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WO2024048397A1 - Composition de résine sensible aux rayons actiniques ou à un rayonnement, film sensible aux rayons actiniques ou à un rayonnement, procédé de formation de motif, et procédé de fabrication de dispositif électronique - Google Patents

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

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Publication number
WO2024048397A1
WO2024048397A1 PCT/JP2023/030369 JP2023030369W WO2024048397A1 WO 2024048397 A1 WO2024048397 A1 WO 2024048397A1 JP 2023030369 W JP2023030369 W JP 2023030369W WO 2024048397 A1 WO2024048397 A1 WO 2024048397A1
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WIPO (PCT)
Prior art keywords
group
sensitive
radiation
compound
acid
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PCT/JP2023/030369
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English (en)
Japanese (ja)
Inventor
悠花 上農
知昭 吉岡
文博 吉野
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Fujifilm Corp
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Fujifilm Corp
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Priority to KR1020257005881A priority Critical patent/KR20250041033A/ko
Priority to JP2024544170A priority patent/JPWO2024048397A1/ja
Publication of WO2024048397A1 publication Critical patent/WO2024048397A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method. More specifically, the present invention relates to an ultra-microlithography process applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the manufacturing process of nanoimprint molds, the manufacturing process of high-density information recording media, etc. The present invention relates to actinic ray-sensitive or radiation-sensitive resin compositions, actinic ray-sensitive or radiation-sensitive films, pattern forming methods, and electronic device manufacturing methods that can be suitably used in other photofabrication processes.
  • ultra-microlithography process applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the manufacturing process of nanoimprint molds, the manufacturing process of high-density information recording media, etc.
  • the present invention relates to actinic ray-sensitive or radiation
  • Patent Documents 1 and 2 describe resist compositions containing a resin having a specific structure, a photoacid generator, and an acid diffusion control agent.
  • LWR performance refers to the ability to reduce the LWR of a pattern.
  • actinic ray-sensitive or radiation-sensitive resin composition is required in the manufacturing process to have little effect on performance due to the passage of time from exposure to post-exposure bake (PEB). Excellent PED (Post Exposure Time Delay) stability is desired.
  • an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and PED stability.
  • the present invention also provides an actinic ray-sensitive or radiation-sensitive film formed using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and a pattern using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.
  • An object of the present invention is to provide a method for forming an electronic device and a method for manufacturing an electronic device.
  • An actinic ray-sensitive or radiation-sensitive resin composition containing at least At least one of the compound (A) and the acid diffusion control agent (B) is a compound represented by the following formula (Z-1), An actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).
  • Ar 1 , Ar 2 and Ar 3 each independently represent an aryl group or a heteroaryl group. At least two of Ar 1 , Ar 2 and Ar 3 may be bonded to each other via a single bond or a linking group.
  • X ⁇ represents an anion.
  • the sulfonium cation in formula (Z-1) satisfies the following condition (i).
  • salt (a) and salt (b) each was added so that "number of moles of added salt/(total mass of the resin (P) and added salt)" was 0.4 mmol/g.
  • DR a dissolution rate of the film formed by adding salt (a) in an alkaline developer
  • DR b dissolution rate of the film formed by adding salt (b) in an alkaline developer
  • Ar a1 represents an aromatic ring.
  • R a1 represents a substituent.
  • k1 represents an integer from 0 to 7.
  • k1 represents an integer from 0 to 7.
  • k1 represents 2 or more, a plurality of Ra1s may be the same or different from each other.
  • k1 is 2 or more, a plurality of R a1 may be bonded to each other to form a ring.
  • [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the compound (A) contains an anion represented by the following formula (ca1).
  • Ar a2 represents an aromatic ring.
  • R a2 represents a substituent.
  • k2 represents an integer from 0 to 7.
  • k2 represents an integer from 0 to 7.
  • k2 is 2 or more, a plurality of R a2s may be the same or different from each other.
  • k2 is 2 or more, a plurality of R a2 may be bonded to each other to form a ring.
  • the actinic ray-sensitive or radiation-sensitive resin composition described above.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the resin (P) contains a repeating unit represented by the following formula (Pa1).
  • R P1 represents a hydrogen atom or an alkyl group.
  • R P2 represents a group that is eliminated by the action of an acid.
  • Pa2 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the resin (P) contains a repeating unit represented by the following formula (Pa2).
  • R P3 represents a hydrogen atom or an alkyl group.
  • R P4 represents a group that is eliminated by the action of an acid.
  • R Z1 , R Z2 and R Z3 each independently represent an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, or an aryl group.
  • n1 represents an integer from 1 to 5.
  • n2 and n3 each independently represent an integer from 0 to 5.
  • the plurality of R Z1 , R Z2 and R Z3 may be the same or different from each other. At least two of R Z1 , R Z2 and R Z3 may be bonded to each other via a single bond or a linking group. Further, the benzene rings in formula (Z-2) may be bonded to each other through a single bond or a linking group.
  • X ⁇ represents an anion.
  • a pattern forming method comprising the steps of: exposing a radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
  • the resin (P) contains a repeating unit represented by the following formula (Pa2), At least one of the compound (A) and the acid diffusion control agent (B) is a compound represented by the following formula (Z-2), An actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).
  • R P3 represents a hydrogen atom or an alkyl group.
  • R P4 represents a group that is eliminated by the action of an acid.
  • R Z1 , R Z2 and R Z3 each independently represent an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, or an aryl group.
  • n1 represents an integer from 1 to 5.
  • n2 and n3 each independently represent an integer from 0 to 5.
  • the plurality of R Z1s may be the same or different from each other, or may be bonded to each other to form a ring.
  • the plurality of R Z2s may be the same or different, or may be bonded to each other to form a ring.
  • the plurality of R Z3s may be the same or different from each other, and may be bonded to each other.
  • the benzene rings in formula (Z-2) may be bonded to each other through a single bond or a linking group.
  • X ⁇ represents an anion represented by the following formula (xa1).
  • Ar a1 represents an aromatic ring.
  • R a1 represents a substituent.
  • k1 represents an integer from 0 to 7.
  • k1 is 2 or more, a plurality of Ra1s may be the same or different from each other.
  • k1 is 2 or more, a plurality of R a1 may be bonded to each other to form a ring.
  • the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and PED stability. 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.
  • active rays or “radiation” include, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV), X-rays, soft X-rays, and electron It means a line (EB: Electron Beam) or the like.
  • light means actinic rays or radiation.
  • exposure refers not only to exposure to the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also to electron beams and ion beams, unless otherwise specified. It also includes drawing using particle beams such as beams.
  • " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • (meth)acrylate represents at least one of acrylate and methacrylate.
  • (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin are determined using a GPC (Gel Permeation Chromatography) apparatus (HLC manufactured by Tosoh Corporation).
  • GPC Gel Permeation Chromatography
  • the notation that does not indicate substituted or unsubstituted includes a group containing a substituent as well as a group having no substituent.
  • alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • organic group refers to a group containing at least one carbon atom.
  • monovalent substituents are preferred. Examples of the substituent include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.
  • substituent T examples include halogen atoms such as fluorine, chlorine, bromine and iodine; alkoxy groups such as methoxy, ethoxy and tert-butoxy; cycloalkyloxy; phenoxy and p-tolyloxy groups; Aryloxy groups; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl groups; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy groups; acetyl Acyl groups such as benzoyl, isobutyryl, acryloyl, methacryloyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; phenylsulfanyl groups; alkyls
  • substituent T when these substituents can further have one or more substituents, the further substituent is a group having one or more substituents selected from the above-mentioned substituents (for example, a monoalkylamino group). , dialkylamino group, arylamino group, trifluoromethyl group, etc.) are also included as examples of the substituent T.
  • the direction of bonding of the divalent groups described is not limited unless otherwise specified.
  • Y in the compound represented by the formula "X-Y-Z" is -COO-
  • Y may be -CO-O- or -O-CO- Good too.
  • the above compound may be "X-CO-O-Z" or "X-O-CO-Z”.
  • acid dissociation constant refers to pKa in an aqueous solution, and specifically, it is a value based on Hammett's substituent constant and a database of known literature values using the following software package 1. is the value obtained by calculation. All pKa values described herein are values calculated using this software package.
  • Software package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
  • pKa can also be determined by molecular orbital calculation method.
  • a specific method for this includes a method of calculating H 2 + dissociation free energy in an aqueous solution based on a thermodynamic cycle.
  • the H + dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to this. .
  • DFT density functional theory
  • there is a plurality of software that can perform DFT and one example is Gaussian 16.
  • pKa refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using software package 1, as described above. If calculation is not possible, a value obtained by Gaussian 16 based on DFT (density functional theory) is used.
  • pKa refers to "pKa in aqueous solution” as described above, but if pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is adopted. shall be.
  • solid content means a component that forms an actinic ray-sensitive or radiation-sensitive film, and does not include a solvent. Furthermore, if the component forms an actinic ray-sensitive or radiation-sensitive film, it is considered to be a solid content even if the component is liquid.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "composition of the present invention") is A resin (P) containing a repeating unit having a phenolic hydroxyl group and a repeating unit having an acid-decomposable group, A compound (A) that generates an acid with a pKa of less than 0 upon irradiation with actinic rays or radiation, and an acid diffusion control agent (B)
  • An actinic ray-sensitive or radiation-sensitive resin composition containing at least At least one of the compound (A) and the acid diffusion control agent (B) is a compound represented by the following formula (Z-1), An actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).
  • Ar 1 , Ar 2 and Ar 3 each independently represent an aryl group or a heteroaryl group. At least two of Ar 1 , Ar 2 and Ar 3 may be bonded to each other via a single bond or a linking group.
  • X ⁇ represents an anion.
  • the sulfonium cation in formula (Z-1) satisfies the following condition (i).
  • salt (a) and salt (b) each was added so that "number of moles of added salt/(total mass of the resin (P) and added salt)" was 0.4 mmol/g.
  • DR a dissolution rate of the film formed by adding salt (a) in an alkaline developer
  • DR b dissolution rate of the film formed by adding salt (b) in an alkaline developer
  • the present inventors speculate as follows. Since the resin (P) contains repeating units having a phenolic hydroxyl group, which is a hydrophilic part, and repeating units having an acid-decomposable group, which is a hydrophobic part, the dissolution rate in the developer varies. By adding the compound represented by the formula (Z-1) to the resin (P), the dissolution rate (especially the dissolution rate of hydrophilic parts) of the resin (P) is reduced (this effect is referred to as "infusion"). It is thought that this is because the dissolution rate variation was suppressed, and as a result, the resolution, LWR performance, and PED stability were improved. It is also believed that resolution, LWR performance, and PED stability were further improved when the content of acid diffusion control agent (B) was 80 mol% or more relative to the content of compound (A). It will be done.
  • 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 (P) contained in the composition of the present invention is a resin containing a repeating unit having a phenolic hydroxyl group and a repeating unit having an acid-decomposable group.
  • the resin (P) is an acid-decomposable resin, and when an alkaline developer is typically used as a developer in the pattern forming method using the composition of the present invention, a positive pattern is preferable. When an organic developer is used as the developer, a negative pattern is suitably formed.
  • An acid-decomposable group is a group that decomposes and increases in polarity under the action of an acid.
  • 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 (P) 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 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 is preferably 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, or t-butyl group.
  • 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 (P) contains a repeating unit represented by the following formula (Pa1).
  • the repeating unit represented by the following formula (Pa1) is a repeating unit having an acid-decomposable group.
  • R P1 represents a hydrogen atom or an alkyl group.
  • R P2 represents a group that is eliminated by the action of an acid.
  • the alkyl group represented by R P1 may be linear or branched.
  • the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.
  • the alkyl group may have a substituent.
  • Examples of the group that is eliminated by the action of an acid represented by R P2 include the groups represented by the above-mentioned formulas (Y1) to (Y4). By eliminating R P2 , a hydroxy group (phenolic hydroxyl group) is generated in formula (Pa1).
  • the resin (P) contains a repeating unit represented by the following formula (Pa2).
  • the repeating unit represented by the following formula (Pa2) is a repeating unit having an acid-decomposable group.
  • R P3 represents a hydrogen atom or an alkyl group.
  • R P4 represents a group that is eliminated by the action of an acid.
  • the alkyl group represented by R P3 may be linear or branched.
  • the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.
  • the alkyl group may have a substituent.
  • Examples of the group represented by R P4 that leaves by the action of an acid include the groups represented by the above-mentioned formulas (Y1) to (Y4). When R P4 is eliminated, a carboxyl group is generated in formula (Pa2).
  • the content of the repeating unit having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on all the repeating units in the resin (P). Further, the content of the repeating unit having an acid-decomposable group is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on all the repeating units in the resin (P). .
  • the number of repeating units having an acid-decomposable group contained in the resin (P) may be one type or two or more types.
  • the resin (P) contains two or more types of repeating units having acid-decomposable groups, the total content thereof is preferably within the above-mentioned preferred content range.
  • the repeating unit having a phenolic hydroxyl group contained in the resin (P) will be explained.
  • the repeating unit having a phenolic hydroxyl group is preferably a repeating unit different from the above-mentioned repeating unit having an acid-decomposable group.
  • the repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following formula (Pa3).
  • 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 formula (Pa3) 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 R 101 , R 102 and R 103 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, particularly preferably from 1 to 3.
  • Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.
  • the number of carbon atoms in the cycloalkyl group of R 101 , R 102 and R 103 is not particularly limited, but is preferably from 3 to 20, more preferably from 5 to 15.
  • Examples of the cycloalkyl group for R 101 , R 102 and R 103 include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • a polycyclic cycloalkyl group is preferred.
  • halogen atom for R 101 , R 102 and R 103 examples 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 R 101 , R 102 and R 103 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.
  • Ar A in formula (Pa3) 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 formula (Pa3) 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 104 -, an alkylene group, or a combination of two or more of these groups.
  • R 104 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 104 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 formula (Pa3) 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.
  • the content of the repeating unit having a phenolic hydroxyl group in the resin (P) 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 (P). It is more preferable that the amount is 40 mol% or more. Further, the content of repeating units having a phenolic hydroxyl 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 (P). It is more preferable that it is the following.
  • the number of repeating units having a phenolic hydroxyl group contained in the resin (P) may be one type or two or more types.
  • the resin (P) contains two or more types of repeating units having phenolic hydroxyl groups, the total content thereof is preferably within the range of the above-mentioned preferred content.
  • the resin (P) may contain other repeating units.
  • the contents of [0112] to [0172] of International Publication No. 2022/024928 are cited.
  • Resin (P) can be synthesized according to conventional methods (eg, radical polymerization).
  • the weight average molecular weight (Mw) of the resin (P) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000 as a polystyrene equivalent value determined by GPC method.
  • the degree of dispersion (molecular weight distribution, Pd, Mw/Mn) of the resin (P) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.0 to 3.0, and 1.1 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 (P) 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 (P) may be used alone or in combination of two or more. When using two or more types of resins (P), it is preferable that their total content is within the above-mentioned preferred content range.
  • the compound represented by formula (Z-1) may be a compound (A) that generates an acid with a pKa of less than 0 upon irradiation with actinic rays or radiation, or may be an acid diffusion control agent (B). Good too. Further, both the compound (A) and the acid diffusion control agent (B) may be a compound represented by formula (Z-1). Note that a compound that generates an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation is an acid diffusion control agent (B).
  • the pKa of the acid with the smallest pKa is less than 0 among the acids generated, it is classified as compound (A).
  • the pKa of the acid with the smallest pKa among the acids is 0 or more, it is used as an acid diffusion control agent (B).
  • the compound represented by formula (Z-1) is preferably an acid diffusion control agent (B).
  • the pKa of the acid generated from the compound represented by formula (Z-1) is preferably 0 or more, more preferably 1 or more, and even more preferably 2 or more. Furthermore, the pKa of the acid generated from the compound represented by formula (Z-1) is preferably 10 or less, more preferably 9 or less.
  • Ar 1 , Ar 2 and Ar 3 each independently represent an aryl group or a heteroaryl group. At least two of Ar 1 , Ar 2 and Ar 3 may be bonded to each other via a single bond or a linking group.
  • X ⁇ represents an anion.
  • the aryl group represented by Ar 1 , Ar 2 and Ar 3 is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and is a phenyl group or a naphthyl group. is more preferred, and phenyl group is particularly preferred.
  • the aryl group may have a substituent.
  • the heteroaryl group represented by Ar 1 , Ar 2 and Ar 3 is preferably a heteroaryl group having 3 to 20 carbon atoms.
  • the heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms. Examples of the heteroaryl group include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue.
  • the heteroaryl group may have a substituent.
  • Ar 1 , Ar 2 and Ar 3 represent an aryl group.
  • At least two of Ar 1 , Ar 2 and Ar 3 may be bonded to each other via a single bond or a linking group.
  • the linking group include -O-, -S-, -CO-, -CO 2 -, -SO-, -SO 2 -, alkylene group (preferably having 1 to 5 carbon atoms), alkenylene group (preferably (having 2 to 5 carbon atoms), and groups formed by combining two or more of these.
  • X ⁇ in formula (Z-1) represents an anion.
  • anions 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, aralkyl carboxylic acid anions, etc.) ), sulfonylimide anion, bis(alkylsulfonyl)imide anion, tris(alkylsulfonyl)methide anion, and the like.
  • 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.
  • anions include, for example, fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), and fluorinated antimony (eg, SbF 6 ⁇ ).
  • X ⁇ is preferably represented by the following formula (xa1).
  • Ar a1 represents an aromatic ring.
  • R a1 represents a substituent.
  • k1 represents an integer from 0 to 7.
  • k1 is 2 or more, a plurality of Ra1s may be the same or different from each other.
  • k1 is 2 or more, a plurality of R a1 may be bonded to each other to form a ring.
  • the aromatic ring represented by Ar a1 may be an aromatic hydrocarbon ring or an aromatic heterocycle.
  • the number of ring carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
  • the number of ring members of the aromatic heterocycle is preferably 4 to 20, more preferably 5 to 10.
  • the aromatic heterocycle preferably contains at least one of a sulfur atom, a nitrogen atom, and an oxygen atom.
  • aromatic heterocycles include five-membered aromatic heterocycles such as pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole ring, furan ring, and thiophene ring;
  • aromatic heterocycles include six-membered aromatic heterocycles such as a pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, thiazine ring, and oxazine ring.
  • the substituent represented by R a1 is not particularly limited, but includes, for example, the above-mentioned substituent T, and a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, and a halogen atom are preferred.
  • k1 represents an integer of 0 to 7, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3.
  • the compound represented by formula (Z-1) is preferably a compound represented by formula (Z-2) below.
  • R Z1 , R Z2 and R Z3 each independently represent an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, or an aryl group.
  • n1 represents an integer from 1 to 5.
  • n2 and n3 each independently represent an integer from 0 to 5.
  • R Z1 , R Z2 and R Z3 When a plurality of R Z1 , R Z2 and R Z3 exist, the plurality of R Z1 , R Z2 and R Z3 may be the same or different from each other. At least two of R Z1 , R Z2 and R Z3 may be bonded to each other via a single bond or a linking group. Further, the benzene rings in formula (Z-2) may be bonded to each other through a single bond or a linking group.
  • X ⁇ represents an anion.
  • the alkyl groups of R Z1 , R Z2 and R Z3 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, particularly preferably from 1 to 3.
  • the alkyl group may have a substituent. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and trifluoromethyl group.
  • alkyl group and acyloxy group contained in the alkoxy group, alkylthio group, alkoxycarbonyl group, alkylaminocarbonyl group and alkylsulfonyl group of R Z1 , R Z2 and R Z3 is an alkylcarbonyloxy group
  • the alkyl group and acylamino group are The explanation, specific examples and preferred ranges of the alkyl group when it is an alkylcarbonylamino group are the same as those for the alkyl groups of R Z1 , R Z2 and R Z3 above.
  • the cycloalkyl groups of R Z1 , R Z2 and R Z3 may be monocyclic or polycyclic.
  • the number of carbon atoms in the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15.
  • Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • the cycloalkyl group may have a substituent.
  • One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a hetero atom such as an oxygen atom, a group having a hetero atom such as a carbonyl group and an ester bond, or a vinylidene group. Further, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
  • the cycloalkyl group and acyloxy group contained in the cycloalkyloxy group, cycloalkylthio group, cycloalkyloxycarbonyl group, cycloalkylaminocarbonyl group and cycloalkylsulfonyl group of R Z1 , R Z2 and R Z3 are cycloalkylcarbonyloxy groups.
  • the explanation, specific examples and preferred ranges of the cycloalkyl group when the cycloalkyl group and acylamino group in some cases are cycloalkylcarbonylamino groups are the same as the cycloalkyl groups in R Z1 , R Z2 and R Z3 above. .
  • the aryl group of R Z1 , R Z2 and R Z3 is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and is a phenyl group or a naphthyl group. is more preferable, and phenyl group is particularly preferable.
  • the aryl group may have a substituent.
  • Aryl group and acylamino when the aryl group and acyloxy group contained in the aryloxy group, arylthio group, aryloxycarbonyl group, arylaminocarbonyl group and arylsulfonyl group of R Z1 , R Z2 and R Z3 are arylcarbonyloxy groups
  • the explanation, specific examples, and preferred ranges of the aryl group are the same as those for the aryl group of R Z1 , R Z2 and R Z3 above.
  • the heteroaryl groups R Z1 , R Z2 and R Z3 are preferably heteroaryl groups having 3 to 20 carbon atoms.
  • the heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms. Examples of the heteroaryl group include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue.
  • the heteroaryl group may have a substituent.
  • At least two of R Z1 , R Z2 and R Z3 may be bonded to each other via a single bond or a linking group.
  • the benzene rings in formula (Z-2) (the benzene rings to which R Z1 , R Z2 and R Z3 are bonded) may be bonded to each other through a single bond or via a linking group.
  • the linking group include -O-, -S-, -CO-, -CO 2 -, -SO-, -SO 2 -, alkylene group (preferably having 1 to 5 carbon atoms), alkenylene group (preferably (having 2 to 5 carbon atoms), and groups formed by combining two or more of these.
  • X ⁇ in formula (Z-2) represents an anion.
  • the explanation, specific examples, and preferred range of X ⁇ are the same as those for X ⁇ in formula (Z-1) above.
  • condition (i) The sulfonium cation in formula (Z-1) (sulfonium cation represented by formula (Z-1c) below) satisfies the following condition (i).
  • salt (a) and salt (b) each was added so that "number of moles of added salt/(total mass of the resin (P) and added salt)" was 0.4 mmol/g.
  • DR a dissolution rate of the film formed by adding salt (a) in an alkaline developer
  • DR b dissolution rate of the film formed by adding salt (b) in an alkaline developer
  • the composition of the present invention has stronger inhibition than when using salt (b), and the dissolution of resin (P) is improved. Variations in speed are suppressed, and resolution, LWR performance, and PED stability can be improved.
  • DR a and DR b are measured as follows.
  • the film (La) is developed (dissolved) in an alkaline developer (an aqueous solution containing tetramethylammonium hydroxide at a concentration of 2.38% by mass) for 600 seconds, and then rinsed with pure water for 30 seconds.
  • the film thickness after development is measured with a spectroscopic ellipsometer (for example, M-2000D (manufactured by JA Woollam Japan Co., Ltd.)), and the difference between the film thickness before and after development is calculated as the developed film thickness. do.
  • the value obtained by dividing the developed film thickness by the development time (600 seconds) is defined as DR a .
  • the film (Lb) is developed (dissolved) for 600 seconds with an alkaline developer (aqueous solution with a concentration of tetramethylammonium hydroxide of 2.38% by mass), and then rinsed with pure water for 30 seconds.
  • the film thickness after development is measured with a spectroscopic ellipsometer (for example, M-2000D (manufactured by JA Woollam Japan Co., Ltd.)), and the difference between the film thickness before and after development is calculated as the developed film thickness. do.
  • the value obtained by dividing the developed film thickness by the development time (600 seconds) is defined as DR b .
  • DR a /DR b is 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, and even more preferably 0.2 or less. Moreover, it is preferable that DR a /DR b is 0.01 or more, and it is more preferable that it is 0.02 or more. It is particularly preferable that DR a and DR b satisfy the following formula (i-2) because stronger inhibition can provide even better resolution, LWR performance, and PED stability. DR a /DR b ⁇ 0.10 ...(i-2)
  • ClogP of the sulfonium cation in formula (Z-1) is preferably 3 or more and 11 or less, more preferably 3 or more and 8 or less, and 4 It is particularly preferable that the number is 8 or less.
  • ClogP is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water.
  • Compound (A) is a compound that generates an acid having a pKa of less than 0 upon irradiation with actinic rays or radiation.
  • the pKa of the acid generated from compound (A) upon irradiation with actinic rays or radiation is preferably -0.1 or less, more preferably -0.5 or less. Further, the pKa of the acid generated from the compound (A) upon irradiation with actinic rays or radiation is preferably -1.5 or more, more preferably -1.0 or more.
  • Compound (A) may be a compound represented by formula (Z-1), or may be a compound different from the compound represented by formula (Z-1).
  • Compound (A) may be in the form of a low molecular weight compound or may be incorporated into a part of the polymer. Further, a form of a low molecular compound and a form incorporated into a part of a polymer may be used together.
  • the molecular weight of compound (A) 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 compound (A) is incorporated into a part of the polymer, it may be incorporated into a part of the resin (P), or may be incorporated into a resin different from the resin (P).
  • Compound (A) is preferably in the form of a low molecular weight compound.
  • Examples of the compound (A) include a compound represented by "M + X - " (onium salt), and preferably a compound that generates an organic acid upon exposure to light.
  • Examples of the organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.), carbonylsulfonylimide acid, bis(alkylsulfonyl)imidic acid, and tris(alkylsulfonyl)methide acid.
  • sulfonic acids aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.
  • carboxylic acids aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.
  • carbonylsulfonylimide acid bis(al
  • M + represents an organic cation.
  • a cation represented by the formula (ZaI) (hereinafter also referred to as “cation (ZaI)”).
  • cation (ZaII) a cation represented by formula (ZaII) (hereinafter also referred to as “cation (ZaII)" is preferable.
  • R 201 , R 202 , and R 203 each independently represent an organic group.
  • the number of carbon atoms in the organic groups of 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.
  • the organic groups of R 201 , R 202 , and R 203 are preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group.
  • the alkyl group 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.
  • Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.
  • the number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably from 3 to 20, more preferably from 5 to 15.
  • cycloalkyl group monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are preferable.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, even more preferably a phenyl group or a naphthyl group, and preferably a phenyl group. is particularly preferred.
  • the heteroaryl group is preferably a heteroaryl group having 3 to 20 carbon atoms.
  • the heteroaryl group preferably contains at least one heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen atoms.
  • Examples of the heteroaryl group include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue.
  • the cation represented by formula (ZaI) may be a sulfonium cation represented by formula (Z-1c).
  • R 204 and R 205 each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group of R 204 and R 205 may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group of R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, butyl group, pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (e.g., carbon number 1 to 15), a cycloalkyl group (e.g., carbon number 3 to 15), an aryl group (eg, carbon number 6 to 15), an alkoxy group (eg, carbon number 1 to 15), a halogen atom, a hydroxyl group, and a phenylthio group.
  • the substituents of R 204 and R 205 each independently form an acid-decomposable group using any combination of substituents.
  • X - represents an anion.
  • X ⁇ is the same as X ⁇ in formula (Z-1) described above, but X ⁇ is preferably an anion represented by the following formula (ca1). That is, the compound (A) preferably contains an anion represented by the following formula (ca1).
  • Ar a2 represents an aromatic ring.
  • R a2 represents a substituent.
  • k2 represents an integer from 0 to 7.
  • k2 is 2 or more, a plurality of R a2s may be the same or different from each other.
  • a plurality of R a2 may be bonded to each other to form a ring.
  • the aromatic ring represented by Ar a2 may be an aromatic hydrocarbon ring or an aromatic heterocycle.
  • the number of ring carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
  • the number of ring members of the aromatic heterocycle is preferably 4 to 20, more preferably 5 to 10.
  • the aromatic heterocycle preferably contains at least one of a nitrogen atom and an oxygen atom.
  • aromatic heterocycles include five-membered aromatic heterocycles such as pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, and triazole ring, pyridine ring, pyrazine ring, Examples include six-membered aromatic heterocycles such as a pyrimidine ring, a pyridazine ring, a triazine ring, a thiazine ring, and an oxazine ring.
  • the aromatic ring represented by Ar a2 is preferably an aromatic hydrocarbon ring.
  • the substituent represented by R a2 is not particularly limited, but includes, for example, the above-mentioned substituent T, with preference given to a hydroxy group, a carboxy group, an alkyl group, an alkoxy group, and a halogen atom.
  • k2 represents an integer of 0 to 7, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3.
  • Compound (A) may be at least one selected from the group consisting of compounds (I) to (II) below.
  • 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 site X A structural site consisting of an anionic site A 1 - and a cationic site M 1 + , and which forms a first acidic site represented by HA 1 by irradiation with actinic rays or radiation
  • Structural site Y Anionic site A structural site consisting of A 2 ⁇ and a cationic site M 2 + and forming 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. At least one of the acid dissociation constants a1 is less than 0.
  • 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.
  • Compound (II) is a compound having two or more of the above structural moieties It is a compound that generates an acid containing two or more sites and the above structural site Z.
  • Structural site Z nonionic site capable of neutralizing acids
  • compound (II) is, for example, an acid-generating compound having two of the first acidic sites derived from the structural site X and the structural site Z
  • the compound PII is a compound having two HA 1 Compounds”
  • the acid dissociation constant when compound PII becomes "a compound having one A 1 - and one HA 1 " and "one A 1 - and one HA 1" are determined.
  • the acid dissociation constant when a "compound having 1 " becomes "a compound having two A 1 - " corresponds to the acid dissociation constant a1.
  • the acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. At least one of the acid dissociation constants a1 is less than 0.
  • 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.
  • the content of compound (A) in the composition of the present invention is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, based on the total solid content of the composition of the present invention.5. More preferably, it is 0% by mass or more.
  • the content of compound (A) is preferably 30.0% by mass or less, more preferably 25.0% by mass or less, and even more preferably 20.0% by mass or less, based on the total solid content of the composition of the present invention. .
  • Compound (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.
  • the acid diffusion control agent (B) acts as a quencher that traps the acid generated from, for example, the compound (A) during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to the excess generated acid. do.
  • the type of acid diffusion control agent (B) is not particularly limited, and examples thereof include a basic compound (BA), a low molecular compound (BB) having a nitrogen atom and a group that is eliminated by the action of an acid, and an active compound. Examples include compounds (BC) whose ability to control acid diffusion decreases or disappears when irradiated with light or radiation.
  • the compound (BC) includes, for example, an onium salt compound (BD) of an acid that becomes a weak acid relative to the acid generated from the compound (A), etc., and an acid onium salt compound (BD) whose basicity decreases or disappears by irradiation with actinic rays or radiation.
  • Examples include basic compounds (BE).
  • Specific examples of basic compounds (BA) include those described in paragraphs [0132] to [0136] of International Publication No. 2020/066824; Specific examples of basic compounds (BE) that disappear include those described in paragraphs [0137] to [0155] of International Publication No. 2020/066824, and those described in paragraph [0164] of International Publication No. 2020/066824.
  • low molecular weight compounds (BB) having a nitrogen atom and a group that is eliminated by the action of an acid include paragraphs [0156] to [0163] of International Publication No. 2020/066824. Examples include those described in .
  • an onium salt compound (BD) that is a relatively weak acid with respect to the acid generated from compound (A), etc. see paragraphs [0305] to [0314] of International Publication No. 2020/158337. Examples include those listed below.
  • the acid diffusion control agent (B) is preferably a compound that generates an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation.
  • the acid diffusion control agent (B) may be a compound represented by formula (Z-1) or a compound different from the compound represented by formula (Z-1), but A compound represented by (Z-1) is preferred. It is preferable that the acid diffusion control agent (B) contains an anion represented by the above-mentioned formula (xa1).
  • the content of the acid diffusion control agent (B) in the composition of the present invention is preferably 3.0% by mass or more, more preferably 5.0% by mass or more, based on the total solid content of the composition of the present invention. , more preferably 10.0% by mass or more.
  • the content of compound (A) is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less, based on the total solid content of the composition of the present invention. .
  • the acid diffusion control agent (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 ratio of the content of the acid diffusion control agent (B) to the content of the compound (A) is preferably 100 mol% or more, more preferably 130 mol% or more, and 150 mol% or more. is particularly preferred. Further, the ratio of the content of the acid diffusion control agent (B) to the content of the compound (A) is preferably 450 mol% or less, more preferably 400 mol% or less, and 350 mol% or less. It is particularly preferable that there be.
  • the total amount of compounds that generate acid upon irradiation with actinic rays or radiation is preferably 0.3 mmol/g or more, and preferably 0.35 mmol/g or more based on the total solid content. is more preferable, and particularly preferably 0.40 mmol/g or more.
  • the total amount of compounds that generate acids upon irradiation with actinic rays or radiation is preferably 1.5 mmol/g or less, more preferably 1.2 mmol/g or less, and 1.5 mmol/g or less based on the total solid content. It is particularly preferable that it is .0 mmol/g or less.
  • the proportion of the compound represented by formula (Z-1) to the total amount of compounds that generate acid upon irradiation with actinic rays or radiation is preferably 50 mol% or more, and 75 mol%. More preferably, it is 100 mol% (all compounds in the composition of the present invention that generate acid upon irradiation with actinic rays or radiation are compounds represented by formula (Z-1)). is particularly preferred.
  • the composition of the present invention may further contain a hydrophobic resin (also referred to as "resin (T)”) different from resin (P).
  • 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
  • the hydrophobic resin preferably has at least one of a fluorine atom, a silicon atom, and a CH 3 partial structure contained in the side chain portion of the resin, and two or more of them are preferred. 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 from 0.1 to 1.0% by mass.
  • One type of surfactant or two or more types of surfactants may be used. When two or more types are used, it is preferable that the total content is within the range of the above-mentioned preferred content.
  • 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 present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition having the following structure.
  • the resin (P) contains a repeating unit represented by the following formula (Pa2), At least one of the compound (A) and the acid diffusion control agent (B) is a compound represented by the following formula (Z-2),
  • An actinic ray-sensitive or radiation-sensitive resin composition wherein the content of the acid diffusion control agent (B) is 80 mol% or more relative to the content of the compound (A).
  • R P3 represents a hydrogen atom or an alkyl group.
  • R P4 represents a group that is eliminated by the action of an acid.
  • R Z1 , R Z2 and R Z3 each independently represent an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, or an aryl group.
  • n1 represents an integer from 1 to 5.
  • n2 and n3 each independently represent an integer from 0 to 5.
  • the plurality of R Z1s may be the same or different from each other, or may be bonded to each other to form a ring.
  • the plurality of R Z2s may be the same or different, or may be bonded to each other to form a ring.
  • the plurality of R Z3s may be the same or different from each other, and may be bonded to each other.
  • the benzene rings in formula (Z-2) may be bonded to each other through a single bond or a linking group.
  • X ⁇ represents an anion represented by the following formula (xa1).
  • Ar a1 represents an aromatic ring.
  • R a1 represents a substituent.
  • k1 represents an integer from 0 to 7.
  • k1 is 2 or more, a plurality of Ra1s may be the same or different from each other.
  • k1 is 2 or more, a plurality of R a1 may be bonded to each other to form a ring.
  • 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 invention also relates to a patterning method.
  • the pattern forming method of the present invention includes the steps of forming an actinic ray-sensitive or radiation-sensitive film (typically a resist film) on a substrate using the composition of the present invention, and forming an actinic ray-sensitive or radiation-sensitive film on a substrate.
  • the pattern forming method includes the steps of exposing to light and developing the exposed actinic ray-sensitive or radiation-sensitive 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 onto substrates (eg, silicon, silicon dioxide coated) such as those used in the manufacture of integrated circuit devices by any suitable application method such as a spinner or coater.
  • 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 (an inorganic film, an organic film, an 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.).
  • ⁇ Resin (P)> As the resin (P), P-1 to P-9 were used. The types and contents of repeating units contained in P-1 to P-9 are shown in Table 1 below. The content of repeating units is the molar ratio to all repeating units in the resin. The weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (the amount is in terms of polystyrene). Further, the content of repeating units was measured by 13 C-NMR (nuclear magnetic resonance).
  • T-1 was used as the hydrophobic resin (resin (T)).
  • the structural formula, repeating unit content, Mw and Mw/Mn of T-1 are shown below.
  • the content of repeating units contained in T-1 is the molar ratio to all repeating units in the resin.
  • Mw and Mw/Mn were measured by GPC (carrier: tetrahydrofuran (THF)) (they are polystyrene equivalent amounts).
  • the content of repeating units was measured by 13 C-NMR.
  • A-1 to A-18 and AR-1 were used as compounds (A) that generate acids with a pKa of less than 0 upon irradiation with actinic rays or radiation.
  • A-1 to A-18 and AR-1 are compounds containing cations and anions shown in Tables 2 and 3 below, respectively. Tables 2 and 3 below also list the pKa of the acid generated from each compound (generated acid) upon irradiation with actinic rays or radiation.
  • B-1 to B-31 and BR-1 were used as the acid diffusion control agent (B).
  • B-1 to B-26 and BR-1 are compounds containing cations and anions shown in Table 4 below, respectively.
  • B-28 to B-31 are compounds each containing a cation and anion shown in Table 5 below. Tables 4 and 5 below also list the pKa of the acid generated from each compound (generated acid) upon irradiation with actinic rays or radiation.
  • B-27 is a compound represented by the following structural formula.
  • Me represents a methyl group.
  • the ratio (mol %) of the content of the acid diffusion control agent (B) to the content of the compound (A) was written in the column "(B)/(A)".
  • the ratio (mmol/g) of the compound (total amount) that generates an acid upon irradiation with actinic rays or radiation to the total solid content of the resist composition is listed in the "PAG total amount” column. Enter the ratio (mol%) of the compound represented by formula (Z-1) to the total amount of compounds that generate acid upon irradiation with actinic rays or radiation in the column of "Ratio of (Z-1) in the total amount of PAG". Described.
  • ⁇ 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. Note that similar results can be obtained even if the Si wafer is replaced with a chromium substrate.
  • HMDS hexamethyldisilazane
  • ⁇ Pattern formation method (1) EB exposure, alkaline development (positive)>
  • the wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam drawing device (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, drawing was performed so that a 1:1 line and space was formed.
  • electron beam drawing it was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. . Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then baked at 95° C. for 60 seconds to dry it.
  • TMAH tetramethylammonium hydroxide
  • Line width dimension (L0h) when the line width dimension of a 1:1 line and space pattern with a line width of 50 nm and a space width of 50 nm is 50 nm, and PEB treatment is performed immediately after exposure, and After 1 hour, the line width dimension (L2h) after PEB treatment was measured, and the rate of change in line width was calculated using the following formula. Note that the PEB treatment was performed by heating at 100° C. for 60 seconds. Line width change rate (%) 100 x (L2h-L0h) nm/50 nm The smaller the value, the better the performance, and it was used as an index of PED stability. In addition, B or higher is preferable in practical terms, and A is more preferable. A: Line width change rate is less than 2% B: Line width change rate is 2% or more and less than 5% C: Line width change rate is 5% or more and less than 10% D: Line width change rate is 10% or more
  • the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution, LWR performance, and PED stability. 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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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

L'invention fournit une composition de résine sensible aux rayons actiniques ou à un rayonnement excellente en termes de résolution, de performances d'irrégularité de largeur de trait (LWR) et de stabilité de retard après exposition (PED). L'invention fournit également un film sensible aux rayons actiniques ou à un rayonnement, un procédé de formation de motif et un procédé de fabrication de dispositif électronique qui mettent en œuvre ladite composition de résine sensible aux rayons actiniques ou à un rayonnement.　Plus précisément, l'invention concerne une composition de résine sensible aux rayons actiniques ou à un rayonnement qui comprend : une résine (P) qui contient une unité de répétition possédant un groupe hydroxyle phénolique et une unité de répétition possédant un groupe décomposable sous l'effet d'un acide ; un composé (A) générant un acide de pKa inférieur à 0 par irradiation au moyen de rayons actiniques ou d'un rayonnement ; et un agent de régulation de diffusion d'acide (B). Le composé (A) et/ou l'agent de régulation de diffusion d'acide (B) consiste en un composé spécifique. La teneur en agent de régulation de diffusion d'acide (B) est supérieure ou égale à 80% en moles par rapport à la teneur en composé (A). L'invention concerne également un film sensible aux rayons actiniques ou à un rayonnement, un procédé de formation de motif et un procédé de fabrication de dispositif électronique qui mettent en œuvre ladite composition de résine sensible aux rayons actiniques ou à un rayonnement.
PCT/JP2023/030369 2022-08-31 2023-08-23 Composition de résine sensible aux rayons actiniques ou à un rayonnement, film sensible aux rayons actiniques ou à un rayonnement, procédé de formation de motif, et procédé de fabrication de dispositif électronique Ceased WO2024048397A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025225219A1 (fr) * 2024-04-24 2025-10-30 東京応化工業株式会社 Composition de réserve, procédé de formation de motif de réserve, composé, générateur d'acide, et agent de régulation de diffusion d'acide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017115629A1 (fr) * 2015-12-28 2017-07-06 富士フイルム株式会社 Procédé de formation de motif, et procédé de fabrication d'un dispositif électronique
WO2022172689A1 (fr) * 2021-02-12 2022-08-18 富士フイルム株式会社 Composition de résine sensible aux rayons actifs ou sensible aux rayonnements, film de réserve, procédé de formation de motif et procédé de fabrication de dispositif électronique

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JP7373059B2 (ja) 2020-04-28 2023-11-01 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、マスクブランクス、パターン形成方法及び電子デバイスの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017115629A1 (fr) * 2015-12-28 2017-07-06 富士フイルム株式会社 Procédé de formation de motif, et procédé de fabrication d'un dispositif électronique
WO2022172689A1 (fr) * 2021-02-12 2022-08-18 富士フイルム株式会社 Composition de résine sensible aux rayons actifs ou sensible aux rayonnements, film de réserve, procédé de formation de motif et procédé de fabrication de dispositif électronique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025225219A1 (fr) * 2024-04-24 2025-10-30 東京応化工業株式会社 Composition de réserve, procédé de formation de motif de réserve, composé, générateur d'acide, et agent de régulation de diffusion d'acide

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