WO2023022040A1 - 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
WO2023022040A1
WO2023022040A1 PCT/JP2022/030243 JP2022030243W WO2023022040A1 WO 2023022040 A1 WO2023022040 A1 WO 2023022040A1 JP 2022030243 W JP2022030243 W JP 2022030243W WO 2023022040 A1 WO2023022040 A1 WO 2023022040A1
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group
carbon atoms
hydrocarbon group
monovalent
formula
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PCT/JP2022/030243
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English (en)
Japanese (ja)
Inventor
龍一 根本
正之 三宅
倫広 三田
甫 稲見
昇 大塚
峰規 川上
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Jsr株式会社
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Publication of WO2023022040A1 publication Critical patent/WO2023022040A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • 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
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/20—Esters containing oxygen in addition to the carboxy oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • Photolithography technology that uses resist compositions is used to form fine circuits in semiconductor devices.
  • the film of the resist composition is exposed to radiation through a mask pattern to generate an acid, and a chemical reaction involving the generated acid causes an exposed area and an unexposed area.
  • a difference in solubility in the developer is generated between the two, thereby forming a resist pattern on the substrate.
  • 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 can be solved by making a radiation-sensitive composition of a specific composition containing a polymer having a specific lactone structure. 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.
  • a 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a lactone is a divalent cyclic organic group having 6 to 20 carbon atoms having a structure, a cyclic carbonate structure or a sultone structure, and X 1 represents -O-, -COO-, -OCO-, -O-CO-O-, - NHCO- or -CONH- R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • k is an integer of 0 to 2
  • m is an integer of 1 to 10
  • n is an integer of 1 to 4.
  • 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 when forming a resist pattern. At the same time, excellent LWR performance and pattern rectangularity can be exhibited.
  • the radiation-sensitive composition of the present disclosure (hereinafter also referred to as “this composition”) comprises a polymer having a specific lactone structure (hereinafter also referred to as “[A] polymer”) and a photodegradable base. contains.
  • 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 straight-chain 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.
  • organic group refers to an atomic group obtained by removing an arbitrary hydrogen atom from a compound containing carbon (ie, an organic compound).
  • (Meth)acryl is a term that includes "acryl” and "methacryl”.
  • the polymer is a polymer having a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (I)”).
  • structural unit (I) The lactone structure in structural unit (I) is attached to the polymer backbone at the site of the carbon atom adjacent to the oxygen atom (--O--) in the lactone structure.
  • R 1 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group.
  • a 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a lactone is a divalent cyclic organic group having 6 to 20 carbon atoms having a structure, a cyclic carbonate structure or a sultone structure, and X 1 represents -O-, -COO-, -OCO-, -O-CO-O-, - NHCO- or -CONH- R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • k is an integer of 0 to 2
  • m is an integer of 1 to 10
  • n is an integer of 1 to 4.
  • R 1 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).
  • the divalent hydrocarbon group having 1 to 20 carbon atoms represented by A 1 includes, for example, a chain divalent hydrocarbon group having 1 to 20 carbon atoms and a divalent alicyclic group having 3 to 20 carbon atoms. Examples thereof include hydrocarbon groups and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.
  • any methylene group constituting a carbocyclic ring of a bivalent monocyclic or polycyclic saturated alicyclic hydrocarbon group is —COO—, —O—CO Groups substituted with -O- or -SO 2 -O- may be mentioned.
  • monocyclic divalent alicyclic saturated hydrocarbon groups include groups obtained by removing two hydrogen atoms from the same or different carbon atoms constituting the ring of cyclopentane, cyclohexane, cycloheptane or cyclooctane. .
  • the polycyclic divalent alicyclic saturated hydrocarbon group includes bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane or tricyclo[3.3.1.1 3, 7 ] groups obtained by removing two hydrogen atoms from the same or different carbon atoms constituting a ring of decane (adamantane), and the like.
  • the alkyl group having 1 to 5 carbon atoms represented by R 2 and R 3 may be linear or branched.
  • the alkyl group is preferably linear.
  • R 2 and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom, in that the solubility in the developer can be easily adjusted. preferable.
  • the C 1-5 alkyl groups represented by R 4 , R 5 , R 6 , R 7 and R 8 may be linear or branched.
  • the alkyl group is preferably linear.
  • R 4 is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, in that the difference in dissolution contrast in the developer can be increased between the exposed area and the unexposed area. is more preferred.
  • R 5 to R 8 are preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.
  • k is preferably 0 or 1, more preferably 0.
  • m is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.
  • a preferred combination of k and m can be determined by appropriately combining the above numerical ranges.
  • k and m in the above formula (1) are 0 or 1 and m is 1. ⁇ 3 is preferred, k is 0 or 1 and m is more preferably 1, and k is 0 and m is 1.
  • n is preferably 1 to 3, more preferably 1 or 2.
  • Examples of the structural unit (I) 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 (I) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, relative to the total structural units constituting the [A] polymer.
  • the content of structural unit (I) is preferably 75 mol % or less, more preferably 70 mol % or less, and even more preferably 65 mol % or less, relative to all structural units constituting the [A] polymer.
  • the polymer may further contain a structural unit different from the structural unit (I) (hereinafter also referred to as "another structural unit") together with the structural unit (I).
  • Other structural units include, for example, the following structural units (II) to (V).
  • the polymer preferably further contains a structural unit (II) having an acid-labile group.
  • the acid-dissociable group is a group that substitutes a hydrogen atom of an acidic group such as a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group and a sulfo group, and is dissociated by the action of an acid.
  • the acid-dissociated group is dissociated by the acid generated by exposing the present composition to generate an acidic group, and the solubility of the polymer component in the developer changes. As a result, the present composition can be endowed with good lithographic properties.
  • Structural unit (II) is not particularly limited as long as it contains an acid-labile group.
  • the structural unit (II) include a structural unit having a tertiary alkyl ester moiety, a structural unit having a structure in which the hydrogen atom of the phenolic hydroxyl group is substituted with a tertiary alkyl group, a structural unit having an acetal bond, and the like. is mentioned.
  • Structural unit (II) 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 (II-1)”) is preferred.
  • R 12 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group.
  • R 13 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 14 and R 15 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 14 and R 15 represents a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms combined with the carbon atoms to which R 14 and R 15 are bonded.
  • R 12 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 (II-1).
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 13 include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. Examples thereof include hydrocarbon groups and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.
  • Examples of monovalent chain hydrocarbon groups having 1 to 10 carbon atoms represented by R 13 to R 15 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 13 to R 15 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.
  • these alicyclic hydrocarbons include saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; unsaturated alicyclic hydrocarbons such as cyclopentene, cyclohexene, cycloheptene and cyclooctene. and cyclodecene etc .; Decane (adamantane) and the like can be mentioned, respectively.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 13 include groups obtained by removing one hydrogen atom from an aromatic ring such as benzene, naphthalene, anthracene, indene and fluorene. .
  • R 13 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 14 and R 15 are combined and formed together with the carbon atoms to which R 14 and R 15 are bonded is a monocyclic or polycyclic hydrocarbon group having the above carbon number. There is no particular limitation as long as it is a group obtained by removing two hydrogen atoms from the same carbon atom that constitutes an alicyclic hydrocarbon.
  • the divalent alicyclic hydrocarbon group formed by combining R 14 and R 15 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.
  • the condensed alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group composed of a plurality of aliphatic rings sharing a side (a bond between two adjacent carbon atoms).
  • a bridged alicyclic hydrocarbon group is a polycyclic alicyclic ring in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic ring are linked by a bond chain containing one or more carbon atoms.
  • the saturated hydrocarbon group is preferably a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, or the like, and the unsaturated hydrocarbon group is a cyclopentenediyl group.
  • cyclohexenediyl group, cycloheptenediyl group and cyclooctenediyl group are preferred.
  • 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), bicyclo[2.2.2]octane-2,2-diyl group, tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group), etc. is preferred.
  • R 14 and R 15 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 14 and R 15 are preferably combined to represent a C 3-12 divalent alicyclic hydrocarbon group composed together with the carbon atoms to which R 14 and R 15 are attached.
  • R 14 and R 15 are combined with each other and R 14 and R 15 preferably represent a C 3-8 divalent monocyclic aliphatic hydrocarbon group composed together with the carbon atom to which R 15 is attached.
  • Structural unit (II-1) has the following formula (3- It is particularly preferred to contain a structural unit represented by A).
  • R 12 is a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or an alkoxyalkyl group
  • R 16 is a monovalent hydrocarbon group having 1 to 8 carbon atoms
  • R 17 and R 18 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 17 and R 18 together represent a divalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms formed together with the carbon atoms to which R 17 and R 18 are bonded.
  • R 12 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the structural unit represented by the above formula (3-A), and the methyl group is more preferred.
  • R 16 , R 17 and R 18 examples of the corresponding carbon numbers described for R 13 , R 14 and R 15 in formula (3) above can be adopted.
  • R 16 is preferably a linear or branched monovalent saturated 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 hydrocarbon group of 1 to 3 or a monovalent alicyclic hydrocarbon group of 3 to 5 carbon atoms is more preferred.
  • R 17 and R 18 are a monovalent chain saturated hydrocarbon group having 1 to 4 carbon atoms, or R 17 and R 18 are combined with each other and formed together with the carbon atom to which R 17 and R 18 are attached It preferably represents a divalent monocyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms.
  • R 16 is an alkyl group having 1 to 4 carbon atoms
  • R 17 and R 18 are R It is preferred that 17 and R 18 are combined together to form a monocyclic cycloalkane structure having 3 to 6 carbon atoms together with the carbon atoms to which they are attached.
  • structural unit (II) examples include structural units represented by the following formulas (3-1) to (3-6).
  • R 12 to R 15 have the same definitions as in formula (3) above.
  • i and j are each independently an integer of 1 to 4.
  • h and g are each independently 0 or 1.
  • i and j are preferably 1 or 2, more preferably 1.
  • R 13 is preferably a methyl group, an ethyl group or an isopropyl group.
  • R 14 and R 15 are preferably a methyl group or an ethyl group.
  • the content of the structural unit (II) 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 (II) is preferably 80 mol% or less, more preferably 75 mol% or less, and 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 [A] polymer may have only one type of the structural unit (II), or may contain two or more types in combination.
  • the content ratio of the structural unit represented by the above formula (3-A) is It is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 25 mol % or more, relative to all structural units constituting the polymer.
  • the polymer may further contain a structural unit having a polar group (hereinafter also referred to as "structural unit (III)").
  • structural unit (III) By further having the structural unit (III) in the polymer, the solubility in an alkaline developer can be more easily adjusted, and lithography performance such as resolution can be improved.
  • Polar groups possessed by the structural unit (III) include, 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.
  • Structural unit (III) is a structural unit different from the structural unit having a phenolic hydroxyl group (structural unit (IV)) 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. This aliphatic hydrocarbon structure may be a chain hydrocarbon or an alicyclic hydrocarbon.
  • Structural unit (III) includes, for example, a structural unit represented by the following formula. However, the structural unit (III) 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 (III) is preferably 2 mol% or more, preferably 5 mol%, relative to the total structural units constituting the [A] polymer.
  • the above is more preferable, and 10 mol % or more is even more preferable.
  • the content of the structural unit (III) is preferably 40 mol % or less, more preferably 35 mol % or less, and even more preferably 30 mol % or less, relative to the total structural units constituting the [A] polymer.
  • the polymer may further have a structural unit having a phenolic hydroxyl group (hereinafter also referred to as "structural unit (IV)").
  • structural unit (IV) By having the structural unit (IV) 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 (IV) can be preferably applied in pattern formation using exposure to radiation with a wavelength of 50 nm or less, such as electron beams and EUV.
  • the [A] polymer preferably has the structural unit (II) together with the structural unit (I) and the structural unit (IV).
  • Structural unit (IV) is not particularly limited as long as it contains a phenolic hydroxyl group.
  • Structural units (IV) include, for example, structural units derived from hydroxystyrene or derivatives thereof, structural units derived from (meth)acrylic compounds having a hydroxybenzene structure, and the like.
  • the structural unit that gives the structural unit (IV) by hydrolysis is preferably a structural unit represented by the following formula (4-1) or a structural unit represented by the following formula (4-2).
  • 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 13 in structural unit (II).
  • 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 (IV) in the [A] polymer is 10 per all structural units constituting the [A] polymer. mol % or more is preferable, and 20 mol % or more is more preferable.
  • the content of the structural unit (IV) in the [A] polymer is preferably 70 mol % or less, more preferably 60 mol % or less, relative to all structural units constituting the [A] polymer.
  • the polymer 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 a structural unit different from the structural unit (I) (hereinafter referred to as "structural unit ( V)”) may further be included.
  • structural unit (V) By introducing the structural unit (V), it is possible to further adjust the solubility of the polymer [A] in the developer, improve the adhesion of the resist film, and further improve the etching resistance. .
  • Examples of the structural unit (V) include structural units represented by the following formulas (5-1) to (5-10).
  • 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 group having 3 to 8 carbon atoms combined with the carbon atoms to which R 1 L4 and R 2 L5 are bonded, and L 2 is a single bond or a divalent linking group.
  • X is an oxygen atom or a methylene group
  • the divalent alicyclic 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 includes R 14 and R 14 in the above formula (3).
  • R 14 and R 14 in the above formula (3).
  • Groups from 3 to 8 are included.
  • One or more hydrogen atoms on this alicyclic group may be replaced with a hydroxy group.
  • the divalent linking group represented by L 2 includes, for example, a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms, and a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms. groups, or groups composed of one or more of these hydrocarbon groups and at least one group selected from -CO-, -O-, -NH- and -S-.
  • the content of the structural unit (V) is preferably 40 mol% or less, and 35 mol%, based on the total structural units constituting the [A] polymer. The following are more preferable, and 30 mol % or less is even more preferable.
  • the polymer can be synthesized, for example, by polymerizing monomers that give each structural unit using a radical polymerization initiator or the like in an appropriate solvent.
  • Radical polymerization initiators include azobisisobutyronitrile (AIBN), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-cyclopropylpropio nitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), azo radical initiators such as dimethyl 2,2'-azobis isobutyrate; benzoyl peroxide, t-butyl hydroperoxide, cumene Examples include peroxide-based radical initiators such as hydroperoxide. Among these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical initiators can be used individually by 1 type or in mixture of 2 or more types.
  • solvents used in the polymerization include alkanes, cycloalkanes, aromatic hydrocarbons, halogenated hydrocarbons, saturated carboxylic acid esters, ketones, ethers, alcohols, and the like. Specific examples thereof include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylenedibromide, chlorobenzene, etc.
  • saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; ketones such as acetone, methyl ethyl ketone, 4-methyl-2-pentanone and 2-heptanone; Classes include tetrahydrofuran, dimethoxyethanes, diethoxyethanes and the like; alcohols include methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol and the like.
  • the solvents used for the polymerization may be used singly or in combination of two or more.
  • the reaction temperature in the above polymerization is usually 40°C to 150°C, preferably 50°C to 120°C.
  • the reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.
  • 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.
  • the content of [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" means 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.
  • a photodegradable base is a type of acid diffusion control agent that suppresses the diffusion of acid generated in the resist film by exposure, thereby suppressing the chemical reaction caused by the acid in the unexposed area. It has the function to In the present composition, by using a photodegradable base as an acid diffusion control agent together with the [A] polymer, a resist film having high sensitivity and excellent LWR performance and pattern rectangularity can be obtained. .
  • a photodegradable base is a compound that generates an acid when exposed to radiation.
  • the acid generated by the photodisintegrating base is a weak acid that does not induce dissociation of the acid-labile group under normal conditions.
  • normal conditions refers to conditions for post-exposure baking (PEB) at 110° C. for 60 seconds.
  • onium salts that generate weak acids (preferably carboxylic acids), sulfonic acids or sulfonamides upon exposure to radiation are preferably used.
  • 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, so the difference in solubility between the exposed area and the unexposed area becomes more pronounced.
  • the combination of the function of the photodegradable base and the inclusion of the [A] polymer can form a resist film excellent in LWR performance and pattern rectangularity.
  • an onium salt having a sulfonium cation structure or an iodonium cation structure can be preferably used in that a resist film with higher LWR performance can be formed.
  • Preferred specific examples of the photodisintegrating base include a compound represented by the following formula (2A-1), a compound represented by the following formula (2A-2), a compound represented by the following formula (2B-1), and At least one compound selected from the group consisting of compounds represented by the following formula (2B-2) can be mentioned.
  • (J a ) + is a sulfonium cation.
  • (E a ) - is OH - , R ⁇ -COO - , R ⁇ -SO 3 - or R ⁇ -N - (SO 2 R f2 ), where R ⁇ is a monovalent hydrocarbon group, or any methylene group in the monovalent hydrocarbon group is —O—, —CO—, —COO—, a monovalent group substituted with —O—CO—O—, —S—, —SO 2 — or —CONR ⁇ — (hereinafter also referred to as “group F A ”); Hydrocarbon group or group F A monovalent group in which any hydrogen atom of A is replaced with a fluorine atom, an iodine atom or a hydroxyl group, R ⁇ is a hydrogen atom or a monovalent hydrocarbon group, R f2 is a perfluoroalkyl group.
  • (E b ) - 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 any methylene group in the hydrocarbon group of is replaced with -O-, -CO-, -COO-, -O-CO-O-, -S-, -SO 2 - or -CONR ⁇ - (hereinafter also referred to as “group FB ”), or a divalent hydrocarbon group or a divalent group in which any hydrogen atom of the group FB is replaced by a fluorine atom or a hydroxyl group .
  • R ⁇ is a hydrogen atom or a monovalent hydrocarbon group.
  • (Q a ) - is OH - , R ⁇ -COO - , R ⁇ -SO 3 - or R ⁇ -N - (SO 2 R f2 ), where each R ⁇ is independently a monovalent hydrocarbon group, a group F A , or a monovalent hydrocarbon group or a group F A is a monovalent group in which any hydrogen atom of is replaced with a fluorine atom or a hydroxyl group.
  • R ⁇ is a hydrogen atom or a monovalent hydrocarbon group.
  • R f2 is a perfluoroalkyl group.
  • (U b ) + is a group having an iodonium cation structure.
  • (Q b ) - is * 2 -COO - , * 2 -SO 3 - or * 2 -N - ( SO 2 R f2 ), “* 2 ” represents a bond, R f2 is a perfluoroalkyl group, R 32 is a single bond, a divalent hydrocarbon group, or the group F B , or a divalent hydrocarbon group or group F A divalent group in which any hydrogen atom of B is replaced by a fluorine atom or a hydroxyl group, R ⁇ is a hydrogen atom or a monovalent hydrocarbon It is a hydrogen group.
  • the monovalent hydrocarbon group to be used examples include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a 6 to 20 carbon atom A monovalent aromatic hydrocarbon group and the like can be mentioned. Specific examples thereof include the groups exemplified as the monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 13 in the above formula (3).
  • the monovalent hydrocarbon group represented by R ⁇ includes a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a monovalent alicyclic hydrocarbon group having 6 to 12 carbon atoms. 12 monovalent aromatic hydrocarbon groups and the like.
  • 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.
  • R 21 and R 22 are each independently an alkyl group having 1 to 20 carbon atoms.
  • the sulfonium cation represented by (J a ) + includes the following formula (X-1), formula (X-2), formula (X-3) or formula (X-4) ) are sulfonium cations.
  • Examples of the iodonium cation represented by (U a ) + in the above formula (2B-1) include 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 C 1-12 linear or branched alkyl group, alkoxy group or alkoxycarbonyl an oxy group, a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxy group, a halogen atom, —OSO 2 —R P , —SO 2 —R Q , —S—R T , or two or more of R a1 , R a2 and R a3 are combined together to form a ring structure.
  • 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 C 1-12 linear or branched alkyl group, a substituted or unsubstituted C 5-25 monovalent It is an alicyclic hydrocarbon group 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 linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms, a halogen atom or a hydroxy group.
  • nk is 0 or 1; When nk is 0, k4 is an integer of 0-4, and when nk is 1, k4 is an integer of 0-7.
  • R b1 When there are a plurality of R b1 , the plurality of R b1 may be the same or different, and the plurality of R b1 may represent a ring structure formed by being combined with each other.
  • R b2 is a substituted or unsubstituted C 1-7 linear or branched alkyl group or a substituted or unsubstituted C 6 or 7 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 C 1-12 linear or branched alkyl group.
  • R g1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
  • nk2 is 0 or 1; When n k2 is 0, k 10 is an integer of 0-4, and when n k2 is 1, k 10 is an integer of 0-7.
  • R g1 When there are a plurality of R g1 , the plurality of R g1 may be the same or different, and the plurality of R g1 may represent a ring structure formed by being combined with each other.
  • R g2 and R g3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, an alkoxy group or an alkoxycarbonyloxy group, a substituted or unsubstituted C 3- 12 monocyclic or polycyclic cycloalkyl groups, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 12 carbon atoms, hydroxy groups, halogen atoms, or R g2 and R g3 combined with each other represents a ring structure.
  • k11 and k12 are each independently an integer of 0-4. When each of R g2 and R g3 is plural, the plural R g2 and R g3 are the same or different from each other.
  • R d1 and R d2 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, alkoxy group or alkoxycarbonyl group, substituted or an unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a nitro group, or two or more of these groups combined with each other Represents the ring structure that is composed.
  • k6 and k7 are each independently an integer from 0 to 5; When each of R d1 and R d2 is plural, the plural R d1 and R d2 are the same or different.
  • R e1 and R e2 are each independently a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • k8 and k9 are each independently an integer of 0-4.
  • Specific examples of the group represented by “-(J b ) + ” in formula (2A-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 b ) + ” in formula (2B-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 base examples include onium salt compounds obtained by combining any one of the anions exemplified above with any one of the cations exemplified above.
  • photodisintegrating bases examples 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 15 parts by mass or less, and even more preferably 12 parts by mass or less, relative to 100 parts by mass of the [A] polymer.
  • compositions may contain include a radiation-sensitive acid generator, a solvent, and a high-fluorine-containing polymer.
  • 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.
  • 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 acidic 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 9 , R 10 and R 11 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 are those in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic ring are linked by a linking chain containing one or more carbon atoms. It is a polycyclic alicyclic hydrocarbon.
  • Specific examples of bridged alicyclic hydrocarbons 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.
  • a condensed alicyclic hydrocarbon is a polycyclic alicyclic hydrocarbon composed of multiple aliphatic rings sharing an edge (a bond between two adjacent carbon atoms).
  • Specific examples of condensed alicyclic hydrocarbons include decahydronaphthalene and octahydronaphthalene.
  • the alicyclic polycyclic structure is preferably a bridged alicyclic saturated hydrocarbon structure such as bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane or tricyclo[3.3. 1.1 3,7 ]decane (adamantane) 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 9 , R 10 , R 11 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 9 , R 10 , R 11 and R f is
  • R 9 , R 10 , R 11 and R f are preferably a fluorine atom or a trifluoromethyl group in terms of improving 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.
  • the solvent is not particularly limited as long as it can dissolve or disperse the components to be incorporated in the present composition.
  • solvents include alcohols, ethers, ketones, amides, esters, hydrocarbons and the like.
  • 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 at least one selected from the group consisting of polyhydric alcohol partial ether carboxylates and cyclic ketones. It more preferably contains seeds, and more preferably contains 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-containing 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, but is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 4% by mass or more. More than % by mass is particularly preferred.
  • 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, structural unit (fa) and structural unit (fb) shown below.
  • 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) is a structural unit represented by the following formula (7-1).
  • the [E] polymer can adjust the fluorine atom content by having the structural unit (fa).
  • 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 1 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 giving 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 hydrogen atom 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 hydrocarbon group having 1 to 20 carbon atoms, or It is 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 monovalent hydrocarbon group having 1 to 30 carbon atoms.
  • 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 is dissociated by the action of alkali to increase the 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, --CO--O-* or --SO 2 --O-*. "*" indicates the site that binds to R61 .
  • X 12 is a single bond, a 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''-, -CO-O-* or - SO 2 —O—*
  • the “*” indicates the site that binds to R 61 .
  • 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.
  • X 12 or R 61 has a fluorine atom on the carbon atom bonded to A 11 or on the adjacent carbon atom.
  • a 11 is an oxygen atom
  • X 12 or R 60 is a single bond
  • 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.
  • s is 2 or 3
  • the plurality of R 60 , X 12 , A 11 and R 61 are each the same or different.
  • the structural unit (fb) has an alkali-dissociable group, the resist film surface 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 —CO—O—* 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, in addition to the structural unit (fa) and the structural unit (fb), a structural unit (II) having an acid-dissociable 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 1a is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 2a 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 2a includes 3 to 3 carbon atoms represented by R 13 to R 15 in the above formula (3).
  • 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 (II) 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. Further, the content of the structural unit (II) 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 is prepared by mixing components such as a solvent in a desired ratio in addition to the [A] polymer as necessary, and filtering the resulting mixture preferably through a filter (for example, 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 using a developer containing an organic solvent. can also be used.
  • the method for forming a resist pattern in the present disclosure comprises a step of applying the present 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.
  • the composition is used to form a resist film, so that a resist pattern having good sensitivity and lithography properties and few development defects can be formed. 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-peeling 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-peeling protective film that is peeled off simultaneously with development in the developing 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.
  • organic solvents such as hydrocarbons, ethers, esters, ketones, alcohols, or solvents containing such organic solvents can be mentioned.
  • 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. can be shown. Therefore, the present composition can be suitably used for the processing of semiconductor devices, which are expected to become more miniaturized in the future.
  • the present disclosure is not limited, the reason why the present composition described above can exhibit excellent LWR performance and pattern rectangularity while exhibiting high sensitivity in resist pattern formation is speculated as follows. be done. Taking the case where the lactone structure is a ⁇ -butyrolactone structure as an example, the case where the lactone structure is bonded to the main chain of the polymer at the ⁇ -position, or the lactone structure is bonded to the main chain of the polymer at the ⁇ -position. When conjugated, ring opening of the lactone structure produces a primary hydroxy group (see schemes (A) and (B) below).
  • the ring-opening reaction of the lactone structure in the polymer proceeds more easily, and in the case of a positive type, the ring-opening of the lactone structure increases the solubility of the unexposed area in the developer, and as a result, the shape of the upper part of the resist pattern. It is considered that the excessive rounding of the edge tends to cause deterioration of the LWR performance and the pattern rectangularity.
  • the present composition contains a photodegradable base together with the polymer [A], the photodegradable base acts as an acid diffusion control agent in the unexposed area while preventing the action of the acid generated in the exposed area from being hindered.
  • the difference in solubility in the developer between the exposed area and the unexposed area can be increased. Therefore, in the resist film formed using the present composition, the difference in solubility in the developer between the exposed area and the unexposed area becomes more pronounced, and a resist film having excellent LWR performance and pattern rectangularity can be formed. Conceivable.
  • this composition is applied to a negative type, it is thought that the decrease in the solubility of the unexposed area in the organic solvent developer can be suppressed, thereby improving the resist performance and the pattern shape.
  • [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 includes a compound represented by the above formula (2A-1), a compound represented by the above formula (2A-2), a compound represented by the above formula (2B-1), and The radiation-sensitive composition according to [Means 1] above, which is at least one compound selected from the group consisting of compounds represented by formula (2B-2) above.
  • [Means 3] The radiation-sensitive composition according to the above [Means 1] or [Means 2], which further contains a compound represented by the above formula (6).
  • [Means 4] The radiation-sensitive composition according to [Means 3], wherein W 1 in the formula (6) is a monovalent group having an alicyclic hydrocarbon structure or an aliphatic heterocyclic ring structure.
  • [Means 5] The radiation-sensitive composition according to [Means 3] or [Means 4], wherein W 1 in the formula (6) does not have a fluorine atom.
  • [Means 6] The radiation-sensitive composition according to any one of [Means 1] to [Means 5], wherein the polymer further has a structural unit containing an acid-labile group.
  • [Means 7] The radiation-sensitive composition according to [Means 6] above, which has a structural unit represented by the above formula (3-A) as the structural unit containing the acid-labile group.
  • [Means 8] The radiation-sensitive composition according to any one of [Means 1] to [Means 7], wherein m in formula (1) is 1.
  • [Means 9] The radiation-sensitive composition according to any one of [Means 1] to [Means 8], wherein k in the above formula (1) is 0.
  • [Means 10] A step of applying the radiation-sensitive composition according to any one of [Means 1] to [Means 9] on a substrate to form a resist film, a step of exposing the resist film, and an exposure. and a step of developing the resist film.
  • Mw and Mn of the polymer were measured using Tosoh GPC columns (G2000HXL: 2, G3000HXL: 1, G4000HXL: 1), flow rate: 1.0 mL/min, elution solvent: tetrahydrofuran, sample concentration: 1.
  • GPC gel permeation chromatography
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the cooled polymerization solution was poured into methanol (2,000 parts by mass), and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with methanol, filtered, and dried at 50° C. for 24 hours to obtain a white powdery resin (A-1) (yield: 83%).
  • Resin (A-1) had Mw of 7,800 and Mw/Mn of 1.58.
  • the content ratio of each structural unit derived from the monomer (m-1) and the monomer (M-1) is 51.0 mol% and 49.0 mol%, respectively. Met.
  • 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 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). Then, methanol (500 parts by mass), triethylamine (50 parts by mass) and ultrapure water (10 parts by mass) were added, and hydrolysis reaction was carried out at 70° C. for 6 hours while stirring.
  • methanol 500 parts by mass
  • triethylamine 50 parts by mass
  • ultrapure water 10 parts by mass
  • Resin (A-26) had an Mw of 5,200 and an Mw/Mn of 1.60. Further, as a result of 13 C-NMR analysis, the content ratio of each structural unit derived from the monomer (m-2), the monomer (M-1) and the monomer (m-24) was 51.5%. They were 3 mol %, 9.9 mol % and 38.8 mol %.
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the operation of adding hexane (100 parts by mass) and stirring to recover the acetonitrile layer was repeated three times.
  • the high fluorine content resin (E-1) had Mw of 6,000 and Mw/Mn of 1.62.
  • the content ratio of each structural unit derived from the monomer (m-2) and the monomer (m-26) is 19.9 mol% and 80.1 mol%, respectively. Met.
  • 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-10 compounds represented by the following formulas (C-1) to (C-10) cc-1 to cc-9: the following formulas (cc-1) ⁇ compound represented by formula (cc-9)
  • 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 40 nm line-and-space pattern is defined as the optimum exposure dose, and this optimum exposure dose is defined as sensitivity (mJ/cm 2 ). bottom. A sensitivity of 30 mJ/cm 2 or less was evaluated as “good”, and a sensitivity of more than 30 mJ/cm 2 was evaluated as "bad”.
  • LWR performance A 40 nm line-and-space resist pattern was formed by irradiating with the optimum exposure amount determined by the above sensitivity evaluation. The formed resist pattern was observed from above the pattern using the scanning electron microscope. Line width variation was measured at a total of 500 points, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as LWR (nm). LWR indicates that the smaller the value, the smaller the roughness of the line and the better. The LWR performance was evaluated as "good” when it was 2.5 nm or less, and as "bad” when it exceeded 2.5 nm.
  • a 40 nm line-and-space resist pattern formed by irradiating the optimum exposure dose determined in the evaluation of sensitivity was observed using the scanning electron microscope, and the cross-sectional shape of the line-and-space pattern was evaluated.
  • the rectangularity of the resist pattern is "A" (very good) if the ratio of the length of the lower side to the length of the upper side in the cross-sectional shape is 1 or more and 1.05 or less, and if it is more than 1.05 and 1.10 or less. If it is more than 1.10, it is evaluated as "B" (good), and if it exceeds 1.10, it is evaluated as "C" (bad).
  • the radiation-sensitive resin compositions used in Examples had good sensitivity, LWR performance and pattern rectangularity when used for ArF exposure.
  • the radiation-sensitive resin compositions used in the comparative examples had the same sensitivity as the examples, but were inferior to the examples in the LWR performance and the pattern rectangularity.
  • both the LWR performance and the pattern rectangularity were evaluated as "poor". From these results, when the radiation-sensitive resin compositions of Examples 1 to 43 containing the polymer having the structural unit represented by the above formula (1) and the photodegradable base were used for ArF exposure, high sensitivity was obtained. It can be said that a resist pattern having good LWR performance and good pattern rectangularity can be formed.
  • EUV extreme ultraviolet
  • 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 .
  • the spin coater was used to apply the radiation-sensitive resin composition for EUV exposure onto the underlayer film, followed by PB 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 optimum exposure dose was defined as the sensitivity (mJ/cm 2 ).
  • a sensitivity of 30 mJ/cm 2 or less was evaluated as “good”, and a sensitivity of more than 30 mJ/cm 2 was evaluated as "bad”.
  • LWR performance A resist pattern was formed by adjusting the mask size so as to form a 32 nm line-and-space pattern by irradiating with the optimum exposure amount determined by the evaluation of sensitivity. The formed resist pattern was observed from above the pattern using the scanning electron microscope. Line width variation was measured at a total of 500 points, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as LWR (nm). LWR indicates that the smaller the value, the smaller the jolting of the line and the better. The LWR performance was evaluated as "good” when it was 3.0 nm or less, and as “poor” when it exceeded 3.0 nm.
  • a 32 nm line-and-space resist pattern formed by irradiating the optimum exposure dose determined in the evaluation of sensitivity was observed using the scanning electron microscope, and the cross-sectional shape of the line-and-space pattern was evaluated.
  • the rectangularity of the resist pattern is "A" (very good) if the ratio of the length of the lower side to the length of the upper side in the cross-sectional shape is 1 or more and 1.05 or less, and if it is more than 1.05 and 1.10 or less. If it is more than 1.10, it is evaluated as "B" (good), and if it exceeds 1.10, it is evaluated as "C" (bad).
  • the radiation-sensitive resin compositions used in Examples had good sensitivity, LWR performance and pattern rectangularity when used for EUV exposure.
  • the radiation-sensitive resin composition used in the comparative example was evaluated as "bad” in all of the sensitivity, LWR performance and pattern rectangularity, and was inferior to the examples.
  • a resist pattern having good sensitivity to exposure light and excellent LWR performance and pattern shape performance can be formed. Therefore, these materials can be suitably used for the processing of semiconductor devices, which are expected to be further miniaturized in the future.

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 ; A1 représente un groupe hydrocarboné bivalent ayant de 1 à 20 atomes de carbone ou un groupe organique cyclique bivalent ayant de 6 à 20 atomes de carbone et ayant une structure de lactone, une structure de carbonate cyclique ou une structure de sultone ; X1 représente -O-, -COO-, -OCO-, -O-CO-O-, -NHCO- ou -CONH- ; R2 à R8 représentent indépendamment un atome d'hydrogène ou un groupe alkyle ayant de 1 à 5 atomes de carbone ; k représente un nombre entier de 0 à 2 ; m représente un nombre entier de 1 à 10 ; et n représente un nombre entier de 1 à 4.
PCT/JP2022/030243 2021-08-20 2022-08-08 Composition sensible aux rayonnements et procédé de formation de motifs WO2023022040A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014078000A (ja) * 2012-09-21 2014-05-01 Sumitomo Chemical Co Ltd 樹脂、レジスト組成物及びレジストパターンの製造方法
JP2014178479A (ja) * 2013-03-14 2014-09-25 Fujifilm Corp パターン形成方法、電子デバイスの製造方法、及び、電子デバイス
JP2016099483A (ja) * 2014-11-20 2016-05-30 Jsr株式会社 感放射線性樹脂組成物、重合体及び化合物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014078000A (ja) * 2012-09-21 2014-05-01 Sumitomo Chemical Co Ltd 樹脂、レジスト組成物及びレジストパターンの製造方法
JP2014178479A (ja) * 2013-03-14 2014-09-25 Fujifilm Corp パターン形成方法、電子デバイスの製造方法、及び、電子デバイス
JP2016099483A (ja) * 2014-11-20 2016-05-30 Jsr株式会社 感放射線性樹脂組成物、重合体及び化合物

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