WO2022172736A1 - Composition de résine sensible au rayonnement et procédé de formation de motif - Google Patents

Composition de résine sensible au rayonnement et procédé de formation de motif Download PDF

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Publication number
WO2022172736A1
WO2022172736A1 PCT/JP2022/002365 JP2022002365W WO2022172736A1 WO 2022172736 A1 WO2022172736 A1 WO 2022172736A1 JP 2022002365 W JP2022002365 W JP 2022002365W WO 2022172736 A1 WO2022172736 A1 WO 2022172736A1
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group
radiation
resin composition
carbon atoms
sensitive resin
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PCT/JP2022/002365
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English (en)
Japanese (ja)
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龍一 根本
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Jsr株式会社
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Priority to JP2022581299A priority Critical patent/JPWO2022172736A1/ja
Publication of WO2022172736A1 publication Critical patent/WO2022172736A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • 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 and a pattern forming method.
  • Photolithography technology that uses resist compositions is used to form fine circuits in semiconductor devices.
  • an acid is generated by exposing the film of the resist composition to radiation through a mask pattern, and the acid is used as a catalyst to react with the resin in the exposed area and the unexposed area.
  • a resist pattern is formed on a substrate by creating a difference in solubility in an organic developer.
  • Patent Document 1 an acid generator capable of imparting a strong acid has been studied by substituting the proximal carbon of the sulfonic acid group with fluorine.
  • LWR Line Width Roughness
  • CDU Critical Dimension Uniformity
  • An object of the present invention is to provide a radiation-sensitive resin composition and a pattern forming method capable of forming a resist film exhibiting sufficient levels of sensitivity, LWR performance, CDU performance, pattern rectangularity, and etching resistance. .
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • n is an integer of 0 to 3, and when n is 2 or more, a plurality of R 1 and R 2 are the same or different.
  • L is a divalent hydrocarbon group having 3 to 40 carbon atoms containing a cyclic structure.
  • R 3 is a monovalent organic group having 1 to 40 carbon atoms and having no acid dissociable group.
  • Z + is a monovalent radiation-sensitive onium cation.
  • the radiation-sensitive resin composition contains an onium salt compound having a structure represented by the above formula (1) as a radiation-sensitive acid generator (hereinafter also referred to as "compound (1)”)
  • the resist pattern Excellent sensitivity, LWR performance, CDU performance, pattern rectangularity, and etching resistance can be exhibited during formation.
  • the reason for this is presumed as follows.
  • an organic group means a group containing at least one carbon atom.
  • the step of directly or indirectly applying the radiation-sensitive resin composition onto a substrate to form a resist film the step of directly or indirectly applying the radiation-sensitive resin composition onto a substrate to form a resist film; exposing the resist film; and developing the exposed resist film with a developer.
  • the radiation-sensitive resin composition capable of forming a resist film having excellent sensitivity, LWR performance, CDU performance, pattern rectangularity and etching resistance is used, a high-quality resist pattern can be efficiently formed. can be formed.
  • the radiation-sensitive resin composition (hereinafter also simply referred to as "composition") according to the present embodiment contains compound (1), a resin containing a structural unit having an acid-labile group, and a solvent. Furthermore, an acid diffusion control agent is included as needed.
  • the above composition may contain other optional components as long as they do not impair the effects of the present invention. Since the radiation-sensitive resin composition contains the compound (1) as a radiation-sensitive acid generator, the resist film of the radiation-sensitive resin composition exhibits a high level of sensitivity, LWR performance, CDU performance, and pattern rectangularity. And etching resistance can be imparted.
  • Compound (1) is represented by the above formula (1) and functions as a radiation-sensitive acid generator that generates acid upon exposure to radiation.
  • Examples of the monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by R 1 and R 2 include a monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms and a chain hydrocarbon group having 3 to 10 carbon atoms.
  • a monovalent fluorinated alicyclic hydrocarbon group and the like are included.
  • Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms include trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 2,2,3,3, 3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropyl group, heptafluoro n-propyl group, heptafluoro i-propyl group, nonafluoro n-butyl group, nonafluoro i-butyl group, nonafluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoro n-pentyl group, tridecafluoro n-hexyl group, 5,5,5-trifluoro-1,1- a fluorinated alkyl group such as a diethylpentyl group; fluorinated alkenyl groups such as a trifluoroetheny
  • Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms include a fluorocyclopentyl group, a difluorocyclopentyl group, a nonafluorocyclopentyl group, a fluorocyclohexyl group, a difluorocyclohexyl group, an undecafluorocyclohexylmethyl group, fluorinated cycloalkyl groups such as a fluoronorbornyl group, a fluoroadamantyl group, a fluorobornyl group, a fluoroisobornyl group, and a fluorotricyclodecyl group; and fluorinated cycloalkenyl groups such as a fluorocyclopentenyl group and a nonafluorocyclohexenyl group.
  • the fluorinated hydrocarbon group is preferably a monovalent fluorinated chain hydrocarbon group having 1 to 8 carbon atoms, more preferably a monovalent fluorinated chain hydrocarbon group having 1 to 4 carbon atoms.
  • R 1 and R 2 are preferably hydrogen atoms from the viewpoint of the degree of freedom of the peripheral structure of the sulfo group and the acidity of the generated acid.
  • n is preferably an integer of 1 or more (that is, an integer of 1 to 3), more preferably 1 or 2, and particularly preferably 1.
  • the divalent hydrocarbon group having 3 to 40 carbon atoms containing a cyclic structure represented by L may be formed only from hydrocarbons having a cyclic structure, and a hydrocarbon having a cyclic structure and a hydrocarbon having a chain structure. may be formed by combining Groups obtained by removing two hydrogen atoms from these structures are included.
  • the cyclic structure is preferably an alicyclic structure having 3 to 20 carbon atoms, an aromatic ring structure having 6 to 20 carbon atoms, or a combination thereof.
  • Examples of the alicyclic structure having 3 to 20 carbon atoms include an alicyclic monocyclic structure having 3 to 20 carbon atoms and an alicyclic polycyclic structure having 6 to 20 carbon atoms.
  • the alicyclic monocyclic structure having 3 to 20 carbon atoms and the alicyclic polycyclic structure having 6 to 20 carbon atoms may be either a saturated hydrocarbon structure or an unsaturated hydrocarbon structure.
  • the alicyclic polycyclic structure may be either a bridged alicyclic hydrocarbon structure or a condensed alicyclic hydrocarbon structure.
  • the bridged alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic ring are linked by a bond chain containing one or more carbon atoms.
  • a condensed alicyclic hydrocarbon structure refers to a polycyclic alicyclic hydrocarbon structure in which a plurality of alicyclic rings share a side (a bond between two adjacent carbon atoms).
  • preferred saturated hydrocarbon structures include cyclopentane, cyclohexane, cycloheptane and cyclooctane
  • preferred unsaturated hydrocarbon structures include cyclopentene, cyclohexene, cycloheptene, cyclooctene and cyclodecene
  • the alicyclic polycyclic structure is preferably a bridged alicyclic saturated hydrocarbon structure, such as bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane, tricyclo[3.3 .1.1 3,7 ]decane (adamantane) and the like are preferred.
  • Examples of the aromatic ring structure having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, indene, and fluorene.
  • the chain structure for L includes a chain hydrocarbon group having 1 to 37 carbon atoms, and the structure includes a linear or branched saturated hydrocarbon group having 1 to 37 carbon atoms, or a saturated hydrocarbon group having 1 to 37 carbon atoms. straight-chain or branched-chain unsaturated hydrocarbon groups.
  • the divalent hydrocarbon group represented by L above is preferably represented by any one of the following formulas (L-1) to (L-7).
  • n L1 , n L2 , n L3 and n L4 are each independently an integer of 1-4.
  • one * is a bond with the oxygen atom in the above formula (1), and the other * is the carbonyl group in the above formula (1). It is a joiner with
  • the divalent hydrocarbon group represented by L above is more preferably represented by any one of formulas (L-1) and (L-4) to (L-6) above.
  • the monovalent organic group having 1 to 40 carbon atoms and not having an acid-labile group represented by R 3 is not particularly limited as long as it does not have an acid-labile group, and may be a chain structure, a cyclic structure, or a combination thereof. may be either.
  • Examples of the chain structure include chain hydrocarbon groups that may be saturated or unsaturated, linear or branched.
  • the above cyclic structures include cyclic hydrocarbon groups which may be alicyclic, aromatic or heterocyclic.
  • the cyclic structure is preferably an alicyclic structure having 3 to 20 carbon atoms, an aromatic ring structure having 6 to 20 carbon atoms, or a combination thereof.
  • the monovalent organic group includes a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms and a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. , a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof.
  • a group in which some or all of the hydrogen atoms contained in a group having a chain structure or a group having a cyclic structure is substituted with a substituent, carbon-carbon of these groups, CO, CS, O, S, SO Groups containing 2 or NR′, or a combination of two or more of these are also included.
  • R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched unsaturated hydrocarbon group having 1 to 20 carbon atoms.
  • a hydrocarbon group etc. can be mentioned.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic or polycyclic saturated hydrocarbon group, a monocyclic or polycyclic unsaturated hydrocarbon group, and the like.
  • Preferred monocyclic saturated hydrocarbon groups are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
  • Preferred polycyclic cycloalkyl groups are bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl and tetracyclododecyl groups.
  • Monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • Polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norbornenyl, tricyclodecenyl, and tetracyclododecenyl groups.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; benzyl group, phenethyl group and naphthylmethyl group; An aralkyl group and the like can be mentioned.
  • heterocyclic cyclic hydrocarbon group examples include a group obtained by removing one hydrogen atom from an aromatic heterocyclic structure and a group obtained by removing one hydrogen atom from an alicyclic heterocyclic structure.
  • the heterocyclic structure also includes a 5-membered ring aromatic structure having aromaticity by introducing a heteroatom.
  • Heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and the like.
  • aromatic heterocyclic structures examples include oxygen atom-containing aromatic heterocyclic structures such as furan, pyran, benzofuran, and benzopyran; nitrogen atom-containing aromatic heterocyclic structures such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, acridine, phenazine, carbazole; sulfur atom-containing aromatic heterocyclic structures such as thiophene; Examples include aromatic heterocyclic structures containing multiple heteroatoms such as thiazole, benzothiazole, thiazine, and oxazine.
  • Examples of the alicyclic heterocyclic structures include oxygen atom-containing alicyclic heterocyclic structures such as oxirane, tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane; nitrogen atom-containing alicyclic heterocyclic structures such as aziridine, pyrrolidine, piperidine, piperazine; Sulfur atom-containing alicyclic heterocyclic structures such as thietane, thiolane, and thiane; Examples include alicyclic heterocyclic structures containing multiple heteroatoms such as morpholine, 1,2-oxathiolane, and 1,3-oxathiolane.
  • the cyclic structures also include structures containing lactone structures, cyclic carbonate structures, sultone structures and cyclic acetals. Examples of such structures include structures represented by the following formulas (H-1) to (H-10).
  • m is an integer of 1-3.
  • sulfonate anion moiety of compound (1) include, but are not limited to, structures represented by formulas (1-1) to (1-91) below.
  • Z + is a radiation sensitive onium cation.
  • the monovalent radiation-sensitive onium cation represented by Z + includes, for example, S, I, O, N, P, Cl, Br, F, As, Se, Sn, Sb , Te, and Bi, and examples thereof include sulfonium cations, tetrahydrothiophenium cations, iodonium cations, phosphonium cations, diazonium cations, and pyridinium cations. Among them, a sulfonium cation or an iodonium cation is preferred. Sulfonium cations or iodonium cations are preferably represented by the following formulas (X-1) to (X-6).
  • R a1 , R a2 and R a3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, alkoxy group or alkoxycarbonyl oxy group, substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 12 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, hydroxy group, halogen atom, —OSO 2 —R P , —SO 2 —R Q or —S—R T , or represents a ring structure composed of two or more of these groups combined together.
  • the ring structure may contain a heteroatom such as O or S between the carbon-carbon bonds forming the skeleton.
  • R P , R Q and R T are each independently a substituted or unsubstituted linear or branched C 1-12 alkyl group, a substituted or unsubstituted C 5-25 alicyclic It is a hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • k1, k2 and k3 are each independently an integer from 0 to 5; When R a1 to R a3 and R P , R Q and R T are each plural, R a1 to R a3 and R P , R Q and R T may be the same or different.
  • R b1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
  • nk is 0 or 1; When nk is 0, k4 is an integer of 0-4, and when nk is 1, k4 is an integer of 0-7.
  • R b1 When there are a plurality of R b1 , the plurality of R b1 may be the same or different, and the plurality of R b1 may represent a ring structure formed by being combined with each other.
  • R b2 is a substituted or unsubstituted C 1-7 linear or branched alkyl group or a substituted or unsubstituted C 6 or 7 aromatic hydrocarbon group.
  • LC is a single bond or a divalent linking group.
  • k5 is an integer from 0 to 4;
  • the plurality of Rb2 's may be the same or different, and the plurality of Rb2 's may represent a ring structure formed by being combined with each other.
  • q is an integer from 0 to 3;
  • the ring structure containing S + may contain a heteroatom such as O or S between the carbon-carbon bonds forming the skeleton.
  • R c1 , R c2 and R c3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group.
  • R g1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
  • nk2 is 0 or 1; When nk2 is 0, k10 is an integer of 0-4, and when nk2 is 1, k10 is an integer of 0-7.
  • R g1 When there are a plurality of R g1 , the plurality of R g1 may be the same or different, and the plurality of R g1 may represent a ring structure formed by being combined with each other.
  • R g2 and R g3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, an alkoxy group or an alkoxycarbonyloxy group, a substituted or unsubstituted C 3 -12 monocyclic or polycyclic cycloalkyl groups, substituted or unsubstituted C6-12 aromatic hydrocarbon groups, hydroxy groups, halogen atoms, or these groups combined together Represents a ring structure.
  • k11 and k12 are each independently an integer of 0-4. When each of R g2 and R g3 is plural, the plural R g2 and R g3 may be the same or different.
  • R d1 and R d2 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, alkoxy group or alkoxycarbonyl group, substituted or an unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a nitro group, or two or more of these groups combined with each other Represents the ring structure that is composed.
  • k6 and k7 are each independently an integer from 0 to 5; When each of R d1 and R d2 is plural, the plural R d1 and R d2 may be the same or different.
  • R e1 and R e2 are each independently a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • k8 and k9 are each independently an integer of 0-4.
  • radiation-sensitive onium cations include, but are not limited to, the structures of the following formulas.
  • the compound (1) includes a structure in which the anion moiety and the radiation-sensitive onium cation are arbitrarily combined.
  • Specific examples of compound (1) include, but are not limited to, onium salt compounds represented by formulas (1-1-1) to (1-1-95) below (hereinafter, formula (1-1-1 ) to (1-1-95) are also referred to as “compounds (1-1-1) to (1-1-95)”).
  • the lower limit of the content of the compound (1) (the total thereof when multiple types of compounds (1) are included) is preferably 0.02 parts by mass, more preferably 0.1 parts by mass, with respect to 100 parts by mass of the resin described later. It is preferably 1 part by mass, more preferably 5 parts by mass.
  • the upper limit of the content is preferably 50 parts by mass, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
  • the content of compound (1) is appropriately selected according to the type of resin used, exposure conditions, required sensitivity, and the like. As a result, excellent sensitivity, LWR performance, CDU performance, pattern rectangularity, and etching resistance can be exhibited when forming a resist pattern.
  • L, R 3 and Z + have the same meanings as in formula (1) above.
  • An ester is obtained by reacting 2-bromo-2,2-difluoroethanol with hydroxycarboxylic acid.
  • the bromo portion of the ester form is converted to a sulfonate with a dithionite and an oxidizing agent, and reacted with an onium cation halide (bromide in the scheme) corresponding to the onium cation portion to proceed with salt exchange to proceed with the onium salt.
  • the desired onium salt compound (1a) can be synthesized by reacting the hydroxy group of the onium salt with an acyl halide (acyl chloride in the scheme).
  • Compounds (1) having other structures can also be synthesized by appropriately selecting starting materials and precursors corresponding to the anion portion and the onium cation portion.
  • the resin is an assembly of polymers having a structural unit containing an acid-labile group (hereinafter also referred to as “structural unit (I)”) (hereinafter also referred to as “base resin”).
  • structural unit (I) an acid-labile group
  • base resin base resin
  • the term “acid-dissociable group” refers to a group that substitutes a hydrogen atom of a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfo group, or the like, and is dissociated by the action of an acid.
  • the radiation-sensitive resin composition has excellent pattern formability because the resin has the structural unit (I).
  • the base resin preferably has a structural unit (II) containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, which will be described later. ) and (II) may have other structural units. Each structural unit will be described below.
  • Structural unit (I) is a structural unit containing an acid-labile group.
  • the structural unit (I) is not particularly limited as long as it contains an acid-dissociable group.
  • a structural unit having a tertiary alkyl ester moiety a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a tertiary alkyl group and a structural unit having an acetal bond.
  • a structural unit represented by the following formula (3) hereinafter referred to as "structure Unit (I-1)
  • structure Unit (I-1) is preferred.
  • R 17 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 18 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 19 and R 20 are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or these groups represents a divalent alicyclic group having 3 to 20 carbon atoms which is combined with the carbon atoms to which they are bonded.
  • R 17 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit (I-1).
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 18 include a chain hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. groups, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and the like.
  • the chain hydrocarbon group having 1 to 10 carbon atoms represented by R 18 to R 20 includes a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms, or a linear or branched hydrocarbon group having 1 to 10 carbon atoms.
  • a branched chain unsaturated hydrocarbon group is mentioned.
  • the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms in R 3 of the above formula (1) can be preferably employed.
  • the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 18 As the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 18 , the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in R 3 of the above formula (1) is shown. groups can be suitably employed.
  • R 18 above is preferably a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • a divalent alicyclic group having 3 to 20 carbon atoms in which the chain hydrocarbon groups or alicyclic hydrocarbon groups represented by R 19 and R 20 are combined together and formed together with the carbon atoms to which they are bonded, is not particularly limited as long as it is a group obtained by removing two hydrogen atoms from the same carbon atoms constituting the carbocyclic ring of the above-mentioned monocyclic or polycyclic alicyclic hydrocarbon having the number of carbon atoms.
  • Either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group may be used, and the polycyclic hydrocarbon group may be either a bridged alicyclic hydrocarbon group or a condensed alicyclic hydrocarbon group.
  • the condensed alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which a plurality of alicyclic rings share a side (a bond between two adjacent carbon atoms).
  • the saturated hydrocarbon group is preferably a cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, or the like
  • the unsaturated hydrocarbon group is a cyclopentenediyl group.
  • cyclohexenediyl group, cycloheptenediyl group, cyclooctenediyl group, cyclodecenediyl group and the like are preferable.
  • the polycyclic alicyclic hydrocarbon group is preferably a bridged alicyclic saturated hydrocarbon group, such as a bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl group ), bicyclo[2.2.2]octane-2,2-diyl group, tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group) etc. are preferred.
  • a bridged alicyclic saturated hydrocarbon group such as a bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl group ), bicyclo[2.2.2]octane-2,2-diyl group, tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group) etc.
  • R 18 is an alkyl group having 1 to 4 carbon atoms
  • R 19 and R 20 are combined with each other and the alicyclic structure composed together with the carbon atom to which they are bonded is a polycyclic or monocyclic cycloalkane.
  • a structure is preferred.
  • structural unit (I-1) for example, structural units represented by the following formulas (3-1) to (3-6) (hereinafter referred to as “structural units (I-1-1) to (I-1- 6)”) and the like.
  • R 17 to R 20 have the same meanings as in formula (3).
  • i and j are each independently an integer of 1 to 4;
  • k and l are 0 or 1;
  • R 18 is preferably a methyl group, an ethyl group or an isopropyl group.
  • R 19 and R 20 are preferably a methyl group or an ethyl group.
  • the base resin may contain one or a combination of two or more structural units (I).
  • the content ratio of the structural unit (I) (the total content ratio when multiple types are included) is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol of the total structural units constituting the base resin. % or more is more preferable, and 35 mol % or more is particularly preferable. Also, it is preferably 80 mol % or less, more preferably 75 mol % or less, even more preferably 70 mol % or less, and particularly preferably 65 mol % or less.
  • Structural unit (II) is a structural unit containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure.
  • the base resin can adjust the solubility in the developer, and as a result, the radiation-sensitive resin composition improves lithography performance such as resolution. be able to.
  • the adhesion between the resist pattern formed from the base resin and the substrate can be improved.
  • Structural units (II) include, for example, structural units represented by the following formulas (T-1) to (T-10).
  • R L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R L2 to R L5 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a hydroxy group, a hydroxymethyl group, or a dimethylamino group; be.
  • R L4 and R L5 may be a divalent alicyclic group having 3 to 8 carbon atoms combined with each other and composed together with the carbon atoms to which they are attached.
  • L2 is a single bond or a divalent linking group.
  • X is an oxygen atom or a methylene group.
  • k is an integer from 0 to 3;
  • m is an integer of 1-3.
  • the divalent alicyclic group having 3 to 8 carbon atoms formed together with the carbon atoms to which R L4 and R L5 are combined is represented by R 19 and R 20 in the above formula (3).
  • One or more hydrogen atoms on this alicyclic group may be replaced with a hydroxy group.
  • Examples of the divalent linking group represented by L 2 include a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms, and a divalent alicyclic carbonized group having 4 to 12 carbon atoms.
  • a hydrogen group, or a group composed of one or more of these hydrocarbon groups and at least one group selected from -CO-, -O-, -NH- and -S- may be mentioned.
  • a structural unit containing a lactone structure is preferable, a structural unit containing a norbornanelactone structure is more preferable, and a structural unit derived from norbornanelactone-yl (meth)acrylate is even more preferable.
  • the content of the structural unit (II) is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 35 mol% or more, relative to the total structural units constituting the base resin. Also, it is preferably 75 mol % or less, more preferably 70 mol % or less, and even more preferably 65 mol % or less.
  • the radiation-sensitive resin composition can further improve the lithography performance such as resolution and the adhesion of the formed resist pattern to the substrate. .
  • the base resin optionally has other structural units in addition to the structural units (I) and (II).
  • Examples of other structural units above include structural units (III) containing a polar group (excluding structural units (II)).
  • the base resin can adjust the solubility in the developer, and as a result, the lithography performance such as the resolution of the radiation-sensitive resin composition can be improved. can be done.
  • the polar group include a hydroxy group, a carboxyl group, a cyano group, a nitro group, a sulfonamide group and the like. Among these, a hydroxy group and a carboxy group are preferred, and a hydroxy group is more preferred.
  • Structural units (III) include, for example, structural units represented by the following formula.
  • RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the content of the structural unit (III) is preferably 5 mol% or more, and 8 mol, based on the total structural units constituting the base resin. % or more is more preferable, and 10 mol % or more is even more preferable. Also, it is preferably 40 mol % or less, more preferably 35 mol % or less, and even more preferably 30 mol % or less.
  • Structural unit (IV) In the base resin, as other structural units, in addition to the structural unit (III) having a polar group, a structural unit derived from hydroxystyrene or a structural unit having a phenolic hydroxyl group (hereinafter both are collectively referred to as "structural unit (IV )”). Structural unit (IV) contributes to improvement of etching resistance and improvement of developer solubility difference (dissolution contrast) between exposed and unexposed areas. In particular, it can be suitably applied to pattern formation using exposure to radiation with a wavelength of 50 nm or less, such as electron beams and EUV. In this case, the resin preferably has the structural unit (I) together with the structural unit (IV).
  • the phenolic hydroxyl group is protected by a protective group such as an alkali-dissociable group, and then polymerized, followed by hydrolysis and deprotection to obtain the structural unit (IV).
  • a protective group such as an alkali-dissociable group
  • the structural unit that gives the structural unit (IV) by hydrolysis is preferably represented by the following formulas (4-1) and (4-2).
  • R 11 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 12 is a monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group. Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms for R 12 include monovalent hydrocarbon groups having 1 to 20 carbon atoms for R 8 in structural unit (I). Alkoxy groups include, for example, methoxy, ethoxy and tert-butoxy groups.
  • R 12 above is preferably an alkyl group or an alkoxy group, more preferably a methyl group or a tert-butoxy group.
  • the content of the structural unit (IV) is preferably 10 mol% or more, more preferably 20 mol% or more, relative to the total structural units constituting the resin. Moreover, 70 mol% or less is preferable, and 60 mol% or less is more preferable.
  • the base resin can be synthesized, for example, by polymerizing monomers that give each structural unit using a radical polymerization initiator or the like in an appropriate solvent.
  • radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-cyclopropylpropyl pionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), azo radical initiators such as dimethyl 2,2'-azobis isobutyrate; benzoyl peroxide, t-butyl hydroperoxide, Examples include peroxide-based radical initiators such as cumene hydroperoxide. Among these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical initiators can be used individually by 1 type or in mixture of 2 or more types.
  • Solvents used in the above polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, methyl ethyl ketone, 4-methyl
  • the reaction temperature in the above polymerization is usually 40°C to 150°C, preferably 50°C to 120°C.
  • the reaction time is generally 1 hour to 48 hours, preferably 1 hour to 24 hours.
  • the molecular weight of the base resin is not particularly limited, but the lower limit of the polystyrene equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is preferably 1,000, more preferably 2,000, and further 3,000. Preferably, 4,000 is particularly preferred.
  • the upper limit of Mw is preferably 50,000, more preferably 30,000, still more preferably 15,000, and particularly preferably 12,000. If the Mw of the base resin is less than the above lower limit, the resulting resist film may have reduced heat resistance. When the Mw of the base resin exceeds the above upper limit, the developability of the resist film may deteriorate.
  • the ratio (Mw/Mn) of Mw to the polystyrene equivalent number average molecular weight (Mn) of the base resin measured by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.
  • the Mw and Mn of the resin herein are values measured using gel permeation chromatography (GPC) under the following conditions.
  • the content of the base resin is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more, relative to the total solid content of the radiation-sensitive resin composition.
  • the radiation-sensitive resin composition of the present embodiment may contain, as another resin, a resin having a higher mass content of fluorine atoms than the base resin (hereinafter also referred to as "high fluorine content resin"). good.
  • high fluorine content resin a resin having a higher mass content of fluorine atoms than the base resin.
  • structural unit (V) As the high fluorine content resin, for example, it is preferable to have a structural unit represented by the following formula (5) (hereinafter also referred to as “structural unit (V)”), and if necessary, the structural unit in the base resin It may have (I) or structural unit (III).
  • R 13 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • G L is a single bond, an oxygen atom, a sulfur atom, -COO-, -SO 2 ONH-, -CONH- or -OCONH-.
  • R 14 is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • R 13 is preferably a hydrogen atom and a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that provides the structural unit (V).
  • GL is preferably a single bond or -COO-, more preferably -COO-, from the viewpoint of copolymerizability of the monomer providing the structural unit (V).
  • R 14 As the monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms represented by R 14 , some or all of the hydrogen atoms possessed by a linear or branched alkyl group having 1 to 20 carbon atoms are fluorine Those substituted by atoms are included.
  • the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 14 includes a part of the hydrogen atoms of a monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms, or Those completely substituted with fluorine atoms are included.
  • R 14 above is preferably a fluorinated chain hydrocarbon group, more preferably a fluorinated alkyl group, 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoropropyl and 5,5,5-trifluoro-1,1-diethylpentyl groups are more preferred.
  • the content of the structural unit (V) is preferably 30 mol% or more, preferably 40 mol%, based on the total structural units constituting the high fluorine content resin. 45 mol % or more is more preferable, and 50 mol % or more is particularly preferable. Also, it is preferably 95 mol % or less, more preferably 90 mol % or less, and even more preferably 85 mol % or less.
  • the high fluorine content resin has a fluorine atom-containing structural unit (hereinafter also referred to as structural unit (VI)) represented by the following formula (f-2) together with or in place of the structural unit (V). ). Since the high fluorine content resin has the structural unit (f-2), the solubility in an alkaline developer is improved, and the occurrence of development defects can be suppressed.
  • structural unit (VI) fluorine atom-containing structural unit represented by the following formula (f-2)
  • Structural unit (VI) has (x) an alkali-soluble group and (y) a group that dissociates under the action of an alkali to increase solubility in an alkali developing solution (hereinafter also simply referred to as an "alkali-dissociable group"). ) is roughly divided into two cases. Common to both (x) and (y), in the above formula (f-2), R 1 C is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R D is a single bond, a (s+1) -valent hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, -NR dd -, a carbonyl group, -COO- or It is a structure in which -CONH- is bonded, or a structure in which some of the hydrogen atoms of this hydrocarbon group are replaced with an organic group having a heteroatom.
  • R dd is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. s is an integer from 1 to 3;
  • R F is a hydrogen atom and A 1 is an oxygen atom, —COO-* or —SO 2 O-*. * indicates the site that binds to RF.
  • W 1 is a single bond, a hydrocarbon group having 1 to 20 carbon atoms or a divalent fluorinated hydrocarbon group.
  • a 1 is an oxygen atom
  • W 1 is a fluorinated hydrocarbon group having a fluorine atom or a fluoroalkyl group at the carbon atom to which A 1 is bonded.
  • R E is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • a plurality of R E , W 1 , A 1 and R F may be the same or different.
  • the affinity for an alkaline developer can be increased and development defects can be suppressed.
  • Structural unit (VI) having an alkali-soluble group when A 1 is an oxygen atom and W 1 is a 1,1,1,3,3,3-hexafluoro-2,2-methanediyl group is particularly preferred.
  • R F is a monovalent organic group having 1 to 30 carbon atoms
  • a 1 is an oxygen atom, -NR aa -, -COO-* or —SO 2 O—*.
  • R aa is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * indicates the site that binds to RF.
  • W 1 is a single bond or a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
  • R E is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • W 1 or R F has a fluorine atom on the carbon atom bonded to A 1 or on the adjacent carbon atom.
  • a 1 is an oxygen atom
  • W 1 and R E are single bonds
  • R D is a hydrocarbon group having 1 to 20 carbon atoms and a carbonyl group is attached to the end of the R E side
  • R F is an organic group having a fluorine atom.
  • s is 2 or 3
  • a plurality of R E , W 1 , A 1 and R F may be the same or different.
  • Structural units (VI) having an alkali-dissociable group are particularly preferably those in which A 1 is —COO-* and R F or W 1 or both of them have a fluorine atom.
  • R C is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit (VI).
  • R E is a divalent organic group
  • a group having a lactone structure is preferred, a group having a polycyclic lactone structure is more preferred, and a group having a norbornane lactone structure is more preferred.
  • the content of the structural unit (VI) is preferably 40 mol% or more, preferably 50 mol%, based on the total structural units constituting the high fluorine content resin.
  • the above is more preferable, and 60 mol % or more is even more preferable. Also, it is preferably 95 mol % or less, more preferably 90 mol % or less, and even more preferably 85 mol % or less.
  • the high fluorine content resin may contain a structural unit having an alicyclic structure represented by the following formula (6) as a structural unit other than the structural units listed above.
  • R 1 ⁇ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 2 ⁇ is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 2 ⁇ is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms in R 3 of the above formula (1).
  • a cyclic hydrocarbon group can be preferably employed.
  • the content of the structural unit having the alicyclic structure is 10 mol% or more with respect to the total structural units constituting the high fluorine content resin. is preferred, 20 mol % or more is more preferred, and 30 mol % or more is even more preferred. Moreover, it is preferably 70 mol % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less.
  • the lower limit of Mw of the high fluorine content resin is preferably 1,000, more preferably 2,000, even more preferably 3,000, and particularly preferably 5,000.
  • the upper limit of Mw is preferably 50,000, more preferably 30,000, even more preferably 20,000, and particularly preferably 15,000.
  • the Mw/Mn of the high fluorine content resin is usually 1 or more, more preferably 1.1 or more. Moreover, it is usually 5 or less, preferably 3 or less, more preferably 2 or less, and still more preferably 1.9 or less.
  • the content of the high fluorine content resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and 1.5 parts by mass with respect to 100 parts by mass of the base resin. Part by mass or more is particularly preferred. Also, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • the radiation-sensitive resin composition may contain one or more high fluorine content resins.
  • the high fluorine content resin can be synthesized by a method similar to the method for synthesizing the base resin described above.
  • the radiation-sensitive resin composition may contain an acid diffusion controller, if necessary.
  • the acid diffusion control agent has the effect of controlling the diffusion phenomenon in the resist film of the acid generated from the compound (1) upon exposure and suppressing unfavorable chemical reactions in the unexposed areas.
  • the storage stability of the resulting radiation-sensitive resin composition is improved.
  • the resolution of the resist pattern is further improved, and the line width change of the resist pattern due to the fluctuation of the holding time from exposure to development can be suppressed, and a radiation-sensitive resin composition excellent in process stability is obtained. be done.
  • nitrogen-containing compound (I) a compound represented by the following formula (7)
  • nitrogen-containing compounds (II) a compound having two nitrogen atoms in the same molecule
  • nitrogen-containing compounds (III) compounds having three nitrogen atoms
  • amide group-containing compounds urea compounds, nitrogen-containing heterocyclic compounds, and the like.
  • R 22 , R 23 and R 24 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or It is a substituted or unsubstituted aralkyl group.
  • nitrogen-containing compound (I) examples include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; and aromatic amines such as aniline. be done.
  • nitrogen-containing compound (II) examples include ethylenediamine and N,N,N',N'-tetramethylethylenediamine.
  • nitrogen-containing compound (III) examples include polyamine compounds such as polyethyleneimine and polyallylamine; polymers such as dimethylaminoethylacrylamide.
  • amide group-containing compounds include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. be done.
  • Urea compounds include, for example, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea.
  • nitrogen-containing heterocyclic compounds examples include pyridines such as pyridine and 2-methylpyridine; morpholines such as N-propylmorpholine and N-(undecylcarbonyloxyethyl)morpholine; pyrazine and pyrazole.
  • a compound having an acid dissociable group can also be used as the nitrogen-containing organic compound.
  • Nitrogen-containing organic compounds having such an acid-labile group include, for example, Nt-butoxycarbonylpiperidine, Nt-butoxycarbonylimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2 -Phenylbenzimidazole, N-(t-butoxycarbonyl)di-n-octylamine, N-(t-butoxycarbonyl)diethanolamine, N-(t-butoxycarbonyl)dicyclohexylamine, N-(t-butoxycarbonyl)diphenylamine , Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonyl-4-acetoxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine and the like.
  • a radiation-sensitive weak acid generator that generates a weak acid upon exposure
  • the acid generated from the radiation-sensitive acid generator is a weak acid that does not induce the dissociation of the acid-dissociable groups in the resin under the conditions for dissociating the acid-dissociable groups.
  • "dissociation" of an acid-dissociable group means dissociation upon post-exposure baking at 110°C for 60 seconds.
  • Examples of radiation-sensitive weak acid generators include onium salt compounds that are decomposed by exposure to lose acid diffusion controllability.
  • onium salt compounds include sulfonium salt compounds represented by the following formula (8-1) and iodonium salt compounds represented by the following formula (8-2).
  • J + is a sulfonium cation and U + is an iodonium cation.
  • Sulfonium cations represented by J + include sulfonium cations represented by the above formulas (X-1) to (X-3), and examples of iodonium cations represented by U + include the above formulas (X- 4) to (X-5) include iodonium cations.
  • E - and Q - are each independently anions represented by R ⁇ -O - , R ⁇ -COO - and R ⁇ -SO 3 - .
  • R ⁇ is an alkyl group, an aryl group or an aralkyl group.
  • a hydrogen atom in the aromatic ring of the aryl group or aralkyl group represented by R ⁇ is substituted with a hydroxy group, a fluorine atom-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • Examples of the radiation-sensitive weak acid generator include compounds represented by the following formula.
  • the radiation-sensitive weak acid generator is preferably a sulfonium salt, more preferably a triarylsulfonium salt, and more preferably triphenylsulfonium salicylate and triphenylsulfonium 10-camphorsulfonate.
  • the lower limit of the content of the acid diffusion control agent is preferably 3 parts by mass, more preferably 4 parts by mass, and 5 parts by mass with respect to a total of 100 parts by mass of the radiation-sensitive acid generator (including compound (1)). is more preferred.
  • the upper limit of the content is preferably 80 parts by mass, more preferably 70 parts by mass, and even more preferably 50 parts by mass.
  • the radiation-sensitive resin composition may contain one or more acid diffusion control agents.
  • the radiation-sensitive resin composition according to this embodiment contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve or disperse at least the compound (1), the resin, and optionally the radiation-sensitive acid generator and the like.
  • solvents examples include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents.
  • alcohol solvents include carbon such as iso-propanol, 4-methyl-2-pentanol, 3-methoxybutanol, n-hexanol, 2-ethylhexanol, furfuryl alcohol, cyclohexanol, 3,3,5-trimethylcyclohexanol, diacetone alcohol; Monoalcoholic solvents of numbers 1 to 18; Polyethylene glycol having 2 to 18 carbon atoms such as ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol. a alcohol-based solvent; A polyhydric alcohol partial ether solvent obtained by etherifying a part of the hydroxy groups of the above polyhydric alcohol solvent may be used.
  • ether solvents examples include Dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether); Examples thereof include polyhydric alcohol ether solvents obtained by etherifying the hydroxy groups of the above polyhydric alcohol solvents.
  • ketone solvents include linear ketone solvents such as acetone, butanone, and methyl-iso-butyl ketone: Cyclic ketone solvents such as cyclopentanone, cyclohexanone, and methylcyclohexanone: 2,4-pentanedione, acetonylacetone, acetophenone and the like.
  • amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; Chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and the like.
  • ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; Polyhydric alcohol partial ether acetate solvents such as diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; Lactone solvents such as ⁇ -butyrolactone and valerolactone; Carbonate solvents such as diethyl carbonate, ethylene carbonate, propylene carbonate; Polyvalent carboxylic acid diester solvents such as propylene glycol diacetate, methoxytriglycol acetate, diethyl oxalate, ethyl acetoacetate, ethyl lactate and diethyl phthalate can be used.
  • monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate
  • hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene, di-iso-propylbenzene, n-amylnaphthalene and the like are included.
  • ester-based solvents and ketone-based solvents are preferred, polyhydric alcohol partial ether acetate-based solvents, cyclic ketone-based solvents, and lactone-based solvents are more preferred, and propylene glycol monomethyl ether acetate, cyclohexanone, and ⁇ -butyrolactone are even more preferred.
  • the radiation-sensitive resin composition may contain one or more solvents.
  • the radiation-sensitive resin composition may contain other optional components in addition to the components described above.
  • other optional components include a cross-linking agent, an uneven distribution promoter, a surfactant, an alicyclic skeleton-containing compound, a sensitizer, and the like. These other optional components may be used alone or in combination of two or more.
  • the radiation-sensitive resin composition can be prepared, for example, by mixing compound (1), a resin, a radiation-sensitive acid generator, optionally a high fluorine content resin, etc., and a solvent in a predetermined ratio. After mixing, the radiation-sensitive resin composition is preferably filtered through a filter having a pore size of about 0.05 ⁇ m to 0.20 ⁇ m.
  • the solid content concentration of the radiation-sensitive resin composition is usually 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass.
  • a pattern forming method comprises: A step (1) of directly or indirectly coating the radiation-sensitive resin composition on a substrate to form a resist film (hereinafter also referred to as a “resist film forming step”); Step (2) of exposing the resist film (hereinafter also referred to as “exposure step”); and a step (3) of developing the exposed resist film (hereinafter also referred to as “development step”).
  • the radiation-sensitive resin composition capable of forming a resist film having excellent sensitivity, LWR performance, CDU performance, pattern rectangularity, and etching resistance in the exposure process is used, high quality is obtained. can form a resist pattern.
  • Each step will be described below.
  • a resist film is formed from the radiation-sensitive resin composition.
  • the substrate on which the resist film is formed include conventionally known substrates such as silicon wafers, silicon dioxide, and aluminum-coated wafers. Further, for example, an organic or inorganic antireflection film disclosed in JP-B-6-12452, JP-A-59-93448, etc. may be formed on the substrate. Examples of coating methods include spin coating, casting coating, and roll coating. After coating, if necessary, prebaking (PB) may be performed in order to volatilize the solvent in the coating film.
  • the PB temperature is usually 60°C to 140°C, preferably 80°C to 120°C.
  • the PB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.
  • the thickness of the resist film to be formed is preferably 10 nm to 1,000 nm, more preferably 10 nm to 500 nm.
  • an immersion protective film that is insoluble in the immersion liquid may be provided.
  • a solvent peelable protective film that is peeled off with a solvent before the development process see, for example, JP-A-2006-227632
  • a developer peelable protective film that is peeled off at the same time as development in the development process For example, see WO2005-069076 and WO2006-035790
  • the exposure step which is the next step, is performed with radiation having a wavelength of 50 nm or less
  • the resist film formed in the resist film forming step (step (1) above) is coated through a photomask (in some cases, through an immersion medium such as water). , emit radiation and expose. Radiation used for exposure depends on the line width of the desired pattern. A charged particle beam and the like can be mentioned. Among these, far ultraviolet rays, electron beams, and EUV are preferred, and ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), electron beams, and EUV are more preferred. The following electron beams and EUV are more preferable.
  • the immersion liquid used When exposure is performed by immersion exposure, examples of the immersion liquid used include water and fluorine-based inert liquids.
  • the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible so as to minimize distortion of the optical image projected onto the film.
  • excimer laser light wavelength: 193 nm
  • water it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above viewpoints.
  • an additive that reduces the surface tension of water and increases surface activity may be added in a small proportion. This additive preferably does not dissolve the resist film on the wafer and has negligible effect on the optical coating on the bottom surface of the lens. Distilled water is preferred as the water used.
  • a post-exposure bake is performed to accelerate the dissociation of the acid-dissociable groups of the resin or the like by the acid generated from the radiation-sensitive acid generator upon exposure in the exposed portions of the resist film.
  • This PEB causes a difference in solubility in a developer between the exposed area and the unexposed area.
  • the PEB temperature is usually 50°C to 180°C, preferably 80°C to 130°C.
  • the PEB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.
  • step (3) above the resist film exposed in the exposure step (step (2) above) is developed. Thereby, a predetermined resist pattern can be formed. After development, it is common to wash with a rinsing liquid such as water or alcohol and dry.
  • a rinsing liquid such as water or alcohol
  • TMAH tetramethylammonium hydroxide
  • a TMAH aqueous solution is preferable, and a 2.38% by mass TMAH aqueous solution is more preferable.
  • organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, or solvents containing organic solvents can be used.
  • the organic solvent include one or more of the solvents listed above as the solvent for the radiation-sensitive resin composition.
  • ether-based solvents, ester-based solvents, and ketone-based solvents are preferred.
  • the ether solvent a glycol ether solvent is preferable, and ethylene glycol monomethyl ether and propylene glycol monomethyl ether are more preferable.
  • ester solvent an acetate solvent is preferable, and n-butyl acetate and amyl acetate are more preferable.
  • ketone solvent a chain ketone is preferred, and 2-heptanone is more preferred.
  • the content of the organic solvent in the developer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more.
  • Components other than the organic solvent in the developer include, for example, water and silicon oil.
  • the developer may be either an alkaline developer or an organic solvent developer. It can be appropriately selected depending on whether the desired positive pattern or negative pattern is desired.
  • Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension (puddle method).
  • dip method a method of immersing the substrate in a tank filled with a developer for a certain period of time
  • puddle method a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension
  • spray method a method in which the developer is sprayed onto the surface of the substrate
  • dynamic dispensing method a method in which the developer is continuously applied while scanning the developer dispensing nozzle at a constant speed on the substrate rotating at a constant speed
  • Mw Weight average molecular weight
  • Mn number average molecular weight
  • 13 C-NMR analysis 13 C-NMR analysis of the resin was performed using a nuclear magnetic resonance apparatus (“JNM-Delta400” manufactured by JEOL Ltd.).
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the cooled polymerization solution was poured into methanol (2,000 parts by mass), and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with methanol, filtered, and dried at 50° C. for 24 hours to obtain a white powdery resin (A-1) (yield: 83%).
  • Resin (A-1) had Mw of 8,800 and Mw/Mn of 1.50.
  • the content ratio of each structural unit derived from (M-1), (M-2) and (M-13) is 41.3 mol% and 13.8 mol%, respectively. and 44.9 mol%.
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the cooled polymerization solution was poured into hexane (2,000 parts by mass), and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with hexane, filtered, and dissolved in 1-methoxy-2-propanol (300 parts by mass).
  • methanol 500 parts by mass
  • triethylamine 50 parts by mass
  • ultrapure water 10 parts by mass
  • Resin (A-12) had an Mw of 5,200 and an Mw/Mn of 1.60.
  • the content ratios of structural units derived from (M-1) and (M-18) were 51.3 mol % and 48.7 mol %, respectively.
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the operation of adding hexane (100 parts by mass) and stirring to recover the acetonitrile layer was repeated three times.
  • the high fluorine content resin (E-1) had Mw of 6,000 and Mw/Mn of 1.62.
  • the contents of the structural units derived from (M-1) and (M-20) were 19.9 mol % and 80.1 mol %, respectively.
  • a sulfonic acid sodium salt compound was obtained by extracting with acetonitrile and distilling off the solvent. 20.0 mmol of triphenylsulfonium bromide was added to the above sulfonic acid sodium salt compound, and a mixed solution of water:dichloromethane (1:3 (mass ratio)) was added to obtain a 0.5 M solution. After vigorously stirring at room temperature for 3 hours, dichloromethane was added for extraction, and the organic layer was separated. After drying the resulting organic layer with sodium sulfate, the solvent was distilled off and the residue was purified by column chromatography to obtain an onium salt in good yield.
  • [[C] acid diffusion control agent] C-1 to C-5 compounds represented by the following formulas (C-1) to (C-5)
  • Example 1 [A] 100 parts by mass of (A-1) as a resin, [B] 12.0 parts by mass of (B-1) as a radiation-sensitive acid generator (compound (1)), and [C] an acid diffusion controller (C-1) 3.0 parts by mass as [E] high fluorine content resin (E-1) 3.0 parts by mass (solid content), and [D] (D-1) as solvent
  • a radiation-sensitive resin composition (J-1) is prepared by mixing 3,230 parts by mass of a mixed solvent of /(D-2)/(D-3) and filtering through a membrane filter with a pore size of 0.2 ⁇ m. did.
  • a spin coater (“CLEAN TRACK ACT12" available from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower antireflection film ("ARC66" available from Bulwer Science).
  • a lower antireflection film having an average thickness of 100 nm was formed by heating at 205° C. for 60 seconds.
  • the positive radiation-sensitive resin composition for ArF exposure prepared above was applied onto the lower antireflection film using the spin coater, and PB (pre-baking) was performed at 100° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 90 nm was formed.
  • TMAH tetramethylammonium hydroxide
  • the exposure dose for forming a 40 nm line-and-space pattern is defined as the optimum exposure dose, and this optimum exposure dose is defined as sensitivity (mJ/cm 2 ). did.
  • the sensitivity was evaluated as "good” when it was 25 mJ/cm 2 or less, and as “bad” when it exceeded 25 mJ/cm 2 .
  • LWR performance A 40 nm line-and-space resist pattern was formed by irradiating with the optimum exposure amount determined by the above sensitivity evaluation. The formed resist pattern was observed from above the pattern using the scanning electron microscope. Line width variation was measured at a total of 500 points, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as LWR (nm). LWR indicates that the smaller the value, the smaller the roughness of the line and the better. The LWR performance was evaluated as "good” when less than or equal to 3.3 nm, and as “poor” when greater than 3.3 nm.
  • a 40 nm line-and-space resist pattern formed by irradiating the optimum exposure dose determined in the evaluation of sensitivity was observed using the scanning electron microscope, and the cross-sectional shape of the line-and-space pattern was evaluated.
  • the rectangularity of the resist pattern is "A" (very good) if the ratio of the length of the lower side to the length of the upper side in the cross-sectional shape is 1 or more and 1.05 or less, and if it is more than 1.05 and 1.10 or less. If it is more than 1.10, it is evaluated as "B" (good), and if it exceeds 1.10, it is evaluated as "C" (bad).
  • the resist composition prepared above was applied onto a silicon wafer substrate by spin coating. Next, the substrate was heated at 100° C. for 60 seconds in an air atmosphere to form a resist film having an average thickness of 100 nm, thereby obtaining a substrate with a resist film formed thereon.
  • the etching rate (nm / min) was calculated from the time required for the resist film to disappear, and the ratio to the etching rate in Comparative Example 1 was obtained and used as a measure of etching resistance.
  • the etching resistance is "A” (extremely good) when the above ratio is 0.95 or less, "B” (good) when it is more than 0.95 and 1.00 or less, and "C” when it is more than 1.00. (bad). Note that "-" in Table 5 indicates that Comparative Example 1 is the standard for evaluation of etching resistance.
  • the radiation-sensitive resin compositions of Examples had good sensitivity, LWR performance, pattern rectangularity and etching resistance when used for ArF exposure, whereas the radiation-sensitive resin compositions of Comparative Examples , each characteristic was inferior to those of the examples. Therefore, when the radiation-sensitive resin composition of the example is used for ArF exposure, a resist pattern with high sensitivity, good LWR performance and good cross-sectional shape can be formed.
  • Example 45 [A] 100 parts by mass of (A-12) as a resin, [B] 17.0 parts by mass of (B-1) as a radiation-sensitive acid generator (compound (1)), and [C] an acid diffusion controller (C-2) 5.0 parts by mass as [E] high fluorine content resin (E-5) 3.0 parts by mass (solid content), and [D] (D-1) as solvent
  • a radiation-sensitive resin composition (J-45) was prepared by mixing 6,110 parts by mass of a mixed solvent of /(D-4) and filtering through a membrane filter with a pore size of 0.2 ⁇ m.
  • a spin coater (“CLEAN TRACK ACT12" available from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower antireflection film ("ARC66" available from Bulwer Science).
  • a lower antireflection film having an average thickness of 105 nm was formed by heating at 205° C. for 60 seconds.
  • the positive radiation-sensitive resin composition for EUV exposure prepared above was applied onto this lower antireflection film using the above spin coater, and PB was performed at 130° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 55 nm was formed.
  • the exposure dose for forming a 32 nm line-and-space pattern is defined as the optimum exposure dose, and the optimum exposure dose is defined as sensitivity (mJ/cm 2 ). did.
  • the sensitivity was evaluated as "good” when it was 30 mJ/cm 2 or less, and as “bad” when it exceeded 30 mJ/cm 2 .
  • LWR performance A resist pattern was formed by adjusting the mask size so as to form a 32 nm line-and-space pattern by irradiating with the optimum exposure amount determined by the evaluation of sensitivity. The formed resist pattern was observed from above the pattern using the scanning electron microscope. Line width variation was measured at a total of 500 points, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as LWR (nm). LWR indicates that the smaller the value, the smaller the jolting of the line and the better. The LWR performance was evaluated as "good” when less than 3.5 nm and "poor" when greater than 3.5 nm.
  • a 32 nm line-and-space resist pattern formed by irradiating the optimum exposure dose determined in the evaluation of sensitivity was observed using the scanning electron microscope, and the cross-sectional shape of the line-and-space pattern was evaluated.
  • the rectangularity of the resist pattern is "A" (very good) if the ratio of the length of the lower side to the length of the upper side in the cross-sectional shape is 1 or more and 1.05 or less, and if it is more than 1.05 and 1.10 or less. If it is more than 1.10, it is evaluated as "B" (good), and if it exceeds 1.10, it is evaluated as "C" (bad).
  • the resist composition prepared above was applied onto a silicon wafer substrate by spin coating. Next, the substrate was heated at 100° C. for 60 seconds in an air atmosphere to form a resist film having an average thickness of 100 nm, thereby obtaining a substrate with a resist film formed thereon.
  • the etching rate (nm / min) was calculated from the time required for the resist film to disappear, and the ratio to the etching rate in Comparative Example 20 was obtained and used as a measure of etching resistance.
  • the etching resistance is "A” (extremely good) when the above ratio is 0.95 or less, "B” (good) when it is more than 0.95 and 1.00 or less, and "C” when it is more than 1.00. (bad). Note that "-" in Table 7 indicates that Comparative Example 20 is the standard for evaluation of etching resistance.
  • Example 58 [A] 100 parts by mass of (A-5) as a resin, [B] 15.0 parts by mass of (B-1) as a radiation-sensitive acid generator (compound (1)), and [C] an acid diffusion controller (C-5) 5.0 parts by mass as [E] high fluorine content resin (E-4) 3.0 parts by mass (solid content), and [D] (D-1) as solvent
  • a radiation-sensitive resin composition (J-58) was prepared by mixing 3,230 parts by mass of a mixed solvent of /(D-2)/(D-3) and filtering through a membrane filter with a pore size of 0.2 ⁇ m. did.
  • a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower antireflection film ("ARC66" from Bulwer Science).
  • a lower antireflection film having an average thickness of 100 nm was formed by heating at 205° C. for 60 seconds.
  • the negative type radiation-sensitive resin composition for ArF exposure (J-58) prepared above was applied onto this lower antireflection film using the above spin coater, and PB (pre-baking) was performed at 100° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 90 nm was formed.
  • the exposure dose for forming a resist pattern with 40 nm holes and a 105 nm pitch is defined as the optimum exposure dose, and the optimum exposure dose is the sensitivity (mJ/cm 2 ).
  • the sensitivity was evaluated as "good” when it was 30 mJ/cm 2 or less, and as “bad” when it exceeded 30 mJ/cm 2 .
  • CDU performance A total of 1,800 lengths of a 40 nm hole, 105 nm pitch resist pattern were measured at arbitrary points from the top of the pattern using the scanning electron microscope. The dimensional variation (3 ⁇ ) was determined and defined as the CDU performance (nm). CDU indicates that the smaller the value, the smaller the dispersion of the hole diameter in the long period and the better.
  • the resist pattern using the above negative radiation-sensitive resin composition for ArF exposure was evaluated as described above.
  • the radiation-sensitive resin composition of Example 58 formed a negative resist pattern by ArF exposure. In both cases, sensitivity and CDU performance were good.
  • a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower antireflection film ("ARC66" from Bulwer Science).
  • a lower antireflection film having an average thickness of 105 nm was formed by heating at 205° C. for 60 seconds.
  • the negative type radiation-sensitive resin composition for EUV exposure (J-59) prepared above was applied onto this lower antireflection film using the above spin coater, and PB was performed at 130° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 55 nm was formed.
  • the resist pattern using the negative radiation-sensitive resin composition for EUV exposure was evaluated in the same manner as the resist pattern using the negative radiation-sensitive resin composition for ArF exposure.
  • the radiation-sensitive resin composition of Example 59 exhibited good sensitivity and CDU performance even when a negative resist pattern was formed by EUV exposure.
  • the radiation-sensitive resin composition and the method for forming a resist pattern described above it is possible to form a resist pattern having good sensitivity to exposure light and excellent LWR performance, CDU performance, pattern rectangularity and etching resistance. . Therefore, these materials can be suitably used in the processing of semiconductor devices, which are expected to further miniaturize in the future.

Abstract

L'invention concerne : une composition de résine sensible au rayonnement avec laquelle il est possible de former un film de réserve permettant de présenter des niveaux satisfaisants de sensibilité, de performance de LWR, de performance de CDU, de rectangularité de motif et de résistance à la gravure ; et un procédé de formation de motif. Cette composition de résine sensible aux rayonnements contient un composé de sel d'onium représenté par la formule (1), une résine contenant une unité structurelle ayant un groupe pouvant être dissocié par un acide, et un solvant. (Dans la formule [1], R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un atome de fluor ou un groupe hydrocarboné fluoré monovalent en C1-10. n est un nombre entier de 0 à 3 ; lorsque n est égal à 2 ou plus, la pluralité de R1 et R2 sont identiques ou différents l'un de l'autre. L est un groupe hydrocarboné divalent en C3-40 comprenant une structure cyclique. R3 est un groupe organique monovalent en C1-40 qui ne possède pas de groupe dissociable par un acide. Z+ est un cation onium monovalent sensible aux rayonnements.)
PCT/JP2022/002365 2021-02-10 2022-01-24 Composition de résine sensible au rayonnement et procédé de formation de motif WO2022172736A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023048128A1 (fr) * 2021-09-24 2023-03-30 東京応化工業株式会社 Composition de réserve, procédé de formation de motif de réserve, composé et générateur d'acide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011115138A1 (fr) * 2010-03-17 2011-09-22 Jsr株式会社 Composition de résine sensible aux radiations et procédé de formation d'un motif résistant
WO2015174215A1 (fr) * 2014-05-12 2015-11-19 富士フイルム株式会社 Procédé de formation de motifs, composition de résine sensible aux rayons actiniques ou aux rayonnements, film sensible aux rayons actiniques ou aux rayonnements, procédé de formation de motifs, procédé de production de dispositif électronique, et dispositif électronique
JP2019120729A (ja) * 2017-12-28 2019-07-22 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法、及び化合物
JP2020111564A (ja) * 2019-01-16 2020-07-27 信越化学工業株式会社 新規オニウム塩、化学増幅レジスト組成物、及びパターン形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011115138A1 (fr) * 2010-03-17 2011-09-22 Jsr株式会社 Composition de résine sensible aux radiations et procédé de formation d'un motif résistant
WO2015174215A1 (fr) * 2014-05-12 2015-11-19 富士フイルム株式会社 Procédé de formation de motifs, composition de résine sensible aux rayons actiniques ou aux rayonnements, film sensible aux rayons actiniques ou aux rayonnements, procédé de formation de motifs, procédé de production de dispositif électronique, et dispositif électronique
JP2019120729A (ja) * 2017-12-28 2019-07-22 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法、及び化合物
JP2020111564A (ja) * 2019-01-16 2020-07-27 信越化学工業株式会社 新規オニウム塩、化学増幅レジスト組成物、及びパターン形成方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023048128A1 (fr) * 2021-09-24 2023-03-30 東京応化工業株式会社 Composition de réserve, procédé de formation de motif de réserve, composé et générateur d'acide
JP7466782B2 (ja) 2021-09-24 2024-04-12 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法、化合物及び酸発生剤

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