WO2021049592A1 - Composition de résine sensible au rayonnement, procédé de formation d'un motif de réserve et générateur d'acide sensible au rayonnement - Google Patents

Composition de résine sensible au rayonnement, procédé de formation d'un motif de réserve et générateur d'acide sensible au rayonnement Download PDF

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WO2021049592A1
WO2021049592A1 PCT/JP2020/034375 JP2020034375W WO2021049592A1 WO 2021049592 A1 WO2021049592 A1 WO 2021049592A1 JP 2020034375 W JP2020034375 W JP 2020034375W WO 2021049592 A1 WO2021049592 A1 WO 2021049592A1
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group
radiation
carbon atoms
acid
sensitive
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PCT/JP2020/034375
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English (en)
Japanese (ja)
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克聡 錦織
和也 桐山
拓弘 谷口
秀斗 森
研 丸山
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Jsr株式会社
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Priority to JP2021545602A priority Critical patent/JP7396360B2/ja
Publication of WO2021049592A1 publication Critical patent/WO2021049592A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/70—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with ring systems containing two or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C07D321/02—Seven-membered rings
    • C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a radiation-sensitive resin composition, a resist pattern forming method, and a radiation-sensitive acid generator.
  • Radiation-sensitive resin compositions used for micromachining by lithography include far-ultraviolet rays such as ArF excimer laser light (wavelength 193 nm) and KrF excimer laser light (wavelength 248 nm), and extreme ultraviolet rays (EUV) (wavelength 13.5 nm).
  • An acid is generated in the exposed part by irradiation with radiation such as an electromagnetic wave or a charged particle beam such as an electron beam, and a chemical reaction using this acid as a catalyst causes a difference in the dissolution rate of the exposed part and the non-exposed part in the developing solution. This forms a resist pattern on the substrate.
  • the radiation-sensitive resin composition has good sensitivity to exposure light such as extreme ultraviolet rays and electron beams, and also has excellent LWR (Line Width Rougness) performance and resolvability, which indicate uniformity of line width. Excellent is required.
  • the refining of the resist pattern has progressed to the level of line width 40 nm or less, the required level of the above performance is further increased, and the above-mentioned conventional radiation-sensitive resin composition satisfies the above-mentioned requirement. Not done.
  • the present invention has been made based on the above circumstances, and an object of the present invention is radiation-sensitive property capable of forming a resist pattern having good sensitivity to exposure light and excellent LWR performance and resolvability. It is an object of the present invention to provide a resin composition, a resist pattern forming method, and a radiation-sensitive acid generator.
  • the invention made to solve the above problems is a polymer having a first structural unit containing a first acid dissociative group that dissociates by the action of an acid to give an alkali-soluble group (hereinafter, "[A] polymer”).
  • a compound containing a radiation-sensitive acid generator hereinafter, also referred to as “[B] acid generator”
  • the radiation-sensitive acid generator has a sulfonate anion and a radiation-sensitive onium cation.
  • the above-mentioned sulfonate anion is a radiation-sensitive resin composition having a (thio) acetal structure, a carbonyloxy group and a second acid dissociative group which dissociates by the action of an acid to give a carboxy group.
  • Another invention made to solve the above problems includes a step of directly or indirectly coating the substrate with the radiation-sensitive resin composition, a step of exposing the resist film formed by the coating step, and a step of exposing the resist film formed by the coating step.
  • a radiation-sensitive acid generator containing a compound having a sulfonate anion and a radiation-sensitive onium cation, wherein the sulfonate anion has a (thio) acetal structure. It is a radiation-sensitive acid generator ([B] acid generator) having an acid dissociative group that dissociates by the action of a carbonyloxy group and an acid to give a carboxy group.
  • [B] acid generator having an acid dissociative group that dissociates by the action of a carbonyloxy group and an acid to give a carboxy group.
  • the radiation-sensitive resin composition and the resist pattern forming method of the present invention it is possible to form a resist pattern having good sensitivity to exposure light and excellent LWR performance and resolution.
  • the radiation-sensitive acid generator of the present invention can be suitably used as a component of the radiation-sensitive resin composition. Therefore, these can be suitably used for processing processes of semiconductor devices, which are expected to be further miniaturized in the future.
  • the radiation-sensitive resin composition contains a [A] polymer and a [B] acid generator.
  • the radiation-sensitive resin composition usually contains an organic solvent (hereinafter, also referred to as “[D] organic solvent”).
  • the radiation-sensitive resin composition may contain an acid diffusion control body (hereinafter, also referred to as “[C] acid diffusion control body”) as a suitable component.
  • the radiation-sensitive resin composition may contain other optional components as long as the effects of the present invention are not impaired.
  • the radiation-sensitive resin composition forms a resist pattern having good sensitivity to exposure light and excellent LWR performance and resolution.
  • the reason why the radiation-sensitive resin composition exerts the above-mentioned effect by having the above-mentioned constitution is not always clear, but it can be inferred as follows, for example. That is, when the [B] acid generator contained in the radiation-sensitive resin composition contains a sulfonate anion having a specific structure, the dissolution rate of the exposed portion in the developing solution is improved. As a result, it is considered that the radiation-sensitive resin composition can form a resist pattern having good sensitivity to exposure light and excellent LWR performance and resolution.
  • the polymer is a structural unit containing a first acid dissociative group (hereinafter, also referred to as “acid dissociative group (a)”) that dissociates by the action of an acid to give an alkali-soluble group (hereinafter, “structural unit”). (I) ”).
  • the [A] polymer preferably has a structural unit containing a phenolic hydroxyl group (hereinafter, also referred to as “structural unit (II)”) in addition to the structural unit (I).
  • structural unit (II) a structural unit containing a phenolic hydroxyl group
  • the polymer may further have a structural unit (I) and other structural units other than the structural unit (II).
  • the radiation-sensitive resin composition may contain one or more [A] polymers.
  • the structural unit (I) is a structural unit containing an acid dissociative group (a) that dissociates by the action of an acid to give an alkali-soluble group.
  • the "alkali-soluble group” means a carboxy group or a hydroxy group
  • the "acid dissociative group (a)” is a group that substitutes a hydrogen atom in an alkali-soluble group by the action of an acid. A group that dissociates to give an alkali-soluble group.
  • the acid dissociative group (a) is dissociated to generate an alkali-soluble group, and the solubility of the [A] polymer in the developing solution in the exposed portion changes. Thereby, a resist pattern can be formed.
  • the structural unit (I) includes, for example, a structural unit represented by the following formula (I-1A) (hereinafter, also referred to as “structural unit (I-1A)”) and a structure represented by the following formula (I-1B).
  • the acid-dissociable group (a) are, for example, the following formula (I-1A), a -C binding etheric oxygen atom of the carbonyl group (R X) (R Y) (R Z).
  • RT is a hydrogen atom, a fluorine atom, a methyl group or It is a trifluoromethyl group.
  • RX is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • RY and R Z are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, or have 3 to 3 ring members composed of carbon atoms in which these groups are combined with each other and bonded to each other. It is a part of 20 saturated alicyclic structures.
  • R B , R C and R E are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • RA and R D are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, or the number of ring members composed of these groups combined with each other and an unsaturated carbon chain to which they are bonded. It is part of an unsaturated alicyclic structure of 4-20.
  • R U and R V are each independently a monovalent hydrocarbon group having a hydrogen atom or a carbon atoms 1 ⁇ 20, R W is or a monovalent hydrocarbon group having 1 to 20 carbon atoms, it is part of an alicyclic structure composed ring members 3-20 together with the carbon atom to which R U and R V are combined they are bound to each other or R U and R W are carbon atoms and R W that keyed R U, bonded to each other is part of the aliphatic heterocyclic structure configured with an oxygen atom ring members 5-20 that binds.
  • the "hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. This “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the "chain hydrocarbon group” refers to a hydrocarbon group that does not contain a cyclic structure and is composed only of a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
  • the "alicyclic hydrocarbon group” refers to a hydrocarbon group containing only an alicyclic structure as a ring structure and not containing an aromatic ring structure, and refers to a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group. Contains both hydrocarbon groups.
  • aromatic hydrocarbon group refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure, and a chain structure or an alicyclic structure may be included as a part thereof.
  • R X, R Y, R Z , R A, R B, R C, examples of the monovalent hydrocarbon group R D, R E, R U , carbon atoms represented by R V and R W 1 ⁇ 20 are
  • a monovalent chain hydrocarbon group having 1 to 20 carbon atoms a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like can be mentioned. Be done.
  • Examples of monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, iso-butyl group and tert.
  • -Alkyl groups such as butyl groups
  • Alkenyl groups such as ethenyl group, propenyl group, butenyl group
  • Examples thereof include an alkynyl group such as an ethynyl group, a propynyl group and a butynyl group.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include an alicyclic saturated hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a tricyclodecyl group and a tetracyclododecyl group; Examples thereof include alicyclic unsaturated hydrocarbon groups such as cyclopentenyl group, cyclohexenyl group, norbornenyl group, tricyclodecenyl group and tetracyclododecenyl group.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aryl group such as a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and an anthryl group; Examples thereof include an aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group and an anthrylmethyl group.
  • Examples of the saturated alicyclic structure having 3 to 20 ring members in which RY and R Z are combined with each other and composed of carbon atoms to which they are bonded include a single ring such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, and a cyclohexane structure.
  • Saturated alicyclic structure examples include a polycyclic saturated alicyclic structure such as a norbornane structure and an adamantane structure.
  • the alicyclic structure R U and R V are combined with each other configured with the carbon atoms to which they are attached ring members 3-20, for example, cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a single ring such as cyclohexane structure Saturated alicyclic structure; Polycyclic saturated alicyclic structure such as norbornane structure and adamantane structure; Monocyclic unsaturated alicyclic structures such as cyclopropene structure, cyclobutene structure, cyclopentene structure, cyclohexene structure; Examples include a polycyclic unsaturated alicyclic structure such as a norbornene structure.
  • an unsaturated alicyclic structure having 4 to 20 ring members, in which RA and R D are combined with each other and formed together with an unsaturated carbon chain to which they are bonded a monocyclic non-cyclic structure such as a cyclobutene structure, a cyclopentene structure, or a cyclohexene structure is used.
  • Saturated alicyclic structure examples include a polycyclic unsaturated alicyclic structure such as a norbornene structure.
  • the aliphatic heterocyclic structure R U and R W is an oxygen atom and R W that keyed R U, bonded to each other is formed with the carbon atom bonded ring members 5-20, for example oxacyclobutane structure, oxacyclopentane Saturated oxygen-containing heterocyclic structure such as structure and oxacyclohexane structure; Examples thereof include unsaturated oxygen-containing heterocyclic structures such as an oxacyclobutene structure, an oxacyclopentene structure, and an oxacyclohexene structure.
  • a hydrogen atom or a methyl group is preferable from the viewpoint of copolymerizability of the monomer giving the structural unit (I).
  • the R X preferably a chain hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group or an aryl group, a methyl group, an ethyl group, i- propyl, and tert- butyl group or a phenyl group more preferable.
  • RY and R Z are a part of a saturated alicyclic structure having 3 to 20 ring members, in which they are combined with each other and composed of carbon atoms to which they are bonded.
  • a monocyclic saturated alicyclic structure is preferable, and a cyclopentane structure is more preferable.
  • the R B and R C, a hydrogen atom is preferable.
  • the R E preferably a hydrogen atom or a chain hydrocarbon group, more preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.
  • R A and R D are preferably part of an unsaturated alicyclic structure in which they are combined with each other and composed of carbon atoms to which they are bonded.
  • unsaturated alicyclic structure a monocyclic unsaturated alicyclic structure is preferable, and a cyclopentene structure or a cyclohexene structure is more preferable.
  • the structural unit (I), the structural unit (I-1A) or the structural unit (I-1C) is preferable.
  • the structural unit (I-1A) is a structural unit represented by the following formulas (I-1A-1) to (I-1A-5) (hereinafter, "structural unit (I-1A-1) to (I-)”. 1A-5) ”) is preferable.
  • RT is synonymous with the above formula (I-1A).
  • the structural unit (I-1C) is a structural unit represented by the following formulas (I-1C-1) to (I-1C-2) (hereinafter, "structural unit (I-1C-1) to (I-)”. 1C-2) ”) is preferable.
  • RT is synonymous with the above formula (I-1C).
  • the lower limit of the content ratio of the structural unit (I) 5 mol% is preferable, 10 mol% is more preferable, 15 mol% is further preferable, and 20 mol is more preferable with respect to all structural units constituting the polymer [A] % Is particularly preferable.
  • the upper limit of the content ratio is preferably 90 mol%, more preferably 80 mol%, further preferably 70 mol%, and particularly preferably 65 mol%.
  • the structural unit (II) is a structural unit containing a phenolic hydroxyl group.
  • the "phenolic hydroxyl group” refers not only to the hydroxy group directly connected to the benzene ring but to all the hydroxy groups directly connected to the aromatic ring.
  • the sensitivity of the radiation-sensitive resin composition to exposure light can be further increased by having the structural unit (II) in the [A] polymer.
  • the structural unit (II) is, for example, a structural unit represented by the following formulas (II-1) to (II-15) (hereinafter, also referred to as “structural unit (II-1) to (II-15)”) and the like. Can be mentioned.
  • RP is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the R P from the viewpoint of copolymerizability of the monomer giving the structural unit (II), preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • the structural unit (II) As the structural unit (II), the structural unit (II-1) or the structural unit (II-2) is preferable.
  • the lower limit of the content ratio of the structural unit (II) is preferably 10 mol%, preferably 20 mol%, based on all the structural units constituting the [A] polymer. More preferably mol%, more preferably 25 mol%.
  • the upper limit of the content ratio is preferably 80 mol%, more preferably 60 mol%, still more preferably 50 mol%.
  • structural unit (III) structural unit containing alcoholic hydroxyl groups
  • structural unit (III) structural unit containing alcoholic hydroxyl groups
  • lactone structures lactone structures
  • cyclic carbonate structures lactone structures
  • sultone structures or combinations thereof.
  • structural unit (III) examples include a structural unit represented by the following formula.
  • the polymer [A] can further improve the LWR performance and the resolvability by further having the structural unit (III).
  • RL2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the upper limit of the content ratio of the other structural units is preferably 30 mol%, preferably 15 mol%, based on all the structural units constituting the [A] polymer. Is more preferable.
  • the lower limit of the content ratio of the [A] polymer in the radiation-sensitive resin composition is preferably 50% by mass, preferably 60% by mass, based on all the components of the radiation-sensitive resin composition other than the [D] organic solvent. % Is more preferable, and 70% by mass is further preferable.
  • the upper limit of the content ratio is preferably 99% by mass, more preferably 95% by mass.
  • Mw polystyrene-equivalent weight average molecular weight of the polymer by gel permeation chromatography (GPC)
  • 1,000 is preferable, 3,000 is more preferable, 4,000 is further preferable, and 5, 000 is particularly preferable.
  • Mw polystyrene-equivalent weight average molecular weight
  • 50,000 is preferable, 30,000 is more preferable, 20,000 is further preferable, and 10,000 is particularly preferable.
  • the upper limit of the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) of the polymer by GPC (hereinafter, also referred to as “dispersity” or “Mw / Mn”) is preferably 5 and more preferably 3. 2 is more preferable, and 1.8 is particularly preferable.
  • the lower limit of the above ratio is usually 1, preferably 1.1.
  • the Mw and Mn of the polymer in the present specification are values measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC column 2 "G2000HXL", 1 "G3000HXL” and 1 "G4000HXL” from Tosoh Corporation
  • Elution solvent Tetrahydrofuran (Fuji Film Wako Pure Chemical Industries, Ltd.)
  • Flow velocity 1.0 mL / min
  • Sample concentration 1.0 mass%
  • Sample injection volume 100 ⁇ L
  • Detector Differential refractometer Standard material: Monodisperse polystyrene
  • the acid generator has a sulfonate anion and a radiation-sensitive onium cation, and the sulfonate anion is dissociated by the action of a (thio) acetal structure, a carbonyloxy group and an acid to give a carboxy group. It includes a compound having a sex group (hereinafter, also referred to as “acid dissociative group (b)”) (hereinafter, also referred to as “compound (B)”).
  • Compound (B) is a substance that generates an acid upon irradiation with radiation.
  • Examples of radiation include visible light, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), electromagnetic waves such as X-rays and ⁇ -rays, charged particle beams such as electron beams and ⁇ rays.
  • the acid generated from the compound (B) by irradiation with radiation dissociates the acid dissociative group (a) and the like contained in the structural unit (I) of the [A] polymer to generate an alkali-soluble group.
  • A] A resist pattern can be formed by changing the solubility of the polymer in a developing solution.
  • the radiation-sensitive resin composition may contain one or more [B] acid generators.
  • the compound (B) has an exposed portion due to the acid dissociation group (b) of the compound (B) being dissociated by an acid or the like generated from the compound (B) by irradiation (exposure) of radiation to generate a carboxy group.
  • the difference in solubility of the resist film in the developer (dissolution contrast) between the unexposed portion and the unexposed portion is further increased. Therefore, it is considered that the radiation-sensitive resin composition can form a resist pattern having excellent LWR performance and resolution.
  • the sulfonate anion has a (thio) acetal structure, an acid dissociative group (b) that dissociates by the action of a carbonyloxy group and an acid to give a carboxy group.
  • the sulfonate anion preferably further has an alicyclic structure (hereinafter, also referred to as “alicyclic structure (c)”) other than the acid dissociative group (b).
  • the sulfonate anion preferably further has a partial structure represented by the following formula (3) (hereinafter, also referred to as “partial structure (d)”). Further, the sulfonate anion may have a structure other than the above structure, if necessary.
  • ((Tio) acetal structure) is a concept that includes both “acetal structure” and “thioacetal structure”. Further, the “(thio) acetal structure” includes both a “chain (thio) acetal structure” and a “cyclic (thio) acetal structure”. Furthermore, the “thioacetal structure” includes both the “monothioacetal structure” and the “dithioacetal structure”.
  • a cyclic (thio) acetal structure is preferable when focusing on the structure, and an acetal structure or a monothioacetal structure is preferable when focusing on the constituent atoms. Since the (thio) acetal structure has the above structure, the LWR performance and resolution of the radiation-sensitive resin composition can be further enhanced. That is, as the (thio) acetal structure, a cyclic (thio) acetal structure is preferable, a cyclic acetal structure or a cyclic monothioacetal structure is more preferable, and a cyclic acetal structure is further preferable.
  • Examples of the cyclic (thio) acetal structure include a structure represented by the following formula (1).
  • X 1 and X 2 are independently -O- or -S-, respectively.
  • R 1 is a (n + 2) -valent hydrocarbon group having 1 to 10 carbon atoms.
  • n is an integer of 0 to 2. * Indicates the binding site of the sulfonate anion with a portion other than the structure represented by the above formula (1).
  • X 1 and X 2 it is preferable that at least one of X 1 and X 2 is ⁇ O ⁇ . In this case, the sensitivity, LWR performance, and resolution of the radiation-sensitive resin composition to exposure light can be further enhanced.
  • Examples of the (n + 2) -valent hydrocarbon group having 1 to 10 carbon atoms represented by R 1 include a group obtained by removing (n + 2) hydrogen atoms from an alkane such as methane, ethane, n-propane, and n-butane. Can be mentioned.
  • R 1 a hydrocarbon group having a carbon number of 5 or 7 having a cyclic (thio) acetal structure represented by the above formula (1) is preferable. That is, as R 1 , a group obtained by removing (n + 2) hydrogen atoms from ethane or n-butane is preferable.
  • the "number of ring members of the cyclic (thio) acetal structure” means the number of atoms constituting the ring structure of the cyclic (thio) acetal structure.
  • the acid dissociative group (b) is dissociated from the carbonyloxy group by the action of the acid to generate a carboxy group.
  • the acid dissociative group (b) is a group that dissociates by the action of an acid to give a carboxy group. More specifically, the "acid dissociative group (b)" is a group that replaces a hydrogen atom in a carboxy group and is a group that dissociates by the action of an acid to give a carboxy group.
  • Examples of the acid dissociative group (b) include a group represented by the following formula (2-1) and a group represented by the following formula (2-2).
  • ** indicates the binding site of the carbonyloxy group with the etheric oxygen atom in the sulfonate anion.
  • R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a group containing the above (thio) acetal structure.
  • R 3 and R 4 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, or have 3 to 3 ring members composed of carbon atoms in which these groups are combined with each other and bonded to each other. It is a part of 20 saturated alicyclic structures.
  • R 6 , R 7 and R 9 are independently hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms.
  • R 5 and R 8 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, or the number of ring members composed of these groups combined with each other and an unsaturated carbon chain to which they are bonded. It is part of an unsaturated alicyclic structure of 4-20.
  • R 2 Examples of the monovalent hydrocarbon group R 3 and the carbon number of 1 to 20 represented as R 4, for example R X, the number of carbon atoms represented by R Y and R Z of the formula (I-1A) Examples thereof include groups similar to those exemplified as 1 to 20 monovalent hydrocarbon groups.
  • saturated alicyclic structure having 3 to 20 ring members, in which R 3 and R 4 are combined with each other and formed together with carbon atoms to which they are bonded, for example, saturation composed of RY and R Z of the above formula (I-1A) is used.
  • saturated alicyclic structure include structures similar to those exemplified.
  • R 5, R 6, R 7 Examples of the monovalent hydrocarbon group of R 8 and 1 to 20 carbon atoms represented by R 9, for example, R A of the formula (I-1C), R B , R C , R D and RE , and the same groups as those exemplified as monovalent hydrocarbon groups having 1 to 20 carbon atoms can be mentioned.
  • R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms
  • R 2 is preferably a chain hydrocarbon group, more preferably an alkyl group, and even more preferably a methyl group or an ethyl group.
  • R 2 is a group containing the above (thio) acetal structure
  • R 2 is preferably a group containing a cyclic (thio) acetal structure, and is a group containing the structure represented by the above formula (1). It is more preferable that the group contains the structure represented by the above formula (1) and the alicyclic structure (c) described later.
  • the R 2 is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms. Since R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, the sensitivity to exposure light, LWR performance and resolution can be further improved.
  • R 3 and R 4 are monovalent hydrocarbon groups having 1 to 20 carbon atoms, as R 3 and R 4 , a chain hydrocarbon group is preferable, an alkyl group is more preferable, and a methyl group or an ethyl group is preferable. More preferred.
  • the alicyclic structure is a saturated alicyclic structure.
  • a monocyclic saturated alicyclic structure is more preferable, and a cyclopentane structure is further preferable.
  • Hydrogen atoms are preferable as R 6 and R 7.
  • a chain hydrocarbon group is preferable, an alkyl group is more preferable, and a methyl group is further preferable.
  • R 5 and R 8 are preferably part of an unsaturated alicyclic structure having 4 to 20 ring members, which are composed of unsaturated carbon chains to which they are combined and bonded to each other.
  • unsaturated alicyclic structure a monocyclic unsaturated alicyclic structure is preferable, and a cyclohexene structure is more preferable.
  • the sulfonate anion preferably further has an alicyclic structure (alicyclic structure (c)) other than the acid dissociative group (b).
  • alicyclic structure (c) a saturated alicyclic structure is preferable, and a cyclohexane structure, a norbornane structure, or an adamantane structure is more preferable.
  • the alicyclic structure (c) shares a carbon atom or a part of a carbon chain with the above (thio) acetal structure.
  • the alicyclic structure (c) has a norbornane structure
  • some carbon chains constituting the norbornane structure and some carbon chains constituting the (thio) acetal structure are common.
  • the alicyclic structure (c) has a cyclohexane structure or an adamantane structure
  • one carbon atom constituting the cyclohexane structure or the adamantane structure and one carbon atom constituting the (thio) acetal structure are common. Examples thereof include.
  • the sulfonate anion preferably further has a partial structure (partial structure (d)) represented by the following formula (3).
  • a partial structure (d) represented by the following formula (3).
  • R 10 and R 11 are independently hydrogen atoms, fluorine atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms, or monovalent fluorinated hydrocarbons having 1 to 20 carbon atoms. It is a hydrogen group. However, at least one of R 10 and R 11 is a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
  • m is an integer from 1 to 10. When m is 2 or more, the plurality of R 10s are the same or different from each other, and the plurality of R 11s are the same or different from each other. *** indicates the binding site of the sulfonate anion with a portion other than the structure represented by the formula (3).
  • Examples of the monovalent hydrocarbon group of the above include groups similar to those exemplified.
  • Examples thereof include a group in which at least one hydrogen atom of the group exemplified as the 20 monovalent hydrocarbon group is replaced with a fluorine atom.
  • the sulfonate anion may have each of the above-mentioned structures, and the position and orientation of the (thio) acetal structure, the carbonyloxy group and the acid dissociative group (b) are not particularly limited in the chemical structure of the sulfonate anion.
  • the sulfonate anion preferably has an acid dissociative group (b) at the end.
  • the sulfonate anion has an acid dissociative group (b) at the end, the sensitivity to exposure light, LWR performance and resolution can be further improved.
  • the (thio) acetal structure is a cyclic (thio) acetal structure represented by the above formula (1), it is preferable that R 1 is oriented toward the SO 3-side. When R 1 of the above formula (1) is oriented toward the SO 3- side, the sensitivity to exposure light, LWR performance, and resolution can be further improved.
  • Examples of the sulfonate anion include a structure represented by the following formula (4-1) or a structure represented by the following formula (4-2).
  • X is a group containing a (thio) acetal structure.
  • Y is an acid dissociative group (b).
  • L 1 and L 2 are independently single-bonded or divalent linking groups, respectively.
  • Examples of the divalent linking group represented by L 1 and L 2 include a divalent heteroatom-containing group, a divalent hydrocarbon group, and the divalent heteroatom content between carbons of the hydrocarbon group.
  • a group containing a group hereinafter, also referred to as "group ( ⁇ )"
  • group ( ⁇ ) a group in which a part or all of the hydrogen atoms of the above hydrocarbon group is replaced with a monovalent heteroatom-containing group
  • group ( ⁇ ) A group in which a part or all of the hydrogen atom of the group ( ⁇ ) is replaced with a monovalent heteroatom-containing group (hereinafter, also referred to as “group ( ⁇ )”) and the like.
  • divalent heteroatom-containing group examples include -CO-, -CS-, -NH-, -O-, -S-, and a group combining these.
  • Examples of the monovalent heteroatom-containing group include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, a halogen atom and the like.
  • Examples of the divalent hydrocarbon group for example, the above formula (I-1A) R X, the groups exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R Y and R Z 1 single Examples include groups excluding hydrogen atoms.
  • the alicyclic structure (c) is contained in a divalent linking group represented by L 1 or L 2 , or is contained in a (thio) acetal structure and an alicyclic.
  • the structure (c) shares a carbon atom or a part of a carbon chain.
  • L 2 contains the structure of ⁇ (CR 10 R 11 ) m ⁇ in the above formula (3).
  • the structure represented by the above formula (4-1) is preferable.
  • the sulfonate anion is of the above formula (4-1)
  • the sensitivity to exposure light, LWR performance and resolvability can be further improved.
  • Examples of the structure represented by the above formula (4-1) include a structure represented by the following formula (4-1-1) or a structure represented by the formula (4-1-2).
  • L 11 is a divalent linking group
  • L 12 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms
  • L 11 and L 12 are. It is a part of a ring structure having 3 to 20 ring members, which is composed of carbon atoms that are combined with each other and bonded to each other.
  • L 21 is a divalent linking group
  • L 22 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms
  • L 21 and L 22 are. It is a part of a ring structure having 3 to 20 ring members, which is composed of carbon atoms that are combined with each other and bonded to each other.
  • Organic group means a group containing at least one carbon atom.
  • Examples of the divalent linking group represented by L 11 and L 21 include a group similar to the group exemplified as the divalent linking group represented by L 1 and L 2 in the above formula (4-1). Can be mentioned.
  • Examples of the monovalent organic group having 1 to 20 carbon atoms represented by L 12 and L 22 include a monovalent hydrocarbon group having 1 to 20 carbon atoms and a divalent carbon-carbon group of the above hydrocarbon group.
  • a group containing a heteroatom-containing group hereinafter, also referred to as "group ( ⁇ ')”
  • group ( ⁇ ') a group in which a part or all of the hydrogen atoms of the above hydrocarbon group is substituted with a monovalent heteroatom-containing group
  • Group ( ⁇ ') a group in which a part or all of the hydrogen atom of the group ( ⁇ ') is replaced with a monovalent heteroatom-containing group (hereinafter, also referred to as“ group ( ⁇ ') ”).
  • group ( ⁇ ') a monovalent heteroatom-containing group
  • Examples of the ring structure having 3 to 20 ring members, in which L 11 and L 12 or L 21 and L 22 are combined with each other and are composed of carbon atoms to which they are bonded, include RY and R Z of the above formula (I-1A).
  • Examples of the alicyclic structure constructed by the above include structures similar to those exemplified.
  • the structure represented by the above formula (4-1) is preferable.
  • the sulfonate anion has the above formula (4-1-1)
  • the sensitivity to exposure light, LWR performance and resolution can be further improved.
  • the radiation-sensitive onium cation is represented by, for example, a monovalent cation represented by the following formula (ra) (hereinafter, also referred to as “cation (ra)”) or a following formula (rb).
  • a monovalent cation represented by the following formula (ra) hereinafter, also referred to as “cation (ra)”
  • a monovalent cation represented by the following formula (rb) hereinafter, also referred to as “cations (rb)”
  • monovalent cations hereinafter, also referred to as “cations (rc)
  • cations (rc) monovalent cations represented by the following formula (rc)
  • b1 is an integer of 0 to 4.
  • RB1 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
  • the plurality of RB1s are the same or different from each other and are monovalent organic groups having 1 to 20 carbon atoms, hydroxy groups, nitro groups or halogen atoms, or these groups are combined with each other. It is a part of a ring structure having 4 to 20 ring members, which is composed of a carbon chain to which these are bonded.
  • b2 is an integer from 0 to 4.
  • RB2 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
  • the plurality of RB2s are the same or different from each other and are monovalent organic groups having 1 to 20 carbon atoms, hydroxy groups, nitro groups or halogen atoms, or these groups are combined with each other. It is a part of a ring structure having 4 to 20 ring members, which is composed of a carbon chain to which these are bonded.
  • R B3 and R B4 are each independently a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or R B3 and R B4 are combined with each other. Represents a single bond.
  • b3 is an integer from 0 to 11.
  • RB5 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
  • the plurality of RB5s are the same or different from each other and are monovalent organic groups having 1 to 20 carbon atoms, hydroxy groups, nitro groups or halogen atoms, or these groups are combined with each other. It is a part of a ring structure having 4 to 20 ring members, which is composed of a carbon chain to which these are bonded.
  • n b1 is an integer of 0 to 3.
  • b4 is an integer from 0 to 9. If b4 is 1, R B6 represents a monovalent organic group having 1 to 20 carbon atoms, hydroxy group, a nitro group or a halogen atom. When b4 is 2 or more, the plurality of RB6s are the same or different from each other and are monovalent organic groups having 1 to 20 carbon atoms, hydroxy groups, nitro groups or halogen atoms, or these groups are combined with each other. It is a part of a ring structure having 4 to 20 ring members, which is composed of a carbon chain to which these are bonded. b5 is an integer from 0 to 10.
  • RB7 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
  • the plurality of RB7s are the same or different from each other and are monovalent organic groups having 1 to 20 carbon atoms, hydroxy groups, nitro groups or halogen atoms, or these groups are combined with each other. It is a part of a ring structure having 3 to 20 ring members, which is composed of a carbon atom or a carbon chain to which these are bonded.
  • n b3 is an integer of 0 to 3.
  • RB8 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • n b2 is an integer of 0 to 2.
  • b6 is an integer of 0 to 5.
  • RB9 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
  • the plurality of RB9s are the same or different from each other and are monovalent organic groups having 1 to 20 carbon atoms, hydroxy groups, nitro groups or halogen atoms, or these groups are combined with each other. It is a part of a ring structure having 4 to 20 ring members, which is composed of a carbon chain to which these are bonded.
  • b7 is an integer from 0 to 5.
  • RB10 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
  • the plurality of RB10s are the same or different from each other and are monovalent organic groups having 1 to 20 carbon atoms, hydroxy groups, nitro groups or halogen atoms, or these groups are combined with each other. It is a part of a ring structure having 4 to 20 ring members, which is composed of a carbon chain to which these are bonded.
  • Examples of monovalent organic groups having 1 to 20 carbon atoms represented by R B1 , R B2 , R B3 , R B4 , R B5 , R B6 , R B7 , R B9 and R B10 include the above formula (4-). Examples thereof include a group similar to the group exemplified as a monovalent organic group having 1 to 20 carbon atoms represented by L 12 in 1-1).
  • the divalent organic group represented by RB8 is, for example, one from the group exemplified as a monovalent organic group having 1 to 20 carbon atoms represented by L 12 of the above formula (4-1-1). Examples include groups excluding hydrogen atoms.
  • a halogen atom, a hydroxy group or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, a halogen atom, a hydroxy group or an alicyclic hydrocarbon group is more preferable, and a halogen atom.
  • a hydroxy group or a saturated alicyclic hydrocarbon group is more preferred, and a fluorine atom, a hydroxy group or a cyclohexyl group is particularly preferred.
  • R B3 and R B4 it is preferable that a hydrogen atom or a single bond in which R B4 and R B5 are combined with each other.
  • 0 to 2 is preferable, 0 or 1 is more preferable, and 0 is further preferable.
  • b3, 0 to 4 is preferable, 0 to 2 is more preferable, and 0 or 1 is further preferable.
  • n b1 , 0 or 1 is preferable.
  • a cation (ra) is preferable.
  • cation (ra) examples include cations represented by the following formulas (ra-1) to (ra-8) (hereinafter, “cations (ra-1) to (raa-)”. 8) ”).
  • the compound (B) can appropriately combine the above-mentioned sulfonate anion and the above-mentioned radiation-sensitive onium cation.
  • compounds represented by the following formulas (B1) to (B13) (hereinafter, also referred to as “compounds (B1) to (B13)") are preferable.
  • the acid dissociative group (b) containing the (thio) acetal structure include compounds (B11) to (B13).
  • T + is the above-mentioned radiation-sensitive onium cation.
  • the lower limit of the content of the [B] acid generator in the radiation-sensitive resin composition is preferably 5 parts by mass, more preferably 10 parts by mass, and 15 parts by mass with respect to 100 parts by mass of the [A] polymer. Is even more preferable.
  • the upper limit of the content is preferably 65 parts by mass, more preferably 60 parts by mass, and even more preferably 55 parts by mass.
  • the [C] acid diffusion controller has an effect of controlling the diffusion phenomenon of the acid generated from the [B] acid generator or the like in the resist film by exposure and suppressing an unfavorable chemical reaction in the non-exposed portion.
  • the storage stability of the radiation-sensitive resin composition can be improved, and the resolution can be further improved. Further, it is possible to suppress the change in the line width of the resist pattern due to the fluctuation of the leaving time from the exposure to the development process, and it is possible to obtain a radiation-sensitive resin composition having excellent process stability.
  • Examples of the form of the [C] acid diffusion control body in the radiation-sensitive resin composition include the form of a low molecular weight compound (hereinafter, also appropriately referred to as “[C] acid diffusion control agent”), the [A] polymer, and the like. Examples include forms incorporated as part of the polymer, and both forms.
  • the radiation-sensitive resin composition may contain one or more [C] acid diffusion controllers.
  • Examples of the [C] acid diffusion control agent include nitrogen atom-containing compounds, photodisintegrating bases that are exposed to exposure and generate weak acids, and the like.
  • nitrogen atom-containing compound examples include amine compounds such as trypentylamine and trioctylamine, amide group-containing compounds such as formamide and N, N-dimethylacetamide, urea compounds such as urea and 1,1-dimethylurea, and pyridine.
  • nitrogen-containing heterocyclic compounds such as N- (undecylcarbonyloxyethyl) morpholine and Nt-pentyloxycarbonyl-4-hydroxypiperidin.
  • Examples of the photodisintegrating base include compounds containing an onium cation and a weak acid anion that are decomposed by exposure.
  • the photodisintegrating base generates an acid in the exposed portion to increase the solubility or insolubility of the polymer [A] in the developing solution, and as a result, suppresses the roughness of the exposed portion surface after development.
  • a high acid trapping function by the anion is exhibited and functions as a quencher to capture the acid diffused from the exposed area. That is, since it functions as a quencher only in the non-exposed portion, the contrast of the deprotection reaction is improved, and as a result, the resolution can be further improved.
  • Examples of the onium cation decomposed by the above exposure include those similar to the radiation-sensitive onium cation exemplified in the above section ⁇ [B] Acid Generator>.
  • anion of the weak acid examples include anions represented by the following formulas (C1) to (C4).
  • the photodisintegrating base a compound in which the onium cation decomposed by the above exposure and the anion of the weak acid are appropriately combined can be used.
  • the lower limit of the content ratio of the [C] acid diffusion control agent is 1 mol with respect to 100 mol% of the [B] acid generator. % Is preferred, 5 mol% is more preferred, and 10 mol% is even more preferred.
  • the upper limit of the content is preferably 100 mol%, more preferably 50 mol%, still more preferably 30 mol%.
  • the radiation-sensitive resin composition usually contains [D] an organic solvent.
  • the [D] organic solvent may be a solvent capable of dissolving or dispersing at least the [A] polymer and the [B] acid generator, and the [C] acid diffusion controller and other optional components contained as necessary. There is no particular limitation.
  • organic solvent examples include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents and the like.
  • the organic solvent may contain one kind or two or more kinds.
  • the alcohol solvent examples include an aliphatic monoalcohol solvent having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol, and an alicyclic monoalcohol solvent having 3 to 18 carbon atoms such as cyclohexanol.
  • examples thereof include a solvent, a polyhydric alcohol solvent having 2 to 18 carbon atoms such as 1,2-propylene glycol, and a polyhydric alcohol partial ether solvent having 3 to 19 carbon atoms such as propylene glycol-1-monomethyl ether.
  • ether-based solvent examples include dialkyl ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether and diheptyl ether, cyclic ether-based solvents such as tetrahydrofuran and tetrahydropyran, and diphenyl ethers.
  • dialkyl ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether and diheptyl ether, cyclic ether-based solvents such as tetrahydrofuran and tetrahydropyran, and diphenyl ethers.
  • aromatic ring-containing ether-based solvent such as anisole.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, and the like.
  • Chain ketone solvents such as di-iso-butyl ketone and trimethylnonanone
  • cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone, 2,4-pentandione and acetonylacetone. , Acetphenone and the like.
  • amide solvent examples include cyclic amide solvents such as N, N'-dimethylimidazolidinone and N-methylpyrrolidone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, and N.
  • chain amide solvents such as -methylacetamide, N, N-dimethylacetamide and N-methylpropionamide.
  • ester solvent examples include a monocarboxylic acid ester solvent such as n-butyl acetate and ethyl lactate, a lactone solvent such as ⁇ -butyrolactone and valerolactone, a polyhydric alcohol carboxylate solvent such as propylene glycol acetate, and propylene acetate.
  • ester solvent examples include a polyhydric alcohol partial ether carboxylate solvent such as glycol monomethyl ether, a polyvalent carboxylic acid diester solvent such as diethyl oxalate, and a carbonate solvent such as dimethyl carbonate and diethyl carbonate.
  • hydrocarbon solvent examples include an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as n-pentane and n-hexane, and an aromatic hydrocarbon solvent having 6 to 16 carbon atoms such as toluene and xylene. Be done.
  • an alcohol solvent or an ester solvent is preferable, a polyhydric alcohol partial ether solvent having 3 to 19 carbon atoms or a polyhydric alcohol partial ether carboxylate solvent is more preferable, and propylene glycol-1- More preferably, monomethyl ether or propylene glycol monomethyl ether acetate.
  • the lower limit of the content ratio of the [D] organic solvent is 50% by mass with respect to all the components contained in the radiation-sensitive resin composition. % Is preferable, 60% by mass is more preferable, 70% by mass is further preferable, and 80% by mass is particularly preferable.
  • the upper limit of the content ratio is preferably 99.9% by mass, preferably 99.5% by mass, and even more preferably 99.0% by mass.
  • Other optional components include, for example, surfactants.
  • the radiation-sensitive resin composition may contain one or more other optional components, respectively.
  • the radiation-sensitive resin composition includes, for example, a [A] polymer and a [B] acid generator, a [C] acid diffusion controller contained as necessary, an [D] organic solvent, and other optional components. Is mixed at a predetermined ratio, and preferably the obtained mixture can be prepared by filtering with a membrane filter having a pore size of 0.2 ⁇ m or less.
  • the radiation-sensitive resin composition can be used for forming a positive resist pattern using an alkaline developer and for forming a negative resist pattern using an organic solvent-containing developer.
  • the radiation-sensitive resin composition is for exposure with radiation (exposure light) irradiated in the exposure step in the resist pattern forming method described later.
  • Extreme ultraviolet rays (EUV) or electron beams have relatively high energy among the exposure lights, but according to the radiation-sensitive resin composition, exposure is performed even when extreme ultraviolet rays or electron beams are used as the exposure light. It is possible to form a resist pattern having good sensitivity to light and excellent LWR performance and resolvability. Therefore, the radiation-sensitive resin composition can be particularly preferably used for extreme ultraviolet exposure or electron beam exposure.
  • the resist pattern forming method involves directly or indirectly coating a substrate with the radiation-sensitive resin composition (hereinafter, also referred to as “coating step”) and exposing the resist film formed by the coating step.
  • a step of developing the exposed resist film hereinafter, also referred to as “exposure step”
  • a step of developing the exposed resist film hereinafter, also referred to as “development step”.
  • the resist pattern forming method by using the radiation-sensitive resin composition described above in the coating step, a resist pattern having good sensitivity to exposure light and excellent LWR performance and resolution is formed. be able to.
  • the radiation-sensitive resin composition is applied directly or indirectly to the substrate.
  • a resist film is formed.
  • the substrate include conventionally known wafers such as silicon wafers, silicon dioxide, and wafers coated with aluminum.
  • examples of the case where the radiation-sensitive resin composition is indirectly applied to the substrate include, for example, the case where the radiation-sensitive resin composition is applied onto the antireflection film formed on the substrate.
  • examples of such an antireflection film include organic or inorganic antireflection films disclosed in Japanese Patent Application Laid-Open No. 6-12452 and JP-A-59-93448.
  • Examples of the coating method include rotary coating (spin coating), casting coating, roll coating, and the like.
  • prebaking hereinafter, also referred to as “PB” may be performed in order to volatilize the solvent in the coating film.
  • PB prebaking
  • the upper limit of the temperature is preferably 150 ° C., more preferably 140 ° C.
  • the lower limit of the PB time 5 seconds is preferable, and 10 seconds is more preferable.
  • the upper limit of the time is preferably 600 seconds, more preferably 300 seconds.
  • the lower limit of the average thickness of the resist film formed is preferably 10 nm, more preferably 20 nm.
  • the upper limit of the average thickness is preferably 1,000 nm, more preferably 500 nm.
  • the resist film formed by the above coating step is exposed.
  • This exposure is performed by irradiating the exposure light through a photomask (in some cases, through an immersion medium such as water).
  • the exposure light includes electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, and ⁇ -rays; charged particles such as electron beams and ⁇ -rays, depending on the line width of the target pattern. Examples include lines.
  • EUV or electron beams are preferable, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV (wavelength 13.5 nm) or electron beams are more preferable, and ArF excimer laser light.
  • EUV or electron beam is more preferable, and EUV or electron beam is particularly preferable.
  • PEB post-exposure baking
  • the [A] polymer or the like due to the acid generated from the [B] acid generator or the like by the exposure is formed. It is preferable to promote the dissociation of the acid dissociative group having. With this PEB, it is possible to increase the difference in solubility in the developing solution between the exposed portion and the non-exposed portion.
  • the upper limit of the temperature is preferably 180 ° C., more preferably 130 ° C.
  • As the lower limit of the PEB time 5 seconds is preferable, 10 seconds is more preferable, and 30 seconds is even more preferable.
  • the upper limit of the time is preferably 600 seconds, more preferably 300 seconds, and even more preferably 100 seconds.
  • the exposed resist film is developed. As a result, a predetermined resist pattern can be formed. After development, it is generally washed with a rinse solution such as water or alcohol and dried.
  • the developing method in the developing step may be alkaline development or organic solvent development.
  • the developing solution used for development includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-.
  • TMAH tetramethylammonium hydroxide
  • Examples thereof include an alkaline aqueous solution in which at least one alkaline compound such as -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonen are dissolved.
  • the TMAH aqueous solution is preferable, and the 2.38 mass% TMAH aqueous solution is more preferable.
  • examples of the developing solution include organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents and alcohol solvents, and solutions containing the above organic solvents.
  • examples of the organic solvent include one or more of the solvents exemplified as the [D] organic solvent of the above-mentioned radiation-sensitive resin composition.
  • an ester solvent or a ketone solvent is preferable.
  • the ester solvent an acetic acid ester solvent is preferable, and n-butyl acetate is more preferable.
  • the ketone solvent a chain ketone is preferable, and 2-heptanone is more preferable.
  • the lower limit of the content of the organic solvent in the developing solution is preferably 80% by mass, more preferably 90% by mass, further preferably 95% by mass, and particularly preferably 99% by mass.
  • the components other than the organic solvent in the developing solution include water, silicone oil and the like.
  • Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method). ), A method of spraying the developer on the surface of the substrate (spray method), a method of continuing to apply the developer on the substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic discharge method). And so on.
  • Examples of the pattern formed by the resist pattern forming method include a line-and-space pattern and a hole pattern.
  • the radiation-sensitive acid generator has a sulfonate anion and a radiation-sensitive onium cation, and the sulfonate anion is dissociated by the action of a (thio) acetal structure, a carbonyloxy group and an acid to give a carboxy group. Contains a compound having a group.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured under the conditions described in the above section ⁇ [A] Polymer>.
  • the dispersity (Mw / Mn) was calculated from the measurement results of Mw and Mn.
  • a cooled polymerization solution was put into hexane (500 parts by mass with respect to the polymerization solution), and the precipitated white powder was filtered off.
  • the filtered white powder was washed twice with 100 parts by mass of hexane based on the polymerization solution, filtered, and dissolved in propylene glycol-1-monomethyl ether (300 parts by mass).
  • Methanol 500 parts by mass
  • triethylamine 50 parts by mass
  • ultrapure water 10 parts by mass
  • the Mw of the polymer (A-1) was 5,700, and the Mw / Mn was 1.61.
  • the content ratio of each structural unit derived from the monomer (M-1) and the monomer (M-3) in the polymer (A-1) was 41.2 mol. % And 58.8 mol%.
  • TPS + is a triphenylsulfonium cation.
  • [Example 1] [A] 100 parts by mass of (A-1) as a polymer, [B] 20 parts by mass of (B-1) as an acid generator, and (C-1) as an [C] acid diffusion control agent (B). -1) 20 mol% with respect to 100 mol%, and (D-1) 4,800 parts by mass and (D-2) 2,000 parts by mass as a solvent are mixed to form a radiation-sensitive resin composition.
  • the product (R-1) was prepared.
  • the resist film was subjected to PEB at 130 ° C. for 60 seconds. Then, using a 2.38 mass% TMAH aqueous solution, the mixture was developed at 23 ° C. for 30 seconds to form a positive resist pattern (32 nm line and space pattern).
  • the exposure amount for forming the 32 nm line-and-space pattern was defined as the optimum exposure amount, and this optimum exposure amount was defined as Eop (unit: mJ / cm 2 ).
  • the sensitivity can be evaluated as "good” when the Eop is 30 mJ / cm 2 or less, and as “poor” when the Eop exceeds 30 mJ / cm 2.
  • LWR performance Using the scanning electron microscope, the resist pattern formed in the formation of the resist pattern was observed from above. A total of 50 points of line width were measured at arbitrary points, and a 3-sigma value was obtained from the distribution of the measured values, which was defined as LWR (unit: nm). The LWR indicates that the smaller the value, the smaller the rattling of the line and the better. The LWR performance can be evaluated as "good” when the LWR is 4.0 nm or less, and as "bad” when the LWR exceeds 4.0 nm.
  • the size of the minimum resist pattern that is resolved when the size of the mask pattern forming the line and space (1L / 1S) is changed is measured, and this measured value is used as the resolution (unit: nm). And said. The smaller the value, the finer the pattern can be formed and the better the resolution is. The resolution can be evaluated as "good” when the resolution is 25 nm or less, and as “poor” when the resolution exceeds 25 nm.
  • the radiation-sensitive resin composition and the resist pattern forming method of the present invention a resist pattern having good sensitivity to exposure light and excellent LWR performance and resolution can be formed.
  • the radiation-sensitive acid generator of the present invention can be suitably used as a component of the radiation-sensitive resin composition. Therefore, these can be suitably used for processing processes of semiconductor devices, which are expected to be further miniaturized in the future.

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  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une composition de résine sensible au rayonnement avec laquelle il est possible de former un motif de réserve ayant une excellente sensibilité à la lumière d'exposition et ayant une performance de LWR et une résolution exceptionnelles, un procédé de formation de motif de réserve et un générateur d'acide sensible au rayonnement. L'invention concerne une composition de résine sensible au rayonnement qui contient un générateur d'acide sensible au rayonnement et un polymère ayant un premier motif structural qui contient un premier groupe dissociable par un acide dissocié par l'action d'un acide pour produire un groupe soluble dans les alcalis, la composition de résine sensible au rayonnement étant telle que le générateur d'acide sensible au rayonnement contient un composé ayant un anion sulfonate et un cation onium sensible au rayonnement, et l'anion sulfonate possède un second groupe dissociable par un acide qui se dissocie par l'action d'une structure (thio)acétal, un groupe carbonyloxy et un acide pour produire un groupe carboxy.
PCT/JP2020/034375 2019-09-12 2020-09-10 Composition de résine sensible au rayonnement, procédé de formation d'un motif de réserve et générateur d'acide sensible au rayonnement WO2021049592A1 (fr)

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Cited By (2)

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CN113429377A (zh) * 2021-06-23 2021-09-24 徐州博康信息化学品有限公司 含无氟光致产酸剂的可降解型树脂单体及其制备方法和应用
WO2023153059A1 (fr) * 2022-02-09 2023-08-17 Jsr株式会社 Composition de résine sensible au rayonnement, procédé de formation d'un motif de réserve et polymère

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JP2014160143A (ja) * 2013-02-19 2014-09-04 Fujifilm Corp 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜及びパターン形成方法
JP2016204370A (ja) * 2015-04-24 2016-12-08 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法
JP2018145185A (ja) * 2017-03-08 2018-09-20 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法
JP2019104721A (ja) * 2017-12-08 2019-06-27 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法

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JP2014160143A (ja) * 2013-02-19 2014-09-04 Fujifilm Corp 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜及びパターン形成方法
JP2016204370A (ja) * 2015-04-24 2016-12-08 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法
JP2018145185A (ja) * 2017-03-08 2018-09-20 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法
JP2019104721A (ja) * 2017-12-08 2019-06-27 住友化学株式会社 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429377A (zh) * 2021-06-23 2021-09-24 徐州博康信息化学品有限公司 含无氟光致产酸剂的可降解型树脂单体及其制备方法和应用
WO2023153059A1 (fr) * 2022-02-09 2023-08-17 Jsr株式会社 Composition de résine sensible au rayonnement, procédé de formation d'un motif de réserve et polymère

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