WO2011070947A1 - 感放射線性樹脂組成物、重合体、単量体及び感放射線性樹脂組成物の製造方法 - Google Patents

感放射線性樹脂組成物、重合体、単量体及び感放射線性樹脂組成物の製造方法 Download PDF

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WO2011070947A1
WO2011070947A1 PCT/JP2010/071398 JP2010071398W WO2011070947A1 WO 2011070947 A1 WO2011070947 A1 WO 2011070947A1 JP 2010071398 W JP2010071398 W JP 2010071398W WO 2011070947 A1 WO2011070947 A1 WO 2011070947A1
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group
substituent
general formula
polymer
radiation
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French (fr)
Japanese (ja)
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研 丸山
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Jsr株式会社
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Priority to JP2011545179A priority Critical patent/JP5655792B2/ja
Priority to KR1020127011846A priority patent/KR101761434B1/ko
Publication of WO2011070947A1 publication Critical patent/WO2011070947A1/ja
Priority to US13/479,268 priority patent/US8632945B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • 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
    • C08F12/00—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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/16—Halogens
    • C08F12/20—Fluorine
    • 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
    • C08F12/00—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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • 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
    • C08F12/00—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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C08F12/24—Phenols or alcohols
    • 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
    • C08F12/00—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 an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/30—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography

Definitions

  • the present invention relates to a radiation-sensitive resin composition, a polymer, a monomer, and a method for producing the radiation-sensitive resin composition. More specifically, the present invention relates to various kinds of radiation such as KrF excimer laser, ArF excimer laser, F 2 excimer laser, EUV (extreme) far ultraviolet rays, synchrotron radiation, etc., X-rays, electron beam, etc. Radiation-sensitive resin composition used as a chemically amplified resist suitable for microfabrication by means of, a novel sulfonate-containing polymer used in the composition, a novel monomer used in the polymer, and radiation sensitivity The present invention relates to a method for producing a conductive resin composition.
  • Lithography using an electron beam or EUV light is positioned as a next-generation or next-generation pattern formation technology, and a resist with high sensitivity and high resolution is desired.
  • high sensitivity is a very important issue for shortening the wafer processing time.
  • resists for electron beams and EUV if high sensitivity is pursued, not only the resolution is lowered but also the nano edge roughness deteriorates. Therefore, it is strongly desired to develop a resist that simultaneously satisfies these characteristics. It is rare. Nano edge roughness is designed when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist.
  • lithography using KrF and ArF excimer laser light it is also important to satisfy high sensitivity, high resolution, good pattern shape, and good nano edge roughness at the same time.
  • a solution is needed.
  • a resist suitable for a lithography process using KrF excimer laser light, electron beam, or EUV light a chemically amplified resist mainly utilizing an acid-catalyzed reaction is used from the viewpoint of high sensitivity.
  • a phenolic polymer (hereinafter referred to as “phenolic acid-decomposable polymer”), which is insoluble or sparingly soluble in an aqueous alkali solution and becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid
  • a chemically amplified resist composition comprising a generator is effectively used.
  • a chemically amplified resist is also used as a resist suitable for a lithography process using ArF excimer laser light, and a positive resist has an acid-dissociable group that becomes alkali-soluble by the action of an acid as a main component
  • a chemically amplified resist composition comprising a (meth) acrylic polymer and an acid generator is effectively used.
  • sulfonic acid generator compounds that generate sulfonic acid upon irradiation with actinic rays or radiation using a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer
  • sulfonic acid generator compounds that generate sulfonic acid upon irradiation with actinic rays or radiation using a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer
  • the present invention has been made in view of the above circumstances, and is effectively sensitive to X-rays such as KrF excimer laser, ArF excimer laser, EUV (extreme) deep ultraviolet rays, synchrotron radiation, electron beams, etc.
  • Radiation-sensitive resin composition capable of forming a chemically amplified positive resist film that is excellent in edge roughness, sensitivity and resolution, and can form a fine pattern with high accuracy and stability, and a novel used in the composition
  • An object of the present invention is to provide a novel sulfonate-containing polymer, a novel monomer used in the polymer, and a method for producing a radiation-sensitive resin composition.
  • R 1 to R 3 each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S —R 6 group (R 6 represents an optionally substituted alkyl group or aryl group) or a group having two or more heteroatoms.
  • R 1 is a group having two or more heteroatoms.
  • l represents an integer of 1 to 5.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group. .
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent.
  • each of R 1 to R 3 independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, or a —SR 6 group.
  • R 6 represents an alkyl group or an aryl group which may have a substituent
  • a group having two or more heteroatoms However, at least one of R 1 is a group having two or more heteroatoms.
  • l represents an integer of 1 to 5.
  • m and n each independently represents an integer of 0 to 5.
  • the radiation-sensitive resin composition according to the above [5] which has at least a structural unit represented by the following general formula (c-1) as the structural unit having an acid dissociable group.
  • R 12 each independently represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • Each R 13 is independently of each other a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or a substituted group.
  • an aryl group having 6 to 22 carbon atoms which may have a group, or any two R 13 's bonded to each other, and each having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded.
  • a divalent alicyclic hydrocarbon group or a group derived therefrom is formed, and the remaining one R 13 is a linear or branched alkyl group having 1 to 4 carbon atoms, 1 having 4 to 20 carbon atoms, or the like.
  • each R 13 independently represents a monovalent organic group.
  • Z ⁇ represents R 15 O ⁇ or R 15 COO — (R 15 represents a monovalent organic group).
  • q independently represents an integer of 0 to 5.
  • R 1 to R 3 each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group.
  • a group, —S—R 6 group R 6 represents an optionally substituted alkyl group or aryl group), or a group having two or more heteroatoms; However, at least one of R 1 is a group having two or more heteroatoms.
  • l represents an integer of 1 to 5.
  • m and n each independently represents an integer of 0 to 5.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent.
  • R 1 to R 3 each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S —R 6 group (R 6 represents an optionally substituted alkyl group or aryl group) or a group having two or more heteroatoms.
  • at least one of R 1 is a group having two or more heteroatoms.
  • l represents an integer of 1 to 5.
  • m and n each independently represents an integer of 0 to 5.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent.
  • R 1 to R 3 each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S —R 6 group (R 6 represents an optionally substituted alkyl group or aryl group) or a group having two or more heteroatoms.
  • at least one of R 1 is a group having two or more heteroatoms.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent. ]
  • the radiation sensitive resin composition of the present invention KrF excimer laser, ArF excimer laser, EUV and other (extreme) deep ultraviolet rays, synchrotron radiation and other X-rays and electron beams are effectively sensitive to nano edge roughness, A chemically amplified resist film having excellent sensitivity and resolution and capable of forming a fine pattern with high accuracy and stability can be formed.
  • the novel polymer of this invention generate
  • the novel monomer of the present invention is suitably used as a monomer that gives the polymer.
  • the method for producing the radiation-sensitive resin composition of the present invention it is effectively sensitive to X-rays such as KrF excimer laser, ArF excimer laser, EUV, (extreme) far ultraviolet rays, synchrotron radiation, and electron beams. It is possible to easily produce a radiation-sensitive resin composition capable of forming a chemically amplified resist film that is excellent in nano edge roughness, sensitivity and resolution, and can form a fine pattern with high accuracy and stability. .
  • Radiation sensitive resin composition (i) The radiation-sensitive resin composition (i) of the present invention is characterized by containing a specific polymer and a solvent.
  • the radiation-sensitive resin composition of the present invention includes a polymer component having at least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II).
  • a polymer hereinafter, also referred to as “polymer (A)”.
  • This polymer (A) is an alkali-insoluble or hardly-alkali-soluble polymer that becomes readily alkali-soluble by the action of an acid.
  • R 1 to R 3 each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S —R 6 group (R 6 represents an optionally substituted alkyl group or aryl group) or a group having two or more heteroatoms.
  • R 1 is a group having two or more heteroatoms.
  • l represents an integer of 1 to 5.
  • m and n each independently represents an integer of 0 to 5.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent.
  • Examples of the halogen atom in R 1 to R 3 in the general formulas (I) and (II) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group in R 1 to R 3 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable.
  • Examples of the cycloalkyl group in R 1 to R 3 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among these, those having 5 to 6 carbon atoms are preferable.
  • Examples of the alkoxy group in R 1 to R 3 include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable.
  • One or more hydrogen atoms in each of the alkyl group, cycloalkyl group and alkoxy group may be substituted.
  • the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), phenyl group, acetoxy group, alkyl group, alkoxy group and the like.
  • Examples of the alkyl group of R 6 in the —SR 6 group of R 1 to R 3 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 2-methylpropyl group. , 1-methylpropyl group, t-butyl group and the like.
  • Examples of the aryl group for R 6 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group. Among these, those having 6 to 12 carbon atoms are preferable.
  • one or more hydrogen atoms in each of the alkyl group and aryl group of R 6 may be substituted with the above-described substituent.
  • the group having two or more heteroatoms in R 1 to R 3 is not particularly limited. It is considered that when R 1 to R 3 have two or more heteroatoms, acid generation efficiency is improved, and nanoedge roughness, sensitivity, and resolution are excellent.
  • the hetero atom include a sulfur atom (S), an oxygen atom (O), and a nitrogen atom (N), and at least two selected from these are preferable.
  • Such groups include —OSO 2 —Rx, —SO 2 —Rx, —O—CO—Rx, —CO—O—Rx, —CONH—Rx, and —SO 2 N (Ry) —Rx
  • Rx Each independently represents an optionally substituted alkyl group, cycloalkyl group, alkoxy group, or aryl group, and Ry represents a hydrogen atom or a group similar to Rx, provided that two or more In the case where the group having a hetero atom is the above-mentioned —CO—O—Rx, Rx is not an alkoxy group.
  • at least one of —OSO 2 —Rx and —SO 2 —Rx is preferable from the viewpoint of acid generation efficiency.
  • the substituent in Rx is preferably a halogen atom.
  • alkyl group in Rx examples include linear or branched alkyl groups having 1 to 10 carbon atoms. Such alkyl groups include methyl, ethyl, propyl, i-propyl, n-butyl, s-butyl, t-butyl, i-butyl, n-pentyl, and i-pentyl. Group, neo-pentyl group and the like. This alkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, and a carboxyl group.
  • Examples of the cycloalkyl group in Rx include monocyclic or polycyclic cycloalkyl groups having 4 to 15 carbon atoms.
  • Examples of such a cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, an adamantyl group, and the like.
  • This cycloalkyl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group.
  • alkoxy group for Rx examples include linear or branched alkoxyl groups having 1 to 10 carbon atoms. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, and a butoxy group. This alkoxy group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, and a carboxyl group.
  • Examples of the aryl group of Rx include a phenyl group, a naphthyl group, and an anthranyl group. This aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group.
  • Ry represents a hydrogen atom or a group similar to Rx described above.
  • group having two or more heteroatoms include groups having structures represented by the following formulas (h1) to (h15). Among these, groups represented by (h1) and (h2) are preferable.
  • L in the general formulas (I) and (II) represents an integer of 1 to 5.
  • m and n each independently represents an integer of 0 to 5.
  • l + m + n is an integer of 1 to 2. That is, the general formulas (I) and (II) each have at least one group having two or more heteroatoms.
  • Examples of the halogen atom in R 7 to R 11 in the general formulas (I) and (II) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group in R 7 to R 11 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable.
  • One or more hydrogen atoms in the alkyl group may be substituted with the above-described substituent.
  • Examples of the aralkyl group in R 8 to R 10 include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. Among these, those having 6 to 12 carbon atoms are preferable.
  • Examples of the alkoxy group in R 8 to R 10 include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable.
  • One or more hydrogen atoms in each of the aralkyl group and the alkoxy group in R 8 to R 10 may be substituted with the above-described substituent.
  • Examples of the alkyl group of R 12 in the —NR 12 — group of A in the general formula (II) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like. Among these, those having 1 to 6 carbon atoms are preferable.
  • Examples of the aryl group of R 12 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group. Among these, those having 6 to 12 carbon atoms are preferable.
  • One or more hydrogen atoms in each of the alkyl group and aryl group in A may be substituted with the above-described substituent.
  • alkylene group in D of the general formula (II) examples include ethylene group; propylene group such as 1,3-propylene group and 1,2-propylene group; tetramethylene group, pentamethylene group, hexamethylene group, 1- Methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4- And a butylene group.
  • those having 2 to 6 carbon atoms are preferable.
  • Examples of the arylene group of D include phenylene group, naphthylene group, methylphenylene, ethylphenylene, chlorophenylene group, bromophenylene group, fluorophenylene group and the like. Among these, those having 6 to 12 carbon atoms are preferable.
  • one or more hydrogen atoms in each of the methylene group, the alkylene group, and the arylene group in D may be substituted with the above-described substituent.
  • the repeating units (I) and (II) can be obtained by using, for example, compounds represented by the following general formulas (Im) and (II-m) as monomers, respectively.
  • R 1 to R 3 each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group.
  • a group, —S—R 6 group R 6 represents an optionally substituted alkyl group or aryl group), or a group having two or more heteroatoms; However, at least one of R 1 is a group having two or more heteroatoms.
  • l represents an integer of 1 to 5.
  • m and n each independently represents an integer of 0 to 5.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent. ]
  • R 1 to R 3 , R 7 to R 11 , l, m, n, A and D are the same as those in the general formulas (I) and (II). It is synonymous with R 1 to R 3 , R 7 to R 11 , l, m, n, A and D.
  • Specific monomers represented by formulas (Im) and (II-m) include, for example, compounds represented by formulas (I-1) to (I-5), and formula (II- Examples thereof include compounds represented by 1) to (II-21).
  • the monomer represented by the general formula (Im) includes, for example, a compound represented by the general formula (Y) and a compound represented by the general formula (YY) as represented by the following reaction formula: Can be produced in a methylene chloride / water mixed solvent. Further, the monomer represented by the general formula (II-m) is represented by the compound represented by the general formula (X) and the general formula (XX) as represented by the following reaction formula, for example. It can be produced by reacting a compound with a methylene chloride / water mixed solvent. Furthermore, the compound represented by the general formula (XX) or (YY) can be produced, for example, by the method described in JP-A No. 2003-423516.
  • R 1 to R 3 , R 7 to R 11 , l, m, n, A and D have the same meanings as R 1 to R 3 , R 7 to R 11 , l, m, n, A and D in the general formulas (I) and (II).
  • M + represents an alkali metal ion
  • X ⁇ represents a halide ion.
  • the polymer (A) further includes a repeating unit represented by the following general formula (1) [hereinafter referred to as “repeating unit (1)”. ] May be included.
  • the polymer (A) contains this repeating unit (1) because the polymer (A) becomes sufficiently alkali-soluble by the action of an acid.
  • R 15 represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
  • R 16 represents an aryl group having 6 to 22 carbon atoms which may have a substituent.
  • X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom.
  • the carbon number of the alicyclic hydrocarbon group formed by X and Y is not particularly limited, but is preferably 5 to 25, more preferably 5 to 20, and still more preferably 5 to 15.
  • the alicyclic hydrocarbon group may be monocyclic or polycyclic. Specific examples of the structure of the alicyclic moiety include the following structures (a-1) to (a-50).
  • the alicyclic hydrocarbon group formed by X in the general formula (1) together with Y is preferably a group having a monocyclo, bicyclo, tricyclo, or tetracyclo structure.
  • alicyclic hydrocarbon group examples include, for example, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group; adamantyl group, noradamantyl group Group, decalin residue (decalinyl group), tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group and the like.
  • a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group
  • adamantyl group noradamanty
  • a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group; an adamantyl group, a decalin residue, a norbornyl group, and the like are preferable.
  • a cycloalkyl group having 5 to 15 carbon atoms is preferable.
  • the alicyclic hydrocarbon group may be substituted or unsubstituted.
  • substituents include, for example, hydroxy group, carboxyl group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc. Can be mentioned.
  • Examples of the aryl group having 6 to 22 carbon atoms of R 16 include groups derived from the following structures (x-1) to (x-3).
  • R 16 is a group derived from the following (x-2) (ie, a naphthyl group)
  • the bonding position bonded to Y in the general formula (1) is either the 1-position or the 2-position. May be.
  • R 16 is a group derived from the following (x-3) (namely, an anthryl group)
  • the bonding positions bonded to Y in the general formula (1) are the 1-position, 2-position and 9-position. Either may be sufficient.
  • the aryl group may be substituted.
  • substituents include, for example, methyl group, ethyl group, hydroxy group, carboxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group) Etc.), alkyloxycarbonyl groups and the like.
  • the repeating unit (1) is a repeating unit represented by the following general formula (1-1) [hereinafter referred to as “repeating unit (1-1)”. ].
  • R 15 represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
  • X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom.
  • the repeating unit (1) can be obtained, for example, by using a compound represented by the following general formula (m-1) as a monomer.
  • R 15 represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
  • R 16 represents an aryl group having 6 to 22 carbon atoms which may have a substituent.
  • X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom.
  • R 15 in the general formula (m-1) R 16, X and Y have the same meanings as R 15, R 16, X and Y in the general formula (1).
  • this repeating unit (1) when the repeating unit (1) is contained in the polymer (A), this repeating unit (1) may be contained only 1 type, and may be contained 2 or more types.
  • the polymer (A) in the present invention is further represented by a repeating unit represented by the following general formula (2) [hereinafter referred to as “repeating unit (2)”. ], A repeating unit represented by the following general formula (3) [hereinafter referred to as “repeating unit (3)”. ], A repeating unit represented by the following general formula (4) [hereinafter referred to as “repeating unit (4)”. ] And a repeating unit represented by the following general formula (5) [hereinafter referred to as “repeating unit (5)”. ] May be included.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents a hydrogen atom or a monovalent organic group
  • i represents an integer of 1 to 3
  • j represents an integer of 0 to 3.
  • i + j ⁇ 5 is satisfied.
  • R 6 represents a hydrogen atom or a methyl group
  • R 7 represents a hydrogen atom or a monovalent organic group
  • k represents an integer of 1 to 3
  • l represents an integer of 0 to 3.
  • k + l ⁇ 5 is satisfied.
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 represents a hydrogen atom or a monovalent organic group
  • m represents an integer of 1 to 3
  • n represents an integer of 0 to 3.
  • m + n ⁇ 5 is satisfied.
  • R a represents a hydrogen atom or a methyl group
  • R b represents a hydrogen atom or a monovalent organic group
  • r represents an integer of 1 to 3
  • s represents an integer of 0 to 3.
  • Examples of the monovalent organic group represented by R 5 in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, and a 1-methyl group.
  • a linear or branched alkyl group having 1 to 12 carbon atoms such as propyl group and t-butyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methyl
  • a methyl group, an ethyl group, an n-butyl group, and a t-butyl group are preferable.
  • i in the general formula (2) is an integer of 1 to 3, and is more preferably 1 or 2.
  • j in the general formula (2) is an integer of 0 to 3, and more preferably 0 to 2.
  • repeating unit (2) represented by the general formula (2) include repeating units represented by the following formulas (2-1) to (2-4).
  • this repeating unit (2) when the repeating unit (2) is contained in the polymer (A), this repeating unit (2) may be contained only 1 type, and may be contained 2 or more types.
  • k in the general formula (3) is an integer of 1 to 3, and is more preferably 1 or 2.
  • l in the general formula (3) is an integer of 0 to 3, and is more preferably 0 or 1.
  • repeating unit (3) represented by the general formula (3) include repeating units represented by the following formulas (3-1) and (3-2).
  • this repeating unit (3) when the repeating unit (3) is contained in the polymer (A), this repeating unit (3) may be contained only 1 type, and may be contained 2 or more types.
  • n in the general formula (4) is an integer of 0 to 3, and more preferably 0 or 1.
  • repeating unit (4) represented by the general formula (4) include repeating units represented by the following formulas (4-1) and (4-2).
  • this repeating unit (4) may be contained only 1 type, and may be contained 2 or more types.
  • r in the general formula (5) is an integer of 1 to 3, and more preferably 1 or 2.
  • s in the general formula (5) is an integer of 0 to 3, and more preferably 0 or 1.
  • repeating unit (5) represented by the general formula (5) examples include repeating units represented by the following formulas (5-1) and (5-2).
  • this repeating unit (5) when the repeating unit (5) is contained in the polymer (A), this repeating unit (5) may be contained only 1 type, and may be contained 2 or more types.
  • Each repeating unit represented by the formulas (2-1) to (2-3) can be obtained by using a corresponding hydroxystyrene derivative as a monomer. Furthermore, it can also obtain by using as a monomer the compound from which a hydroxy styrene derivative is obtained by hydrolyzing.
  • the monomer used for generating each repeating unit represented by the above formulas (2-1) to (2-3) p-acetoxystyrene, p- (1-ethoxyethoxy) styrene and the like are preferable. .
  • each of the repeating units represented by the formulas (2-1) to (2-3) may be formed by a side chain hydrolysis reaction after forming a polymer. it can.
  • each of the formulas (2-4), (3-1), (3-2), (4-1), (4-2), (5-1) and (5-2) The repeating unit can be obtained by using a corresponding monomer.
  • Each repeating unit represented by the formula (2-4), (3-1), (3-2), (4-1), (4-2), (5-1) and (5-2) Monomers used to produce p-isopropenylphenol, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacryl Amide, 5-hydroxynaphthalen-1-yl methacrylate, 5-hydroxynaphthalen-1-yl acrylate and the like are preferable.
  • the polymer (A) of the present invention contains repeating units derived from non-acid dissociable compounds (hereinafter referred to as “repeating units (hereinafter referred to as“ repeating units ”). 6) "), and a repeating unit derived from an acid dissociable compound (hereinafter also referred to as” repeating unit (7) ").
  • non-acid dissociable compound examples include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, isobornyl acrylate, tricyclodecanyl (meth) acrylate, and tetracyclodone.
  • decenyl (meth) acrylate examples include decenyl (meth) acrylate and compounds represented by the following formulas (b-1) to (b-4).
  • styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, tricyclodecanyl (meth) acrylate, the following formula (b-1), the following formula (b-2) ), Compounds represented by the following formula (b-3) and the following formula (b-4) are preferred.
  • this repeating unit (6) when the said repeating unit (6) is contained in the polymer (A), this repeating unit (6) may be contained only 1 type and may be contained 2 or more types.
  • examples of the repeating unit (7) include structural units represented by the following general formula (c-1) or (c-2). Among these, the structural unit represented by the general formula (c-1) is preferable.
  • R 12 each independently represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • Each R 13 is independently of each other a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or a substituted group. Or an aryl group having 6 to 22 carbon atoms which may have a group, or any two R 13 's bonded to each other, and each having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded.
  • a divalent alicyclic hydrocarbon group or a group derived therefrom is formed, and the remaining one R 13 is a linear or branched alkyl group having 1 to 4 carbon atoms, 1 having 4 to 20 carbon atoms, or the like.
  • Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in R 13 of the general formulas (c-1) and (c-2) include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples include -propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.
  • Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms in R 13 of the general formulas (c-1) and (c-2) include, for example, norbornane, tricyclodecane, tetracyclododecane, And a group consisting of an alicyclic ring derived from adamantane, cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
  • Examples of the group derived from this alicyclic hydrocarbon group include the above-mentioned monovalent alicyclic hydrocarbon groups such as methyl, ethyl, n-propyl, i-propyl, n- Groups substituted with one or more linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group Etc.
  • the alicyclic hydrocarbon group of R 13 is a group composed of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, or cyclohexane, or an alicyclic ring thereof.
  • a group obtained by substituting a group consisting of the above alkyl group is preferred.
  • Examples of the aryl group having 6 to 22 carbon atoms in R 13 of the general formulas (c-1) and (c-2) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and Examples thereof include 1-phenanthryl group.
  • One or more hydrogen atoms in the aryl group may be substituted.
  • Specific examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), phenyl group, acetoxy group, alkyl group, alkoxy group and the like.
  • any two R 13 in the general formulas (c-1) and (c-2) are bonded to each other, together with the carbon atom to which each is bonded (the carbon atom bonded to the oxygen atom).
  • the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms to be formed include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
  • the above-described divalent alicyclic hydrocarbon group may be, for example, a methyl group, an ethyl group, or the like.
  • Linear, branched or cyclic alkyl having 1 to 4 carbon atoms such as n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group
  • Examples include groups substituted with one or more groups or one or more groups.
  • a cyclopentylene group, a cyclohexylene group, a group obtained by substituting the divalent alicyclic hydrocarbon group with the alkyl group, and the like are preferable.
  • repeating unit (7) examples include repeating units represented by the following general formulas (7-1) to (7-8).
  • R 14 each independently represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group
  • R 15 each independently represents a carbon number of 1 to 4 linear or branched alkyl groups are represented.
  • this repeating unit (7) when the said repeating unit (7) is contained in the polymer (A), this repeating unit (7) may be contained only 1 type and may be contained 2 or more types.
  • the repeating unit (7) can be obtained, for example, by using compounds represented by the following general formulas (c-1-m) and (c-2-m) as monomers.
  • the total content of the repeating units (I) and (II) in the polymer (A) of the present invention is 1 mol% or more when the total of all repeating units in the polymer (A) is 100 mol%. More preferably, it is 1 to 45 mol%, more preferably 2 to 30 mol%. This content is preferably 1 mol% or more from the viewpoint of good sensitivity, high resolution, and reduced nano edge roughness.
  • the content of the repeating unit (1) in the polymer (A) of the present invention is preferably 1 mol% or more when the total of all repeating units in the polymer (A) is 100 mol%, More preferably, it is 5 to 80 mol%, and still more preferably 10 to 50 mol%.
  • this content is 1 mol% or more, when the polymer (A) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition, it can be excellent in nano edge roughness. .
  • the content of the repeating unit (6) is usually 80 mol% or less, preferably 0 to 60 mol%, when the total of all repeating units in the polymer (A) is 100 mol%. .
  • this content is 80 mol% or less, when this polymer (A) is used as an acid-dissociable group-containing polymer in a radiation-sensitive composition, the resolution performance and the performance of nanoedge roughness It can be excellent in balance.
  • the content of the repeating unit (7) is usually 60 mol% or less, preferably 0 to 50 mol%, when the total of all repeating units in the polymer (A) is 100 mol%. .
  • the total content of the repeating units (6) and (7) is 90 mol% or less, preferably 0 to 0 when the total of all repeating units in the polymer (A) is 100 mol%. 80 mol%.
  • this content is 90 mol% or less, when this polymer (A) is used as an acid-dissociable group-containing polymer in the radiation-sensitive composition, the resolution performance and the performance of nanoedge roughness It can be excellent in balance.
  • the method for synthesizing the polymer (A) in the present invention is not particularly limited, and can be obtained by, for example, known radical polymerization. Further, the side chain hydroxystyrene unit in other repeating units can be obtained by subjecting the obtained polymer (A) to hydrolysis of an acetoxy group or the like in the presence of a base or acid in an organic solvent.
  • radical polymerization for example, necessary monomers such as the compounds (Im) and (II-m) are stirred in a suitable organic solvent in a nitrogen atmosphere in the presence of a radical polymerization initiator. It can be carried out by heating.
  • radical polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy). -2,4-dimethylvaleronitrile) 2,2'-azobismethylbutyronitrile, 2,2'-azobiscyclohexanecarbonitrile, cyanomethylethylazoformamide, 2,2'-azobis (2,4-dimethyl) Azo compounds such as methyl propionate) and 2,2'-azobiscyanovaleric acid; benzoyl peroxide, lauroyl peroxide, 1,1'-bis- (t-butylperoxy) cyclohexane, 3,5,5-trimethyl And organic peroxides such as hexanoyl peroxide and t-butylperoxy-2-ethylhexanoate, and hydrogen peroxide.
  • a polymerization aid such as 2,
  • the reaction temperature in the radical polymerization is not particularly limited, and is appropriately selected depending on the type of initiator and the like (for example, 50 to 200 ° C.). In particular, when an azo initiator or a peroxide initiator is used, a temperature at which the half life of the initiator is about 10 minutes to about 30 hours is preferable, and more preferably, the half life of the initiator is about 30 minutes to about 10 hours. Temperature.
  • the reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases is about 0.5 to 24 hours.
  • examples of the acid used for the hydrolysis reaction include p-toluenesulfonic acid and its hydrate, methane Organic acids such as sulfonic acid, trifluoromethanesulfonic acid, malonic acid, oxalic acid, 1,1,1-fluoroacetic acid; inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid; or pyridinium p-toluenesulfonate, ammonium Examples thereof include salts such as p-toluenesulfonate and 4-methylpyridinium p-toluenesulfonate.
  • examples of the base include inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate; organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine, and tetramethylammonium hydroxide.
  • inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate
  • organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine, and tetramethylammonium hydroxide.
  • organic solvent used for the polymerization or hydrolysis examples include ketones such as acetone, methyl ethyl ketone, and methyl amyl ketone; ethers such as diethyl ether and tetrahydrofuran (THF); methanol, ethanol, propanol, and the like.
  • Alcohols such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated alkyls such as chloroform, bromoform, methylene chloride, methylene bromide, and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves; dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, etc. Protic polar solvents, and the like.
  • acetone, methyl amyl ketone, methyl ethyl ketone, tetrahydrofuran, methanol, ethanol, propanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.
  • the polymer (A) has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably from 1,000 to 100,000, more preferably from 2,000 to 40,000. More preferably, it is 2000 to 25000. Further, the ratio (Mw / Mn) of Mw of the polymer (A) and polystyrene-reduced number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 To 4, more preferably 1 to 3.
  • the radiation-sensitive resin composition of the present invention contains a novel sulfonate-containing polymer [the polymer (A)], it has excellent sensitivity. From this point of view, this radiation-sensitive resin composition is effectively sensitive to X-rays such as KrF excimer laser, ArF excimer laser, EUV and the like, and X-rays such as synchrotron radiation and electron beams in the lithography process. In addition, it is possible to form a chemically amplified positive resist film having low roughness, excellent sensitivity and resolution, and capable of forming a fine pattern with high accuracy and stability.
  • the radiation sensitive resin composition of the present invention further comprises an acid diffusion control agent (hereinafter also referred to as “acid diffusion control agent (B)”). It is preferable to contain.
  • the acid diffusion control agent (B) is a component having an action of controlling a diffusion phenomenon in the resist film (resist film) of an acid generated from the polymer (A) by exposure and suppressing an undesirable chemical reaction in a non-exposed region. It is.
  • the storage stability of the resulting radiation sensitive resin composition is improved, and the resist film formed is The resolution can be sufficiently improved.
  • a radiation-sensitive resin composition that can suppress a change in the line width of the resist pattern due to fluctuations in the holding time (PED) from the exposure to the heat treatment after the exposure, and has excellent process stability. can get.
  • a nitrogen-containing organic compound or a photosensitive basic compound is preferably used. Of these, it is preferable to use a photosensitive basic compound.
  • the nitrogen-containing organic compound include a compound represented by the following general formula (i) (hereinafter referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “ Nitrogen-containing compound (ii) ”), polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as“ nitrogen-containing compound (iii) ”), amide group-containing compounds, urea compounds, nitrogen-containing compounds Examples include heterocyclic compounds.
  • each R 17 is independently a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, an aryl group which may be substituted, or a substituent. Represents an aralkyl group which may be substituted.
  • nitrogen-containing compound (i) mono (cyclo) alkylamines, di (cyclo) alkylamines, tri (cyclo) alkylamines, substituted alkylamines, and aromatic amines are preferable.
  • nitrogen-containing compound (ii) examples include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino.
  • nitrogen-containing compound (iii) for example, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer and the like are preferable.
  • Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)- ( ⁇ )-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxy Piperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycar Nilpiperazine, N, N-di-t-butoxycarbonyl-1-adamanty
  • urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. Thiourea and the like are preferable.
  • nitrogen-containing heterocyclic compound examples include imidazoles; pyridines; piperazines; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidineethanol, 3-piperidino-1,2-propanediol, Morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2 2.2.2] Octane and the like are preferable.
  • the photosensitive basic compound (photo-degradable basic compound) is a component that decomposes in the exposed region and loses basicity, and remains in the unexposed portion without being decomposed. Since such a photosensitive basic compound can effectively use an acid generated in an exposed portion (that is, an exposed region) as compared with a non-photosensitive basic compound, the nano edge roughness and resolution can be reduced. Can be improved.
  • the type of the photosensitive basic compound is not particularly limited as long as it has the above properties.
  • compounds represented by the following general formulas (B1) and (B2) can be suitably used.
  • the compound represented by the following general formula (B1) is preferable.
  • R 13 and R 14 are each a monovalent organic group.
  • Z - is, R 15 O -, or R 15 COO - and is, R 15 is a monovalent organic group.
  • q independently represents an integer of 0 to 5.
  • Examples of the monovalent organic group for R 13 and R 14 in the general formulas (B1) and (B2) include a hydrogen atom, a halogen atom, and an alkyl group having 1 to 10 carbon atoms that may have a substituent, Or the alicyclic hydrocarbon group etc. which may have a substituent are mentioned.
  • alkyl group having 1 to 10 carbon atoms that may have a substituent include a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, and a trifluoromethyl group.
  • the alkyl group includes a hydroxy group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), alkyloxycarbonyl group. It may be substituted with a substituent such as (t-butoxycarbonylmethyloxy group and the like).
  • Examples of the alicyclic hydrocarbon group which may have a substituent include the structures of the general formulas (a-1) to (a-50).
  • the alicyclic hydrocarbon group includes a hydroxy group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), It may be substituted with a substituent such as an alkyloxycarbonyl group (such as t-butoxycarbonylmethyloxy group).
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 13 and R 14 are preferably a hydrogen atom or a tert-butyl group.
  • all of R 13 may be the same or a part or all of them may be different.
  • R 14 may be the same or different.
  • Each Z ⁇ in the general formulas (B1) and (B2) is R 15 O ⁇ or R 15 COO — .
  • Examples of the monovalent organic group for R 15 include an alkyl group which may have a substituent and an aryl group which may have a substituent.
  • Z ⁇ is preferably CH 3 COO ⁇ and compounds (Z-1) to (Z-4) represented by the following formulae.
  • photosensitive basic compound examples include a triphenylsulfonium compound [compound represented by the general formula (1)], in which an anion portion (Z ⁇ ) is CH 3 COO ⁇ , Examples thereof include compounds (Z-2) or (Z-3).
  • the said acid diffusion control agent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the acid diffusion controller (B) is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, still more preferably 100 parts by mass of the polymer (A). 0.005 to 5 parts by mass.
  • the compounding amount of the acid diffusion controller (B) exceeds 15 parts by mass, the sensitivity of the formed resist film and the developability of the exposed part may be deteriorated.
  • the blending amount is less than 0.001 part by mass, the pattern shape and dimensional fidelity of the formed resist film may be lowered depending on the process conditions.
  • the radiation-sensitive resin composition of the present invention includes, in addition to the polymer (A), other acid-generating compounds that generate acid upon decomposition by irradiation with actinic rays or radiation. May be contained.
  • the ratio of the total of the repeating units (I) and (II) in the polymer (A) in the present invention to the other acid generating compound is 100/0 to 20/80, preferably 100/0 in terms of molar ratio. -40/60, more preferably 100 / 0-50 / 50.
  • acid-generating compounds include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or acids by known light used in microresists. Can be selected and used as appropriate.
  • onium salt compounds examples include sulfonium salts (including tetrahydrothiophenium salts), iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. In addition, these compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
  • sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept.
  • triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluoro-n-butanesulfonate and triphenylphosphonium 1,1,2,2-tetrafluoro-6- (1-adamantane carbonyloxy) -hexane- 1-sulfonate is preferred.
  • tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium.
  • Nonafluoro-n-butanesulfonate 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphor Sulfonate, 1- (6-n-butoxynaphthalene-2-y ) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydr
  • 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium par Fluoro-n-octane sulfonate and 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butane sulfonate are preferred.
  • iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl.
  • the onium salt compound is particularly preferably an iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the general formula (PAG4).
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group.
  • preferred substituents include alkyl groups, haloalkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, nitro groups, carboxyl groups, alkoxycarbonyl groups, hydroxy groups, mercapto groups, and halogen atoms.
  • R 203 , R 204 and R 205 each independently represents a substituted or unsubstituted alkyl group or aryl group.
  • Preferred substituents include aryl groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, nitro groups, carboxyl groups, hydroxy groups and halogen atoms for aryl groups.
  • Z ⁇ represents a counter anion, and represents a perfluoroalkanesulfonate anion such as CF 3 SO 3 — or a pentafluorobenzenesulfonate anion.
  • R 203 , R 204 , and R 205 and Ar 1 and Ar 2 may be bonded via a single bond or a substituent.
  • the radiation-sensitive resin composition of the present invention may further include a resin having a group that increases solubility in an alkali developer, an alkali-soluble resin, a low molecular acid, if necessary.
  • a resin having a group that increases solubility in an alkali developer an alkali-soluble resin, a low molecular acid, if necessary.
  • Decomposable dissolution inhibiting compounds, dyes, pigments, plasticizers, surfactants, photosensitizers, compounds having two or more phenolic OH groups that promote solubility in a developer, and the like can be included.
  • solvent used for the preparation of the radiation sensitive resin composition solution examples include linear or branched solvents such as 2-pentanone, 2-hexanone, 2-heptanone, and 2-octanone. Ketones; Cyclic ketones such as cyclopentanone and cyclohexanone; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Methyl 2-hydroxypropionate and Ethyl 2-hydroxypropionate Alkyl 2-hydroxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
  • ethylene glycol monomethyl ether examples include methyl acid, ethyl pyruvate, N-methylpyrrolidone, and ⁇ -butyrolactone.
  • a solvent may be used individually by 1 type and may be used in combination of 2 or more type.
  • a surfactant may be added to the solvent.
  • the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan triole
  • the compounding amount of the surfactant is usually 2 parts by mass or less, preferably 1 part by mass or less per 100 parts by mass of the solid content in the composition of the present invention.
  • These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the solvent in the radiation-sensitive composition of the present invention is preferably such that the total solid concentration in the composition is 1 to 20% by mass, more preferably 1 to 15% by mass. The amount is more preferably 1 to 10% by mass.
  • the radiation-sensitive composition of the present invention can be obtained by blending the polymer (A) and a solvent. Specifically, necessary components such as the polymer (A) other than the solvent can be prepared by uniformly dissolving in the solvent so that the total solid content concentration falls within the above range. In addition, after preparing in this way, it is preferable to filter with a filter with a pore diameter of about 0.2 ⁇ m, for example.
  • Radiation sensitive resin composition (ii)
  • the radiation-sensitive resin composition (ii) of the present invention is characterized by containing a specific polymer, a specific cation, and a solvent.
  • the radiation-sensitive resin composition of the present invention comprises, as a polymer component, at least one of a repeating unit represented by the following general formula (Ia) and a repeating unit represented by the following general formula (II-a):
  • a polymer having one side hereinafter also referred to as “polymer (A2)” is contained.
  • This polymer (A2) is an alkali-insoluble or hardly alkali-soluble polymer, and becomes a polymer that becomes readily alkali-soluble by the action of an acid.
  • R 7 and R 11 each independently represent a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group.
  • R 8 to R 10 each independently represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group.
  • A represents an —O— group or a —NR 12 — group (R 12 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group).
  • D represents a methylene group, an alkylene group, or an arylene group which may have a substituent. ]
  • R 7 to R 11 , A and D are those in the general formulas (I) and (II) in the above-mentioned radiation-sensitive resin composition (i). It is synonymous with R 7 to R 11 , A and D.
  • the polymer (A2) may further contain one or more of the repeating units (1) to (7) described in the radiation sensitive resin composition (i).
  • it preferably contains a structural unit having an acid dissociable group (repeating unit (7)).
  • the total content of the repeating unit represented by the general formula (Ia) and the repeating unit represented by the general formula (II-a) in the polymer (A) of the present invention is the polymer (A2).
  • the total of all repeating units in is 100 mol%, it is preferably 1 mol% or more, more preferably 1 to 45 mol%, still more preferably 2 to 30 mol%.
  • This content is preferably 1 mol% or more from the viewpoint of good sensitivity, high resolution, and reduced nano edge roughness.
  • the content of the repeating unit (1) in the polymer (A2) of the present invention is preferably 1 mol% or more when the total of all repeating units in the polymer (A2) is 100 mol%, More preferably, it is 5 to 80 mol%, and still more preferably 10 to 50 mol%. When this content is 1 mol% or more, the nano edge roughness can be excellent.
  • the content of the repeating unit (6) is usually 80 mol% or less, preferably 0 to 60 mol%, when the total of all repeating units in the polymer (A2) is 100 mol%. . When this content is 80 mol% or less, it can be excellent in performance balance between resolution performance and nanoedge roughness. Further, the content of the repeating unit (7) is usually 60 mol% or less, preferably 0 to 50 mol%, when the total of all repeating units in the polymer (A2) is 100 mol%. . When this content is 60 mol% or less, it can be excellent in performance balance between resolution performance and nanoedge roughness.
  • the total content of the repeating units (6) and (7) is 90 mol% or less, preferably 0 to 0 when the total of all repeating units in the polymer (A2) is 100 mol%. 80 mol%.
  • this content is 90 mol% or less, it can be excellent in performance balance between resolution performance and nanoedge roughness.
  • the method for synthesizing the polymer (A2) in the present invention is not particularly limited, and can be obtained by, for example, known radical polymerization. Further, the side chain hydroxystyrene unit in other repeating units can be obtained by subjecting the obtained polymer (A2) to hydrolysis of an acetoxy group or the like in the presence of a base or an acid in an organic solvent.
  • the radical polymerization can be carried out, for example, by stirring and heating necessary monomers in a suitable organic solvent in a nitrogen atmosphere in the presence of a radical polymerization initiator.
  • a radical polymerization initiator for example, by stirring and heating necessary monomers in a suitable organic solvent in a nitrogen atmosphere in the presence of a radical polymerization initiator.
  • the polymer (A2) has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably from 1,000 to 100,000, more preferably from 2,000 to 40,000. More preferably, it is 2000 to 25000.
  • Mw polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography
  • Mn polystyrene-equivalent weight average molecular weight measured by GPC
  • the radiation-sensitive resin composition of the present invention contains a cation represented by the following general formula (III).
  • each of R 1 to R 3 independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, or a —SR 6 group.
  • R 6 represents an alkyl group or an aryl group which may have a substituent
  • l represents an integer of 1 to 5.
  • m and n each independently represents an integer of 0 to 5.
  • R 1 ⁇ R 3, l, m and n R 1 ⁇ R 3 in the general formula (I) in the radiation-sensitive resin composition of the above (i), l, m and It is synonymous with n.
  • the cation represented by the general formula (III) may be introduced into the radiation-sensitive resin composition (ii) in any manner. Specifically, it may be introduced as a polymer having a corresponding anion moiety, or may be introduced as an acid generating compound having a corresponding anion moiety.
  • the radiation-sensitive resin composition (ii) of the present invention further increases solubility in an acid generator, an acid diffusion controller, and an alkali developer as necessary.
  • Resin having a group, alkali-soluble resin, low molecular acid decomposable dissolution inhibiting compound, dye, pigment, plasticizer, surfactant, photosensitizer, and two phenolic OH groups that promote solubility in developer The compounds having the above can be contained.
  • the blending amount of the solvent in the radiation-sensitive composition (ii) of the present invention is preferably such that the total solid content concentration in the composition is 1 to 20% by mass, more preferably 1 to 15%.
  • the radiation-sensitive composition (ii) of the present invention can be obtained, for example, by blending a polymer (A2), a compound having a cation represented by the general formula (III), and a solvent.
  • necessary components such as the polymer (A2) other than the solvent can be prepared by uniformly dissolving in the solvent so that the total solid content concentration falls within the above range.
  • the monomer of the present invention is characterized by being represented by the aforementioned general formula (Im) or general formula (II-m).
  • This monomer can be suitably used as a monomer for synthesizing the polymer (A) in the radiation-sensitive resin composition of the present invention.
  • the polymer of the present invention has at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II). It is a feature.
  • This polymer generates sulfonic acid upon irradiation with an electron beam, extreme salt ultraviolet rays, or the like, and can be suitably used as a polymer component in the radiation-sensitive resin composition of the present invention.
  • the radiation-sensitive resin composition of the present invention is useful as a material capable of forming a chemically amplified positive resist film.
  • an acid-dissociable group in the polymer (A) is eliminated by the action of an acid generated from the polymer (A) by exposure, and the polymer (A) is alkali-soluble.
  • the polymer (A) is alkali-soluble.
  • This alkali-soluble portion is an exposed portion of the resist, and this exposed portion can be dissolved and removed by an alkali developer. In this way, a positive resist pattern having a desired shape can be formed. This will be specifically described below.
  • a resist film is formed using the radiation-sensitive resin composition of the present invention.
  • the radiation-sensitive resin composition for example, as described above, after adjusting the total solid content concentration, it can be filtered with a filter having a pore diameter of about 0.2 ⁇ m.
  • a resist film is formed.
  • heat treatment hereinafter referred to as “PB”) may be performed in advance at a temperature of about 70 to 160 ° C.
  • the resist film is exposed so that a predetermined resist pattern is formed.
  • radiation that can be used for this exposure include (extreme) far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV (extreme ultraviolet light, wavelength 13.5 nm, etc.), and synchro Examples include X-rays such as tron radiation, and charged particle beams such as electron beams.
  • exposure conditions, such as exposure amount can be suitably selected according to the composition of the radiation-sensitive resin composition, the type of additive, and the like. This exposure can also be immersion exposure.
  • PEB heat processing
  • a predetermined resist pattern is formed by developing the exposed resist film.
  • the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine.
  • An alkaline aqueous solution in which at least one kind of alkaline compound such as [4.3.0] -5-nonene is dissolved is preferable.
  • the concentration of the alkaline aqueous solution is preferably 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer.
  • the developer is preferably pH 8 to 14, more preferably pH 9 to 14.
  • an organic solvent can be added to the developer composed of the alkaline aqueous solution.
  • the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl Alcohols such as alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane And esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and
  • the blending amount of the organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution.
  • the blending amount of the organic solvent exceeds 100 parts by volume, the developability is lowered, and there is a possibility that the remaining development in the exposed part increases.
  • an appropriate amount of a surfactant or the like can be added to the developer composed of an alkaline aqueous solution.
  • it can also wash with water and can be dried.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • MALLS was used as a detector for measuring the molecular weight (Mw, Mn) of the resin.
  • a GPC column TSKgel ⁇ -2500, TSKgel ⁇ -M
  • a flow rate of 1.0 ml / min, 30 mmol / l of LiBr and 10 mmol / l of H 3 PO 4 as elution solvents were dissolved in dimethylformamide.
  • the sample was measured by gel permeation chromatography (GPC) using MALLS (manufactured by Wyatt, DAWN DSP, cell type K5, laser wavelength 632.8 nm) as a detector under the analysis conditions with a column temperature of 40 ° C.
  • GPC gel permeation chromatography
  • MALLS manufactured by Wyatt, DAWN DSP, cell type K5, laser wavelength 632.8 nm
  • Measurement was performed using a nuclear magnetic resonance apparatus “JNM-EX270” (model name) manufactured by JEOL.
  • ⁇ 13 C-NMR analysis> Measurement was performed using a nuclear magnetic resonance apparatus “JNM-EX270” (model name) manufactured by JEOL.
  • the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
  • the polymerization solution was cooled to 30 ° C. or less by water cooling, and after cooling, it was poured into 2000 g of 2-propanol, and the precipitated white solid was separated by filtration.
  • the filtered white powder was washed twice with 100 g of 2-propanol as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (52g, 52% of yield).
  • This polymer has Mw of 5000 and Mw / Mn of 2.1.
  • the repeating unit derived from compound (M-1) repeating unit derived from compound (M-2): compound ( It was a copolymer having a content ratio (molar ratio) of the repeating unit derived from P-1) of 47:37:16.
  • this polymer is referred to as a polymer (A-1).
  • the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
  • the polymerization solution was cooled to 30 ° C. or less by water cooling, and after cooling, it was poured into 2000 g of n-hexane, and the precipitated white solid was separated by filtration. Subsequently, the filtered white powder was washed twice with 100 g of n-hexane as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (55g, yield 55%).
  • the copolymer was a copolymer having a content ratio (molar ratio) of the repeating unit derived from P-2) of 62:28:10.
  • this polymer is referred to as a polymer (A-2).
  • the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
  • the polymerization solution was cooled to 30 ° C. or less by water cooling, and after cooling, it was poured into 2000 g of 2-propanol, and the precipitated white solid was separated by filtration.
  • the filtered white powder was washed twice with 100 g of 2-propanol as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (50g, yield 50%).
  • the copolymer was a copolymer having a content ratio (molar ratio) of the repeating unit derived from P-3) of 45:44:11.
  • this polymer is referred to as a polymer (A-3).
  • the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
  • the polymerization solution was cooled to 30 ° C. or less by water cooling, and after cooling, it was poured into 2000 g of 2-propanol, and the precipitated white solid was separated by filtration.
  • the filtered white powder was washed twice with 100 g of 2-propanol as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (52g, 52% of yield).
  • the repeating unit derived from compound (M-3) repeating unit derived from compound (M-2): compound (
  • the copolymer was a copolymer having a content ratio (molar ratio) of the repeating unit derived from P-4) of 44:45:11.
  • this polymer is referred to as a polymer (A-4).
  • the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
  • the polymerization solution was cooled to 30 ° C. or less by water cooling, and after cooling, it was poured into 2000 g of 2-propanol, and the precipitated white solid was separated by filtration.
  • the filtered white powder was washed twice with 100 g of 2-propanol as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of white powder (68g, yield 68%).
  • the repeating unit derived from compound (M-6) repeating unit derived from compound (M-2): compound ( The content ratio (molar ratio) of the repeating unit derived from P-5) was a copolymer of 47: 50: 3.
  • this polymer is referred to as a polymer (A-5).
  • the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
  • the polymerization solution was cooled to 30 ° C. or less by water cooling, and after cooling, it was poured into 2000 g of n-hexane, and the precipitated white solid was separated by filtration. Subsequently, the filtered white powder was washed twice with 100 g of n-hexane as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (52g, 52% of yield).
  • this polymer is referred to as a comparative polymer (a1).
  • the inside of the flask was heated to 80 ° C. while stirring with a magnetic stirrer.
  • a monomer solution prepared in advance was added dropwise over 2 hours.
  • the reaction was further continued for 1 hour, and 10 g of isopropanol solution of 3.05 g (15 mol%) of vinyl sulfonic acid was dropped over 30 minutes, and then the reaction was further continued for 1 hour. It cooled to 30 degrees C or less, and the copolymer liquid was obtained.
  • the obtained copolymer solution was concentrated to 150 g, and then transferred to a separatory funnel.
  • the separatory funnel was charged with 50 g of methanol and 600 g of n-hexane to carry out separation and purification. After separation, the lower layer solution was recovered. This lower layer solution was diluted with isopropanol to 100 g, and again transferred to a separatory funnel. 50 g of methanol and 600 g of n-hexane were put into the above separatory funnel, followed by separation and purification. After separation, the lower layer solution was recovered. The recovered lower layer solution was replaced with 4-methyl-2-pentanol, and the total amount was adjusted to 250 g. After the adjustment, 250 g of water was added for separation and purification. After separation, the upper layer liquid was recovered.
  • the recovered upper layer liquid was replaced with 4-methyl-2-pentanol to obtain a resin solution.
  • Mw of the copolymer contained in the obtained resin solution was 9,760, Mw / Mn was 1.51, and the yield was 65%.
  • This copolymer is referred to as “resin (A-7)”.
  • Sensitivity (L / S)
  • a pattern [a so-called line-and-space pattern (1L1S)] composed of a line portion having a line width of 150 nm and a space portion (that is, a groove) having an interval of 150 nm formed by adjacent line portions is 1: 1.
  • the exposure amount formed in the line width was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.
  • FIG. 1 is a plan view schematically showing the shape of a line and space pattern.
  • FIG. 2 is a cross-sectional view schematically showing the shape of the line and space pattern. However, the unevenness shown in FIGS. 1 and 2 is exaggerated from the actual.
  • Nano-edge roughness Line-and-space pattern (1L1S) with a design line width of 150 nm is scanned with a scanning electron microscope for semiconductors (high resolution FEB measuring device, trade name “S-9220”, manufactured by Hitachi, Ltd.) ).
  • high resolution FEB measuring device trade name “S-9220”, manufactured by Hitachi, Ltd.
  • FIG. 1 and FIG. 2 the line width and the design line at the most conspicuous portion of the unevenness generated along the lateral surface 2a of the line portion 2 of the resist film formed on the silicon wafer 1 are shown.
  • the difference “ ⁇ CD” from the width of 150 nm was measured by CD-SEM (manufactured by Hitachi High-Technologies Corporation, “S-9220”) to evaluate nanoedge roughness.
  • MEEF Mesk Error Enhancement Factor
  • the exposure amount at which a line-and-space (LS) pattern with a line width of 50 nm is formed by exposing through a mask pattern with a target size of 50 nm 1 L / 1S under the above evaluation conditions was defined as the optimum exposure amount.
  • an LS pattern with a pitch of 100 nm is formed using a mask pattern with an optimum exposure amount and a line width target size of 46 nm, 48 nm, 50 nm, 52 nm, and 54 nm, and the line width formed on the resist film is changed to Hitachi.
  • Measured length SEM measured with CG4000.
  • the slope of the straight line when the target size (nm) was plotted on the horizontal axis and the line width (nm) formed on the resist film using each mask pattern was plotted on the vertical axis was calculated as MEEF. Note that the lower the MEEF value, the lower the mask creation cost.
  • Nano-edge roughness The exposure amount at which a resist pattern having a line width of 50 nm is formed by exposing through a mask pattern having a target size of 50 nm 1 L / 1.8 S under the above evaluation conditions was determined as the optimum exposure amount.
  • the line width was observed at 10 arbitrary points, and the measurement variation was observed.
  • the value expressed in 3 sigma was defined as LWR. It shows that the linearity of a pattern is excellent, so that the value of LWR is low.
  • the radiation-sensitive resin compositions of Examples 11 to 17 containing the polymers (A-1) to (A-5) having specific repeating units are the same as those of Comparative Example 1.
  • Chemical amplification that is more sensitive to electron beam or extreme ultraviolet light than radiation resin composition, has low roughness and excellent resolution, and can form fine patterns with high accuracy and stability. It was confirmed that a positive resist film can be formed.
  • the radiation-sensitive resin composition of the present invention is not only excellent in the resolution of the line and space pattern at the time of pattern formation, but is also excellent in nano edge roughness, so it is useful for forming a fine pattern by an electron beam or extreme ultraviolet rays. . Therefore, the radiation-sensitive resin composition of the present invention is extremely useful as a material capable of forming a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future.

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EP3205640A1 (en) 2016-02-10 2017-08-16 Shin-Etsu Chemical Co., Ltd. Monomer, polymer, resist composition, and patterning process
KR101856812B1 (ko) 2013-12-25 2018-05-10 신에쓰 가가꾸 고교 가부시끼가이샤 고분자 화합물
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US9097971B2 (en) 2011-06-17 2015-08-04 Tokyo Ohka Kogyo Co., Ltd. Compound, radical polymerization initiator, method for producing compound, polymer, resist composition, and method for forming resist pattern
WO2013031878A1 (ja) * 2011-09-02 2013-03-07 セントラル硝子株式会社 重合性単量体、重合体およびそれを用いたレジストならびにそのパターン形成方法
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JP2016023233A (ja) * 2014-07-18 2016-02-08 信越化学工業株式会社 導電性ポリマー用高分子化合物及びその製造方法
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JP2016056168A (ja) * 2014-09-08 2016-04-21 東洋合成工業株式会社 スルホニウム塩の製造方法
EP3205640A1 (en) 2016-02-10 2017-08-16 Shin-Etsu Chemical Co., Ltd. Monomer, polymer, resist composition, and patterning process
JP2019008280A (ja) * 2017-06-21 2019-01-17 信越化学工業株式会社 レジスト材料及びパターン形成方法
WO2023171670A1 (ja) * 2022-03-09 2023-09-14 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法、化合物、及び高分子化合物

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