WO2023120200A1 - Composition sensible aux rayonnements et procédé de formation de motifs - Google Patents

Composition sensible aux rayonnements et procédé de formation de motifs Download PDF

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Publication number
WO2023120200A1
WO2023120200A1 PCT/JP2022/045161 JP2022045161W WO2023120200A1 WO 2023120200 A1 WO2023120200 A1 WO 2023120200A1 JP 2022045161 W JP2022045161 W JP 2022045161W WO 2023120200 A1 WO2023120200 A1 WO 2023120200A1
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group
monovalent
hydrocarbon group
carbon atoms
structural unit
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PCT/JP2022/045161
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English (en)
Japanese (ja)
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龍一 根本
健介 宮尾
希望 坂野
聡司 岡嵜
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Jsr株式会社
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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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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

  • Photolithography technology using resist compositions is used to form fine circuits in semiconductor devices.
  • a film formed from a resist composition hereinafter also referred to as “resist film”
  • resist film is exposed to radiation through a mask pattern.
  • the chemical reaction involving the acid generated by the exposure causes a difference in the dissolution rate in the developer between the exposed and unexposed areas of the resist film, and then the resist film is brought into contact with the developer to form a substrate.
  • a resist pattern is formed thereon.
  • Patent Document 1 discloses a resist composition using an acid-labile group-containing resin having a specific lactone structure in its side chain.
  • the present disclosure has been made in view of the above problems, and provides a radiation-sensitive composition and a pattern forming method that can form a resist film that exhibits good sensitivity and is excellent in LWR performance and pattern rectangularity.
  • the main purpose is to
  • the present inventors found that the above problem could be solved by using a radiation-sensitive composition with a specific composition. Specifically, the present disclosure provides the following means.
  • the present disclosure provides a radiation-sensitive composition containing a polymer having a structural unit represented by formula (1) below and a photodegradable base.
  • R 1 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group
  • X 1 is an alkanediyl group, an oxygen atom or a sulfur atom
  • Y 1 is , a monovalent hydrocarbon group, a monovalent fluorinated hydrocarbon group or a halogen atom.
  • R 2 is a monovalent organic group.
  • B 1 is a single bond or * 1 -COO-. 1 " represents a bond with the carbon atom to which R 1 is bonded.
  • R 3 is a substituted or unsubstituted divalent hydrocarbon group.
  • R 3 is an aromatic is a group hydrocarbon group, and the carbon atom to which R 1 is attached is attached to the aromatic hydrocarbon ring in R 3.
  • Z 1 is a single bond, —O—, —COO—, —OCO—, — OCOO-, -CONR 4 -, -NR 4 CO-, -OCONR 4 -, -NR 4 COO- or -NR 4 CONR 5 - R 4 and R 5 each independently represent a hydrogen atom or 1 is a valent hydrocarbon group, m is an integer of 0 to 5. n is an integer of 1 to 5. When m is 2 or more, a plurality of R 2 are the same or different, when n is 2 or more , multiple R 3 are the same or different, and multiple Z 1 are the same or different.)
  • the steps of coating the radiation-sensitive composition on a substrate to form a resist film, exposing the resist film, and developing the exposed resist film and a step of forming a pattern are sequential steps of coating the radiation-sensitive composition on a substrate to form a resist film, exposing the resist film, and developing the exposed resist film and a step of forming a pattern.
  • a radiation-sensitive composition containing a polymer having a structural unit represented by the above formula (1) and a photodegradable base exhibits high sensitivity and excellent LWR performance. And pattern rectangularity can be expressed.
  • the radiation-sensitive composition of the present disclosure (hereinafter also referred to as “the present composition”) comprises a polymer having a specific structural unit containing a lactone structure (hereinafter also referred to as “[A] polymer”) and photodegradation and a volatile base.
  • the present composition may contain other optional components within a range that does not impair the effects of the present disclosure. Each component will be described in detail below.
  • hydrocarbon group includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • a “chain hydrocarbon group” means a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure and is composed only of a chain structure. However, the chain hydrocarbon group may be saturated or unsaturated.
  • the “alicyclic hydrocarbon group” means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, the alicyclic hydrocarbon group does not have to consist only of an alicyclic hydrocarbon structure, and may partially have a chain structure.
  • aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, the aromatic hydrocarbon group does not need to consist only of an aromatic ring structure, and may partially contain a chain structure or an alicyclic hydrocarbon structure.
  • An “organic group” refers to an atomic group obtained by removing an arbitrary hydrogen atom from a compound containing carbon (ie, an organic compound).
  • Alicyclic polycyclic hydrocarbon includes bridged alicyclic hydrocarbons, fused alicyclic hydrocarbons, and spirocyclic hydrocarbons.
  • (Meth)acryl is a term that includes "acryl” and "methacryl”.
  • the [A] polymer is a polymer having a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (M)”).
  • R 1 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group
  • X 1 is an alkanediyl group, an oxygen atom or a sulfur atom
  • Y 1 is , a monovalent hydrocarbon group, a monovalent fluorinated hydrocarbon group or a halogen atom.
  • R 2 is a monovalent organic group.
  • B 1 is a single bond or * 1 -COO-.
  • R 3 represents a bond with the carbon atom to which R 1 is bonded.
  • R 3 is a substituted or unsubstituted divalent hydrocarbon group.
  • B 1 is a single bond
  • R 3 is an aromatic is a group hydrocarbon group, and the carbon atom to which R 1 is attached is attached to the aromatic hydrocarbon ring in R 3.
  • Z 1 is a single bond, —O—, —COO—, —OCO—, — OCOO-, -CONR 4 -, -NR 4 CO-, -OCONR 4 -, -NR 4 COO- or -NR 4 CONR 5 - R 4 and R 5 each independently represent a hydrogen atom or 1 is a valent hydrocarbon group, m is an integer of 0 to 5. n is an integer of 1 to 5. When m is 2 or more, a plurality of R 2 are the same or different, when n is 2 or more , multiple R 3 are the same or different, and multiple Z 1 are the same or different.)
  • the difference in the dissolution rate in the developer between the exposed area and the unexposed area in the resist film formed from the composition is increased. It is possible. More specifically, in positive development using an alkaline developer in the development process, the solubility of the exposed area in the developer is increased by improving the reactivity between the exposed area and the developer, while the unexposed area is transferred to the developer. It is considered that the solubility of the compound can be sufficiently lowered, and as a result, the etching resistance of the unexposed portion can be increased.
  • the solubility of the unexposed area in the developer is increased by improving the reactivity between the unexposed area and the developer, while the solubility of the exposed area in the developer is increased. It is considered that the etching resistance of the exposed portion was increased because of the sufficiently low value.
  • R 1 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the structural unit (M).
  • B 1 is * 1 -COO-, a methyl group is more preferred.
  • the alkanediyl group represented by X 1 preferably has 1 to 3 carbon atoms.
  • X 1 is preferably a methylene group, an ethylene group, an oxygen atom or a sulfur atom, more preferably a methylene group or an oxygen atom.
  • the monovalent hydrocarbon group represented by Y 1 includes, for example, a monovalent linear hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a 6 to 12 monovalent aromatic hydrocarbon groups and the like are included.
  • the monovalent chain hydrocarbon group having 1 to 10 carbon atoms represented by Y 1 includes a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms and a linear chain having 1 to 10 carbon atoms.
  • a straight or branched unsaturated hydrocarbon group can be mentioned.
  • a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, a linear or branched saturated hydrocarbon group having 1 to 5 carbon atoms is more preferable, and a methyl group or an ethyl group is more preferred.
  • the monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms represented by Y 1 is a saturated alicyclic hydrocarbon having 3 to 12 carbon atoms or an unsaturated alicyclic hydrocarbon having one hydrogen atom. groups excepted. Among these, cycloalkyl groups having 3 to 12 carbon atoms are preferred. Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y 1 include a phenyl group, a methylphenyl group, a benzyl group, a naphthyl group and the like.
  • Examples of the monovalent fluorinated hydrocarbon group include groups in which any hydrogen atom in the group exemplified as the monovalent hydrocarbon group represented by Y1 is substituted with a fluorine atom.
  • Halogen atoms include fluorine, chlorine, bromine and iodine atoms, with fluorine atoms being preferred.
  • Structural unit (M) has a spacer portion represented by "-R 3 -Z 1 -", so that one of the exposed area and the unexposed area (that is, in the case of positive development, the exposed area, the negative In the case of mold development, penetration of the developing solution into the unexposed area is accelerated, increasing the solubility.
  • the structural unit (M) has the spacer portion, so that the solubility of the other (that is, the unexposed area in the case of positive development and the exposed area in the case of negative development) in the developer is increased. By suppressing it, the etching resistance of the resist film is enhanced.
  • Y 1 is preferably an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms or a fluorine atom, and an alkyl group having 1 to 5 carbon atoms or a fluoro
  • An alkyl group or a fluorine atom is more preferred, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms or a fluorine atom is more preferred, and an alkyl group or fluoroalkyl group having 1 to 3 carbon atoms is even more preferred. .
  • Monovalent organic groups represented by R 2 include monovalent hydrocarbon groups, monovalent fluorinated hydrocarbon groups, halogen atoms, alkoxy groups, ester groups and the like.
  • specific examples of the monovalent hydrocarbon group, the monovalent fluorinated hydrocarbon group and the halogen atom include the groups exemplified as the specific examples of Y1 .
  • the alkoxy group preferably has 1 to 10 carbon atoms, and examples thereof include methoxy and ethoxy groups.
  • the group substituting the hydrogen atom of the carboxy group is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • ester groups include alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, and phenyloxycarbonyl groups.
  • m is 1 or more, the position of R2 in the ring structure is not particularly limited.
  • m is preferably 0 or 1, more preferably 0, from the viewpoint of achieving both the etching resistance of the resist film and good LWR performance and pattern rectangularity.
  • R 4 and R 5 are preferably an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group or a phenyl group.
  • Z 1 is -O-, -COO-, -OCO-, -OCOO-, -CONR 4 -, -NR 4 CO-, -OCONR 4 -, -NR 4 COO- or -NR 4 CONR 5 - is preferred, and -O-, -COO-, -OCO-, -OCOO-, -CONR 4 -, -NR 4 CO-, -OCONR 4 - or -NR 4 COO- is more preferred, and -COO-, -OCO-, -OCOO-, -CONR 4 - or -NR 4 CO- is even more preferred.
  • Examples of the divalent hydrocarbon group represented by R 3 include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a divalent hydrocarbon group having 3 to 20 carbon atoms. 6 to 20 divalent aromatic hydrocarbon groups and the like.
  • R3 is an aromatic hydrocarbon group, and the carbon atom to which R1 is bonded is bonded to the aromatic hydrocarbon ring in R3 .
  • the divalent chain hydrocarbon group having 1 to 20 carbon atoms represented by R 3 includes a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms and a saturated divalent hydrocarbon group having 2 to 20 carbon atoms. linear or branched divalent unsaturated hydrocarbon groups, and the like. Among these, a linear or branched divalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferred, and a linear or branched divalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred. .
  • the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 3 includes a monocyclic saturated alicyclic hydrocarbon or unsaturated alicyclic hydrocarbon having 3 to 20 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • a group obtained by removing any two hydrogen atoms from a cyclic polycyclic hydrocarbon can be mentioned.
  • these alicyclic hydrocarbons include monocyclic saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; monocyclic unsaturated alicyclic hydrocarbons such as cyclopentene, Cyclohexene, cycloheptene, cyclooctene, cyclodecene, etc.; .1 3,7 ]decane (adamantane) and the like can be mentioned, respectively.
  • monocyclic saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane
  • monocyclic unsaturated alicyclic hydrocarbons such as cyclopentene, Cyclohexene, cycloheptene, cyclooctene, cyclodecene, etc.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 3 include groups obtained by removing any two hydrogen atoms from an aromatic ring such as benzene, naphthalene, anthracene, indene and fluorene. .
  • R 3 is a substituted hydrocarbon group
  • substituents that R 3 has include an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a halogen atom, and the like.
  • R 3 is, among others, an alkanediyl group having 1 to 10 carbon atoms, cycloalkanediyl group, bicyclo[2.2.1]heptanediyl group, bicyclo[2.2.2]octanediyl group, tricyclo[3.3.1.1 3,7 ]decanediyl group, or phenylene group is preferred.
  • n is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, in that the solubility in the developer can be improved while suppressing the decrease in etching resistance.
  • Preferred specific examples of the structural unit (M) include structural units represented by the following formula (1-1) when B 1 is * 1 -COO-. Further, examples of the case where B 1 is a single bond include structural units represented by the following formula (1-2). (In formulas (1-1) and (1-2), R 1 , R 2 , R 3 , X 1 , Y 1 , Z 1 , m and n are the same as defined in formula (1) above. )
  • Examples of structural units (M) include structural units represented by the following formula.
  • R 1 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group.
  • the content of the structural unit (M) is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 25 mol% or more, relative to the total structural units constituting the [A] polymer.
  • the content of the structural unit (M) is preferably 90 mol% or less, more preferably 70 mol% or less, and even more preferably 65 mol% or less, relative to the total structural units constituting the [A] polymer.
  • the polymer may further contain a structural unit (hereinafter also referred to as "another structural unit”) different from the structural unit (M) together with the structural unit (M).
  • Other structural units include, for example, the following structural units (I) to (III).
  • the polymer preferably further contains a structural unit (I) having an acid-labile group.
  • the acid-dissociable group is a group that substitutes a hydrogen atom of an acid group (for example, a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfo group, etc.) and is dissociated by the action of an acid.
  • the acid-dissociable group Since the polymer has an acid-dissociable group, the acid-dissociable group is dissociated by a chemical reaction involving the acid generated by exposure to generate an acid group, and the [A] polymer dissolves in the developer. You can change your gender. As a result, the present composition can be endowed with good lithographic properties.
  • Structural unit (I) is not particularly limited as long as it contains an acid-labile group.
  • the structural unit (I) include a structural unit having a tertiary alkyl ester moiety, a structural unit having a structure in which the hydrogen atom of a phenolic hydroxyl group is substituted with a tertiary alkyl group, a structural unit having an acetal bond, and the like. is mentioned.
  • Structural unit (I) is preferably a structural unit having a tertiary alkyl ester moiety from the viewpoint of enhancing the pattern formability of the present composition. (hereinafter also referred to as “structural unit (I-1)”) is preferred.
  • R 11 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group.
  • R 12 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 13 and R 14 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 R 13 and R 14 represents a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms combined with the carbon atoms to which R 13 and R 14 are bonded.
  • R 11 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).
  • the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 12 includes a monovalent linear 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.
  • Examples of monovalent chain hydrocarbon groups having 1 to 10 carbon atoms represented by R 12 to R 14 include linear or branched saturated hydrocarbon groups having 1 to 10 carbon atoms and saturated hydrocarbon groups having 1 to 10 carbon atoms. linear or branched unsaturated hydrocarbon groups. Among these, linear or branched saturated hydrocarbon groups having 1 to 10 carbon atoms are preferred.
  • the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 12 to R 14 includes a saturated alicyclic hydrocarbon having 3 to 20 carbon atoms, an unsaturated alicyclic hydrocarbon or an alicyclic A group obtained by removing one hydrogen atom from a formula polycyclic hydrocarbon can be mentioned.
  • Specific examples of these alicyclic hydrocarbons include monocyclic saturated alicyclic hydrocarbons, monocyclic unsaturated alicyclic hydrocarbons and alicyclic Polycyclic hydrocarbons are mentioned.
  • Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R 12 include groups obtained by removing one hydrogen atom from an aromatic ring such as benzene, naphthalene, anthracene, indene and fluorene.
  • R 12 is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms from the viewpoint of sufficiently removing the development residue and from the viewpoint of increasing the dissolution contrast difference between the exposed area and the unexposed area in the developer, A linear or branched monovalent saturated hydrocarbon group having 1 to 8 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 8 carbon atoms is more preferable.
  • a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms in which R 13 and R 14 are combined and formed together with the carbon atoms to which R 13 and R 14 are bonded is a monocyclic or polycyclic hydrocarbon group having the above carbon number.
  • a group obtained by removing two hydrogen atoms from the same carbon atom constituting an alicyclic hydrocarbon can be mentioned.
  • the divalent alicyclic hydrocarbon group formed by combining R 13 and R 14 may be either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group.
  • the divalent alicyclic hydrocarbon group is a polycyclic hydrocarbon group
  • the polycyclic hydrocarbon group may be either a bridged alicyclic hydrocarbon group or a condensed alicyclic hydrocarbon group, Also, it may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • bridged alicyclic hydrocarbon means a polycyclic ring in which two carbon atoms that are not adjacent to each other among the carbon atoms that constitute an aliphatic ring are linked by a linking chain containing one or more carbon atoms.
  • cycloaliphatic hydrocarbons refers to a polycyclic alicyclic hydrocarbon composed of a plurality of alicyclic rings sharing a side (a bond between two adjacent carbon atoms).
  • the saturated hydrocarbon group is a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group or a cyclooctanediyl group.
  • the unsaturated hydrocarbon group is preferably a cyclopentenediyl group, a cyclohexenediyl group, a cycloheptenediyl group or a cyclooctenediyl group.
  • the polycyclic alicyclic hydrocarbon group is preferably a bridged alicyclic saturated hydrocarbon group, bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl group), a bicyclo[2.2.2]octane-2,2-diyl group or a tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group) preferable.
  • R 13 and R 14 are a monovalent chain hydrocarbon group having 1 to 8 carbon atoms or a monovalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms? , or R 13 and R 14 are preferably combined to represent a C 3-12 divalent alicyclic hydrocarbon group composed together with the carbon atoms to which R 13 and R 14 are attached.
  • R 13 and R 14 are, above all, a monovalent linear hydrocarbon group having 1 to 8 carbon atoms or a monovalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, or R 13 and R It is preferred that 14 represents a divalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms combined with the carbon atoms to which R 13 and R 14 are attached.
  • Structural unit (I-1) has the following formula (2A) in that the difference in solubility in a developer between the exposed area and the unexposed area can be increased and a finer pattern can be formed. It is particularly preferred to contain a structural unit represented by (In formula (2A), R 11 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group. R 15 is a monovalent hydrocarbon group having 1 to 8 carbon atoms.
  • R 16 and R 17 are each independently a monovalent chain hydrocarbon group having 1 to 8 carbon atoms or a monovalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, or R 16 and R 17 together represent a divalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms formed together with the carbon atoms to which R 16 and R 17 are bonded.
  • R 11 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 represented by formula (2A).
  • R 15 , R 16 and R 17 examples of the corresponding carbon numbers described for R 12 , R 13 and R 14 in formula (2) above can be adopted.
  • R 15 is preferably a linear or branched monovalent saturated chain hydrocarbon group having 1 to 5 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, A linear or branched monovalent saturated chain hydrocarbon group having 1 to 3 carbon atoms or a monovalent monocyclic aliphatic hydrocarbon group having 3 to 5 carbon atoms is more preferable.
  • R 16 and R 17 are linear or branched monovalent chain saturated hydrocarbon groups having 1 to 4 carbon atoms, or R 16 and R 17 are combined with each other and R 16 and R 17 are bonded preferably represents a divalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms composed together with the carbon atoms.
  • R 15 is an alkyl group having 1 to 4 carbon atoms
  • R 16 and R 17 are R 16 and R 17 are preferably a C 3-6 cycloalkanediyl group composed together with the carbon atoms to which they are attached.
  • structural unit (I) examples include structural units represented by the following formulas (2-1) to (2-6).
  • R 11 to R 14 have the same definitions as in formula (2) above.
  • i and j are each independently an integer of 0 to 4.
  • h and g are each independently 0 or 1.
  • i and j are preferably 1 or 2, more preferably 1.
  • R 12 is preferably a methyl group, an ethyl group or an isopropyl group.
  • R 13 and R 14 are preferably a methyl group or an ethyl group.
  • Structural unit (I) is preferably a structural unit represented by formula (2-1) or formula (2-4) among formulas (2-1) to (2-6), and in formula (2-1) Structural units represented are more preferred.
  • the content of the structural unit (I) is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and 35 mol, based on the total structural units constituting the [A] polymer. % or more is even more preferable.
  • the content of the structural unit (I) is preferably 80 mol% or less, more preferably 75 mol% or less, even more preferably 70 mol% or less, relative to the total structural units constituting the [A] polymer. 65 mol % or less is even more preferable.
  • the content ratio of the structural unit represented by the above formula (2A) constitutes the [A] polymer 5 mol % or more is preferable, 10 mol % or more is more preferable, and 20 mol % or more is still more preferable with respect to the total structural units.
  • the polymer may further contain a structural unit having a polar group (excluding structural unit (M); hereinafter also referred to as "structural unit (II)").
  • structural unit (II) By including the structural unit (II) in the polymer, the solubility in a developer can be more easily adjusted, and lithography performance such as resolution can be improved.
  • the 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, and is different from the structural unit (M) (hereinafter referred to as “structural unit (II-1)”), and a structural unit having a monovalent polar group (hereinafter also referred to as “structural unit (II-2)”).
  • ⁇ Structural unit (II-1) By introducing the structural unit (II-1) into the [A] polymer, the solubility of the [A] polymer in the developer is adjusted, the adhesion of the resist film is improved, and the etching resistance is further improved. It is possible to let Examples of the structural unit (II-1) include structural units represented by the following formulas (3-1) to (3-9). (In formulas (3-1) to (3-9), R L1 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group.
  • R L2 and R L3 are each independently is 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
  • R L4 and R L5 are each independently 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
  • R L4 and R L5 is a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms combined with the carbon atoms to which R 1 L4 and R 2 L5 are bonded, L 2 is a single bond or a divalent linking group
  • X is an oxygen atom or a methylene group
  • the divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms in which R L4 and R L5 are combined and formed together with the carbon atoms to which R L4 and R L5 are bonded is R 13 in the above formula (2) and the description of R 14 includes groups having 3 to 8 carbon atoms.
  • One or more hydrogen atoms on this alicyclic hydrocarbon group may be replaced with a hydroxy group.
  • the divalent linking group represented by L 2 includes, for example, a linear or branched divalent chain hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic group having 4 to 12 carbon atoms, Examples include a hydrocarbon 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—.
  • Structural unit (II-1) is preferably a structural unit represented by formula (3-2) or formula (3-7) among formulas (3-1) to (3-9), and formula (3-2 ) is more preferred.
  • the content of the structural unit (II-1) is preferably 30 mol% or less with respect to the total structural units constituting the [A] polymer. , is more preferably 25 mol % or less, and even more preferably 20 mol % or less.
  • the polar group possessed by the structural unit (II-2) includes, for example, 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 preferable, and a hydroxy group (especially an alcoholic hydroxyl group) is more preferable.
  • the structural unit (II-2) is a structural unit different from the structural unit having a phenolic hydroxyl group (structural unit (III)) described below.
  • phenolic hydroxyl group refers to a group in which a hydroxyl group is directly bonded to an aromatic hydrocarbon structure.
  • Alcoholic hydroxyl group refers to a group in which a hydroxyl group is directly bonded to an aliphatic hydrocarbon structure.
  • the aliphatic hydrocarbon structure to which the hydroxyl group is bonded may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
  • Examples of the structural unit (II-2) include structural units represented by the following formula. However, the structural unit (II-2) is not limited to these.
  • RA is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group.
  • the content of the structural unit (II-2) is preferably 2 mol% or more with respect to the total structural units constituting the [A] polymer. , more preferably 5 mol % or more.
  • the content of the structural unit (II-2) is preferably 30 mol% or less, more preferably 25 mol% or less, and further preferably 20 mol% or less, relative to the total structural units constituting the [A] polymer. preferable.
  • the polymer may further have a structural unit having a phenolic hydroxyl group (hereinafter also referred to as "structural unit (III)").
  • structural unit (III) By having the structural unit (III) in the polymer, it is possible to improve the etching resistance and the difference in developer solubility (dissolution contrast) between the exposed area and the unexposed area. point is preferable.
  • the [A] polymer having the structural unit (III) can be preferably used.
  • the polymer [A] preferably has the structural unit (I) together with the structural unit (M) and the structural unit (III).
  • Structural unit (III) is not particularly limited as long as it contains a phenolic hydroxyl group.
  • Specific examples of the structural unit (III) include structural units derived from hydroxystyrene or derivatives thereof, structural units derived from (meth)acrylic compounds having a hydroxybenzene structure, and the like.
  • R P1 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or an alkoxyalkyl group
  • R P2 is 1 having 1 to 20 carbon atoms; valent hydrocarbon group or alkoxy group.
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 2 P2 include the groups exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms for R 12 in structural unit (I).
  • Alkoxy groups include, for example, methoxy, ethoxy and tert-butoxy groups.
  • R P2 is preferably an alkyl group or an alkoxy group, and more preferably a methyl group or a tert-butoxy group.
  • the content of the structural unit (III) in the [A] polymer is 10 per all structural units constituting the [A] polymer. mol % or more is preferable, and 15 mol % or more is more preferable.
  • the content of the structural unit (III) in the [A] polymer is preferably 60 mol % or less, more preferably 50 mol % or less, relative to all structural units constituting the [A] polymer.
  • the polymer can be synthesized, for example, by polymerizing monomers that give each structural unit using a known radical polymerization initiator or the like in an appropriate solvent.
  • the polystyrene equivalent weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more. ,000 or more is even more preferred.
  • the Mw of the [A] polymer is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the ratio (Mw/Mn) of Mw to the polystyrene equivalent number average molecular weight (Mn) by GPC of the polymer is preferably 5.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. Also, Mw/Mn is usually 1 or more. In addition, below, Mw/Mn is also called "dispersion degree.”
  • the content of the [A] polymer is 70% by mass with respect to the total amount of solids contained in the composition (that is, the total mass of components other than the solvent component contained in the composition).
  • the above is preferable, 75% by mass or more is more preferable, and 80% by mass or more is even more preferable.
  • the content of the [A] polymer is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less, relative to the total amount of solids contained in the present composition.
  • the [A] polymer usually constitutes the base resin of the present composition.
  • the term "base resin" refers to a polymer component that accounts for 50% by mass or more of the total solid content of the composition.
  • the present composition may contain only one type of [A] polymer, or may contain two or more types.
  • the photodisintegrating base is a component that has the function of suppressing the chemical reaction caused by the acid in the unexposed area by suppressing the diffusion of the acid generated in the resist film by exposure in the resist film. Since the present composition contains a photodegradable base together with the [A] polymer, it is possible to obtain a resist film having excellent LWR performance and pattern rectangularity while exhibiting high sensitivity.
  • a photodegradable base is a compound that generates an acid when exposed to radiation.
  • the acid generated by the photodisintegrating base is an acid that does not induce dissociation of the acid-labile group under ordinary conditions.
  • normal conditions used herein refers to conditions for post-exposure baking (PEB) at 110° C. for 60 seconds.
  • PEB post-exposure baking
  • an onium salt that generates carboxylic acid, sulfonic acid or sulfonamide upon exposure to radiation can be preferably used.
  • the photodegradable base When the present composition contains a radiation-sensitive acid generator together with a photodegradable base as a compound that generates an acid upon exposure to radiation, the photodegradable base is stronger than the acid generated by the radiation-sensitive acid generator upon exposure. It is a component that generates a weak acid.
  • the degree of acidity can be evaluated by the acid dissociation constant (pKa).
  • the acid dissociation constant (pKa) of the acid generated by the photodisintegrating base is preferably ⁇ 3 or more, more preferably ⁇ 1 ⁇ pKa ⁇ 7, and still more preferably 0 ⁇ pKa ⁇ 5.
  • Photodegradable bases have basicity in unexposed areas and exhibit an acid diffusion inhibitory action. Inhibitory action is reduced. Therefore, in the resist film containing the photodegradable base, the generated acid works efficiently to dissociate the acid dissociable groups in the resist film in the exposed area. On the other hand, in the unexposed area, the components in the resist film do not change depending on the acid. Thereby, the difference in solubility between the exposed area and the unexposed area appears more clearly.
  • the combination of the function of such a photodegradable base and the inclusion of the [A] polymer enables the formation of a resist film having excellent LWR performance and pattern rectangularity while exhibiting high sensitivity. can.
  • an onium salt having a sulfonium cation structure or an iodonium cation structure can be preferably used in that a resist film having higher LWR performance can be formed while maintaining high sensitivity of the present composition.
  • Specific examples of the photodisintegrating base include a compound represented by the following formula (5-1-1), a compound represented by the following formula (5-1-2), and a compound represented by the following formula (5-2-1). At least one selected from the group consisting of the compounds represented by the following formula (5-2-2) and the compounds represented by the following formula (5-2-2) can be preferably used.
  • J + is a sulfonium cation.
  • E - is OH - , R ⁇ -COO - , R ⁇ -SO 3 - or R ⁇ -N - (SO 2 R f2 ) is an anion represented by R ⁇ is a monovalent hydrocarbon group, or any methylene group in the monovalent hydrocarbon group is —O—, —CO—, —COO—, —O—CO a monovalent group substituted with —O—, —S—, —SO 2 — or —CONR ⁇ — (hereinafter also referred to as “group F A ”), or a monovalent hydrocarbon group or A monovalent group in which any hydrogen atom of the group F A is replaced with a halogen atom or a hydroxyl group, R ⁇ is a hydrogen atom or a monovalent hydrocarbon group, and R f2 is a perfluoroalkyl group.
  • J' + is a group having a sulfonium cation structure.
  • E' - is * 2 -COO - , * 2 -SO 3 - or * 2 -N - (SO 2 R f2 ), “* 2 ” represents a bond, R f2 is a perfluoroalkyl group, and R 31 is a single bond, a divalent hydrocarbon group, or a divalent hydrocarbon group.
  • group F B a divalent group in which any methylene group in a hydrogen group is replaced with -O-, -CO-, -COO-, -O-CO-O-, -S-, -SO 2 - or -CONR ⁇ - (hereinafter also referred to as “group F B ”), or a divalent group in which any hydrogen atom of a divalent hydrocarbon group or group F B is replaced with a halogen atom or a hydroxyl group.
  • ⁇ is a hydrogen atom or a monovalent hydrocarbon group.
  • Q ⁇ is OH ⁇ , R ⁇ —COO ⁇ , R ⁇ —SO 3 — , or R ⁇ —N — (SO 2 R f2 )
  • Each R ⁇ is independently a monovalent hydrocarbon group, or any methylene group in the monovalent hydrocarbon group is —O—, —CO—, —COO— , —O—CO—O—, —S—, —SO 2 — or —CONR ⁇ —, or a monovalent hydrocarbon group or group
  • F A is a monovalent group in which an arbitrary hydrogen atom is replaced with a halogen atom or a hydroxyl group
  • R ⁇ is a hydrogen atom or a monovalent hydrocarbon group
  • R f2 is a perfluoroalkyl group.
  • U' + is a group having an iodonium cation structure.
  • Q'- is * 2 -COO - , * 2 -SO 3 - or * 2 -N - (SO 2 R f2 ), “* 2 ” represents a bond, R f2 is a perfluoroalkyl group, and R 32 is a single bond, a divalent hydrocarbon group, or a divalent hydrocarbon group.
  • monovalent hydrocarbon groups include monovalent linear hydrocarbon groups having 1 to 10 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and monovalent hydrocarbon groups having 6 to 20 carbon atoms. and the like. Specific examples thereof include the groups exemplified as the monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 12 in the above formula (2). Specific examples of the monovalent hydrocarbon group represented by R ⁇ include the groups exemplified as the monovalent hydrocarbon groups represented by R 4 and R 5 in the above formula (1).
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom or an iodine atom is preferred.
  • the perfluoroalkyl group represented by R f2 includes, for example, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a heptafluoro n-propyl group, a heptafluoro i -propyl group, nonafluoro n-butyl group, nonafluoro i-butyl group, nonafluoro t-butyl group and the like.
  • anions represented by E ⁇ or Q ⁇ include structures represented by the following formulas. However, it is not limited to these specific examples.
  • R 21 and R 22 are each independently an alkyl group having 1 to 20 carbon atoms.
  • the sulfonium cation represented by J + is represented by the following formula (X-1), formula (X-2), formula (X-3) or formula (X-4) and sulfonium cations represented.
  • the iodonium cation represented by U + includes iodonium cations represented by the following formula (X-5) or (X-6).
  • R a1 , R a2 and R a3 are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkoxy group or an alkoxycarbonyloxy group having 3 to 12 carbon atoms.
  • the ring structure may contain a heteroatom (oxygen atom, sulfur atom, etc.) between the carbon-carbon bonds forming the skeleton.
  • R P , R Q and R T are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • k1, k2 and k3 are each independently an integer from 0 to 5;
  • R a1 to R a3 and R P , R Q and R T is plural, each of R a1 to R a3 and R P , R Q and R T is the same or different.
  • R b1 is a substituted or unsubstituted alkyl group or alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 2 to 8 carbon atoms, or a substituted or unsubstituted carbon It is a monovalent aromatic hydrocarbon group of number 6-8, a halogen atom or a hydroxy group.
  • nk is 0 or 1; When nk is 0, k4 is an integer of 0-5, 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 alkyl group or a substituted or unsubstituted C 6 or 7 monovalent 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 (oxygen atom, sulfur atom, etc.) between the carbon-carbon bonds forming the skeleton.
  • R c1 , R c2 and R c3 are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.
  • R g1 is a substituted or unsubstituted alkyl or alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acyl group having 2 to 8 carbon atoms, or a substituted or unsubstituted carbon It is an aromatic hydrocarbon group of number 6-8 or a hydroxy group.
  • nk2 is 0 or 1; When nk2 is 0, k10 is an integer of 0-5, and when nk2 is 1, k10 is an integer of 0-7.
  • 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 alkyl group having 1 to 12 carbon atoms, an alkoxy group or an alkoxycarbonyloxy group, or a substituted or unsubstituted monocyclic or polycyclic ring having 3 to 12 carbon atoms.
  • R g2 and R g3 are each independently an integer of 0-4.
  • R g2 and R g3 are plural, the plural R g2 and R g3 are the same or different.
  • R d1 and R d2 are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkoxy group or an alkoxycarbonyl group, a substituted or unsubstituted C 6 to 12 aromatic hydrocarbon groups, halogen atoms, halogenated alkyl groups having 1 to 4 carbon atoms, nitro groups, or a ring structure formed by combining two or more of these groups.
  • 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 are the same or different.
  • R e1 and R e2 are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms. is a group hydrocarbon group.
  • k8 and k9 are each independently an integer of 0-4.
  • perfluoroalkyl group represented by R f2 in E'- in formula (5-1-2) and Q'- in formula (5-2-2) are those represented by formula (5-1 -1) and the groups exemplified as R f2 in formula (5-2-1).
  • divalent hydrocarbon group represented by R 31 in formula (5-1-2) and R 32 in formula (5-2-2) a monovalent hydrocarbon group represented by R ⁇ A group obtained by removing one hydrogen atom from the group exemplified as is mentioned.
  • the halogen atom is preferably a fluorine atom or an iodine atom.
  • Specific examples of the group represented by “-J′ + ” in formula (5-1-2) include sulfonium cations represented by the above formulas (X-1) to (X-4). A group obtained by removing one hydrogen atom can be mentioned.
  • Specific examples of the group represented by “-U′ + ” in formula (5-2-2) include iodonium cations represented by the above formulas (X-5) and (X-6). A group obtained by removing one hydrogen atom can be mentioned.
  • photodisintegrating bases include compounds represented by the following formulas. However, it is not limited to these compounds.
  • the photodisintegrating base used in the preparation of the present composition is preferably a sulfonium salt, more preferably a triarylsulfonium salt.
  • 1 type can be used individually or in combination of 2 or more types.
  • the content of the photodegradable base in the present composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more with respect to 100 parts by mass of the [A] polymer.
  • the content of the photodisintegrating base is preferably 20 parts by mass or less, more preferably 17 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of the [A] polymer.
  • compositions may contain include radiation-sensitive acid generators, solvents, and high fluorine content polymers.
  • the radiation-sensitive acid generator (hereinafter also simply referred to as "acid generator”) is a substance that generates acid when the present composition is exposed to light. However, the acid generator is a component different from the photodegradable base.
  • the acid generator is typically an onium salt containing a radiation-sensitive onium cation and an organic anion, and is an acid stronger than the acid generated by the photodegradable base upon exposure (preferably sulfonic acid, A strong acid such as imide acid or methide acid) is generated to induce dissociation of the acid dissociable group under the usual conditions described above.
  • An acid generator is added to the present composition together with a polymer, and the acid generated by the acid generator eliminates the acid-dissociable groups in the polymer component to generate acid groups, thereby forming the polymer. It is preferred to vary the solubility of the components in the developer.
  • the acid generator to be contained in the present composition is not particularly limited, and known radiation-sensitive acid generators used in resist pattern formation can be used.
  • the radiation-sensitive acid generators to be blended in the present composition compounds represented by the following formula (6) are preferred.
  • W 1 is a monovalent cyclic organic group having 3 to 20 carbon atoms.
  • L 1 is a single bond or a divalent linking group.
  • R 7 , R 8 and R 9 are , each independently a hydrogen atom, a fluorine atom or a fluoroalkyl group, R f is a fluorine atom or a fluoroalkyl group, a is an integer of 0 to 8, and X + is a monovalent cation. .
  • the monovalent cyclic organic group having 3 to 20 carbon atoms represented by W 1 is particularly limited as long as it is a group obtained by removing one hydrogen atom from a cyclic structure having 3 to 20 carbon atoms. not.
  • the cyclic structure include an alicyclic hydrocarbon structure having 3 to 20 carbon atoms, an aliphatic heterocyclic structure having 3 to 20 carbon atoms, and an aromatic ring structure having 6 to 20 carbon atoms. These cyclic structures may have substituents.
  • substituents include an alkoxy group, an alkoxycarbonyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, a cyano group, and the like.
  • the alicyclic hydrocarbon structure having 3 to 20 carbon atoms includes 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.
  • saturated hydrocarbon structures include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like.
  • unsaturated hydrocarbon structures among alicyclic monocyclic structures include cyclopentene, cyclohexene, cycloheptene, cyclooctene and cyclodecene.
  • bridged alicyclic hydrocarbons among alicyclic polycyclic structures include bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane, tricyclo[3.3. 1.1 3,7 ]decane (adamantane), tetracyclo[6.2.1.1 3,6 . 0 2,7 ]dodecane and the like.
  • condensed alicyclic hydrocarbons include decahydronaphthalene and octahydronaphthalene.
  • the alicyclic polycyclic structure is preferably a bridged alicyclic saturated hydrocarbon structure, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane or tricyclo[3.3.1.1 3, 7 ] Decane is preferred.
  • Examples of aliphatic heterocyclic structures having 3 to 20 carbon atoms include cyclic ether structures, lactone structures, cyclic carbonate structures, sultone structures, and thioxane structures.
  • the aliphatic heterocyclic ring structure may be either a monocyclic structure or a polycyclic structure, and may be any of a bridged structure, a condensed ring structure and a spiro ring structure.
  • the aliphatic heterocyclic ring structure having 3 to 20 carbon atoms represented by W 1 may be a combination of two or more of a bridged structure, a condensed ring structure and a spiro ring structure.
  • a “spiro ring structure” refers to a polycyclic ring structure composed of two rings sharing one atom.
  • aromatic ring structures having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, indene, and fluorene.
  • W 1 is preferably a monovalent group having an alicyclic hydrocarbon structure or an aliphatic heterocyclic ring structure, having a bridged alicyclic saturated hydrocarbon structure or a bridged aliphatic heterocyclic ring structure It is more preferable to have Moreover, W1 preferably does not have a fluorine atom from the viewpoint of sensitivity.
  • the divalent linking group represented by L 1 is -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -S-, -SO 2 -, -CONH- or -NHCO- is preferred.
  • fluoroalkyl groups represented by R 7 , R 8 , R 9 and R f 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-diethylpentyl group and the like.
  • the fluoroalkyl group represented by R 7 , R 8 , R 9 and R f is
  • R 7 , R 8 , R 9 and R f are preferably a fluorine atom or a trifluoromethyl group in terms of better sensitivity.
  • a is preferably 0 to 5, more preferably 0 to 2.
  • anion possessed by the compound represented by formula (6) include anions represented by the following formula.
  • X + is a monovalent cation.
  • the monovalent cations represented by X + are preferably monovalent radiation-sensitive onium cations, for example S, I, O, N, P, Cl, Br, F, As, Se, Sn, Sb , Te, Bi, and other radiolytic onium cations.
  • radiolytic onium cations containing such elements include sulfonium cations, tetrahydrothiophenium cations, iodonium cations, phosphonium cations, diazonium cations and pyridinium cations.
  • X + is preferably a sulfonium cation or an iodonium cation, and specifically, preferably a cation represented by each of the above formulas (X-1) to (X-6).
  • Specific examples of the compound represented by the above formula (6) include any one of the specific examples of the anion in the above formula (6), and a monovalent compound represented by X + Specific examples of the cation include onium salt compounds obtained by combining with any one of the cations exemplified above.
  • the compound represented by the above formula (6) is not limited to these combinations.
  • one type may be used alone, or two or more types may be used in combination.
  • the content of the acid generator can be appropriately selected according to the type of [A] polymer used, exposure conditions, required sensitivity, and the like.
  • the content of the acid generator is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more with respect to 100 parts by mass of the [A] polymer.
  • the content of the acid generator is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
  • Solvents include, for example, alcohols, ethers, ketones, amides, esters, and hydrocarbons.
  • alcohols include aliphatic monoalcohols having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; alicyclic monoalcohols having 3 to 18 carbon atoms such as cyclohexanol; polyhydric alcohols having 2 to 18 carbon atoms such as 1,2-propylene glycol; partial ethers of polyhydric alcohols having 3 to 19 carbon atoms such as propylene glycol monomethyl ether;
  • ethers include dialkyl ethers such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; cyclic ethers such as tetrahydrofuran and tetrahydropyran; diphenyl ether, anisole, and the like. and aromatic ring-containing ethers.
  • ketones 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, Chain ketones such as di-iso-butyl ketone and trimethylnonanone: Cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone: 2,4-pentanedione, acetonylacetone, acetophenone , diacetone alcohol, and the like.
  • amides include cyclic amides such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N- Examples include chain amides such as methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and the like.
  • esters include monocarboxylic acid esters such as n-butyl acetate and ethyl lactate; polyhydric alcohol carboxylates such as propylene glycol acetate; polyhydric alcohol partial ether carboxylates such as propylene glycol monomethyl ether acetate; Polycarboxylic acid diesters such as diethyl oxalate; carbonates such as dimethyl carbonate and diethyl carbonate; and cyclic esters such as ⁇ -butyrolactone.
  • monocarboxylic acid esters such as n-butyl acetate and ethyl lactate
  • polyhydric alcohol carboxylates such as propylene glycol acetate
  • polyhydric alcohol partial ether carboxylates such as propylene glycol monomethyl ether acetate
  • Polycarboxylic acid diesters such as diethyl oxalate
  • carbonates such as dimethyl carbonate and diethyl carbonate
  • cyclic esters such as
  • hydrocarbons examples include aliphatic hydrocarbons having 5 to 12 carbon atoms such as n-pentane and n-hexane; aromatic hydrocarbons having 6 to 16 carbon atoms such as toluene and xylene.
  • the solvent preferably contains at least one selected from the group consisting of esters and ketones, and is selected from the group consisting of polyhydric alcohol partial ether carboxylates and cyclic ketones. More preferably at least one of propylene glycol monomethyl ether acetate, ethyl lactate and cyclohexanone.
  • a solvent 1 type(s) or 2 or more types can be used.
  • a high fluorine content polymer (hereinafter also referred to as "[E] polymer”) is a polymer having a higher mass content of fluorine atoms than the [A] polymer.
  • the present composition contains the [E] polymer, the [E] polymer can be unevenly distributed on the surface layer of the resist film with respect to the [A] polymer, whereby the surface of the resist film during immersion exposure can increase the water repellency of
  • the fluorine atom content of the [E] polymer is not particularly limited as long as it is higher than that of the [A] polymer.
  • the fluorine atom content of the polymer is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more, and particularly preferably 7% by mass or more.
  • the fluorine atom content of the polymer is preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the fluorine atom content (% by mass) of the polymer can be calculated from the structure of the polymer determined by 13 C-NMR spectrum measurement or the like.
  • the structural unit containing a fluorine atom (hereinafter also referred to as "structural unit (F)") possessed by the polymer includes, for example, the following structural unit (fa) and structural unit (fb). .
  • the polymer may have either the structural unit (fa) or the structural unit (fb) as the structural unit (F), and has both the structural unit (fa) and the structural unit (fb). You may have
  • Structural unit (fa) Structural unit (fa) is a structural unit represented by the following formula (7-1).
  • the fluorine atom content of the [E] polymer can be easily adjusted.
  • R C is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group
  • G is a single bond, an oxygen atom, a sulfur atom, —COO—, —SO 2 —O —NH—, —CONH— or —O—CO—NH—
  • R E is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 3 to 20 carbon atoms. It is an alicyclic hydrocarbon group.
  • R C is preferably a hydrogen atom and a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer giving the structural unit (fa).
  • G is preferably a single bond or -COO-, more preferably -COO-, from the viewpoint of copolymerizability of the monomer that gives the structural unit (fa).
  • the monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms represented by R E some or all of the hydrogen atoms of a linear or branched alkyl group having 1 to 20 carbon atoms are Those substituted by a fluorine atom are included.
  • the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R E one of the hydrogen atoms of a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 20 carbon atoms Those partially or wholly substituted with fluorine atoms are included.
  • R E is preferably a monovalent fluorinated chain hydrocarbon group, more preferably a monovalent fluorinated alkyl group, a 2,2,2-trifluoroethyl group, 1,1,1,3 ,3,3-hexafluoropropyl group or 5,5,5-trifluoro-1,1-diethylpentyl group is more preferred.
  • the content of the structural unit (fa) is preferably 30 mol% or more with respect to the total structural units constituting the [E] polymer, It is more preferably 40 mol % or more, even more preferably 50 mol % or more.
  • the content of the structural unit (fa) is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less, relative to the total structural units constituting the [E] polymer.
  • Structural unit (fb) Structural unit (fb) is a structural unit represented by the following formula (7-2).
  • the [E] polymer has improved solubility in an alkaline developer by having the structural unit (fb), thereby further suppressing the occurrence of development defects.
  • R F is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
  • Is R 59 an (s+1)-valent hydrocarbon group having 1 to 20 carbon atoms?
  • R 60 is a single bond or a divalent organic group having 1 to 20 carbon atoms
  • X 12 is a single bond, a divalent carbonized group having 1 to 20 carbon atoms, a hydrogen group or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms.
  • a 11 is an oxygen atom, -NR''-, -CO-O-* or -SO 2 -O-* .
  • R′′ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. “*” indicates a bonding site that binds to R 61.
  • R 61 is a hydrogen atom or a C 1 to 30 and s is an integer of 1 to 3. However, when s is 2 or 3, a plurality of R 60 , X 12 , A 11 and R 61 are the same or different.
  • Structural unit (fb) in the case of having an alkali-soluble group, and in the case of having a group that dissociates under the action of alkali to increase solubility in an alkaline developer (hereinafter also simply referred to as "alkali-dissociable group”). divided.
  • R 61 is a hydrogen atom and A 11 is an oxygen atom, --COO-* or --SO 2 O-*. "*" indicates the site that binds to R61 .
  • X 12 is a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms.
  • a 11 is an oxygen atom
  • X 12 is a fluorinated hydrocarbon group having a fluorine atom or a fluoroalkyl group on the carbon atom to which A 11 is attached.
  • R 60 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • the plurality of R 60 , X 12 , A 11 and R 61 are each the same or different.
  • Having an alkali-soluble group in the structural unit (fb) can increase the affinity for an alkaline developer and suppress development defects.
  • As the structural unit (fb) having an alkali-soluble group particularly when A 11 is an oxygen atom and X 12 is a 1,1,1,3,3,3-hexafluoro-2,2-methanediyl group preferable.
  • R 61 is a monovalent organic group having 1 to 30 carbon atoms
  • a 11 is an oxygen atom, -NR''-, -COO-* or -SO 2 O-*
  • the '*' indicates the site that binds to R61 .
  • X 12 is a single bond or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms.
  • R 60 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • a 11 is -COO-* or -SO 2 O-*
  • X 12 or R 61 has a fluorine atom on the carbon atom bonded to A 11 or on the adjacent carbon atom.
  • R 59 is a hydrocarbon group having 1 to 20 carbon atoms with a carbonyl group bonded to the terminal on the R 60 side
  • R 61 is an organic group having a fluorine atom.
  • the structural unit (fb) has an alkali-dissociable group, the surface of the resist film changes from hydrophobic to hydrophilic in the alkali development step. As a result, the affinity for the developer can be enhanced, and development defects can be suppressed more efficiently.
  • the structural unit (fb) having an alkali-dissociable group it is particularly preferred that A 11 is —COO-* and R 61 or X 12 or both of them have a fluorine atom.
  • the content of the structural unit (fb) is preferably 40 mol% or more with respect to the total structural units constituting the [E] polymer, It is more preferably 50 mol % or more, and even more preferably 60 mol % or more. Further, the content of the structural unit (fb) is preferably 95 mol% or less, more preferably 90 mol% or less, more preferably 85 mol%, based on the total structural units constituting the [E] polymer. % or less. By setting the content of the structural unit (fb) within the above range, the water repellency of the resist film during immersion exposure can be further improved.
  • the polymer has a structural unit (I) having an acid-labile group and an alicyclic structure represented by the following formula (8).
  • a structural unit (hereinafter also referred to as “structural unit (G)”) may be included.
  • 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 ⁇ includes 3 to 3 carbon atoms represented by R 12 to R 14 in the above formula (2).
  • the groups exemplified as the 20 monovalent alicyclic hydrocarbon groups can be mentioned.
  • the content of the structural unit is preferably 10 mol% or more with respect to the total structural units constituting the [E] polymer. , more preferably 20 mol % or more, and still more preferably 30 mol % or more. Further, the content ratio of the structural unit represented by the above formula (8) is preferably 70 mol% or less, more preferably 60 mol% or less, more preferably 50 mol, with respect to the total structural units constituting the [E] polymer. % or less is more preferable.
  • the content of the structural unit (I) is preferably 5 mol% or more with respect to the total structural units constituting the [E] polymer, It is more preferably 10 mol % or more.
  • the content of the structural unit (I) is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol%, relative to the total structural units constituting the [E] polymer. % or less.
  • the Mw of the polymer by GPC is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
  • the Mw of the [E] polymer is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less.
  • the molecular weight distribution (Mw/Mn) represented by the ratio of Mn to Mw of the polymer by GPC is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less.
  • the content of the [E] polymer in the present composition is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the [A] polymer, and 0 0.5 parts by mass or more is more preferable, and 1 part by mass or more is even more preferable.
  • the content of the [E] polymer is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less, relative to 100 parts by mass of the [A] polymer.
  • the present composition may contain the [E] polymer singly or in combination of two or more.
  • the present composition further contains components different from the above [A] polymer, photodegradable base, acid generator, solvent and [E] polymer (hereinafter also referred to as “other optional components”).
  • Other optional components include acid diffusion control agents other than photodegradable bases (e.g., nitrogen-containing compounds represented by “N(R N1 ) (R N2 ) (R N3 )” (where R N1 , R N2 and R N3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group)), Surfactants, alicyclic skeleton-containing compounds (eg, 1-adamantanecarboxylic acid, 2-adamantanone, t-butyl deoxycholate, etc.), sensitizers, uneven distribution
  • an acid diffusion control agent other than a photodegradable base is blended in the present composition, from the viewpoint of forming a resist film excellent in LWR performance and pattern rectangularity while exhibiting good sensitivity, the content of the acid diffusion control agent other than 0.5% by mass or less is particularly preferred.
  • the present composition for example, in addition to [A] polymer and photodegradable base, if necessary [D] components such as a solvent are mixed in a desired ratio, and the resulting mixture is filtered, preferably through a filter (e.g. , a filter with a pore size of about 0.2 ⁇ m) or the like.
  • the solid content concentration of the present composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the solid content concentration of the present composition is preferably 50% by mass or less, more preferably 20% by mass or less, and even more preferably 5% by mass or less.
  • the composition thus obtained can be used as a positive pattern forming composition for forming a pattern using an alkaline developer, or as a negative pattern forming composition for forming a pattern using a developer containing an organic solvent. It can also be used as a forming composition.
  • the present composition is particularly suitable as a composition for forming a positive pattern using an alkaline developer in that the effect of forming a resist film excellent in LWR performance and pattern rectangularity while exhibiting high sensitivity is higher. is.
  • the hydrophobicity of the unexposed area can be increased by incorporating the polymer having the structural unit (M) into the resist film, thereby reducing the top loss of the pattern. As a result, it is considered that a resist film having excellent pattern rectangularity was formed.
  • the solubility of the unexposed area in the developing solution decreases due to the diffusion of acid into the unexposed area, and the pattern tends to have a reverse tapered shape or a shape called bulging.
  • the present disclosure by including a polymer having a structural unit (M) in the resist film, the hydrophobicity of the unexposed portion is increased, thereby maintaining the developer solubility. It is considered that a resist film having excellent rectangularity was formed.
  • M structural unit
  • the method for forming a resist pattern in the present disclosure includes a step of applying the composition to one surface of a substrate (hereinafter also referred to as a “coating step”), and a step of exposing the resist film obtained by the coating step (hereinafter , also referred to as an “exposure step”), and a step of developing the exposed resist film (hereinafter also referred to as a “development step”).
  • a coating step a step of exposing the resist film obtained by the coating step
  • an exposure step a step of developing the exposed resist film
  • Examples of patterns formed by the resist pattern forming method of the present disclosure include line-and-space patterns, hole patterns, and the like. Since the resist film is formed using the present composition in the resist pattern forming method of the present disclosure, it is possible to form a resist pattern with good sensitivity and lithography properties and few development defects. Each step will be described below.
  • a resist film is formed on a substrate by applying the present composition onto one surface of the substrate.
  • substrates can be used as the substrate on which the resist film is formed, and examples thereof include silicon wafers, silicon dioxide, and aluminum-coated wafers.
  • an organic or inorganic antireflection film disclosed in JP-B-6-12452, JP-A-59-93448, etc. may be formed on the substrate and used.
  • the coating method of the present composition include spin coating, casting coating, roll coating and the like.
  • prebaking (PB) may be performed to volatilize the solvent in the coating film.
  • the temperature of PB is preferably 60° C. or higher, more preferably 80° C. or higher.
  • the temperature of PB is preferably 140° C. or lower, more preferably 120° C. or lower.
  • the PB time is preferably 5 seconds or longer, more preferably 10 seconds or longer.
  • the PB time is preferably 600 seconds or less, more preferably 300 seconds or less.
  • the average thickness of the resist film to be formed is preferably 10 to 1,000 nm, more preferably 20 to 500 nm.
  • the immersion liquid is applied onto the resist film formed by the composition.
  • an immersion protective film that is insoluble in the immersion liquid may be further provided.
  • a solvent peelable protective film that is peeled off with a solvent before the development process see, for example, Japanese Patent Laid-Open No. 2006-227632
  • a developer peelable protective film that is peeled off simultaneously with development in the development process See, for example, WO2005/069076 and WO2006/035790. From the viewpoint of throughput, it is preferable to use a developer-peeling protective film for liquid immersion.
  • the resist film obtained by the coating step is exposed.
  • This exposure is performed by irradiating the resist film with radiation through a photomask and optionally through an immersion medium such as water.
  • radiation include electromagnetic waves such as visible light, ultraviolet rays, deep ultraviolet rays, extreme ultraviolet rays (EUV), X-rays and ⁇ -rays; charged particle beams such as electron beams and ⁇ -rays; etc.
  • the radiation irradiated to the resist film formed using the present composition is preferably deep ultraviolet rays, EUV or electron beams, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV or electron beams are more preferred, and ArF excimer laser light, EUV or electron beams are even more preferred.
  • PEB post-exposure baking
  • This PEB can increase the difference in solubility in a developer between the exposed area and the unexposed area.
  • the PEB temperature is preferably 50° C. or higher, more preferably 80° C. or higher.
  • the PEB temperature is preferably 180° C. or lower, more preferably 130° C. or lower.
  • the PEB time is preferably 5 seconds or longer, more preferably 10 seconds or longer.
  • the PEB time is preferably 600 seconds or less, more preferably 300 seconds or less.
  • the exposed resist film is developed with a developer.
  • a developer either an alkaline developer or an organic solvent developer may be used, and the developer can be appropriately selected according to the intended pattern (positive pattern or negative pattern).
  • Examples of the developer used for alkali development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5- Alkaline aqueous solution in which at least one of alkaline compounds such as diazabicyclo-[4.3.0]-5-nonene is dissolved.
  • TMAH aqueous solution is preferable, and a 2.38% by mass TMAH aqueous solution is more preferable.
  • examples of the developer include organic solvents such as hydrocarbons, ethers, esters, ketones and alcohols, or solvents containing such organic solvents.
  • examples of the organic solvent include one or more of the solvents listed as solvents that may be blended in the present composition.
  • ethers, esters and ketones are preferred.
  • glycol ethers are preferable, and ethylene glycol monomethyl ether and propylene glycol monomethyl ether are more preferable.
  • esters acetic esters are preferred, and n-butyl acetate and amyl acetate are more preferred.
  • ketones chain ketones are 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 water and silicon oil.
  • 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). method), a method of spraying the developer onto the surface of the substrate (spray method), and a method of continuously ejecting the developer while scanning the developer ejection nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). etc.
  • a rinsing liquid such as water or alcohol and dry.
  • the present composition described above exhibits high sensitivity when forming a resist pattern and exhibits excellent LWR performance and pattern rectangularity by containing a photodegradable base as an acid diffusion control agent together with the [A] polymer. A resist film shown can be obtained. Therefore, the present composition can be suitably used for the processing of semiconductor devices, which are expected to become more miniaturized in the future.
  • [Means 1] A radiation-sensitive composition containing a polymer having a structural unit represented by the above formula (1) and a photodegradable base.
  • the photodegradable base is a compound represented by the above formula (5-1-1), a compound represented by the above formula (5-1-2), or the above formula (5-2-1).
  • [Means 3] The radiation-sensitive composition according to [Means 1] or [Means 2], which further contains a compound represented by the above formula (6).
  • [Means 4] The radiation-sensitive composition according to any one of [Means 1] to [Means 3], wherein the polymer further has a structural unit containing an acid-labile group.
  • [Means 5] The radiation-sensitive composition according to [Means 4], wherein the polymer has a structural unit represented by the above formula (2A) as the structural unit having the acid-labile group.
  • [Means 6] The radiation-sensitive composition according to any one of [Means 1] to [Means 5], wherein Y 1 in the above formula (1) is an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group. .
  • [Means 7] The radiation-sensitive composition according to any one of [Means 1] to [Means 6], wherein n in formula (1) is 1 or 2.
  • [Means 8] A step of coating the radiation-sensitive composition according to any one of [Means 1] to [Means 7] on a substrate to form a resist film, a step of exposing the resist film, and a step of exposing the resist film to light. and developing the resist film.
  • [Means 9] The pattern forming method according to [Means 8], wherein the developing step is a step of developing the exposed resist film with an alkaline developer.
  • Mw and Mn Weight average molecular weight (Mw) and number average molecular weight (Mn)
  • Mw and Mn of the polymer are determined by gel permeation chromatography (GPC) using Tosoh Corporation GPC columns (2 "G2000HXL”, 1 "G3000HXL”, and 1 "G4000HXL”). was measured under the conditions of Further, the degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Mn.
  • Elution solvent Tetrahydrofuran Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass
  • Sample injection volume 100 ⁇ L
  • 13 C-NMR analysis 13 C-NMR analysis of the polymer was performed using a nuclear magnetic resonance apparatus (“JNM-Delta400” manufactured by JEOL Ltd.).
  • the polymerization reaction was carried out for 6 hours with the start of dropping as the start time of the polymerization reaction. After completion of the polymerization reaction, the polymerization solution was cooled with water to 30° C. or below. 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 10 hours to obtain a white powdery polymer (A-1) (yield: 85%). Polymer (A-1) had an Mw of 6,500 and an Mw/Mn of 1.67.
  • 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
  • Radiation-sensitive acid generators B-1 to B-8 compounds represented by the following formulas (B-1) to (B-8)
  • Acid diffusion control agents C-1 to C-16 compounds represented by the following formulas (C-1) to (C-16)
  • a spin coater (“CLEAN TRACK ACT12" available from Tokyo Electron Co., Ltd.) was used to apply a composition for forming an underlayer film ("ARC66" available from Bulwer Science), followed by heating at 205°C.
  • An underlayer film having an average thickness of 100 nm was formed by heating for 60 seconds at .
  • a positive radiation-sensitive resin composition for ArF exposure was applied onto this underlayer 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 50 nm line-and-space pattern was defined as the optimum exposure dose, and this optimal exposure dose was defined as the sensitivity (mJ/cm 2 ). .
  • the sensitivity was evaluated as "good” when it was 30 mJ/cm 2 or less, and was evaluated 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 50 nm line-and-space pattern by irradiating with the optimum exposure amount determined in the above sensitivity evaluation. The formed resist pattern was observed from above the pattern using a scanning electron microscope. The line width was measured at a total of 500 points, the 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 it was 3.0 nm or less, and was evaluated as “poor” when it exceeded 3.0 nm.
  • resist pattern rectangularity A 50 nm line-and-space resist pattern formed by irradiating the optimum exposure dose determined in the above sensitivity evaluation was observed using a 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 1.00 or more and 1.05 or less, and more than 1.05 and 1.10 or less. If it was more than 1.10, it was evaluated as "B” (good), and if it exceeded 1.10, it was evaluated as "C” (bad).
  • the radiation-sensitive resin compositions of Examples 1 to 45 had good sensitivity, LWR performance and resist pattern rectangularity when used for ArF exposure.
  • Comparative Examples 1-15 were inferior to Examples 1-45 in resist pattern rectangularity, and at least one of sensitivity and LWR performance was inferior to Examples 1-45. Therefore, it can be said that when the radiation-sensitive resin compositions of Examples 1 to 45 are used for ArF exposure, a resist pattern having high sensitivity, good LWR performance and good resist pattern shape can be formed.
  • a spin coater (“CLEAN TRACK ACT12" available from Tokyo Electron Co., Ltd.) was used to apply a composition for forming an underlayer film ("ARC66" available from Bulwer Science), followed by heating at 205°C.
  • An underlayer film having an average thickness of 105 nm was formed by heating for 60 seconds at .
  • a positive radiation-sensitive resin composition for EUV exposure was applied onto this underlayer 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.
  • EUV exposure apparatus NXE3300 manufactured by ASML
  • illumination condition: Conventional s 0.89
  • mask imecDEFECT32FFR02.
  • PEB was performed at 120° C. for 60 seconds. Thereafter, the resist film is alkali-developed using a 2.38% by mass TMAH aqueous solution as an alkali developer, washed with water after development, and further dried to form a positive resist pattern (32 nm line and space pattern). formed.
  • the exposure dose for forming a 32 nm line-and-space pattern was defined as the optimum exposure dose, and this optimal exposure dose was defined as the sensitivity (mJ/cm 2 ). .
  • 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 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. The line width was measured at a total of 500 points, the 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 or equal to 3.0 nm, and as “poor” when greater than 3.0 nm.
  • resist pattern rectangularity A 50 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 1.00 or more and 1.05 or less, and more than 1.05 and 1.10 or less. If it was more than 1.10, it was evaluated as "B” (good), and if it exceeded 1.10, it was evaluated as "C” (bad).
  • a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming an underlayer film ("ARC66" from Brewer Science Inc.), followed by heating at 205°C.
  • An underlayer film having an average thickness of 105 nm was formed by heating for 60 seconds at .
  • a negative radiation-sensitive resin composition for ArF exposure J-63 was applied onto the underlayer film using the above spin coater, and PB (pre-baking) was performed at 90° 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.
  • sensitivity, LWR performance and resist pattern rectangularity were evaluated in the same manner as the evaluation of the resist pattern using the positive radiation-sensitive resin composition for ArF exposure. evaluated.
  • the radiation-sensitive resin composition of Example 63 was excellent in sensitivity, LWR performance and resist pattern shape even when a negative resist pattern was formed by ArF exposure.
  • a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming an underlayer film ("ARC66" from Brewer Science Inc.), followed by heating at 205°C.
  • An underlayer film having an average thickness of 105 nm was formed by heating for 60 seconds at .
  • a negative radiation-sensitive resin composition for EUV exposure J-644 was applied onto this underlayer 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.
  • sensitivity, LWR performance and resist pattern rectangularity were evaluated in the same manner as the evaluation of the resist pattern using the positive radiation-sensitive resin composition for EUV exposure. evaluated.
  • the radiation-sensitive resin composition of Example 64 was excellent in sensitivity, LWR performance and resist pattern shape even when a negative resist pattern was formed by EUV exposure.
  • the radiation-sensitive composition and resist pattern forming method of the present disclosure described above it is possible to form a resist pattern having good sensitivity to exposure and excellent LWR performance and resist pattern shape. Therefore, the radiation-sensitive composition and the method of forming a resist pattern of the present disclosure can be suitably used for processing processes of semiconductor devices, which are expected to further miniaturize in the future.

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Abstract

L'invention concerne une composition sensible aux rayonnements comprenant un polymère ayant un motif constitutif représenté par la formule (1) et une base photodégradable. Dans la formule (1), R1 représente un atome d'hydrogène, un atome de fluor, un groupe méthyle, ou similaire. X1 représente un groupe alcanediyle, un atome d'oxygène ou un atome de soufre. Y1 représente un groupe hydrocarboné monovalent, un groupe hydrocarboné fluoré monovalent ou un atome d'halogène. R2 représente un groupe organique monovalent. B1 représente une liaison simple ou *1−COO−. R3 représente un groupe hydrocarboné divalent substitué ou non substitué. Z1 représente une liaison simple, −O−, −COO−, −OCO−, −OCOO−, −CONR4−, −NR4CO−, −OCONR4-, −NR4COO− ou −NR4CONR5−. R4 et R5 représentent des atomes d'hydrogène ou des groupes hydrocarbonés monovalents.
PCT/JP2022/045161 2021-12-22 2022-12-07 Composition sensible aux rayonnements et procédé de formation de motifs WO2023120200A1 (fr)

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