diffusion can be further suppressed.
  • the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • non-aromatic heterocycle examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
  • the heterocycle in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
  • the above cyclic organic group may have a substituent.
  • substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any of them may be used, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and a sulfonic acid ester group.
  • the carbon constituting the cyclic organic group may be carbonyl carbon.
  • Examples of anions represented by formula (AN2) include SO 3 - -CF 2 -CH 2 -OCO-(L) q' -W, SO 3 - -CF 2 -CHF-CH 2 -OCO-(L) q ' -W, SO 3 - -CF 2 -COO- (L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q -W, or SO 3 - - CF 2 -CH(CF 3 )-OCO-(L) q' -W is preferred.
  • L, q and W are the same as in formula (AN2).
  • q' represents an integer from 0 to 10.
  • an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferable.
  • Ar represents an aryl group (such as a phenyl group), and may further have a sulfonic acid anion and a substituent other than the -(DB) group.
  • substituents 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 sulfonic acid ester group, an ester group, and a group consisting of a combination of two or more thereof.
  • B represents a hydrocarbon group.
  • B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an aryl group that may further have a substituent (such as a tricyclohexylphenyl group).
  • a disulfonamide anion is also preferred.
  • the disulfonamide anion is, for example, an anion represented by N - (SO 2 -R q ) 2 .
  • R q represents an alkyl group that may have a substituent, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group.
  • Two R q may be bonded to each other to form a ring.
  • the group formed by bonding two R q's to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group.
  • the alkylene group preferably has 2 to 4 carbon atoms.
  • non-nucleophilic anions include anions represented by the following formulas (d1-1) to (d1-4).
  • R 51 represents a hydrocarbon group (eg, an aryl group such as a phenyl group) which may have a substituent (eg, a hydroxyl group).
  • Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, the carbon atom adjacent to S is not substituted with a fluorine atom).
  • the hydrocarbon group in Z 2c may be linear or branched, or may have a cyclic structure.
  • a carbon atom in the hydrocarbon group (preferably a carbon atom that is a ring member atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-).
  • Examples of the hydrocarbon group include a group having a norbornyl group which may have a substituent.
  • the carbon atom forming the norbornyl group may be a carbonyl carbon.
  • Z 2c —SO 3 ⁇ in formula (d1-2) is preferably different from the anions represented by formulas (AN1) to (AN3) above.
  • Z 2c is preferably other than an aryl group.
  • atoms at the ⁇ -position and ⁇ -position with respect to -SO 3 - are preferably atoms other than carbon atoms having a fluorine atom as a substituent.
  • the atom at the ⁇ -position and/or the atom at the ⁇ -position with respect to -SO 3 - is preferably a ring member atom in a cyclic group.
  • R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), and Y 3 is a linear, branched, or cyclic alkylene group, arylene group, or It represents a carbonyl group, and Rf represents a hydrocarbon group.
  • R 53 and R 54 each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom). R 53 and R 54 may be bonded to each other to form a ring.
  • the organic anions may be used alone or in combination of two or more.
  • the composition of the present invention preferably contains a salt (C) having a group that decomposes under the action of an acid, and as a photoacid generator, it is represented by the following general formula (c1). It is more preferable to contain a compound.
  • L represents a single bond or a divalent linking group.
  • A represents a group that decomposes under the action of an acid.
  • nc represents an integer from 1 to 5.
  • Xc represents a (nc+1)-valent linking group.
  • Mc + represents a sulfonium ion or an iodonium ion.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group represented by L includes -CO-, -O-, -S-, -SO-, -SO 2 -, hydrocarbon groups (for example, alkylene group, cycloalkylene group, alkenylene group, and arylene group, etc.), and a linking group in which a plurality of these are linked.
  • L is preferably an alkylene group, an arylene group, an -arylene group, an alkylene group having a fluorine atom or an iodine atom, a -COO-Rt- group, or an -O-Rt- group.
  • Rt represents an alkylene group or a cycloalkylene group.
  • a phenylene group is preferred.
  • the alkylene group may be linear or branched.
  • the number of carbon atoms in the alkylene group is not particularly limited, but is preferably from 1 to 10, more preferably from 1 to 3.
  • the total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - group.
  • L is particularly preferably an arylene group, alkylene, or a single bond, and most preferably a phenylene group or a single bond.
  • A represents a group that decomposes under the action of an acid.
  • the group that decomposes under the action of an acid preferably has a structure in which a polar group is protected with a group that leaves under the action of an acid (leaving group).
  • Examples of the polar group include the polar groups described in the repeating unit having an acid-decomposable group of the resin (A) above, and among them, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) ), or a sulfonic acid group is preferable, and a carboxyl group or a phenolic hydroxyl group is more preferable.
  • Examples of groups that are eliminated by the action of acids include groups represented by formulas (Y1) to (Y4) described in the resin (A) above.
  • nc represents an integer from 1 to 5. nc is preferably an integer of 1 to 3.
  • Xc represents a (nc+1)-valent linking group.
  • Xc is preferably an aromatic ring group, more preferably an aromatic ring group having 6 to 20 carbon atoms, and even more preferably a benzene ring group.
  • Mc + represents a sulfonium ion or an iodonium ion.
  • the sulfonium ion and iodonium ion include the cation represented by the above-mentioned formula (ZaI) and the cation represented by the formula (ZaII).
  • ZaI-1 the above-mentioned cation
  • ZaI- 2 the above-mentioned cation
  • ZaI-3b cation
  • ZaI-4b cation
  • the compound represented by the above general formula (c1) is more preferably a compound represented by the following general formula (c2).
  • L, A, nc, and Mc + have the same meanings as L, A, nc, and Mc + in general formula (c1) above, and preferred examples are also the same.
  • the photoacid generator is at least one selected from the group consisting of compounds (I) to (II).
  • Compound (I) is a compound having one or more of the following structural moieties X and one or more of the following structural moieties Y, and the following first acidic acid derived from the following structural moiety This is a compound that generates an acid containing the following second acidic site derived from the structural site Y below.
  • Structural moiety _ _ _ A structural site consisting of A 2 - and a cationic site M 2 + , and which forms a second acidic site represented by HA 2 upon irradiation with actinic rays or radiation
  • the above compound (I) satisfies the following condition I .
  • a compound PI obtained by replacing the cation moiety M 1 + in the structural moiety X and the cation moiety M 2 + in the structural moiety Y with H + in the compound (I) is The acid dissociation constant a1 derived from the acidic site represented by HA 1 is obtained by replacing the cationic site M 1 + with H + , and the acid dissociation constant a1 derived from the acidic site represented by HA 1 is obtained by replacing the cationic site M 2 + in the structural site Y with H + It has an acid dissociation constant a2 derived from the acidic site represented by HA 2 , and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
  • compound (I) is, for example, an acid-generating compound having one of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y.
  • compound PI corresponds to "a compound having HA 1 and HA 2 ".
  • the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are defined as, when the acid dissociation constant of the compound PI is determined, the compound PI is a "compound having A 1 - and HA 2 ".
  • compound (I) is, for example, an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y.
  • compound PI corresponds to "a compound having two HA 1 and one HA 2 ".
  • the acid dissociation constant when a compound having one HA 1 and one HA 2 becomes a compound having two A 1 - and one HA 2 corresponds to the acid dissociation constant a1 described above. .
  • the acid dissociation constant when "a compound having two A 1 - and one HA 2 " becomes "a compound having two A 1 - and A 2 - " corresponds to the acid dissociation constant a2.
  • compound PI when it has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 , which is obtained by replacing the cation site M 1 + in the structural site X with H + , it has a plurality of acid dissociation constants.
  • the value of acid dissociation constant a2 is larger than the largest value of a1.
  • the acid dissociation constant when compound PI becomes "a compound having one A 1 - , one HA 1 , and one HA 2 " is aa
  • ab is the acid dissociation constant when a compound with one HA 2 becomes a compound with two A 1 - and one HA 2 , the relationship between aa and ab satisfies aa ⁇ ab. .
  • the acid dissociation constant a1 and the acid dissociation constant a2 are determined by the acid dissociation constant measurement method described above.
  • the above-mentioned compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
  • the structural sites X may be the same or different.
  • two or more of the above A 1 ⁇ and two or more of the above M 1 + may be the same or different.
  • the above A 1 - and the above A 2 - , and the above M 1 + and the above M 2 + may be the same or different, but the above A 1 - and the above A 2 - are preferably different from each other.
  • the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, and 0.5 or more. More preferably, 1.0 or more is even more preferable.
  • the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there is a plurality of acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.
  • the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. Note that the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.
  • the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less. Note that the lower limit of the acid dissociation constant a1 is preferably -20.0 or more.
  • the anionic moiety A 1 - and the anionic moiety A 2 - are structural moieties containing negatively charged atoms or atomic groups, for example, the formulas (AA-1) to (AA-3) and the formula (BB Examples include structural sites selected from the group consisting of -1) to (BB-6).
  • the anion moiety A 1 - is preferably one that can form an acidic moiety with a small acid dissociation constant, and more preferably one of the formulas (AA-1) to (AA-3), and the formula ( More preferably, it is either AA-1) or (AA-3).
  • the anionic moiety A 2 - is preferably one that can form an acidic moiety with a larger acid dissociation constant than the anionic moiety A 1 - , and should be one of formulas (BB-1) to (BB-6). is more preferred, and one of formulas (BB-1) and (BB-4) is even more preferred.
  • * represents the bonding position.
  • R A represents a monovalent organic group.
  • the monovalent organic group represented by R A is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.
  • the cationic site M 1 + and the cationic site M 2 + are structural sites containing positively charged atoms or atomic groups, such as monovalent organic cations.
  • the organic cation includes, for example, the organic cation represented by M + described above.
  • Compound (II) is a compound having two or more of the above structural moieties It is a compound that generates an acid containing two or more sites and the above structural site Z.
  • Structural site Z nonionic site capable of neutralizing acids
  • HA 1 is obtained by replacing the cationic site M 1 + in the structural site X with H + .
  • the preferred range of the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in the above compound PI.
  • compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z
  • compound PII is a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z.
  • the acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above.
  • the above-mentioned compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
  • the two or more structural sites X may be the same or different.
  • the two or more A 1 ⁇ and the two or more M 1 + may be the same or different.
  • the nonionic site that can neutralize the acid in the structural site Z is not particularly limited, and for example, it must be a site that contains a group that can electrostatically interact with protons or a functional group that has electrons. is preferred.
  • the group capable of electrostatic interaction with protons or the functional group having electrons is a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a lone pair of electrons that does not contribute to ⁇ conjugation. Examples include functional groups having a nitrogen atom.
  • a nitrogen atom having a lone pair of electrons that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.
  • Examples of partial structures of functional groups having groups or electrons that can electrostatically interact with protons include crown ether structures, aza crown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures. Among these, primary to tertiary amine structures are preferred.
  • photoacid generators are shown below, but the invention is not limited thereto.
  • photoacid generator for example, compounds C-1 to C-5 used in Examples can be used.
  • the content of the photoacid generator is not particularly limited, it is preferably 0.5% by mass or more based on the total solid content of the composition of the present invention, since the cross-sectional shape of the formed pattern becomes more rectangular. More preferably, the content is 1.0% by mass or more. The content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, based on the total solid content of the composition of the present invention.
  • the photoacid generators may be used alone or in combination of two or more.
  • the composition of the present invention may contain an acid diffusion control agent (D) that does not correspond to the above compound (B).
  • the acid diffusion control agent traps the acid generated from the photoacid generator and the like during exposure, and acts as a quencher to suppress the reaction of the acid-decomposable resin in the unexposed area due to the excess generated acid.
  • the type of acid diffusion control agent is not particularly limited, and examples thereof include a basic compound (DA), a low molecular compound (DB) having a nitrogen atom and a group that is eliminated by the action of an acid, and actinic rays or radiation. Examples include compounds (DC) whose ability to control acid diffusion decreases or disappears when irradiated with.
  • Compounds (DC) include onium salt compounds (DD) that are relatively weak acids with respect to photoacid generators, and basic compounds (DE) whose basicity decreases or disappears when irradiated with actinic rays or radiation. Can be mentioned.
  • Specific examples of basic compounds (DA) include those described in paragraphs [0132] to [0136] of International Publication No. 2020/066824;
  • Specific examples of basic compounds (DE) that disappear include those described in paragraphs [0137] to [0155] of International Publication No. 2020/066824, and those described in paragraph [0164] of International Publication No. 2020/066824.
  • low-molecular compounds (DB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs [0156] to [0163] of International Publication No. 2020/066824.
  • onium salt compounds (DD) that are weak acids relative to photoacid generators include those described in paragraphs [0305] to [0314] of International Publication No. 2020/158337. .
  • paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1 paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1
  • US Patent Application Publication No. 2016/0237190A1 The known compounds disclosed in paragraphs [0403] to [0423] of No. 1, and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents.
  • the content of the acid diffusion control agent (if there are multiple types, the total amount) is 0.1 with respect to the total solid content of the composition of the present invention. ⁇ 15.0% by mass is preferred, and 1.0 ⁇ 15.0% by mass is more preferred. In the composition of the present invention, one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.
  • the composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin (P)") different from resin (A).
  • the hydrophobic resin (P) is preferably designed to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule. It may not contribute to uniform mixing of polar and non-polar substances.
  • the effects of adding the hydrophobic resin (P) include controlling the static and dynamic contact angle of the surface of the actinic ray-sensitive or radiation-sensitive film with respect to water, and suppressing outgassing.
  • the hydrophobic resin (P) preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin, from the viewpoint of uneven distribution on the membrane surface layer. , it is more preferable to have two or more types.
  • the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chains. Examples of the hydrophobic resin (P) include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.
  • the content of the hydrophobic resin (P) is 0.01 to 20.0% by mass based on the total solid content of the composition of the present invention. Preferably, 0.1 to 15.0% by mass is more preferable.
  • the composition of the invention may also contain a surfactant.
  • a surfactant When a surfactant is included, a pattern with better adhesion and fewer development defects can be formed.
  • the surfactant is preferably a fluorine-based and/or silicon-based surfactant. Examples of the fluorine-based and/or silicon-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/193954.
  • One type of surfactant may be used alone, or two or more types may be used.
  • the content of the surfactant is preferably 0.0001 to 2.0% by mass, and 0.0005 to 2.0% by mass, based on the total solid content of the composition of the present invention. It is more preferably 1.0% by mass, and even more preferably 0.1 to 1.0% by mass.
  • the composition of the present invention contains a solvent.
  • the solvent consists of (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable that at least one selected from the group is included. Note that the above solvent may further contain components other than components (M1) and (M2).
  • the above-mentioned solvent and the above-mentioned resin are combined from the viewpoint of improving the coating properties of the composition of the present invention and reducing the number of pattern development defects. Since the above-mentioned solvent has a good balance between the solubility, boiling point, and viscosity of the above-mentioned resin, it is possible to suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of International Publication No. 2020/004306, the contents of which are incorporated herein.
  • the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass based on the total amount of the solvent.
  • the content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. In this way, the applicability of the composition of the present invention can be further improved.
  • the composition of the present invention includes a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or It may further contain an alicyclic or aliphatic compound containing a carboxyl group.
  • a dissolution inhibiting compound for example, a phenol compound having a molecular weight of 1000 or less, or It may further contain an alicyclic or aliphatic compound containing a carboxyl group.
  • dissolution-inhibiting compound is a compound with a molecular weight of 3000 or less that decomposes under the action of an acid and reduces its solubility in an organic developer.
  • composition of the present invention is suitably used as a photosensitive composition for EUV exposure.
  • the invention also relates to actinic- or radiation-sensitive films formed with the compositions of the invention.
  • the actinic ray-sensitive or radiation-sensitive film of the present invention is preferably a resist film.
  • the procedure of the pattern forming method using the composition of the present invention is not particularly limited, it is preferable to include the following steps.
  • Step 1 Step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention
  • Step 2 Step of exposing the actinic ray-sensitive or radiation-sensitive film
  • Step 3 Exposed light-sensitive film Step of developing a photosensitive or radiation-sensitive film using a developer The procedure of each of the above steps will be described in detail below.
  • Step 1 Actinic ray-sensitive or radiation-sensitive film formation step
  • Step 1 is a step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention.
  • Examples of the method for forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention include a method of coating the composition of the present invention on a substrate.
  • the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
  • the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
  • compositions of the present invention can be applied by any suitable application method, such as a spinner or coater, onto substrates (eg, silicon, silicon dioxide coated) such as those used in the manufacture of integrated circuit devices.
  • the coating method is preferably spin coating using a spinner.
  • the rotation speed during spin coating using a spinner is preferably 1000 to 3000 rpm (rotations per minute).
  • the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film.
  • various base films inorganic film, organic film, antireflection film
  • drying method examples include a method of drying by heating. Heating can be carried out using a means provided in an ordinary exposure machine and/or developing machine, or may be carried out using a hot plate or the like.
  • the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
  • the thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming fine patterns with higher precision.
  • the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
  • the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.
  • a top coat may be formed on the actinic ray-sensitive or radiation-sensitive film using a top coat composition.
  • the top coat composition does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the upper layer of the resist film.
  • the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. Can be formed.
  • Specific examples of basic compounds that may be included in the top coat include basic compounds that may be included in the composition of the present invention.
  • the top coat contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
  • Step 2 is a step of exposing the actinic ray-sensitive or radiation-sensitive film.
  • the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask.
  • active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, and 1 to 200 nm.
  • Deep ultraviolet light of wavelengths specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.
  • the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
  • the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called post-exposure bake.
  • Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer to form a pattern.
  • the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
  • Development methods include, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and left to stand for a certain period of time (paddle method). method), a method in which the developer is sprayed onto the surface of the substrate (spray method), and a method in which the developer is continuously discharged while scanning a developer discharge nozzle at a constant speed onto a rotating substrate (dynamic dispensing method). ). Furthermore, after the step of developing, a step of stopping the development may be carried out while substituting another solvent.
  • the development time is not particularly limited as long as the resin in the unexposed areas is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
  • the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
  • alkaline developer it is preferable to use an alkaline aqueous solution containing an alkali.
  • the type of alkaline aqueous solution is not particularly limited, but examples include quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Examples include alkaline aqueous solutions containing.
  • the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc. may be added to the alkaline developer.
  • the alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass.
  • the pH of the alkaline developer is usually preferably 10.0 to 15.0.
  • the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. It is preferable that there be.
  • a plurality of the above-mentioned solvents may be mixed together, or may be mixed with a solvent other than the above-mentioned ones or water.
  • the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
  • the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass or less, based on the total amount of the developer. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.
  • the pattern forming method includes a step of cleaning using a rinsing liquid after step 3.
  • Examples of the rinsing solution used in the rinsing step after the step of developing using an alkaline developer include pure water. Note that an appropriate amount of a surfactant may be added to the pure water. An appropriate amount of surfactant may be added to the rinse solution.
  • the rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and solutions containing common organic solvents can be used.
  • the rinsing liquid should contain at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. is preferred.
  • the method of the rinsing process is not particularly limited, and examples include a method in which the rinsing liquid is continuously discharged onto the substrate rotating at a constant speed (rotary coating method), and a method in which the substrate is immersed in a tank filled with the rinsing liquid for a certain period of time. (dip method) and a method of spraying a rinsing liquid onto the substrate surface (spray method).
  • the pattern forming method may include a heating step (Post Bake) after the rinsing step. In this step, the developer and rinse solution remaining between patterns and inside the patterns due to baking are removed. This step also has the effect of smoothing the resist pattern and improving surface roughness of the pattern.
  • the heating step after the rinsing step is usually carried out at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
  • the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the lower film and the substrate) to form a pattern on the substrate.
  • the method of processing the substrate (or the lower layer film and the substrate) is not particularly limited, but by performing dry etching on the substrate (or the lower layer film and the substrate) using the pattern formed in step 3 as a mask, the substrate is processed.
  • a method of forming a pattern is preferred.
  • the dry etching is preferably oxygen plasma etching.
  • the composition of the present invention and various materials used in the pattern forming method do not contain impurities such as metals. It is preferable not to include it.
  • the content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, still more preferably 100 mass ppt or less, and particularly 10 mass ppt or less. Preferably, 1 mass ppt or less is most preferable.
  • the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
  • examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, Examples include W and Zn.
  • Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph [0321] of International Publication No. 2020/004306.
  • Methods for reducing impurities such as metals contained in various materials include, for example, methods of selecting raw materials with low metal content as raw materials constituting various materials, and methods of filtering raw materials constituting various materials. and a method in which distillation is carried out under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark).
  • impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used.
  • adsorbent known adsorbents can be used, such as inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • inorganic adsorbents such as silica gel and zeolite
  • organic adsorbents such as activated carbon.
  • the content of metal components contained in the cleaning solution after use is preferably 100 parts per trillion or less, more preferably 10 parts per trillion or less, and even more preferably 1 parts per trillion or less.
  • the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
  • Organic processing liquids such as rinsing liquids contain conductive compounds to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. may be added.
  • the conductive compound is not particularly limited, and for example, methanol may be mentioned.
  • the amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less in terms of maintaining favorable development characteristics or rinsing characteristics.
  • the lower limit is not particularly limited, and is preferably 0.01% by mass or more.
  • Examples of chemical liquid piping include SUS (stainless steel), polyethylene or polypropylene treated with antistatic treatment, or various types of piping coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.). can be used.
  • SUS stainless steel
  • polyethylene or polypropylene treated with antistatic treatment or various types of piping coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
  • fluororesin polytetrafluoroethylene, perfluoroalkoxy resin, etc.
  • filter and O-ring antistatically treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.
  • the present specification also relates to an electronic device manufacturing method including the above-described pattern forming method, and an electronic device manufactured by this manufacturing method.
  • Preferred embodiments of the electronic device of this specification include embodiments in which it is installed in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.).
  • A-1 to A-17 were used as the resin (A).
  • the structures of A-1 to A-17 are shown below.
  • the content ratio of the following repeating units is a molar ratio.
  • resin A-1 A synthesis example of resin A-1 is shown below. Other resins (A) were also synthesized in the same manner.
  • Cyclohexanone (59 g) was heated to 85°C under a nitrogen stream. While stirring, add AS-1 (63.3 g), 4-vinylphenol (27.0 g), cyclohexanone (109.3 g), and dimethyl 2,2'-azobisisobutyrate [V-601, Fujifilm [manufactured by Wako Pure Chemical Industries, Ltd.] (7.14 g) was added dropwise over 3 hours to obtain a reaction solution. After the dropwise addition was completed, the reaction solution was further stirred at 85° C. for 3 hours.
  • C-1 to C-5 were used as photoacid generators.
  • the structures of C-1 to C-5 are shown below.
  • D-1 to D-7 were used as acid diffusion control agents.
  • W-1 Megafac F176 (manufactured by Dainippon Ink & Chemicals Co., Ltd.; fluorine-based)
  • W-2 Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine and silicone-based)
  • W-3 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based)
  • W-4 Troysol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based)
  • W-5 KH-20 (manufactured by Asahi Glass Co., Ltd.)
  • W-6 PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)
  • SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
  • SL-2 Propylene glycol monomethyl ether propionate
  • SL-3 2-heptanone
  • SL-4 Ethyl lactate
  • SL-5 Propylene glycol monomethyl ether (PGME)
  • SL-6 Cyclohexanone
  • SL-7 ⁇ -butyrolactone
  • SL-8 Propylene carbonate
  • A-2/A-14 indicates that two types of resin (A), A-2 and A-14, were used, and "5/5" indicates that A-2 and A-14 were used as the resin (A). 2 and A-14 were used in an amount of 5 g each.
  • ⁇ Coating of resist composition The prepared resist composition was applied onto a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and dried on a hot plate at 130° C. for 300 seconds. As a result, a resist film having a thickness of 100 nm was obtained. Here, 1 inch is 0.0254 m. Note that similar results can be obtained even if the Si wafer is replaced with a chromium substrate.
  • HMDS hexamethyldisilazane
  • ⁇ Pattern formation method (1) EB exposure, alkaline development (positive)>
  • the wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam drawing device (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, drawing was performed so that a 1:1 line and space was formed.
  • electron beam drawing it was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. . Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then baked at 95° C. for 60 seconds to dry it.
  • TMAH tetramethylammonium hydroxide
  • LWR performance refers to the ability to reduce the LWR of a pattern.
  • a 1:1 line-and-space pattern with a line width of 50 nm is drawn with an electron beam on a 10 ⁇ m square area 1 in FIG.
  • the sensitivity at which one line and space was formed was designated as D.
  • a 1:1 line-and-space pattern with a line width of 50 nm was drawn with an electron beam on a 10 ⁇ m square region 2 in FIG.
  • the sensitivity at which a 1:1 line and space with a line width of 50 nm is formed in region 2 after heating on a hot plate for 60 seconds and developing is defined as B.
  • the sensitivity ratio D/B was used as an evaluation index of density dependence. The smaller the value of D/B, the less the density dependence, and the better the performance.
  • ⁇ Sensitivity> The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.).
  • ⁇ LWR performance> A length-measuring scanning electron microscope (SEM (S-9380II manufactured by Hitachi, Ltd.)) was used to measure the 50 nm (1:1) line-and-space pattern resolved at the exposure dose that shows the sensitivity (Eop) above. Observation was made from the top of the pattern.
  • the line width of the pattern was observed at arbitrary points, and its standard deviation ( ⁇ ) was determined. Measurement variations in line width were evaluated using 3 ⁇ , and the value of 3 ⁇ was defined as LWR (nm). The smaller the LWR value, the better the LWR performance.
  • ⁇ Development defects> A 1:1 line and space pattern with a line width of 50 nm formed at the above sensitivity (Eop) was measured using a defect inspection system KLA2360 manufactured by KLA Tencor, and the pixel size of the defect inspection system was set to 0.16 ⁇ m. The threshold value was set to 20, measurement was performed in random mode, development defects extracted from the difference caused by overlapping the comparison image and pixel by pixel were detected, and the number of development defects per unit area (1 cm 2 ) was calculated. .
  • Table 2 below shows the resist compositions used and the results.
  • the present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that exhibits excellent density dependence in the formation of ultra-fine patterns (for example, line-and-space patterns with line widths of 50 nm or less, hole patterns with pore diameters of 50 nm or less, etc.). can do. Further, the present invention can provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.
  • ultra-fine patterns for example, line-and-space patterns with line widths of 50 nm or less, hole patterns with pore diameters of 50 nm or less, etc.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention fournit une composition de résine sensible aux rayons actiniques ou à un rayonnement qui comprend une résine (A) dont la polarité augmente sous l'effet d'un acide, et un composé (B) spécifique représenté par la formule générale (B-1) décrite dans la description. L'invention fournit également un film sensible aux rayons actiniques ou à un rayonnement mettant en œuvre ladite composition de résine sensible aux rayons actiniques ou à un rayonnement, un procédé de formation de motif, et un procédé de fabrication de dispositif électronique.
PCT/JP2023/026778 2022-07-29 2023-07-21 Composition de résine sensible aux rayons actiniques ou à un rayonnement, film sensible aux rayons actiniques ou à un rayonnement, procédé de formation de motif, et procédé de fabrication de dispositif électronique Ceased WO2024024669A1 (fr)

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JP2020148901A (ja) * 2019-03-13 2020-09-17 東京応化工業株式会社 感光性樹脂組成物、感光性ドライフィルム、感光性ドライフィルムの製造方法、パターン化されたレジスト膜の製造方法、鋳型付き基板の製造方法、及びめっき造形物の製造方法
JP2021076784A (ja) * 2019-11-12 2021-05-20 東京応化工業株式会社 化学増幅型感光性組成物の製造方法、化学増幅型感光性組成物調製用プレミックス液、化学増幅型感光性組成物、感光性ドライフィルムの製造方法及びパターン化されたレジスト膜の製造方法
JP2021107850A (ja) * 2019-12-27 2021-07-29 東京応化工業株式会社 化学増幅型ポジ型感光性組成物、感光性ドライフィルム、感光性ドライフィルムの製造方法、パターン化されたレジスト膜の製造方法及び酸拡散抑制剤
WO2021246448A1 (fr) * 2020-06-03 2021-12-09 昭和電工株式会社 Composition de résine photosensible positive, et paroi de séparation d'élément électroluminescent organique

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JP2019168475A (ja) 2016-08-08 2019-10-03 Jsr株式会社 化学増幅型レジスト材料及びレジストパターン形成方法
JP7790956B2 (ja) 2020-12-18 2025-12-23 住友化学株式会社 レジスト組成物及びレジストパターンの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020148901A (ja) * 2019-03-13 2020-09-17 東京応化工業株式会社 感光性樹脂組成物、感光性ドライフィルム、感光性ドライフィルムの製造方法、パターン化されたレジスト膜の製造方法、鋳型付き基板の製造方法、及びめっき造形物の製造方法
JP2021076784A (ja) * 2019-11-12 2021-05-20 東京応化工業株式会社 化学増幅型感光性組成物の製造方法、化学増幅型感光性組成物調製用プレミックス液、化学増幅型感光性組成物、感光性ドライフィルムの製造方法及びパターン化されたレジスト膜の製造方法
JP2021107850A (ja) * 2019-12-27 2021-07-29 東京応化工業株式会社 化学増幅型ポジ型感光性組成物、感光性ドライフィルム、感光性ドライフィルムの製造方法、パターン化されたレジスト膜の製造方法及び酸拡散抑制剤
WO2021246448A1 (fr) * 2020-06-03 2021-12-09 昭和電工株式会社 Composition de résine photosensible positive, et paroi de séparation d'élément électroluminescent organique

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