WO2024024691A1 - 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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WO2024024691A1
WO2024024691A1 PCT/JP2023/026881 JP2023026881W WO2024024691A1 WO 2024024691 A1 WO2024024691 A1 WO 2024024691A1 JP 2023026881 W JP2023026881 W JP 2023026881W WO 2024024691 A1 WO2024024691 A1 WO 2024024691A1
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group
sensitive
radiation
general formula
acid
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PCT/JP2023/026881
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Japanese (ja)
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修平 山口
孝太郎 高橋
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富士フイルム株式会社
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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method. 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, and the like; 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, and the like.
  • the present invention relates to actinic ray
  • Patent Documents 1 and 2 describe resist compositions containing aromatic dicarboxylic acid salts having multiple phenolic hydroxyl groups.
  • the resist compositions described in Patent Documents 1 and 2 have problems in that they are inferior in density dependence, line width roughness (LWR) performance, and defect suppression performance.
  • the density dependence refers to the sensitivity when forming a certain pattern (for example, a 1:1 line-and-space pattern with a line width of 50 nm) when the exposure amount around the area where the pattern is formed is small (sparse). It refers to the property that there is a difference between sensitivity D and sensitivity B when the exposure amount around the area where the pattern is formed is large (when the exposure is dense). Poor density dependence means that D/B, which is the ratio of the above sensitivity, is large (for example, D/B is 1.99 or more), and excellent density dependence means that D/B is small. (For example, D/B is less than 1.99).
  • LWR performance refers to the ability to reduce the LWR of a pattern.
  • Defect suppression performance refers to performance that can suppress the occurrence of defects.
  • the present inventors have discovered that the above problem can be solved by the following configuration. Although the reason why the above problems can be solved by the present invention is not completely clear, the present inventors assume that it is because the resin (A) and the salt (B) have excellent compatibility. .
  • An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) containing a group that decomposes and increases polarity by the action of an acid, and a salt (B),
  • the resin (A) has at least one repeating unit selected from the group consisting of a repeating unit represented by the following general formula (S1) and a repeating unit represented by the following general formula (S2), and a repeating unit having a polar group.
  • the salt (B) is an actinic ray-sensitive or radiation-sensitive resin composition, which is a compound represented by the following general formula (T1).
  • 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 single bond or a divalent linking 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. Two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
  • 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.
  • Two of Ra 1 to Ra 3 , La 1 and Ra 0 may be bonded to each other to form a ring.
  • na represents an integer from 0 to 4.
  • ma represents an integer from 0 to 2.
  • 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, a cycloalkyloxy group, or an alkenyl group. At least two of Ra 10 to Ra 12 may be bonded to each other to form a ring. At least one of Ra 9 to Ra 12 may bind to Ara.
  • Arb represents an aromatic ring.
  • the above aromatic ring may have a substituent.
  • Q represents an acid residue.
  • the anion in general formula (T1) is a conjugate base of an acid with a pKa of -1 to 9.
  • Rb 1 represents -OH, -ORb 2 , -NRb 3 Rb 4 , -SH, or -SRb 5 , and multiple Rb 1 's may be the same or different.
  • Rb 2 represents an alkyl group, an aryl group, or an acyl group.
  • Rb 3 and Rb 4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.
  • Rb 5 represents an alkyl group, an aryl group, or an acyl group. At least two of Rb 2 to Rb 5 may be bonded to each other to form a ring. When Arb has a substituent, the above substituent and at least one of Rb 2 to Rb 5 may be bonded to form a ring.
  • Lb 1 represents a single bond or a divalent linking group. Lb 1 may be combined with Rb 1 to form a ring by substituting a hydrogen atom contained in Rb 1 . Lb 1 may be bonded to at least one of Rb 2 to Rb 5 to form a ring. When Arb has a substituent, the substituent and Lb 1 may be combined to form a ring.
  • p represents an integer from 2 to 5.
  • G m+ represents an m-valent organic cation.
  • m represents an integer of 1 or more.
  • S3 The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit having a polar group is a repeating unit represented by the following general formula (S3).
  • 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 alkoxycarbonyl group.
  • R 102 may combine with Ar A to form a ring, in which 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.
  • the salt (C) is a compound different from the above salt (B) and contains a salt (C) that generates an acid upon irradiation with actinic rays or radiation, and the above salt (C) has a group that is decomposed by the action of the acid.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5].
  • [7] The actinic ray-sensitive or radiation-sensitive resin composition according to [6], wherein the salt (C) is a compound represented by the following general formula (U1).
  • L represents a single bond or a divalent linking group.
  • A represents a group that decomposes under the action of an acid.
  • n represents an integer from 1 to 5.
  • X represents an n+1-valent linking group.
  • M + represents a sulfonium ion or an iodonium ion.
  • L, A, n, and M + represent the same meanings as L, A, n, and M + in general formula (U1), respectively.
  • a pattern forming method comprising a developing step of developing the exposed resist film using a developer.
  • a method for manufacturing an electronic device including the pattern forming method according to [10].
  • the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in density dependence, LWR performance, and defect suppression performance. 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.
  • 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 adopted.
  • 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 “composition of the present invention”) comprises a resin (A) containing a group that decomposes and increases polarity by the action of an acid, and a salt (B). ), wherein the resin (A) is composed of a repeating unit represented by general formula (S1) and a repeating unit represented by general formula (S2).
  • the salt (B) is an actinic ray-sensitive or radiation-sensitive resin containing at least one repeating unit selected from the group consisting of a repeating unit having a polar group, and the salt (B) is a compound represented by the general formula (T1). It is a composition.
  • 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.
  • the resin (A) contained in the composition of the present invention is a resin containing a group (also referred to as an "acid-decomposable group") that decomposes and increases polarity under the action of an acid.
  • the resin (A) is an acid-decomposable resin, and when an alkaline developer is typically used as the developer in the pattern forming method using the composition of the present invention, a positive pattern is preferably used. When an organic developer is used as the developer, a negative pattern is suitably formed.
  • An acid-decomposable group is typically a group that decomposes under 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).
  • the polarity of the resin (A) increases due to the action of an acid, so that its solubility in an alkaline developer increases and its solubility in an organic solvent decreases.
  • the resin (A) contains at least one repeating unit selected from the group consisting of the repeating unit represented by the general formula (S1) and the repeating unit represented by the general formula (S2). At least one repeating unit selected from the group consisting of the repeating unit represented by general formula (S1) and the repeating unit represented by general formula (S2) is preferably a repeating unit having an acid-decomposable group.
  • 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 single bond or a divalent linking 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. Two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
  • 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.
  • Two of Ra 1 to Ra 3 , La 1 and Ra 0 may be bonded to each other to form a ring.
  • na represents an integer from 0 to 4.
  • ma represents an integer from 0 to 2.
  • 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, a cycloalkyloxy group, or an alkenyl group. At least two of Ra 10 to Ra 12 may be bonded to each other to form a ring. At least one of Ra 9 to Ra 12 may bind to Ara.
  • Ra 1 to Ra 3 in general formula (S1) 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.
  • La 1 in general formula (S1) represents a single bond or a divalent linking group.
  • divalent linking 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.
  • La 1 is preferably a single bond or -COO-, and more preferably a single bond.
  • Ra 4 to Ra 6 in general formula (S1) 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.
  • As the alkenyl group for Ra 4 to Ra 6 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.
  • 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.
  • Two of Ra 4 to Ra 6 may be bonded to each other to form a ring.
  • the group formed by bonding two of Ra 4 to Ra 6 to form a ring is preferably a cycloalkyl group.
  • the above-mentioned cycloalkyl group is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.
  • An alkyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.
  • one of the methylene groups constituting the ring may be replaced with a hetero atom such as an oxygen atom, a group containing a hetero atom such as a carbonyl group, or a vinylidene group.
  • one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
  • -C(Ra 4 )(Ra 5 )(Ra 6 ) in general formula (S1) is preferably a leaving group, and -COO-C(Ra 4 )(Ra 5 )(Ra 6 ) is an acid It is preferable that -C(Ra 4 )(Ra 5 )(Ra 6 ) is eliminated by the action of , thereby producing a carboxyl group.
  • Ra 0 in general formula (S1) 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 alkyl group of Ra 0 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 0 is not particularly limited, but is preferably from 3 to 20, more preferably from 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 with Ra 0 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 alkoxy group of Ra 0 may be either linear or branched.
  • the number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, but is preferably from 1 to 5, more preferably from 1 to 3.
  • the alkyl group that may be contained in the acyloxy group of Ra 0 may be either linear or branched.
  • the number of carbon atoms in the alkyl group that can be contained in the acyloxy group of Ra 0 is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3.
  • the number of carbon atoms in the aryl group that can be contained in the acyloxy group of Ra 0 is not particularly limited, but is preferably from 6 to 20, more preferably from 6 to 10.
  • a phenyl group is most preferable.
  • the alkyl group contained in the alkoxycarbonyl group of Ra 0 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.
  • the number of carbon atoms in the aryl group of Ra 0 is not particularly limited, but is preferably from 6 to 20, more preferably from 6 to 10.
  • a phenyl group is most preferred.
  • the aralkyl group with Ra 0 is preferably a group in which one hydrogen atom in the alkyl group with Ra 0 described above is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), such as a benzyl group, etc. Can be mentioned.
  • the number of carbon atoms in the alkenyl group of Ra 0 is not particularly limited, but is preferably 2 to 5, more preferably 2 to 4.
  • As the alkenyl group with Ra 0 a vinyl group is preferable.
  • the aromatic heterocyclic group with Ra 0 preferably contains at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen 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 with Ra 0 include thienyl group, furanyl group, benzothienyl group, dibenzothienyl group, benzofuranyl group, pyrrole group, oxazolyl group, thiazolyl group, pyridyl group, isothiazolyl group, thiadiazolyl group, etc. Can be mentioned.
  • na represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • ma represents an integer from 0 to 2, preferably represents 0 or 1, and more preferably represents 0.
  • the aromatic ring in general formula (S1) is benzene when ma represents 0, naphthalene when ma represents 1, and anthracene when ma represents 2.
  • repeating unit represented by general formula (S1) are shown below, but are not limited thereto.
  • Ra 7 to Ra 9 in general formula (S2) each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • the explanations, specific examples, and preferred ranges for Ra 7 to Ra 9 are the same as the explanations, specific examples, and preferred ranges for Ra 1 to Ra 3 in general formula (S1) described above.
  • La 2 in general formula (S2) represents a single bond or a divalent linking group.
  • the explanation, specific example, and preferred range for La 2 are the same as the explanation, specific example, and preferred range for La 1 in the general formula (S1) described above.
  • Ara in general formula (S2) represents an aromatic ring group.
  • the aromatic ring group of Ara is preferably an arylene group, more preferably an arylene group having 6 to 20 carbon atoms, even more preferably an arylene group having 6 to 10 carbon atoms, and a phenylene group or a naphthylene group. is particularly preferable, and most preferably a phenylene group.
  • Ra 10 to Ra 12 in general formula (S2) 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, a cycloalkyloxy group, or , represents an alkenyl group.
  • the alkyl group of Ra 10 to Ra 12 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 10 to Ra 12 is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15.
  • Examples of the cycloalkyl group for Ra 10 to Ra 12 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 alkyl group contained in the alkoxy group of Ra 10 to Ra 12 may be either linear or branched.
  • the number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, but is preferably from 1 to 5, more preferably from 1 to 3.
  • the number of carbon atoms in the cycloalkyl group contained in the cycloalkyloxy group of Ra 10 to Ra 12 is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15.
  • the cycloalkyl group contained in the cycloalkyloxy group of Ra 10 to Ra 12 includes monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, as well as norbornyl group, tetracyclodecanyl group, and tetracyclododecanyl group. , and polycyclic cycloalkyl groups such as adamantyl groups are preferred. It may be either linear or branched.
  • the number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, but is preferably from 1 to 5, more preferably from 1 to 3.
  • the number of carbon atoms in the aryl group of Ra 10 to Ra 12 is not particularly limited, but is preferably from 6 to 20, more preferably from 6 to 10.
  • the most preferred aryl group for Ra 10 to Ra 12 is a phenyl group.
  • the aralkyl group of Ra 10 to Ra 12 is preferably a group in which one hydrogen atom in the alkyl group of Ra 10 to Ra 12 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 10 to Ra 12 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 10 to Ra 12 preferably contains at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen 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 10 to Ra 12 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.
  • Ra 10 to Ra 12 may be bonded to each other to form a ring.
  • the group formed by bonding Ra 10 to Ra 12 to form a ring is preferably a cycloalkyl group.
  • the above-mentioned cycloalkyl group is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.
  • An alkyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.
  • one of the methylene groups constituting the ring may be replaced with a hetero atom such as an oxygen atom, a group containing a hetero atom such as a carbonyl group, or a vinylidene group.
  • one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
  • Ra 10 to Ra 12 is an alkoxy group, and one of Ra 10 to Ra 12 is an alkoxy group, and the other two are a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. It is more preferable that
  • -C(Ra 10 )(Ra 11 )(Ra 12 ) in general formula (S2) is preferably a leaving group, and -OC(Ra 10 )(Ra 11 )(Ra 12 ) is an acid It is preferable that -C(Ra 10 )(Ra 11 )(Ra 12 ) is eliminated by the action of , thereby producing a hydroxy group (this hydroxy group is a phenolic hydroxyl group because it is bonded to Ara).
  • repeating unit represented by general formula (S2) are shown below, but are not limited thereto.
  • the content of repeating units selected from the group consisting of repeating units represented by general formula (S1) and repeating units represented by general formula (S2) is 5% relative to all repeating units in resin (A). It is preferably mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more.
  • the content of the repeating unit selected from the group consisting of the repeating unit represented by the general formula (S1) and the repeating unit represented by the general formula (S2) is based on the total repeating units in the resin (A). , is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less.
  • the number of repeating units selected from the group consisting of the repeating unit represented by the general formula (S1) and the repeating unit represented by the general formula (S2) contained in the resin (A) may be one type or two or more types. . When two or more types are included, the total content is preferably within the above-mentioned preferred content range.
  • the repeating unit having a polar group contained in the resin (A) will be explained.
  • the repeating unit having a polar group may be a repeating unit different from the repeating unit selected from the group consisting of the repeating unit represented by the general formula (S1) and the repeating unit represented by the general formula (S2) described above. preferable.
  • Examples of the polar group of the repeating unit having a polar group include a hydroxyl group, a lactone group, a sultone group, a lactam group, an imide group, an amide group, a sulfonamide group, a carbonate group, a urethane group, a urea group, a nitrile group, a sulfoxide group, Examples include sulfonyl groups.
  • the polar group may be an acid group.
  • the polar group is preferably a hydroxyl group or a lactone group, more preferably an aromatic hydroxyl group, and even more preferably a phenolic hydroxyl group.
  • the repeating unit containing a polar group is preferably a repeating unit represented by the following general formula (S3).
  • the repeating unit having a polar group is preferably a repeating unit represented by the following general formula (S3).
  • 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 alkoxycarbonyl group.
  • R 102 may combine with Ar A to form a ring, in which 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 in general formula (S3) each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
  • the explanation, specific examples and preferred ranges of R 101 , R 102 and R 103 are the same as the explanation, specific examples and preferred ranges of Ra 1 to Ra 3 in general formula (S1) described above.
  • Ar A in general formula (S3) represents an aromatic ring group, more specifically represents a (k+1)-valent aromatic ring group.
  • the divalent aromatic ring group when k is 1 is, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, anthracenylene group, or a thiophene ring, a furan ring, a pyrrole ring,
  • a divalent aromatic ring group containing a hetero ring such as 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 is preferred.
  • the above aromatic ring group may have a substituent.
  • Specific examples of (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 are not particularly limited, but include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, - Alkyl groups such as ethylhexyl, octyl and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl; and the like.
  • Ar A preferably represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group, or a biphenylene ring group.
  • LA in general formula (S3) represents a single bond or a divalent linking group.
  • the divalent linking group represented by L A is not particularly limited, but includes, for example, -COO-, -CONR 64 -, an alkylene group, or a group formed by combining two or more of these groups.
  • R 64 represents a hydrogen atom or an alkyl group.
  • the alkylene group is not particularly limited, but alkylene groups having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group are preferable.
  • R 64 represents an alkyl group
  • examples of the alkyl group 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.
  • Examples include alkyl groups having 20 or less carbon atoms, such as groups, and alkyl groups having 8 or less carbon atoms are preferred.
  • the repeating unit represented by general formula (S3) preferably has a hydroxystyrene structure. That is, it is preferable that Ar A represents a benzene ring group. k preferably represents an integer of 1 to 3, more preferably 1 or 2.
  • repeating unit represented by general formula (S3) are shown below, but are not limited thereto.
  • the content of the repeating unit having a polar group in the resin (A) is not particularly limited, but is preferably 20 mol% or more, and 30 mol% or more based on the total repeating units in the resin (A). More preferably, it is 40 mol% or more. Further, the content of the repeating unit having a polar group is preferably 90 mol% or less, more preferably 85 mol% or less, and 80 mol% or less based on the total repeating units in the resin (A). It is more preferable that
  • the number of repeating units having polar groups contained in the resin (A) may be one or two or more. When two or more types are included, the total content is preferably within the above-mentioned preferred content range.
  • 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 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 descriptions in [0120] to [0134] of International Publication No. 2022/024928 can be incorporated as a reference.
  • the resin (A) contains at least one repeating unit selected from the group consisting of a repeating unit represented by general formula (S1) and a repeating unit represented by general formula (S2), and a repeating unit having a polar group. However, in addition to these, other repeating units may also be included.
  • the resin (A) may contain, as other repeating units, repeating units having acid-decomposable groups other than those mentioned above.
  • the acid-decomposable group is preferably a group that is decomposed by the action of an acid to produce a polar group.
  • the above polar group is preferably an alkali-soluble group, such as a carboxy 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) ) methylene group, acidic groups such as tris(alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups.
  • alkali-soluble group such as a carboxy group, phenolic hydroxyl group, fluorinated alcohol group,
  • Examples of the leaving group that leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
  • Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
  • Formula (Y3) -C(R 36 )(R 37 )(OR 38 )
  • Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched chain), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched). 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.
  • 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.
  • Two of Rx 1 to Rx 3 may be bonded to each other to form a ring (which may be monocyclic or polycyclic).
  • the alkyl group for Rx 1 to Rx 3 an alkyl group having 1 to 5 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group is preferable. .
  • Examples of the cycloalkyl group for Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
  • a 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, an anthryl group, and the like.
  • the aralkyl group of Rx 1 to Rx 3 is preferably a group in which one hydrogen atom in the alkyl group of Rx 1 to Rx 3 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.
  • a benzyl group and the like can be mentioned.
  • 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 combining two of Rx 1 to Rx 3 is a cyclopentyl group or a monocyclic cycloalkyl group such as a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
  • the cycloalkyl group formed by bonding two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a group in which one of the methylene groups constituting the ring has a hetero atom such as a carbonyl group, or May be substituted with a group. Further, in these cycloalkyl groups, 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.
  • 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.
  • monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferable that R 36 is a hydrogen atom.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group may include a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group.
  • one or more methylene groups are replaced with a group having 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.
  • 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.
  • Ar is more preferably an aryl group.
  • the resin (A) contains a repeating unit (hereinafter also referred to as unit may have.
  • 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.
  • ⁇ repeating unit having a photoacid generating group> means the ⁇ repeat unit having a lactone group, sultone group, or carbonate group> described below.
  • 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) 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.
  • 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, but the invention is not limited thereto.
  • examples of the repeating unit represented by formula (4) include repeating units described in paragraphs [0094] to [0105] of JP2014-041327A and paragraphs of International Publication No. 2018/193954. Examples include the repeating units described in [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.
  • the repeating units represented by formula (V-1) or (V-2) are illustrated 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 type of repeating unit whose homopolymer Tg is 130°C or higher is not particularly limited, and any repeating unit whose homopolymer Tg calculated by the Bicerano method is 130°C or higher may be used. Note that, depending on the type of functional group in the repeating units represented by formulas (A) to (E) described below, the repeating units correspond to homopolymer Tg of 130° C. or higher.
  • An example of a specific means for achieving the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (A).
  • R A represents a group containing a polycyclic structure.
  • R x represents a hydrogen atom, a methyl group, or an ethyl group.
  • a group containing a polycyclic structure is a group containing a plurality of ring structures, and the plurality of ring structures may or may not be condensed.
  • Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of International Publication No. 2018/193954.
  • An example of a specific means for achieving the above (b) is a method of introducing a repeating unit represented by the formula (B) into the resin (A).
  • R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
  • the types of other organic groups are not particularly limited.
  • at least two or more of the organic groups have three or more constituent atoms excluding hydrogen atoms. It is a substituent.
  • Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of International Publication No. 2018/193954.
  • An example of a specific means for achieving the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (A).
  • R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 has a hydrogen bonding property within 3 atoms from the main chain carbon.
  • a group containing an atom in order to induce interaction between the main chains of the resin (A), it is preferable to have hydrogen atoms capable of hydrogen bonding within 2 atoms (closer to the main chain).
  • Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of International Publication No. 2018/193954.
  • An example of a specific means for achieving the above (d) is a method of introducing a repeating unit represented by the formula (D) into the resin (A).
  • Cyclic represents a group forming a main chain with a cyclic structure.
  • the number of atoms constituting the ring is not particularly limited.
  • Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of International Publication No. 2018/193954.
  • An example of a specific means for achieving the above (e) is a method of introducing a repeating unit represented by the formula (E) into the resin (A).
  • Re each independently represents a hydrogen atom or an organic group.
  • the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, which may have a substituent.
  • Cyclic is a cyclic group containing backbone carbon atoms. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of International Publication No. 2018/193954.
  • 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. Specific examples of repeating units other than the above-mentioned repeating units are illustrated below.
  • 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.
  • all of the repeating units are derived from a compound having an ethylenically unsaturated bond. It is preferable to be composed of repeating units. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, and all of the repeating units are 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, 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 sidewalls of the resist pattern, and the better the roughness.
  • 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 of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
  • Salt (B) is a compound represented by the following general formula (T1).
  • the salt (B) may be a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation, or may not be a photoacid generator, but upon irradiation with actinic rays or radiation, A compound that generates an acid with a pKa of -1 to 9 is preferable.
  • Salt (B) can function as an acid diffusion control agent in the case of a salt of an acid that is a relatively weak acid with respect to the acid generated from a photoacid generator (for example, salt (C) described below). .
  • the acid diffusion control agent traps the acid generated from the photoacid generator (for example, salt (C) described below) etc. during exposure, and prevents the reaction of the acid-decomposable resin in the unexposed area due to the excess generated acid. Acts as a quencher.
  • the photoacid generator for example, salt (C) described below
  • Arb represents an aromatic ring.
  • the above aromatic ring may have a substituent.
  • Q represents an acid residue.
  • the anion in general formula (T1) is a conjugate base of an acid with a pKa of -1 to 9.
  • Rb 1 represents -OH, -ORb 2 , -NRb 3 Rb 4 , -SH, or -SRb 5 , and multiple Rb 1 's may be the same or different.
  • Rb 2 represents an alkyl group, an aryl group, or an acyl group.
  • Rb 3 and Rb 4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.
  • Rb 5 represents an alkyl group, an aryl group, or an acyl group. At least two of Rb 2 to Rb 5 may be bonded to each other to form a ring. When Arb has a substituent, the above substituent and at least one of Rb 2 to Rb 5 may be bonded to form a ring.
  • Lb 1 represents a single bond or a divalent linking group. Lb 1 may be combined with Rb 1 to form a ring by substituting a hydrogen atom contained in Rb 1 . Lb 1 may be bonded to at least one of Rb 2 to Rb 5 to form a ring. When Arb has a substituent, the substituent and Lb 1 may be combined to form a ring.
  • p represents an integer from 2 to 5.
  • G m+ represents an m-valent organic cation. m represents an integer of 1 or more.
  • the molecular weight of the compound represented by general formula (T1) 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.
  • Arb in general formula (T1) represents an aromatic ring.
  • the number of carbon atoms as ring members contained in the aromatic ring is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10.
  • the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, but is preferably an aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, etc., with a benzene ring or a naphthalene ring being preferred, and a benzene ring being more preferred.
  • the aromatic heterocycle is preferably an aromatic heterocycle containing at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom.
  • Lb 1 and Rb 1 are bonded to the aromatic ring represented by Arb
  • the aromatic ring represented by Arb may further have a substituent in addition to these.
  • substituents include organic groups having 1 to 10 carbon atoms, such as alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and aryl groups.
  • Rb 1 in general formula (T1) represents -OH, -ORb 2 , -NRb 3 Rb 4 , -SH, or -SRb 5 .
  • Rb 2 represents an alkyl group, an aryl group, or an acyl group.
  • Rb 3 and Rb 4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.
  • Rb 5 represents an alkyl group, an aryl group, or an acyl group.
  • the alkyl group represented by Rb 2 to Rb 5 may be either linear or branched.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably from 1 to 10, more preferably from 1 to 5.
  • the number of carbon atoms in the aryl group represented by Rb 2 to Rb 5 is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10.
  • a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • the alkyl group that may be contained in the acyl group represented by Rb 2 to Rb 5 may be either linear or branched.
  • the number of carbon atoms in the alkyl group that may be contained in the acyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5.
  • the number of carbon atoms in the aryl group that can be contained in the acyl group represented by Rb 2 to Rb 5 is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10.
  • the aryl group that may be included in the acyl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • Rb 1 is preferably -OH, -NH 2 or -SH. It is particularly preferred that at least one of Rb 1 is -OH.
  • Lb 1 in general formula (T1) represents a single bond or a divalent linking group.
  • the divalent linking group is preferably an organic linking group having 1 to 10 carbon atoms, an ether group, a thioether group, a carbonyl group, or a combination thereof, such as an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, or an arylene group. etc.
  • p in general formula (T1) represents an integer of 2 to 5, preferably represents an integer of 2 to 4, and more preferably represents 2 or 3.
  • Q in general formula (T1) represents an acid residue.
  • the acid residue is represented by a carboxylate anion group (-COO - ), a sulfonate anion group (-SO 3 - ), or a sulfonamide group (-N - -SO 2 R N1 .
  • R N1 is an organic group represents an alkyl group, a fluoroalkyl group, and an aryl group are preferable, and a carboxylate anion group is more preferable.
  • the anion in general formula (T1) (the anion represented by general formula (T1A) below) is a conjugate base of an acid with a pKa of -1 to 9, and a conjugate base of an acid with a pKa of 0 to 7.
  • the pKa of the conjugate acid of the anion represented by the general formula (T1A) is -1 to 9, preferably 0 to 7, and more preferably 1 to 6.
  • Arb, Q, Rb 1 , Lb 1 and p represent the same meanings as Arb, Q, Rb 1 , Lb 1 and p in general formula (T1), respectively.
  • anion in general formula (T1) anion represented by general formula (T1A)
  • T1A anion represented by general formula (T1A)
  • G m+ in general formula (T1) represents an m-valent organic cation.
  • m represents an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, even more preferably 1.
  • the organic cation of G m+ is not particularly limited.
  • a sulfonium cation, an iodonium cation, or an ammonium cation is preferable.
  • Examples of the organic cation include a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)"), or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)"). is more preferable.
  • 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 an oxygen atom, a sulfur atom, or an ester group may be present in the ring. , 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 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.
  • the content of the salt (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention. .
  • the content of the salt (B) is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, and even more preferably 15.0% by mass or less, based on the total solid content of the composition of the present invention.
  • Salt (B) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
  • the composition of the present invention may contain a compound (impurity) produced by oxidizing the salt (B).
  • a compound (impurity) produced by oxidizing the salt (B) include compounds having a quinone structure.
  • the content of the impurities is 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.
  • composition of the present invention may contain other components in addition to the resin (A) and the salt (B).
  • the composition of the present invention may contain a salt (C) which is a compound different from the above-mentioned salt (B) and which generates an acid upon irradiation with actinic rays or radiation.
  • the pKa of the acid generated from the salt (C) upon irradiation with actinic rays or radiation is preferably smaller than the pKa of the conjugate acid of the anion of the salt (B).
  • the absolute value of the difference between the pKa of the acid generated from the salt (C) and the pKa of the conjugate acid of the anion of the salt (B) is preferably 0.1 or more and less than 20, and preferably 1 or more and less than 15.
  • the salt (C) may be in the form of a low molecular compound or may be incorporated into a part of the polymer (for example, the resin (A)). Further, a form of a low molecular compound and a form incorporated into a part of a polymer (for example, resin (A)) may be used together.
  • the molecular weight of the salt (C) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less. The lower limit is not particularly limited, but is preferably 100 or more.
  • the salt (C) is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A).
  • Examples of the salt (C) include a compound represented by "G 1 + 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.
  • G 1 + represents an organic cation.
  • Specific examples and preferred ranges of the organic cation are the same as those of the organic cation represented by G m+ in the general formula (T1) above.
  • 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, 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 preferred.
  • 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.
  • a hydrogen atom is preferable as R 4 and R 5 .
  • L represents a divalent linking group.
  • the definition of L is synonymous with L in formula (AN1).
  • W represents an organic group 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 salt (C) has a group that is decomposed by the action of an acid.
  • the salt (C) is preferably a compound represented by the following general formula (U1).
  • L represents a single bond or a divalent linking group.
  • A represents a group that decomposes under the action of an acid.
  • n represents an integer from 1 to 5.
  • X represents an n+1-valent linking group.
  • M + represents a sulfonium ion or an iodonium ion.
  • X represents an n+1-valent linking group.
  • the linking group represented by Examples include OCO- and a combination of two or more of these groups.
  • the aliphatic group mentioned above is a group obtained by removing n hydrogen atoms from an alkyl group (which may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms).
  • a group obtained by removing n hydrogen atoms from a cycloalkyl group (which may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms) is preferable.
  • the above aliphatic group may have a substituent, and examples of the substituent include the above substituent T.
  • the aliphatic group may have a heteroatom (eg, sulfur atom, oxygen atom, nitrogen atom, etc.) between carbon atoms.
  • the above aromatic group is an aryl group (preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms).
  • the aryl group may also be an aryl group having 6 to 10 carbon atoms. Preferred. Specific examples of the aryl group include phenyl group, terphenyl group, etc.) from which n hydrogen atoms have been removed.
  • the above aromatic group may have a substituent, and examples of the substituent include the above substituent T.
  • the aromatic group may have a heteroatom (eg, sulfur atom, oxygen atom, nitrogen atom, etc.) between carbon atoms.
  • X is an n+1-valent aromatic group.
  • n represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.
  • L represents a single bond or a divalent linking group.
  • the divalent linking group represented by L is not particularly limited, but includes, for example, an aliphatic group (which may be linear, branched, or cyclic), an aromatic group, -O-, -CO-, -COO -, -OCO-, and a combination of two or more of these groups.
  • the aliphatic groups mentioned above include alkylene groups (which may be linear or branched, preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms), and cycloalkylene groups (monocyclic or polycyclic alkylene groups).
  • a cycloalkylene group having preferably 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms is preferred.
  • the above aliphatic group may have a substituent, and examples of the substituent include the above substituent T.
  • the aliphatic group may have a heteroatom (eg, sulfur atom, oxygen atom, nitrogen atom, etc.) between carbon atoms.
  • the aromatic group is preferably an arylene group (preferably an arylene group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms).
  • the above aromatic group may have a substituent, and examples of the substituent include the above substituent T.
  • the aromatic group may have a heteroatom (eg, sulfur atom, oxygen atom, nitrogen atom, etc.) between carbon atoms.
  • L is an arylene group.
  • A represents a group that decomposes under the action of an acid.
  • the group that is decomposed by the action of an acid (acid-decomposable group) represented by A is not particularly limited, and includes, for example, the acid-decomposable groups described in the resin (A) above.
  • the acid-decomposable group preferably has a structure in which a polar group is protected with a group (leaving group) that decomposes and leaves under the action of an acid.
  • a polar group a carboxy group, a phenolic hydroxyl group, and an alcoholic hydroxyl group are preferable.
  • M + represents a sulfonium ion or an iodonium ion, and specific examples and preferred ranges are the same as those in the case where G m+ in general formula (T1) represents a sulfonium ion or an iodonium ion.
  • the salt (C) is preferably a compound represented by the following general formula (U2).
  • L, A, n, and M + represent the same meanings as L, A, n, and M + in general formula (U1), respectively.
  • the salt (C) may be 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.
  • the lower limit of the acid dissociation constant a2 is preferably ⁇ 4 or more.
  • the acid dissociation constant a1 is preferably smaller than the pKa of the conjugate acid of the anion of the salt (B).
  • the absolute value of the difference between the acid dissociation constant a1 and the pKa of the conjugate acid of the anion of the salt (B) is preferably 0.1 or more and less than 20, more preferably 1 or more and less than 15, particularly preferably 2 or more and less than 10.
  • 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 represented by G1 + mentioned above is mentioned, for example.
  • Compound (II) is a compound having two or more of the above structural sites 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.
  • salt (C) Specific examples of the salt (C) are shown below, but the salt (C) is not limited thereto.
  • the content of the salt (C) is preferably 0.5% by mass or more, and 1.0% by mass based on the total solid content of the composition of the present invention.
  • the above is more preferable.
  • the content of salt (B) 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.
  • Salt (C) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
  • the salt (B) can function as an acid diffusion control agent, but the composition of the present invention may further contain an acid diffusion control agent in addition to the salt (B).
  • the acid diffusion control agent is a quenching agent that traps the acid generated from the photoacid generator (for example, salt (C), etc.) during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to the excess generated acid. Acts as a char.
  • 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.
  • the compound (DC) is an onium salt compound (DD) of an acid that becomes a relatively weak acid with respect to the acid generated from a photoacid generator (for example, salt (C), etc.), and irradiation with actinic rays or radiation.
  • Examples include basic compounds (DE) whose basicity decreases or disappears due to 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.
  • the content of the acid diffusion control agent is 0.1 to 15% based on the total solid content of the composition of the present invention. 0% by mass is preferred, and 0.5 to 15.0% by mass is more preferred.
  • Acid diffusion control agents other than the salt (B) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
  • the composition of the present invention may further contain a hydrophobic resin different from the resin (A).
  • the hydrophobic resin is preferably designed so that it is unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and it is necessary to uniformly mix polar and non-polar substances. does not have to contribute to Effects of adding a hydrophobic resin include controlling the static and dynamic contact angle of the resist film surface with water and suppressing outgassing.
  • the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin, and preferably has two or more of them. It is more preferable to have the above.
  • 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 include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.
  • the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and 0.1 to 20.0% by mass, based on the total solid content of the composition of the present invention. 15.0% by mass is more preferred.
  • the hydrophobic resins may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
  • 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.
  • 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.
  • One kind of surfactant may be used, or two or more kinds of surfactants may be used. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
  • 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.
  • the composition of the present invention is suitably used as a photosensitive composition for EUV exposure.
  • EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light, etc., so the number of incident photons when exposed with the same sensitivity is smaller. Therefore, the influence of "photon shot noise" in which the number of photons varies stochastically is large, leading to deterioration of line edge roughness (LER) and bridging defects.
  • One way to reduce photon shot noise is to increase the number of incident photons by increasing the exposure amount, but this comes at a trade-off with the demand for higher sensitivity.
  • the absorption efficiency of EUV light and electron beams of the resist film formed from the resist composition becomes high, which is effective in reducing photon shot noise.
  • the A value represents the EUV light and electron beam absorption efficiency of the mass percentage of the resist film.
  • A ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] x 39.5) / ([H] x 1 + [C] x 12 + [N] x 14 + [O] x 16 + [F] x 19 + [S] x 32 + [I] x 127)
  • the A value is preferably 0.120 or more.
  • the upper limit is not particularly limited, but if the A value is too large, the EUV light and electron beam transmittance of the resist film will decrease, the optical image profile in the resist film will deteriorate, and as a result, it will be difficult to obtain a good pattern shape. Therefore, it is preferably 0.240 or less, more preferably 0.220 or less.
  • [H] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
  • [C] represents the molar ratio of carbon atoms derived from the total solid content to all atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
  • [N] is the actinic ray-sensitive or radiation-sensitive resin composition.
  • [O] is the molar ratio of nitrogen atoms derived from all solids to all atoms of all solids in the actinic ray-sensitive or radiation-sensitive resin composition
  • [F] is the molar ratio of fluorine atoms derived from the total solid content to all atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.
  • [S] represents the molar ratio of sulfur atoms derived from the total solid content to all atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
  • [I] represents the active ray-sensitive or radiation-sensitive resin composition. It represents the molar ratio of iodine atoms derived from the total solid content to all atoms of the total solid content in a radiation-sensitive or radiation-sensitive resin composition.
  • the resist composition includes an acid-decomposable resin, a photoacid generator, an acid diffusion control agent, and a solvent
  • the acid-decomposable resin, the photoacid generator, and the acid diffusion control agent correspond to the solid content. do.
  • all atoms in the total solid content correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent.
  • [H] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms derived from the total solid content, and to explain based on the above example, [H] represents all atoms derived from the acid-decomposable resin. , hydrogen atoms derived from the acid-decomposable resin, hydrogen atoms derived from the photoacid generator, and the acid with respect to the total of all atoms derived from the photoacid generator and all atoms derived from the acid diffusion control agent. It represents the total molar ratio of hydrogen atoms derived from the diffusion control agent.
  • the A value can be calculated by calculating the ratio of the number of atoms contained. Furthermore, even if the constituent components are unknown, it is possible to calculate the constituent atomic ratio using analytical methods such as elemental analysis for a resist film obtained by evaporating the solvent components of the resist composition. .
  • 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 a resist film on a substrate using the composition of the present invention Step 2: Step of exposing the resist film Step 3: Step of developing the exposed resist film using a developer
  • Step 1 Step of forming a resist film on a substrate using the composition of the present invention
  • Step 2 Step of exposing the resist film
  • Step 3 Step of developing the exposed resist film using a developer
  • Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.
  • Examples of the method for forming a resist film on a substrate using the composition of the present invention include a method of applying the composition of the present invention onto 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 a resist film. Note that, if necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist 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 resist film is not particularly limited, but is preferably 10 to 120 nm from the standpoint of forming fine patterns with higher precision. Among these, in the case of EUV exposure, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. In the case of ArF immersion exposure, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.
  • a top coat may be formed on the upper layer of the resist film using a top coat composition. It is preferable that the top coat composition is not mixed with the resist 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. For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-61648 on the resist film. 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 resist film.
  • the exposure method include a method of irradiating the formed resist 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.
  • Particularly preferred are 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 resist 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, 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.
  • 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, even more preferably 100 mass ppt (parts per trillion) or less, and 10 mass ppm (parts per million) or less.
  • a mass ppt or less is particularly preferred, and a mass ppt or less is most preferred.
  • the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
  • metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, 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 liquid after use is preferably 100 mass ppt or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
  • the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
  • Organic processing liquids such as rinsing liquids 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-15 were used. Furthermore, AX-1 to AX-4 were used as resins other than resin (A). For convenience, AX-1 to AX-4 are also listed in the resin (A) column in Table 1 below. The structures of A-1 to A-15 and AX-1 to AX-4 are shown below.
  • the content ratio of the following repeating units is a molar ratio.
  • A-1 to A-15 and AX-1 to AX-4 are acid-decomposable resins.
  • a synthesis example of A-1 is shown below.
  • Other resins (A) were also synthesized in the same manner.
  • B-1 to B-10 were used as salts (B).
  • the structures of B-1 to B-10 are shown below.
  • B-1H to B-10H are acids generated from B-1 to B-10 (conjugate acids of the anions of B-1 to B-10).
  • the structures and pKa of B-1H to B-10H are shown below.
  • C-1H to C-6H are acids generated from C-1 to C-6.
  • the structures and pKa of C-1H to C-6H are shown below.
  • D-1 to D-4 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.)
  • W-5 KH-20 (manufactured by AGC 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-6/A-12 indicates that two types of resin (A), A-6 and A-12, were used, and "5/5" indicates that A-6 and A-12 were used as the resin (A). This indicates that 5g of each of A-6 and A-12 were used.
  • ⁇ 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). After 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
  • 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. 1, heated on a hot plate at 100° C. for 60 seconds, and developed.
  • 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 is 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.
  • Table 2 below shows the resist compositions used in each Example and Comparative Example and the results of each Example and Comparative Example.
  • Comparative Example 5 had poorer density dependence than the Examples, but this was due to the high solubility of the AX-4 used in the developer, and the high solubility of the resin in the developer after AX-4 was deprotected. This is presumed to be due to too high solubility in
  • the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in density dependence, LWR performance, and defect suppression performance. 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.

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Abstract

L'invention fournit une composition de résine sensible aux rayons actiniques ou à un rayonnement qui comprend : une résine (A) qui contient un groupe dégradé et de polarité augmentée sous l'effet d'un acide ; et un sel (B). La résine (A) contient une unité de répétition de structure spécifique, et une unité de répétition présentant un groupe polaire. Le sel (B) consiste en un composé possédant une structure spécifique. 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. La composition de résine sensible aux rayons actiniques ou à un rayonnement de l'invention est excellente en termes de dépendance à la densité, de performances LWR et de performances d'inhibition des défauts.
PCT/JP2023/026881 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 WO2024024691A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011048142A (ja) * 2009-08-27 2011-03-10 Sumitomo Chemical Co Ltd レジスト組成物及びパターン形成方法
JP2017219836A (ja) * 2016-06-07 2017-12-14 信越化学工業株式会社 レジスト材料及びパターン形成方法
WO2020095641A1 (fr) * 2018-11-07 2020-05-14 富士フイルム株式会社 Composition de résine sensible au rayonnement, film de réserve, procédé de formation de motif et procédé de production de dispositif électronique
JP2022007909A (ja) * 2020-03-11 2022-01-13 Jsr株式会社 感放射線性樹脂組成物、パターン形成方法及び単量体化合物の製造方法
WO2022064863A1 (fr) * 2020-09-28 2022-03-31 Jsr株式会社 Composition de résine sensible au rayonnement, et procédé de formation de motif
JP2022066864A (ja) * 2020-10-19 2022-05-02 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
JP2023002462A (ja) * 2021-06-22 2023-01-10 信越化学工業株式会社 レジスト材料及びパターン形成方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011048142A (ja) * 2009-08-27 2011-03-10 Sumitomo Chemical Co Ltd レジスト組成物及びパターン形成方法
JP2017219836A (ja) * 2016-06-07 2017-12-14 信越化学工業株式会社 レジスト材料及びパターン形成方法
WO2020095641A1 (fr) * 2018-11-07 2020-05-14 富士フイルム株式会社 Composition de résine sensible au rayonnement, film de réserve, procédé de formation de motif et procédé de production de dispositif électronique
JP2022007909A (ja) * 2020-03-11 2022-01-13 Jsr株式会社 感放射線性樹脂組成物、パターン形成方法及び単量体化合物の製造方法
WO2022064863A1 (fr) * 2020-09-28 2022-03-31 Jsr株式会社 Composition de résine sensible au rayonnement, et procédé de formation de motif
JP2022066864A (ja) * 2020-10-19 2022-05-02 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法
JP2023002462A (ja) * 2021-06-22 2023-01-10 信越化学工業株式会社 レジスト材料及びパターン形成方法

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