WO2014017618A1 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film using the same, pattern forming method, and method for manufacturing electronic device and electronic device using the same - Google Patents

Actinic ray-sensitive or radiation-sensitive resin composition, resist film using the same, pattern forming method, and method for manufacturing electronic device and electronic device using the same Download PDF

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Publication number
WO2014017618A1
WO2014017618A1 PCT/JP2013/070256 JP2013070256W WO2014017618A1 WO 2014017618 A1 WO2014017618 A1 WO 2014017618A1 JP 2013070256 W JP2013070256 W JP 2013070256W WO 2014017618 A1 WO2014017618 A1 WO 2014017618A1
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WIPO (PCT)
Prior art keywords
group
carbon atoms
sensitive
resin
acid
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PCT/JP2013/070256
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French (fr)
Inventor
Kousuke Koshijima
Shuhei Yamaguchi
Kei Yamamoto
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Fujifilm Corporation
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Publication of WO2014017618A1 publication Critical patent/WO2014017618A1/en

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    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(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
    • G03F7/0045—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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • G—PHYSICS
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    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters

Definitions

  • the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film using the same, a pattern forming method, and a method for manufacturing an electronic device, and an electronic device using the same. More specifically, the present invention relates to a pattern forming method suitably used for a manufacturing process of a semiconductor such as an IC, a manufacturing process of a circuit board of a liquid crystal, a thermal head or the like, and other lithography processes of photofabrication, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used in the pattern forming method, and a method for manufacturing an electronic device, and an electronic device using the same.
  • a pattern forming method suitably used for a manufacturing process of a semiconductor such as an IC, a manufacturing process of a circuit board of a liquid crystal, a thermal head or the like, and other lithography processes of photofabrication, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used in the pattern forming method
  • the present invention relates to a pattern forming method suitably used for the exposure in an ArF exposure apparatus and an ArF liquid immersion projection exposure apparatus, which use far-ultraviolet rays having a wavelength of 300 nm or less as a light source, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used in the pattern forming method, and a method for manufacturing an electronic device, and an electronic device.
  • an image forming method called chemical amplification has been used as an image forming method of a resist in order to compensate for desensitization caused by light absorption.
  • the method is an image forming method in which an acid-generator of an exposed portion is degraded by exposure to produce an acid, and then, by using the generated acid as a reaction catalyst in PEB (Post Exposure Bake), an alkali-insoluble group is changed to an alkali-soluble group to remove the exposed portion by alkali development.
  • PEB Post Exposure Bake
  • the positive type image forming method using the chemical amplification mechanism has become mainstream, and for example, a method of forming a contact hole using the method is also known (see International Publication No. WO2008/149701 and Japanese Patent Application Laid-Open No. 2004-361629).
  • an isolated line or dot pattern may be formed well, but the shape of the pattern easily deteriorates when an isolated space (trench pattern) or fine hole pattern is formed.
  • Japanese Patent Application Laid-Open No. 2011-141494 discloses a technique in which a resesist composition containing a polymer compound having a repeating unit having a substituted or unsubstituted naphthol group as an acid-labile group, an acid generator and an organic solvent is coated on a substrate, and after heat treatment, a developer containing an organic solvent is used to dissolve an unexposed portion, and dissolve exposed portion to obtain a negative pattern in which the exposed portion is not dissolved. According to the technique, it is said that a fine hole pattern may be efficiently formed.
  • the present invention has been made in consideration of the aforementioned problem, and an object thereof is to provide, in forming a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer, a pattern forming method capable of realizing small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used therein, a method for manufacturing an electronic device, and an electronic device using them.
  • a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer
  • a pattern forming method capable of realizing small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used therein, a method for manufacturing an electronic
  • the present invention has the following configuration, and the problem of the present invention may be accordingly solved.
  • An actinic ray-sensitive or radiation-sensitive resin composition including: (A) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group; (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; and (C) a component containing at least one of: a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH 3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid, wherein a content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55% by mole (mol%) or more based on a whole repeating units of the resin (A).
  • actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the actinic ray-sensitive or radiation-sensitive resin composition contains two or more kinds of compounds as the compound (B), and at least one of the two or more kinds of compounds is a compound having no aromatic group or having one or two aromatic groups.
  • a pattern forming method including: exposing the resist film according to [10]; and developing the exposed resist film with a developer containing an organic solvent to form a negative pattern.
  • a method for manufacturing an electronic device including the pattern forming method according to [1 1] or [12].
  • the present invention has the following constitution.
  • a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer
  • a pattern forming method capable of realizing small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used therein, a method for manufacturing an electronic device, and an electronic device using them.
  • an alkyl group includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (a substituted alkyl group).
  • actinic ray or “radiation” in the present specification refers to, for example, a bright line spectrum of a mercury lamp, far-ultraviolet rays represented by an excimer laser, extreme ultraviolet (EUV) rays, X-rays, an electron beam (EB) and the like.
  • light in the present invention refers to the actinic rays or the radiations.
  • exposure in the present specification includes not only the exposure performed using a mercury lamp, far-ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, EUV rays and the like, but also drawing performed by a particle beam such as an electron beam and an ion beam.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invnetion contains:
  • (C) a component containing at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH 3 partial structure in a side chain moiety and having basicity or capable of increasing the basicity by the action of an acid,
  • the content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55 mol% or more based on the whole repeating units of the resin (A).
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invnetion in forming a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer, it is possible to realize small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects.
  • LWR line width roughness
  • DOF depth of focus
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group, and the content of the repeating unit is 55 mol% or more based on the whole repeating units of the resin.
  • the dissolution contrast for an organic solvent between the exposed portion and unexposed portion in the resist film may be further increased, and as a result, roughness performance such as LWR may be enhanced, and reduction in development defects may be realized as well.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a component (C) containing at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH 3 partial structure in a side chain moiety and having basicity or capable of increasing the basicity by the action of an acid.
  • the surface free energy of the component (C) is low, it is easy to be localized on the top layer portion of the resist film at high concentrations.
  • the solubility of the top layer portion of the resist film in the developer containing the organic solvent is enhanced, and as a result, the unexposed portion is remained undissolved, thereby reducing the development defects. Further, it is thought that, during the exposure, the pattern is suppressed from being reverse tapered due to the degradation of the contrast of exposure amounts in the exposed portion and the unexposed portion by diverging from the optimal point of the focus, thereby enhancing DOF.
  • the component (C) is localized on the surface of the resist film at high concentrations, and thus, the solubility of the top layer portion of the resist film in the developer containing an organic solvent is enhanced. As a result, the resultant pattern becomes more rectangular (pattern shape becomes better), thereby reducing the pattern collapse.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is used in a negative type development (development in which the solubility in a developer is decreased when exposed, and tuhs, the exposed portion is remained as a pattern, and the unexposed portion is removed), particularly in the case where a pattern having an ultrafine width (for example, 40 nm or less) is formed on the resist film.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may be used as an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development, which is used for development using a developer containing an organic solvent.
  • the term, for organic solvent development refers to a use that is used in a process of developing a film using a developer containing at least an organic solvent.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition and a negative type resist composition (that is, a resist composition for organic solvent development), from the viewpoint of obtaining a particularly good effect.
  • the composition according to the present invention is typically a chemical amplification resist composition.
  • the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (A) (hereinafter, also referred to as an "acid-decomposable resin” or “resin (A)”) having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group (hereinafter, also referred to as an "acid-decomposable group”).
  • the resin (A) is a resin whose solubility in a developer containing an organic solvent is decreased by the action of an acid.
  • the acid-decomposable resin is preferably a resin in which the group generating a polar group has a structure in which the polar group is protected with a group capable of decomposing and leaving by the action of an acid (hereinafter, also referred to as an "acid-decomposable group").
  • Examples of the resin (A) may include a resin having acid-decomposable groups at the main chain or the side chain, or both of the main chain and the side chain.
  • the resin (A) is also a resin capable of increasing the polarity by the action of an acid to increase the solubility in an alkali developer.
  • the polar group is not particularly limited as long as the polar group is a group that is sparingly soluble or insoluble in a developer containing an organic solvent, but examples thereof may include an acidic group (a group that is dissociated in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, which has been used as a developer of a tranditional resist) such as a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonate group, a sulfonamide group, a sulfonylimide, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group,
  • the alcoholic hydroxyl group is a hydroxyl group that is bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) that is directly bonded to an aromatic ring, and an aliphatic alcohol (for example, a fluorinated alcohol group (a hexafluoroisopropanol group or the like)) which is substituted with an electron-withdrawing group such as a fluorine atom at the a-position is excluded as a hydroxyl group.
  • the alcoholic hydroxyl group is preferably a hydroxyl group having a p a of 12 to 20.
  • Examples of a preferred polar group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) and a sulfonic acid group.
  • a preferred acid-decomposable group is a group obtained by substituting a hydrogen atom of the groups by a group capable of leaving by the action of an acid.
  • Examples of the group capable of leaving by the action of an acid may include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(Roi)(Ro2)(OR 3 9) and the like.
  • R 36 to R 3 9 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be bound with each other to form a ring.
  • Roi and Ro 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the group capable of decomposing and leaving by the action of an acid has preferably 5 or more carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 1 1 to 20 carbon atoms. Accordingly, DOF becomes better.
  • the reason is considered that the volume of the leaving group becomes larger by change in focus, and thus, the change in diffusion length of the acid and the compound having basicity or capable of increasing the basicity by the action of an acid becomes larger with respect to the change in exposure amount in the exposed portion, resulting in suppression of excessive diffusion of an acid into the unexposed portion, which is a factor that the pattern size is diverged from a desired width.
  • the alkyl group of R 36 to R 3 9, Roi and Ro 2 is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a hexyl group, an octyl group and the like.
  • the cycloalkyl group of R 36 to R39, Roi and R 02 may be monocyclic or polycyclic.
  • the monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
  • the polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof may include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an a-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, an androstanyl group and the like.
  • at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
  • the aryl group of R 3 to 3 9 and R ⁇ and Ro 2 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof may include a phenyl group, a naphthyl group, an anthryl group and the like.
  • the aralkyl group of R 36 to R 3 g and Roi and R 02 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof may include a benzyl group, a phenethyl group, a naphthylmethyl group and the like.
  • the alkenyl group of R 36 to R39 and Roi and R 02 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof may include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like.
  • the ring which may be formed by R 36 and R 37 being bound with each other is preferably a cycloalkyl group (monocyclic or polycyclic).
  • the cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group.
  • the group is more preferably monocyclic cycloalkyl group having 5 to 6 carbon atoms, and particularly preferably a monocyclic cycloalkyl group having 5 carbon atoms.
  • the acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group and the like.
  • the group is more preferably a tertiary alkyl ester group.
  • the resin (A) has a repeating unit having an acid-decomposable group.
  • the resin (A) has a repeating unit having a repeating unit represented by the following Formula (I) as a repeating unit having an acid-decomposable group.
  • R 1b a repeating unit having a repeating unit represented by the following Formula (I) as a repeating unit having an acid-decomposable group.
  • X a represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.
  • Ri a , and Ri c each independently represent an alkyl group or a cycloalkyl group. Two of R la , R ⁇ and Ri c may be bound with each other to form a ring structure.
  • the alkyl group of X a may have a substituent, and examples of the substituent may include a hydroxyl group, a halogen atom (preferably, a fluorine atom).
  • the alkyl group of X a is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and preferably a methyl group.
  • X a is preferably a hydrogen atom or a methyl group.
  • the alkyl group of R ] a , Rib and Ri c is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group and an isobutyl group, t-butyl group.
  • the cycloalkyl group of Ri a , Rib and Ri c is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group.
  • the ring structure formed by two of Rj a , R ⁇ and Ri c being bound with each other is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring and a cyclohexyl ring, or a polycylic cycloalkyl group such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring and an adamantane ring.
  • the ring structure is particularly preferably a monocyclic cycloalkane ring having 5 or 6 carbon atoms.
  • Ria, Rib and Ri c are each independently preferably an alkyl group, and more preferably a straight or branched alkyl group having 1 to 4 carbon atoms.
  • Each of the groups may further have a substituent, and examples of the substituent may include a halogen atom, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably a group having 8 or less carbon atoms.
  • Rx represents a hydrogen atom, CH 3 , CF or CH 2 OH.
  • Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms.
  • Z represents a substituent, and when a plurality of Z's is present, Z's may be the same or different, p represents 0 or a positive integer.
  • Specific examples and preferred examples of Z are the same as the specific examples and the preferable examples of a substituent that may be possessed by each group of Ri to R 3 .
  • the repeating unit represented by Formula (I) may be used either alone or in combination of two or more thereof.
  • the resin (A) has a repeating unit represented by the following Formula (AI).
  • Xai represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.
  • T represents a divalent linking group.
  • Rxi to Rx 3 each independently represent an alkyl group or a cycloalkyl group.
  • Two of Rx ⁇ to Rx 3 may be bound with each other to form a ring structure.
  • the divalent linking group of T may be an alkylene group, a -COO-Rt- group, a -O-Rt- group, a phenylene group or the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a -COO-Rt- group.
  • Rt is preferably an alkylene group having lto 5 carbon atoms, and more preferably a -CH 2 - group, a -(CH 2 ) 2 - group or a -(CH 2 ) 3 - group.
  • alkyl group and the cycloalkyl group of Rxi to Rx 3 are the same as the specific examples and the preferred examples of the alkyl group and the cycloalkyl group of Ri a to Ri c in Formula (I).
  • Specific examples and preferred examples of the ring structure formed by two of Rxt to Rx 3 being bound with each other are the same as the specific examples and the preferred examples of the ring structure formed by two of Ri a to Ri c in Formula (I) being bound with each other to form.
  • Each of the groups may have a substituent, and examples of the substituent may include an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 to 8 carbon atoms), a halogen atom, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably a group having 8 or less carbon atoms.
  • the substituent may include an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 to 8 carbon atoms), a halogen atom, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably a group having 8 or less carbon atoms.
  • the substituent is more preferably a substituent which does not have a heteroatom such as an oxygen atom, a nitrogen atom and a sulfur atom (for example, more preferably a substituent which is not an alkyl group substituted with a hydroxyl group), still more preferably a group composed only of hydrogen atoms and carbon atoms, and particularly preferably a straight or branched alkyl group or cycloalkyl group.
  • repeating unit represented by Formula (AI) Specific examples of the repeating unit represented by Formula (AI) are shown below, but the present invention is not limited thereto.
  • Xai represents a hydrogen atom, CH 3 , CF 3 or CH 2 OH.
  • Z represents a substituent, and when a plurality of Z's is present, Z's may be the same or different, p represents 0 or a positive integer.
  • Specific examples and preferred examples of Z are the same as the specific examples and the preferred examples of the substituent which may be possessed by each group of Rxi to Rx 3 .
  • the resin (A) has a repeating unit represented by the followin Formula (rV) as a repeating unit having an acid-decomposable group.
  • X b represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.
  • Ryi to Ry 3 each independently represent an alkyl group or a cycloalkyl group. Two of Ry ⁇ to Ry 3 may be linked with each other to form a ring.
  • Z represents a (p+l)-valent linking group having a polycyclic hydrocarbon structure which may have a heteroatom as a ring member. It is preferred that Z does not contain an ester bond as an atomic group constituting the polycyclic ring (in other words, it is preferred that Z does not contain a lactone ring as a ring constituting the polycyclic ring).
  • L 4 and L 5 each independently represent a single bond or a divalent linking group.
  • p represents an integer of 1 to 3.
  • L 5 's, Ryi 's, Ry 2 's and Ry 3 's may be the same or different, respectively.
  • the alkyl group of X b may have a substituent, and examples of the substituent may include a hydroxyl group and a halogen atom (preferably a fluorine atom).
  • the alkyl group of X b is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and preferably a methyl group.
  • Xb is preferably a hydrogen atom or a methyl group.
  • alkyl group and the cycloalkyl group of Ryi to Ry 3 are the same as the specific examples and the preferred examples of the alkyl group and the cycloalkyl group of R to R tc in Formula (I).
  • Ry ⁇ to Ry 3 are each independently preferably an alkyl group, and more preferably a straight or branched alkyl group having 1 to 4 carbon atoms. Further, the sum of carbon atoms of the alkyl group as Ryi to Ry 3 is preferably 5 or less.
  • Ryi to Ry 3 may further have a substituent, and such a substituent is the same as that exemplified as a substituent which may be further possessed by Rxi to Rx 3 in Formula (AI).
  • the linking group having a polycyclic hydrocarbon structure of Z includes a ring-assembled hydrocarbon ring group and a bridged cyclic hydrocarbon ring group, and examples thereof include a group obtained by removing any (p+1) hydrogen atoms from a ring-assembled hydrocarbon ring and a group obtained by removing any (p+1) hydrogen atoms from a bridged cyclic hydrocarbon ring, respectively.
  • Examples of the ring-assembled hydrocarbon ring group may include a bicyclohexane ring group, a perhydronaphthalene ring group and the like.
  • Examples of the bridged cyclic hydrocarbon ring group may include a bicyclic hydrocarbon ring group such as a pinane ring group, a bornane ring group, a norpinane ring group, a norbornane ring group and a bicyclooctane ring group (a bicyclo[2.2.2]octane ring group, a bicyclo[3.2.1]octane ring group and the like), a tricyclic hydrocarbon ring group such as a homobledane ring group, an adamantane ring group, a tricyclo[5.2.1.0 ' Jdecane ring group and a
  • the bridged cyclic hydrocarbon ring group also includes a condensed cyclic hydrocarbon ring group, for example, a condensed ring group obtained by condensing a plurality of 5- to 8-membered cycloalkane ring groups, such as a perhydronaphthalene (decalin) ring group, a perhydroanthracene ring group, a perhydrophenanthrene ring group, a perhydroacenaphthene ring group, a perhydrofluorene ring group, a perhydroindene ring group and a perhydrophenalene ring group.
  • a condensed cyclic hydrocarbon ring group for example, a condensed ring group obtained by condensing a plurality of 5- to 8-membered cycloalkane ring groups, such as a perhydronaphthalene (decalin) ring group, a perhydroanthracene ring group
  • Preferred examples of the bridged cyclic hydrocarbon ring group may include a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, a
  • bridged cyclic hydrocarbon ring group may include a norbornane ring group and an adamantane ring group.
  • the linking group having a polycyclic hydrocarbon structure represented by Z may have a substituent.
  • the substituent which may be possessed by Z may include a substituent such as an alkyl group, a hydroxyl group, a cyano group, a keto group (an alkylcarbonyl group and the like), an acyloxy group, -COOR, -CON(R) 2 , -S0 2 R, -S0 3 R and -S0 2 N(R) 2 .
  • R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
  • the alkyl group, the alkylcarbonyl group, the acyloxy group, -COR, -COOR, -CON(R) 2 , -S0 2 R, -SO 3 R and -S0 2 N(R) 2 as the substituent which may be possessed by Z may further have a substituent, and examples of the substituent may include a halogen atom (preferably, fluorine atom).
  • the carbon constituting the polycyclic ring (the carbon contributing to ring formation) may be carbonyl carbon.
  • the polycyclic ring may have a heteroatom such as an oxygen atom and a sulfur atom as a ring member.
  • Z does not contain an ester bond as an atomic group constituting the polycyclic ring.
  • Examples of the linking group represented by L 4 and L 5 may include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -0-, -S-, -SO-, -S0 2 -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a linking group formed by combining a plurality of these groups and the like, and a linking group having a total carbon number of 12 or less is preferred.
  • L 5 is preferably a single bond, an alkylene group, -COO-, -OCO-, -CONH-, -NHCO-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, -NHCO-alkylene group-, -CO-, -0-, -S0 2 -, -O-alkylene group- or -O-cycloalkylene group-, and more preferably a single bond, an alkylene group, -COO-alkylene group-, -O-alkylene group- or -O-cycloalkylene group-.
  • the bonding hand "-" at the left side means connecting to the ester bond on the main chain side in L and connecting to Z in L 5
  • the bonding hand "-" at the right side means bonding to Z in L and bonding to the ester bond connected to the group represented by (Ry 1 )(Ry 2 )(Ry 3 )C- in L 5 .
  • Meanwile, L 4 and L 5 may be bonded to the same atom constituting the polycylic ring in Z.
  • p is preferably 1 or 2, and more preferably 1.
  • Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.
  • the resin (A) is a resin capable of generating an alcoholic hydroxyl group and increasing the polarity by the action of an acid to increase the solubility in an alkali developer containing an organic solvent.
  • the structure in which the polar group is protected with a group capable of decomposing and leaving by the action of an acid is preferably (i) a structure represented by the following Formula (b), capable of decomposing by the action of an acid to generate one alcoholic hydroxyl group, or (ii) a structure represented by the following Formula (c), capable of decomposing by the action of an acid to generate two or three alcoholic hydroxyl groups.
  • P 2 represents a monovalent group capable of decomposing and leaving by the action of an acid.
  • P 3 represents a z-valent group capable of decomposing and leaving by the action of an acid, z represents 2 or 3.
  • * represents a bonding hand linked to the main chain or the side chain of the resin.
  • the structure (i) is preferably a group represented by the following Formula (b-1), (b-2 (b-3) or (b-4), and more preferably a group re resented by the following Formula (b-1).
  • Rx 4 's each independently represent a hydrogen atom or a monovalent organic group. Rx 4 's may be bound with each other to form a ring.
  • Rx 5 represents a monovalent organic group.
  • One of Rx 4 's and Rx 5 may be bound with each other to form a ring.
  • Rx 4 ' represents a hydrogen atom or a monovalent organic group.
  • Rx 5 "s each independently represent a monovalent organic group.
  • Rx 5 "s may be bound with each other to form a ring. Further, one of Rx 5 "s and Rx 4 ' may be bound with each other to form a ring.
  • Rx 6 's each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. Two Rx 6 's may be bound with each other to form a ring. However, in the case where one or two of Rx 6 's are a hydrogen atom, at least one of the remaining Rx 6 's represents an aryl group, an alkenyl group or an alkynyl group.
  • Rx 6 "s each independently represent a monovalent organic group. Two Rx 6 "s may be bound with each other to form a ring.
  • Rx 4 and Rx 4 ' each independently represent a hydrogen atom or a monovalent organic group.
  • Rx 4 and Rx 4 ' are each independently preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.
  • the alkyl group of Rx 4 and Rx 4 ' may be straight or branched.
  • the alkyl group has preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.
  • Examples of the alkyl group of Rx 4 may include a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a n-butyl group.
  • the cycloalkyl group of Rx 4 , Rx 4 ' may be monocyclic or polycyclic.
  • the cycloalkyl group has preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms.
  • Examples of the cycloalkyl group of Rx 4 may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.
  • At least one of Rx 4 's is preferably a monovalent organic group.
  • the alkyl group and the cycloalkyl group as Rx 4 and Rx 4 may further have a substituent, and examples of the substituent may include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), an aryl group (having 6 to 10 carbon atoms) and the like, and preferably a substituent having 8 or less carbon atoms.
  • the substituent may include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), an aryl group (having 6 to 10 carbon atoms) and the like, and preferably a substituent
  • Rx 5 and Rx 5 ' each independently represent a monovalent organic group.
  • Rx 5 and Rx 5 ' are each independently preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group.
  • the alkyl group and the cycloalkyl group may further have a substituent, and examples of the substituent may include the groups as described in the substituent which may be possessed by the alkyl group and the cycloalkyl group as Rx 4 and Rx 4 '.
  • the alkyl group of Rx 5 and Rx 5 ' may have no substituent or have one or more aryl groups and/or one or more silyl groups as a substituent.
  • the unsubstituted alkyl group has preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyhl group moiety in the alkyl group substituted with one or more aryl groups has preferably 1 to 25 carbon atoms.
  • alkyl group of Rx 5 , Rx 5 ' may also be exemplified by those described as specific examples of the alkyl group of Rx 4 and Rx .
  • the aryl group in the alkyl group substituted with one or more aryl groups has prererably 6 to 10 carbon atoms, and specific examples thereof may include a phenyl group and a naphthyl group.
  • the alkyl group moiety in the alkyl group substituted with one or more silyl groups has preferably 1 to 30 carbon atoms. Further, in the case wehre the cycloalkyl group of Rx 5 and Rx 5 ' has no substituent, the cycloalkyl group has preferably 3 to 20 carbon atoms, and more preferably 3 to 15 carbon atoms.
  • cycloalkyl group of Rx 5 and Rx 5 ' may also be exemplified by those as described as specific examples of the cycloalkyl group of Rx 4 and Rx '.
  • Rx 6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. However, in the case where one or two of three Rx 6 's are a hydrogen atom, at least one of the remaining Rx 6 's represents an aryl group, an alkenyl group or an alkynyl group. Rx 6 is preferably a hydrogen atom or an alkyl group.
  • the alkyl group, the cycloalkyl group, the aryl group, the alkenyl group and the alkynyl group as Rx 6 may further have a substituent, and examples of the substituent may be exemplified by those as described in the substituent which may be possessed by Rxi to Rx 3 .
  • Examples of the alkyl group and the cycloalkyl group of Rx 6 may also be exemplified by those as described in the alkyl group and the cycloalkyl group of Rx 4 and Rx 4 '. Particularly, in the case where the alkyl group has no substituent, the alkyhl group has preferably 1 to 6 carbon atoms, and more preferably 1 to 3.
  • Examples of the aryl group of Rx 6 may include an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.
  • Examples of the alkenyl group of Rx 6 may include an alkenyl group having 2 to 5 carbon atoms such as a vinyl group, a propenyl group and an allyl group.
  • Examples of the alkynyl group of Rx 6 may include an alkynyl group having 2 to 5 carbon atoms such as a ethynyl group, a propynyl group and a butynyl group.
  • Rx 6 "s are each independently preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or a cycloalkyl group, and still more preferably an alkyl group.
  • alkyl group, the cycloalkyl group and the aryl group for Rx 6 ' may be exemplified by alkyl group and the cycloalkyl group described for Rx 4 and Rx ' and the aryl group described for Rx 6 .
  • the alkyl group, the cycloalkyl group and the aryl group may further have a substituent, and examples of the substituent may include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), an aryl group (having 6 to 10 carbon atoms) and the like, and preferably a group having 8 or less carbon atoms.
  • substituent may include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), an aryl group (having 6 to 10 carbon atoms) and the like, and preferably a group having 8 or less carbon
  • the structure (ii) is preferably a group represented by the following Formula (c-1), (c-2) or (c-3).
  • Rx 7 's each independently represent a hydrogen atom or a monovalent organic group.
  • Rx 7 's may be bound with each other to form a ring.
  • Rx 8 's each independently represent a monovalent organic group.
  • Rx 8 's may be bound with each other to form a ring.
  • Rx 8 ' represents a monovalent organic group.
  • Rx 7 represents a hydrogen atom or a monovalent organic group.
  • Rx 7 is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom or an alkyl group having no substituent.
  • Rx 7 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.
  • the alkyl group and the cycloalkyl group as Rx 7 may further have a substituent, and examples of the substituent may be exemplified by the groups as described in the substituent which may be possessed by Rxi to Rx 3 .
  • alkyl group and the cycloalkyl group of Rx 7 may also be exemplified as those described as specific examples of the alkyl group and the cycloalkyl group of Rx 4 and Rx 4 '.
  • Rx 8 and Rx 8 ' represent a hydrogen atom or a monovalent organic group.
  • Rx 8 and Rx 8 ' are each independently preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.
  • Examples of the alkyl group and the cycloalkyl group of Rx 8 and Rx 8 ' may also be exemplified by those described in the alkyl group and the cycloalkyl group of Rx and Rx 4 '.
  • the resin (A) has preferably a repeating unit in which the polar group is protected with the leaving group capable of decomposing and leaving by the action of an acid (hereinaftger, also referred to as an acid-decomposable repeating unit (a)), and more preferable a repeating unit having the structure (i) or (ii).
  • the repeating unit having any one of the structures (i) and (ii) may be exemplified by a repeating unit represented by the following Formula (1-1) or (1-2).
  • Ra's each independently represent a hydrogen atom, an alkyl group or a group represented by -CH 2 -0-Ra 2 .
  • Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
  • P represents the structcture (i).
  • P's may be the same or different, and may be bound with each other to form a ring.
  • the bound P's may be represented by the structure (ii), and in this case, * in Formula (c) in the structure (ii) represents a bonding hand linked to R ⁇ .
  • Ri represents a (n+l)-valent organic group.
  • Rn represents a divalent organic group.
  • Rn's may be the same or different,
  • n an integer of 1 or more.
  • Li's represents a linking group represented by -COO-, -OCO-, -CONH-, -0-, -Ar-, -S0 3 - or -S0 2 NH-.
  • Ar represents a divalent aromatic group. In the case vide a plurality of Li's is present, Li's may be the same or different.
  • q represents a repeating number of the group represented by -Ru-Li-, and an integer of 0 to 3.
  • Ra represents a hydrogen atom, an alkyl group or a group represented by -CH 2 -0-Ra 2 .
  • the alkyl group of Ra has preferably 6 or less carbon atoms, and the alkyl group and the acyl group of Ra 2 has preferably 5 or less carbon atoms.
  • the alkyl group of Ra, and the alkyl group and the acyl group of Ra 2 may have a substituent.
  • Ra is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 1 to 10 carbon atoms, and specifically, preferably a hydrogen atom, a methyl group, a trifluoromethyl group or hydroxymethyl group, and more preferably a hydrogen atom or a methyl group.
  • Ri represents a (n+l)-valent organic group.
  • Ri is preferably a non-aromatic hydrocarbon group.
  • Ri may be a chained hydrocarbon group or an alicyclic hydrocarbon group.
  • Ri is more preferably an alicyclic hydrocarbon.
  • the chained hydrocarbon as Ri may be straight or branched. Further, the chained hydrocarbon has preferably 1 to 8 carbon atoms.
  • the alkylene group is preferably a methylene group, an ethylene group, a n-propylene group, an isopropylene group, a n-butylene group, an isobutylene group or a sec-butylene group.
  • the alicyclic hydrocarbon as Ri may be monocyclic or polycyclic.
  • the alicyclic hydrocarbon has, for example a monocyclo, bicyclo, tricyclo or tetracyclo structure.
  • the alicyclic hydrocarbon group has generally 5 or more carbon atoms, preferably 6 to 30 carbon atoms, and 7 to 25 carbon atoms.
  • R ⁇ is preferably an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododecanylene group, a norbornylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclodecanylene group or a cyclododecanylene group, and more preferably an adamantylene group, a norbornylene group, a cyclohexylene group, a cyclopentylene group, a tetracyclododecanylene group or a tricyclodecanylene group.
  • the non-aromatic hydrocarbon group of Ri may have a substituent.
  • the substituent may include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group and an alkoxycarbonyl group having 2 to 6 carbon atoms.
  • the aforementiond alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent.
  • Examples of the substituent may include a hydroxyl group, a halogen atom and an alkoxy group.
  • Li represents a linking group represented by -COO-, -OCO-, -CONH-, -0-, -Ar-, -S0 3 - or -S0 2 NH- ("-" at the left side of these linking groups means connecting to the main chain of the resin).
  • Ar represents a divalent aromatic ring group, and is preferably a divalent aromatic ring group having 6 to 10 carbon atoms, such as, for example, a phenylene group and a naphthylene group.
  • Li is preferably a linking group represented by -COO-, -CONH- or -Ar-, and more preferably a linking group represented by -COO- or -CONH-.
  • n is an integer of 1 or more, n is preferably an integer of 1 to 3, and more preferably 1 or 2. Further, when n is an integer of 2 or more, it is possible to further enhance the dissolution contrast for a developer containing an organic solvent. Accordingly, the resolution may be further enhanced, and at the same time, LWR may be further reduced.
  • q represents a repeating number of a group represented by -R1-L1-, and represents an integer of 0 to 3.
  • q is preferably an integer of 0 to 2, and more preferably 0 or 1.
  • Ra and P have the same meaning as Ra and P in Formula (1-1) or (1-2).
  • Pi has the same meaning as Pi in Formula (a).
  • P 3 has the same meaning as P 3 when z is 2 in Formula (c).
  • appropriate examples thereof may also include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(Roi)(Ro2)(OR 3 9) and the like.
  • R 36 to R 3 g each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 3 may be bound with each other to form a ring.
  • Roi and Ro 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like.
  • the group is more preferably a tertiary alkyl ester group.
  • the acid-decomposable repeating unit (a) that may be contained in the resin (A) is a repeating unit represented by the following Formula (a2).
  • Ra each independently represent a hydrogen atom, an alkyl group or a group represented by -CH 2 -0-Ra 2 '.
  • Ra 2 ' represents a hydrogen atom, an alkyl group or an acyl group.
  • Ri' represents a (n'+l)-valent organic group.
  • Rn' represents a divalent organic group.
  • Rn"s may be the same or different.
  • Li' represents a linking gropu represented by -COO-, -OCO-, -CONH-, -0-, -Ar'-, -S0 3 - or -S0 2 NH-.
  • Ar' represents a divalent aromatic ring group.
  • L ⁇ 's may be the same or different.
  • q' represents a repeating number of a group represented by -Rn'-Li', and represents an integer of 0 to 3.
  • n an ingeger of 1 or more.
  • Rx 4 '"s each independently represent a hydrogen atom or a monovalent organic group. Rx 4 "'s may be bound with each other to form a ring.
  • Rx 5 " represents a monovalent organic group.
  • One of Rx 4 "'s and Rx 5 " may be bound with each other to form a ring.
  • ', Ar', Rx 4 ", and Rx 5 " are the same as those described in Ra, Ra 2 , R ls Rn, Li , and Ar in Formula (1-1), and Rx 4 and Rx 5 in the (b-1), respectively.
  • preferred ranges of n and q' in Formula (a2) are the same as the preferred ranges of n and q in Formula (1-1), respectively.
  • repeating unit (a) having an acid-decomposable group Preferred specific examples of the repeating unit (a) having an acid-decomposable group will be shown below, but the present invention is not limited thereto.
  • R 1 , R 10 and Xa represent a hydrogen atom, CH 3 , CF 3 or CH 2 OH.
  • Me represents a methyl group.
  • the repeating unit having an acid-decomposable group may be used either alone or in combination of two or more thereof.
  • the content of the repeating unit having an acid-decomposable group contained in the resin (A) is preferably 55 mol% or more, more preferably 55 mol% to 85 mol%, still more preferably 55 mol% to 70 mol%, and particularly preferably 55 mol% to 65 mol% based on the whole repeating units of the resin (A).
  • the resin (A) may contain a repeating unit having a lactone structure or a sultone structure.
  • the lactone structure or the sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure, and more preferably a 5- to 7-membered ring lactone structure to which another ring structure is condensed to form a bicyclo or spiro structure, or a 5- to 7-membered ring sultone structure to which another ring structure is condensed to form a bicyclo or spiro structure.
  • lactone structure represented by any one of the following Formulas (LCl-1) to (LCI -21) or a sultone structure represented by any one of the following Formulas (SLl-1) to (SL1-3).
  • the lactone structure or the sultone structure may be bonded directly to the main chain.
  • a preferred lactone structure is (LCl-1), (LCl-4), (LCl-5), (LCl-6), (LCl-13), (LCl-14) and (LCI- 17), and a particularly preferred lactone structure is (LCl-4).
  • the lactone structure or the sultone structure moiety may or may not have a substituent (Rb 2 ).
  • Preferred examples of the substituent (Rb 2 ) may include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group and the like.
  • the substituent is more preferably an alkyl group having 1 to 4 carbon atoms, a cyano group and an acid-decomposable group.
  • n 2 represents an integer of 0 to 4.
  • the substituents (Rb 2 's) may be the same as or different.
  • the substituents (Rb 2 's) may be bound with each other to form a ring.
  • the repeating unit having a lactone group or a sultone structure usually has an optical isomer, but any optical isomer may be used. Further, the optical isomer may be used either alone or as a mixture of two or more thereof. When one kind of the optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, and more preferably 95% or more.
  • repeating unit having a lactone structure or a sultone structure is a repeatin unit represented by the following Formula (III).
  • A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).
  • Ro's each independently represent an alkylene group, a cycloalkylene group or a combination thereof.
  • Z's each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond
  • R's each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
  • R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
  • n is a repeating number of a structure represented by -Ro-Z-, represents an integer of 0 to 5, and is preferably 0 or 1, and more preferably 0.
  • n 0, -Ro-Z- is not present, and the structure becomes a single bond.
  • R 7 represents a hydrogen atom, a halogen atom or an alkyl group.
  • the alkylene group and the cycloalkylene group of Ro may have a substituent.
  • Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.
  • the alkyl group of R 7 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and particularly preferably a methyl group.
  • Each of the alkylene group and the cycloalkylene group of Ro and the alkyl group of R 7 may be substituted, and examples of the substituent may include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group and a benzyloxy group, and an acyloxy group such as an acetyloxy group and a propionyloxy group.
  • a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom
  • a mercapto group such as a hydroxyl group
  • an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group and a benzyloxy group
  • R 7 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
  • a preferred chain alkylene group in Ro is preferably a chain alkylene having 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, and examples thereof may include a methylene group, an ethylene group, a propylene group and the like.
  • a preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof may include a cyclohexylene group, a cyclopentylene group, a norbornylene group, an adamantylene group and the like.
  • a chain alkylene group is more preferred, and a methylene group is particularly preferred.
  • the monovalent organic group having a lactone structure or a sultone structure represented by R 8 is not limited as long as the organic group has a lactone structure or a sultone structure, specific examples thereof may include a lactone structure or a sultone structure represented by any one of Formulas (LCl-1) to (LCl-21) and (SLl-1) to (SL1-3), and among them, a structure represented by (LCI -4) is particularly preferred. Further, n 2 in (LCl-1) to (LCl-21) is more preferably 2 or less.
  • R 8 is preferably a monovalent organic group having an unsubstituted lactone structure or a sultone structure, or a monovalent organic group having a lactone structure or a sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent, and more preferably a monovalent organic group having a lactone structure having a cyano group as a substituent (cyanolactone).
  • repeating unit having a group having a lactone structure or a sultone structure will be shown below, but the present is not limited thereto.
  • Rx represents H, CH 3 ,
  • two or more kinds of the repeating units having a lactone structure or a sultone structure may be used in combination as well.
  • the content of the repeating unit having a lactone structure or a sultone structure is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 55 mol%, and still more preferably 10 mol% to 50 mol% based on the whole repeating units of the resin (A).
  • the resin (A) may have a repeating unit having a cyclic carbonate ester structure.
  • repeating unit having a cyclic carbonate ester is a repeating unit represented by the following Formula (A-l).
  • R A ' represents a hydrogen atom or an alkyl group.
  • R A 's each independently represent a substituent.
  • A represents a single bond or a divalent linking group.
  • n is an integer of 0 or more.
  • the alkyl group represented by RA 1 may have a substituent such as a fluorine atom.
  • RA 1 represents preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably a methyl group.
  • the substituent represented by R A 2 is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, an alkoxycarbonyl amino group.
  • the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof may include a straight alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group; a branced alkyl group having 3 to 5 carbon atoms such as an isopropyl group, an isobutyl group and t-butyl group, and the like.
  • the alkyl group may have a substituent such as a hydroxyl group.
  • n is an integer of 0 or more, which represents the number of substituents. n is, for example, preferably 0 to 4, and more preferably 0.
  • Examples of the divalent linking group represented by A may include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond or a combination thereof.
  • the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof may include a methylene group, an ethylene group, a propylene group and the like.
  • A is preferably a single bond or an alkylene group.
  • the "other ring structures" which may form a condensed ring or a spiro ring may be an alic project hydrocarbon group, an aromatic hydrocarbon group or heterocyclic ring.
  • the monomer corresponding to the repeating unit represented by Formula (A-1) may be synthesized by a conventionally known method as described, for example, in Tetrahedron Letters, Vol. 27, No. 32 p. 3741(1986), Organic Letters, Vol. 4, No.15 p. 2561(2002) and the like.
  • the repeating unit represented by Formula (A-1) may be contained either alone or in combination of two or more thereof.
  • the content of the repeating unit having a cyclic carbonate ester structure (preferably, a repeating unit represented by Formula (A-1)) is preferably 3 mol% to 80 mol%, more preferably 3 mol% to 60 mol%, particularly preferably 3 mol% to 30 mol%, and most preferably 10 mol% to 15 mol% based on the whole repeating units constituting the resin (A).
  • repeating unit represented by Formula (A-1) (repeating units (A-la) to (A-lw)) are shown below, but the present invention is not limited thereto.
  • R A ' in the following specific examples have the same meaning as R A ' in Formula (A-1).
  • the content of the repeating unit having cyclic carbonate ester structure is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 55 mol%, and still more preferably 10 mol% to 50 mol% based on the whole repeating unit.
  • the resin (A) may have a repeating unit having a hydroxyl group or a cyano group.
  • the repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group.
  • the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is different from the repeating unit having an acid-decomposable group (That is, preferably a repeating unit which is stable to an acid).
  • the alicyclic hydrocarbon structure in the alicyclic hydrocarbon strucuture substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diadamantyl group or a norbornane group.
  • the repeating unit is more preferably a repeating unit represented by any one of the following formulas (Alia) to (AIIc).
  • Rx represents a hydrogen atom, a methyl group, hydroxymethyl group or a trifluoromethyl group.
  • Ab represents a single bond or a divalent linking group.
  • Examples of the divalent linking group represented by Ab may include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond or a combination thereof.
  • the alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof may include a methylene group, an ethylene group, a propylene group and the like.
  • Ab is preferably a single bond or an alkylene group.
  • Rp represents a hydrogen atom, a hydroxyl group or hydroxyalkyl group.
  • a plurality of Rp's may be the same or different, but at least one of Rp's represents a hydroxyl group or hydroxyalkyl group.
  • the resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but, in the case where the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, the content of the repeating unit having a hydroxyl group or a cyano group is preferably 1 mol% to 40 mol%, more preferably 3 mol% to 30 mol%, and still more preferably 5 mol% to 25 mol% based on the whole repeating units in the resin (A).
  • Specific examples of the repeating unit having a hydroxyl group or a cyano group will be shown below but the present invention is not limited thereto.
  • the resin (A) may have a repeating unit having an acid group.
  • the acid group may include a carboxyl group, a sulfonamide group, a sulfonylimide, a bissulfonylimide, a naphthoic structure, and an aliphatic alcohol group substituted with an electron-withdrawing group at the a-position (for example, a hexafluoroisopropanol group), and it is more preferred to have a repeating unit having a carboxyl group.
  • the repeating unit having an acid group the resolution increases in the usage of contact holes.
  • the repeating unit having an acid group a repeating unit in which the acid group is directly bonded to the main chain of the resin, such as repeating unit by an acrylic acid or a methacrylic acid or a repeating unit in which the acid group is bonded to the main chain of the resin through a linking group, and a repeating unit which is introduced into the end of the polymer chain by using a polymerization initiator having an acid group or a chain transfer agent at the time of polymerization are all preferred, and the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
  • a repeating unit by an acrylic acid or a methacrylic acid is particularly preferred.
  • the resin (A) may or may not contain a repeating unit having an acid group, but in the case of containing a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 25 mol% or less, and more preferably 20 mol% or less, based on the whole repeating units in the resin (A).
  • the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.
  • repeating unit having an acid group Specific examples of the repeating unit having an acid group will be described below, but the present invention is not limited thereto.
  • Rx represents H, CH 3 , CH 2 OH or CF 3 .
  • the resin (A) of the present invention may have a repeating unit having an alicyclic hydrocarbon structure having no polar group (for example, the acid group, the hydroxyl group, and the cyano group) and not exhibiting acid decomposability. Accordingly, elution of low molecular components from the resist film into the liquid for liquid immersion during the liquid immersion exposure may be reduced, and further, the solubility of the resin during the development using a developer containing an organic solvent may be appropriately adjusted.
  • the repeating unit may include a repeating unit represented by Formula (IV).
  • R 5 represents a hydrocarbon group having at least one cyclic structure and having no polar group.
  • Ra represents a hydrogen atom, an alkyl group or a -CH 2 -0-Ra 2 group.
  • Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
  • Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group and a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.
  • the cyclic structure possessed by R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
  • the monocyclic hydrocarbon group may include a cycloalkyl group having 3 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, and a cycloalkenyl group having 3 to 12 carbon atoms, such as a cyclohexenyl group.
  • the monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.
  • the polycyclic hydrocarbon group includes a ring-assembled hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring-assembled hydrocarbon group may include a bicyclohexyl group, a perhydronaphthalenyl group and the like.
  • Examples of the bridged cyclic hydrocarbon ring may include a bicyclic hydrocarbon ring such as a pinane ring, a bornane ring, a norpinane ring, a norboraane ring and a bicyclooctane ring (a bicyclo[2.2.2]octane ring, a bicyclo[3.2.1]octane ring and the like), a tricyclic ydrocarbon ring such as a homobledane ring, an adamantine ring, a tricyclo[5.2.1.0 2 ' 6 ]decane ring and a
  • the bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, for example, a condensed ring obtained by condensing a plurality of 5- to 8-membered cycloalkane rings, such as a perhydronaphthalene (decalin) ring, a perhydroanthracene ring, a perhydrophenanthrene ring, a perhydroacenaphthene ring, a perhydrofluorene ring, a perhydroindene ring and a perhydrophenalene ring.
  • a condensed cyclic hydrocarbon ring for example, a condensed ring obtained by condensing a plurality of 5- to 8-membered cycloalkane rings, such as a perhydronaphthalene (decalin) ring, a perhydroanthracene ring, a perhydrophenanthrene ring, a perhydro
  • Preferred examples of the bridged cyclic hydrocarbon ring may include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo[5,2,l,0 2 ' 6 ]decanyl group and the like. More preferred examples of the bridged cyclic hydrocarbon ring may include a norbornyl group and an adamantyl group.
  • the alicyclic hydrocarbon groups may have a substituent, and preferred examples of the substituent may include a halogen atom, an alkyl group, a hydroxyl group whose hydrogen atom is substituted, an amino group whose hydrogen atom is substituted and the like.
  • Preferred examples of the halogen atom may include a bromine atom, a chlorine atom and a fluorine atom
  • preferred examples of the alkyl group may include a methyl group, an ethyl group, a n-butyl group and a t-butyl group.
  • the aforementioned alkyl group may further have a substituent, and examples of the substituent which may be further possessed by the alkyl group may include a halogen atom, an alkyl group, a hydroxyl group whose hydrogen atom is substituted, and an amino group whose hydrogen atom is substituted.
  • Examples of the substituent for the hydrogen atom may include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
  • Preferred examples of the alkyl group may include an alkyl group having 1 to 4 carbon atoms
  • preferred examples of the substituted methyl group may include a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group, and a 2-methoxyethoxymethyl group
  • examples of the substituted ethyl group may include a 1 -ethoxy ethyl group and a 1 -methyl- 1-methoxyethyl group
  • preferred examples of the acyl group may include an aliphatic acyl group having 1 to 6 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group and a pivaloyl group
  • examples of the alkoxycarbonyl group may include an alkoxycarbonyl group having 1 to 4 carbon atoms and the like.
  • the resin (A) may or may not contain a repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability, but in the case of containing the repeating unit, the content ratio of the repeating unit is preferably 1 mol% to 50 mol%, and more preferably 10 mol% to 50 mol%, based on the whole repeating units in the resin (A).
  • Ra represents H, CH 3 , CH 2 OH or
  • the resin (A) used in the composition of the present invention may have, in addition to the aforementioned repeating structural units, various repeating structural units for the purpose of controlling the dry etching resistance, suitability for a standard developer, adhesion to a substrate and resist profile, and further, resolution, heat resistance, sensitivity and the like, which are properties generally required for an actinic ray-sensitive or radiation-sensitive resin composition.
  • repeating structural units may include repeating structural units corresponding to the monomers described below, but are not limited thereto.
  • dry etching resistance, and the like may be finely adjusted.
  • Examples of the monomer may include a compound having one addition-polymerizable unsaturated bond selected from acrylate esters, me hacrylate esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.
  • an addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the aforementioned various repeating structural units may be copolymerized.
  • the molar ratio of respective repeating structural units contained is appropriately set in order to control dry etching resistance, suitability for a standard developer, adhesion to a substrate and resist profile of the actinic ray-sensitive or radiation-sensitive resin composition, and further, resolution, heat resistance, sensitivity and the like which are performances generally required for the actinic ray-sensitive or radiation-sensitive resin composition.
  • the resin (A) used in the composition of the present invention preferably has substantially no aromatic ring (specifically, the ratio of a repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%, that is, the resin does not have an aromatic group), and the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
  • the form of the resin (A) in the present invention may be any form of a random type, a block type, a comb type, and a star type.
  • the resin (A) may be synthesized, for example, by polymerization of radicals, cations, or anions of an unsaturated monomer, corresponding to each structure. Further, it is also possible to obtain a target resin by using an unsaturated monomer corresponding to a precursor of each structure to perform polymerization, and then performing a polymer reaction.
  • the resin (A) used in the composition of the present invention preferably has substantially no aromatic ring (specifically, the ratio of a repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%, that is, the resin does not have an aromatic group), and the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
  • the resin (A) contains no fluorine atom and no silicon atom from the viewpoint of compatibility with the resin (D) as describe below.
  • the resin (A) used in the composition of the present invention is preferably a resin in which all the repeating units are a (meth)acrylate-based repeating unit.
  • a resin in which all the repeating units are methacrylate-based repeating units a resin in which all the repeating units are an acrylate-based repeating unit, and a resin in which all the repeating units are methacrylate-based repeating units or acrylate-based repeating units, but it is preferred that the acrylate-based repeating unit is present in an amount of 50 mol% or less based on the whole repeating units.
  • the resin (A) further has a hydroxystyrene-based repeating unit.
  • the resin (A) has more preferably a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group and an acid-decomposable repeating unit such as tertiary alkyl (meth)acrylate ester.
  • Preferred examples of the hydroxystyrene-based repeating unit having an acid-decomposable group may include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, tertiary alkyl (meth)acrylate ester and the like, and more preferably 2-alkyl-2-adamantyl(meth)acrylate and dialkyl(l-adamantyl)methyl (meth)acrylate.
  • the resin (A) in the present invention may be synthesized by a conventional method (for example, radical polymerization).
  • a general synthesis method may include a batch polymerization method of dissolving monomer species and an initiator in a solvent and heating the solution to perform the polymerization, a dropping polymerization method of adding dropwise a solution containing monomer species and an initiator to a heated solvent over 1 to 10 hours, and the like, and a dropping polymerization method is preferred.
  • Examples of a reaction solvent may include tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, an ester solvent such as ethyl acetate, an amide solvent such as dimethylformamide, dimethylacetamide, and a solvent capable of dissolving the composition of the present invention described below, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and cyclohexanone.
  • the polymerization is more preferably performed by using the same solvent as the solvent used in the photosensitive composition of the present invention. Accordingly, generation of particles during storage may be suppressed.
  • the polymerization reaction is preferably performed under an inert gas atmosphere such as nitrogen and argon.
  • the polymerization initiator the polymerization is initiated by using a commercially available radical initiator (azo-based initiator, peroxide and the like).
  • the radical initiator is preferably an azo-based initiator, and an azo-based initiator having an ester group, a cyano group or a carboxyl group is preferred.
  • Preferred examples of the initiator may include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate) and the like.
  • the initiator is added additionally or in parts, if desired, and after the completion of reaction, the reaction product is poured in a solvent, and a desired polymer is recovered by a powder or solid recovery method, or the like.
  • the reaction concentration is 5% by mass to 50% by mass, and preferably 10% by mass to 30% by mass.
  • the reaction temperature is usually 10°C to 150°C, preferably 30°C to 120°C, and more preferably 60°C to 100°C.
  • the purification may be performed by a typical method, such as a liquid-liquid extraction method of applying water-washing or combining water-washing with an appropriate solvent to remove residual monomers or oligomer components, a purification method in a solution state, such as ultrafiltration of removing only polymers having a molecular weight not more than a specific molecular weight by virtue of extraction, a reprecipitation method of adding dropwise a resin solution in a poor solvent to solidify the resin in the poor solvent to remove residual monomers and the like, a purification method in a solid state, such as washing of the resin slurry separated by filtration with a poor solvent and the like, and the like.
  • a typical method such as a liquid-liquid extraction method of applying water-washing or combining water-washing with an appropriate solvent to remove residual monomers or oligomer components
  • a purification method in a solution state such as ultrafiltration of removing only polymers having a molecular weight not more than a specific molecular weight by virtue of extraction
  • the resin is precipitated as a solid by contacting the reaction solution with a solvent (poor solvent) in which the resin is sparingly soluble or insoluble and which is in a volumetric amount of 10 times or less and preferably 10 to 5 times the reaction solution.
  • a solvent poor solvent in which the resin is sparingly soluble or insoluble and which is in a volumetric amount of 10 times or less and preferably 10 to 5 times the reaction solution.
  • the solvent (precipitation or reprecipitation solvent) used at the time of operation of precipitation or reprecipitation from the polymer solution may be sufficient if the solvent is a poor solvent for the polymer, and the solvent may be appropriately selected from hydrocarbon, halogenated hydrocarbon, a nitro compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, and a mixed solvent including these solvents, depending on the kind of the polymer.
  • a solvent containing at least alcohol (particularly, methanol or the like) or water is preferred as the precipitation or reprecipitation solvent.
  • the amount of the precipitation or reprecipitation solvent used may be appropriately selected by considering the efficiency, yield and the like, but in general, the amount is 100 parts by mass to 10,000 parts by mass, preferably 200 by parts by mass to 2,000 parts by mass, and more preferably 300 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the polymer solution.
  • the temperature during the precipitation or reprecipitation may be appropriately selected in consideration of the efficiency or operability, but is usually 0 to 50°C, and preferably in the vicinity of room temperature (for example, approximately 20°C to 35°C).
  • the precipitation or reprecipitation operation may be performed by a known method such as batch system and continuous system using a commonly employed mixing vessel such as stirring tank.
  • the precipitated or reprecipitated polymer is usually subjected to commonly employed solid-liquid separation such as filtration and centrifugation, then dried and used.
  • the filtration is performed by using a solvent-resistant filter element, and preferably under pressure.
  • the drying is performed under atmospheric pressure or reduced pressure (preferably under reduced pressure) at a temperature of approximately 30°C to 100°C and preferably at a temperature of approximately 30°C to 50°C.
  • the resin may be dissolved in a solvent again and then brought into contact with a solvent in which the resin is sparingly soluble or insoluble. That is, there may be used a method including, after the completion of radical polymerization reaction, bringing the polymer into contact with a solvent in which the polymer is sparingly soluble or insoluble, to precipitate a resin (process a), separating the resin from the solution (process b), dissolving the resin in a solvent again to prepare a resin solution A (process c), and then bringing the resin solution A into contact with a solvent in which the resin is sparingly soluble or insoluble and which is in a volumetric amount of less than 10 times (volumetric amount of preferably 5 times or less) the resin solution A, to precipitate a resin solid (process d), and separating the precipitated resin (process e).
  • a method including, after the completion of radical polymerization reaction, bringing the polymer into contact with a solvent in which the polymer is sparingly soluble or insoluble, to precipit
  • a process of dissolving the synthesized resin in a solvent to prepare a solution, and heating the solution at approximately 30°C to 90°C for approximately 30 minutes to 4 hours may be added.
  • the weight average molecular weight of the resin (A) in the present invention is 7,000 or more as described above, preferably 7,000 to 200,000, more preferably 7,000 to 50,000, still more preferably 7,000 to 40,000, and particularly preferably 7,000 to 30,000, in terms of polystyrene by the GPC method. If the weight average molecular weight is less than 7,000, the solubility in an organic-based developer becomes higher, and thus, there is a concern that a fine pattern may not be formed.
  • the polydispersity is usually in a range of 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0.
  • the blending ratio of the resin (A) in the entire composition is preferably 30% by mass to 99% by mass, and more preferably 60% by mass to 95% by mass, based on the total solid of the composition of the resin (A).
  • the resin (A) may be used either alone or in combination of two or more thereof.
  • (B) Compound capable of generating an acid upon irradiation with an actinic ray or radiation
  • composition in the present invention contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation (hereinafter, also referred to as an "acid generator” or a “compound (B)).
  • the acid generator is particularly limited as long as the acid generator is known, but is preferably a compound represented by the following Formula (ZI), (ZII) or (ZIII).
  • the organic group as R 20 i , R 202 and R 203 has generally 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
  • two of R 20 i to R 203 may be bound with each other to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group therein.
  • the group in which two of R 20 i to R 203 are bound to form may include an alkylene group (for example, a butylene group and a pentylene group).
  • the acid generator may be a compound having a plurality of structures represented by Formula (ZI).
  • the acid generator may be a compound having a structure in which at least one of R 201 to R 203 of a compound represented by Formula (ZI) is bound via a single bond or a linking group to at least one of R 201 to R 203 of another compound represented by Formula (ZI).
  • Z " represents a non-nucleophilic anion (an anion having an extremely low ability of causing a nucleophilic reaction).
  • Z " may include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion and the like), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkylcarboxylate anion and the like), a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion and the like.
  • a sulfonate anion an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion and the like
  • a carboxylate anion an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkylcarboxylate anion and the like
  • the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and examples thereof may include preferably a straight or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.
  • Examples of the aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion may include preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group and a naphthyl group.
  • the alkyl group, the cycloalkyl group and the aryl group as exemplified above may have a substituent. Specific examples thereof may include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkylaminosulfonyl group (preferably having 2 to 15 carbon atom
  • Examples of the aralkyl group in the aralkylcarboxylate anion may include preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylbutyl group.
  • Examples of the sulfonylimide anion may include a saccharin anion.
  • the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • substituent of the alkyl group may include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group and the like, and preferably a fluorine atom or an alkyl group substituted with a fluorine atom.
  • Examples of the other Z may include fluorinated phosphate (for example, PF 6 " ), fluorinated boron (for example, BF 4 " ), fluorinated antimony (for example, SbF 6 " ) and the like.
  • fluorinated phosphate for example, PF 6 "
  • fluorinated boron for example, BF 4 "
  • fluorinated antimony for example, SbF 6 "
  • Z is preferably an aliphatic sulfonate anion substituted with a fluorine atom at least at the a-position of sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which the alkyl group is substituted with a fluorine atom.
  • the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably having 4 to 8 carbon atoms) and a benzenesulfonate anion having a fluorine atom, and still more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion and a 3,5-bis(trifluoromethyl)benzenesulfonate anion.
  • pKa of the generated acid is -1 or less in order to enhance the sensitivity.
  • Examples of the organic group of R 201 , R 202 and R 203 may include an aryl group (preferably having 6 to 15 carbon atoms), a straight or branched alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15) and the like.
  • R 201 , R 202 and R 203 is an aryl group, and it is more preferred that all three are an aryl group.
  • the aryl group may be a heteroaryl group such as an indole residue structure and a pyrrole residue structure, in addition to a phenyl group, a naphthyl group and the like.
  • the aryl group, the alkyl group and the cycloalkyl group as R 20 i, R 202 and R 203 may have a substituent.
  • the substituent may include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms) and the like, but not limited thereto.
  • two groups selected from R 201 , R 202 and R 203 may be bound via a single bond or a linking group.
  • the linking group may include an alkylene group (preferably having 1 to 3 carbon atoms), -0-, -S-, -CO-, -S0 2 - and the like, but not limited thereto.
  • Preferred structures in the case where at least one of R 20 i, R 202 and R 203 is not an aryl group may include a cation structure such as compounds exemplified in paragraphs 0046 and 0047 of Japanese Patent Application Laid-Open No. 2004-233661 and paragraphs 0040 to 0046 of Japanese Patent Application Laid-Open No. 2003-35948, compounds exemplified as Formula (1-1) to Formual (1-70) in U.S. Patent Application Laid-Open No. 2003/0224288 Al, and compounds exemplified as Formula (IA-1) to Formula (IA-54) and Formula (IB-1) to Formula (IB-24) of U.S. Patent Application Laid-Open No. 2003/0077540A1. More preferred examples of the compound represented by (ZI) may include a compound represented by Formula (ZI-3) or (ZI-4) as described below.
  • Ri represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group,
  • R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R 2 and R 3 may be bound with each other to form a ring,
  • Ri and R 2 may be bound with each other to form a ring
  • Rx and R y each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group
  • R x and R y may be bound with each other to form a ring, and the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond or an amide bond.
  • Z " represents a non-nucleophilic anion
  • the alkyl group as is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specific examples thereof may include a straight alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-an octyl group, a n-dodecyl group, a n-tetradecyl group and a n-octadecyl group, and a branched alkyl group such as an isopropyl group, an isobutyl group, t-butyl group, a neopentyl group and a 2-ethylhexyl group.
  • the alkyl group of may have a substituent, and examples of the alkyl group having a substituent may include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group and the like.
  • the cycloalkyl group as Ri is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. Specific examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like.
  • the cycloalkyl group of R t may have a substituent, and examples of the substituent may include an alkyl group and an alkoxy group.
  • the alkoxy group as Ri is preferably an alkoxy group having 1 to 20 carbon atoms.
  • the alkoxy group of Ri may have a substituent, and examples of the substituent may include an alkyl group and a cycloalkyl group.
  • the cycloalkoxy group as R ⁇ is a cycloalkoxy group having 3 to 20 carbon atoms, and examples thereof may include a cyclohexyloxy group, a norbornyloxy group, an adamantyloxy group and the like.
  • the cycloalkoxy group of Ri may have a substituent, and examples of the substituent may include an alkyl group and a cycloalkyl group.
  • the aryl group as Ri is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof may include a phenyl group, a naphthyl group, a biphenyl group and the like.
  • the aryl group of R ⁇ may have a substituent, and preferred examples of the substituent may include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group and an arylthio group.
  • the alkyl group of Ri as described above may be a cycloalkyl group, an alkoxy group or a cycloalkoxy group.
  • the alkenyl group as Ri may be a vinyl group or an allyl group.
  • R 2 and R 3 represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R 2 and R 3 may be bound with each other to form a ring. However, at least one of R 2 and R 3 represents an alkyl group, a cycloalkyl group or an aryl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for R 2 and R 3 may be the same as the specific examples and preferred examples for Rt as described above. In the case where R 2 and R 3 are bound with each other to form a ring, the sum of the number of carbon atoms contributing to formation of the ring included in R 2 and R 3 is preferably 4 to 7, and particularly preferably 4 or 5.
  • R] and R 2 may be bound with each other to form a ring.
  • R ⁇ is an aryl group (preferably a phenyl group or a naphthyl group, which may have a substituent) and R 2 is an alkylene group having 1 to 4 carbon atoms (preferably a methylene group or an ethylene group), and preferred examples of the substituent may include a substituent which may be possessed by the aryl group as R ⁇ as described above.
  • R ⁇ is a vinyl group and R 2 is an alkylene group having 1 to 4 carbon atoms.
  • the alkyl group represented by Rx and R y is preferably an alkyl group having 1 to 15 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group.
  • the cycloalkyl group represented by R and R y is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.
  • the alkenyl group represented by Rx and R y is preferably an alkenyl group having 2 to 30 carbon atoms, and examples thereof may include a vinyl group, an allyl group and a styryl group.
  • the aryl group represented by Rx and R y is preferably, for example, an aryl group having 6 to 20 carbon atoms, and specific examples thereof may include a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a phenalenyl group, a phenanthracenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, a benzopyrenyl group and the like.
  • the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the alkyl group moiety of the 2-oxoalkyl group and the alkoxycarbonylalkyl group represented by R x and R y may be exemplified by those listed above as R x and R y .
  • the cycloalkyl group moiety of the 2-oxocycloalkyl group and the alkoxycarbonylcycloalkyl group represented by Rx and R y may be exemplified by those listed above as Rx and R y .
  • Z " may be exemplified by those listed above as Z " in Formula (ZI).
  • the compound represented by Formula (ZI-3) is preferably a compound represented by the following Formulas (ZI-3a) and (ZI-3b).
  • Ri, R 2 and R 3 are the same as those defined in Formula (ZI-3).
  • Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom
  • m, n, p and q mean an integer, and are preferably 0 to 3, more preferably 1 to 2, and particularly 1.
  • the alkylene group which links S + and Y may have a substituent, and preferred examples of the substituent may include an alkyl group.
  • R 5 When Y is a nitrogen atom, R 5 represents a monovalent organic group, and when Y is an oxygen atom or a sulfur atom, R 5 does not exist.
  • R 5 is preferably a group containing an electron-withdrawing group, and particularly preferably a group represented by the following Formulas (ZI-3a-l) to (ZI-3a-4).
  • R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group.
  • Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for R may be the same as the specific examples and preferred examples as described above for R t in Formula (ZI-3).
  • R 5 is particularly preferably a group represented by -S0 -R .
  • R4 represents an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for R 4 may be the same as the specific examples and preferred examples as described above for Ri.
  • Z " may be exemplified by those listed above as Z " in Formula (ZI).
  • the compound represented by Formula (ZI-3) is particularly preferably a compound represented by the following Formulas (ZI-3a') and (ZI-3b').
  • R l s R , R 3 , Y and R 5 are the same as those defined in Formulas (ZI-3a) and (ZI-3b).
  • Ri 3 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a cycloalkyl group. These groups may have a substituent.
  • Ri 5 's each independently represent an alkyl group, a cycloalkyl group or a naphthyl group.
  • Two R 15 's may be bound with each other to form a ring, and may contain a heteroatom such as an oxygen atom, a sulfur atom and a nitrogen atom as an atom constituting the ring. These groups may have a substituent.
  • 1 represents an integer of 0 to 2.
  • r represents an integer of 0 to 8.
  • Z " represents a non-nucleophilic anion, and may be exemplified by the same non-nucleophilic anion as Z " in Formula (ZI).
  • the alkyl group of Ri 3 , R 14 and R 15 is straight or branched, and preferably has 1 to 10 carbon atoms.
  • the cycloalkyl group of R 13 , R 14 and R] 5 may be a monocyclic or polycyclic cycloalkyl group.
  • the alkoxy group of R 13 and Ri 4 is straight or branched, and preferably has 1 to 10 carbon atoms.
  • the alkoxycarbonyl group of Ri 3 and Ri 4 is straight or branched, and preferably has 2 to 1 1 carbon atoms.
  • the group having a cycloalkyl group of i 3 and R] may be a monocyclic or polycyclic group having a cycloalkyl group. These groups may further have a substituent.
  • the alkyl group in the alkylcarbonyl group of R 14 may be exemplified by the specific examples of the alkyl group as Ri 3 to Ri 5 as described above.
  • the alkylsulfonyl group and the cycloalkylsulfonyl group of Ri 4 are straight, branched or cyclic, and preferably have 1 to 10 carbon atoms.
  • Examples of the substituent which may be possessed by each of the groups may include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group and the like.
  • a halogen atom for example, a fluorine atom
  • Examples of the ring structure which may be formed by two Ri 5 's being bound with each other may include a 5- or 6-membered ring formed by two R] 5 's together with the sulfur atom in Formula (ZI-4), particularly preferably 5-membered ring (that is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group.
  • the divalent Ri 5 may have a substituent, and examples of the substituent may include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group and the like.
  • a plurality of substituents for the ring structure may exist, and these may be bound with each other to form a ring.
  • R 15 in Formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent gropu in which two R 15 's are bound with each other to form a tetrahydrothiophene ring structure together with a sulfur atom, or the like, and particularly preferably a divalent gropu in which two R 15 's are bound with each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
  • the substituent which may be possessed by Ri 3 and Ri 4 is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group or a halogen atom (particularly, a fluorine atom).
  • 1 is preferably 0 or 1, and more preferably 1.
  • r is preferably 0 to 2.
  • Specific examples of the cation structure possessed by the compound represented by Formula (ZI-3) or (ZI-4) as described above may include, in addition to the cation structure such as compounds exemplified in Japanese Patent Application Laid-Open No. 2004-233661, Japanese Patent Application Laid-Open No. 2003-35948, U.S. Patent Application Laid-Open No. 2003/0224288 A 1 and U.S. Patent Application Laid-Open No. 2003/0077540A1 as described above, for example, a cation structure in chemical structures exemplified in paragraphs 0046, 0047, 0072 to 0077 and 0107 to 0110 of Japanese Patent Application Laid-Open No.
  • R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group, the alkyl group and the cycloalkyl group of R 204 to R 207 are the same as the aryl group, the alkyl group and the cycloalkyl group of R 201 to R 203 in the compound (ZI) as described above.
  • the aryl group, the alkyl group and the cycloalkyl group of R 204 to R 207 may have a substituent.
  • substituent may also include those which may be possessed by the aryl group, the alkyl group and the cycloalkyl group of R 201 to R203 in the compound (ZI) as described above.
  • Z " may be exemplified by those listed above as Z " in Formula (ZI).
  • the compound represented by the following Formula ( ⁇ ) is also preferred as an acid generator.
  • the compound represented by the following Formula ( ⁇ ) the permeability of exposure light is enhanced, and thus, LWR and DOF become better.
  • X' represents an oxygen atom, a sulfur atom or -N(Rx)-.
  • Ri' and R 2 ' each independently represent an alkyl group, a cycloalkyl group or an aryl group.
  • R 3 ' to R9' each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group or an arylcarbonyloxy group.
  • Rx represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an alkoxycarbonyl group, an aryl group, an arylcarbonyl group or an aryloxycarbonyl group.
  • Ri and R 2 ' may be bound with each other to form a ring. Further, any two or more of Re' to R9 , R 3 ' and R9 , R and R 5 ', R 5 ' and Rx, and R ⁇ and Rx each may be bound with each other to form a ring.
  • X' is preferably a sulfur atom or -N(Rx)- from the viewpoint of suppressing the abso tivity(for example, absorbance at a wavelength of 193 run) to a low level.
  • Z " may be exemplified by those listed above as Z " in Formula (ZI).
  • the alkyl group as R ⁇ to R 9 ' and Rx may have a substituent, is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain.
  • Specific examples thereof may include a straight alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-an octyl group, a n-dodecyl group, a n-tetradecyl group and a n-octadecyl group, and a branched alkyl group such as an isopropyl group, an isobutyl group, a t-butyl group, a neopentyl group and a 2-ethylhexyl group.
  • a straight alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group,
  • examples of the alkyl group having a substituent with respect to Rx may include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group and the like.
  • alkyl group having a substituent with respect to Ri' and R 2 ' may include a methoxyethyl group and the like.
  • examples thereof may also include particularly a group in which a straight or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue structure and the like) and the like.
  • a cycloalkyl group for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue structure and the like
  • the cycloalkyl group as R ⁇ to R 9 ' and Rx may have a substituent, is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring. Specific examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like.
  • the acyl group as R 3 ' to R9' and Rx may have a substituent, and is preferably an acyl group having 1 to 10 carbon atoms. Specific examples thereof may include an acetyl group, a propionyl group, an isobutyryl group and the like.
  • the alkenyl group as Rx is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof may include a vinyl group, an allyl group, a butenyl group and the like.
  • the alkoxy group as R 3 ' to R 9 ' may have a substituent, and is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples thereof may include a methoxy group, an ethoxy group, an isopropyloxy group, a cyclohexyloxy group and the like.
  • the alkoxycarbonyl group as R 3 ' to R9' may have a substituent, and is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Specific examples thereof may include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a cyclohexyloxycarbonyl group and the like.
  • the alkylcarbonyloxy group as R 3 ' to R9' may have a substituent, and is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms. Specific examples thereof may include a methylcarbonyloxy group, an ethylcarbonyloxy group, an isopropylcarbonyloxy group, a cyclohexylcarbonyloxy group and the like.
  • the aryl group as R ⁇ to R9' and Rx may have a substituent, is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof may include a phenyl group, a naphthyl group and the like.
  • the aryloxy group as R 3 ' to R9 1 may have a substituent, is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof may include a phenyloxy group, a naphthyloxy group and the like.
  • the aryloxycarbonyl group as R 3 ' to R9' and Rx may have a substituent, is preferably an aryloxycarbonyl group having 7 to 15 carbon atoms, and examples thereof may include a phenyloxycarbonyl group, a naphthyloxycarbonyl group and the like.
  • the arylcarbonyloxy group as R 3 ' to R9' may have a substituent, is preferably an arylcarbonyloxy group having 7 to 15 carbon atoms, and examples thereof may include a phenylcarbonyloxy group, a naphthylcarbonyloxy group and the like.
  • the arylcarbonyl group as Rx may have a substituent, is preferably an arylcarbonyl group having 7 to 15 carbon atoms, and examples thereof may include a phenyl carbonyl group, a naphthylcarbonyl group and the like.
  • Examples of the ring structure which may be formed by R ⁇ and R 2 ' being bound with each other may include a 5- or 6-membered ring formed by divalent Ri' and R 2 ' (for example, an ethylene group, a propylene group, a 1,2-cyclohexylene group and the like) together with a sulfur atom in Formula ( ⁇ ), particularly preferably 5-membered ring (that is, a tetrahydrothiophene ring).
  • Ri' and R 2 ' for example, an ethylene group, a propylene group, a 1,2-cyclohexylene group and the like
  • a sulfur atom in Formula ( ⁇ ) particularly preferably 5-membered ring (that is, a tetrahydrothiophene ring).
  • R ' and R 2 ' are not bound with each other to form a ring.
  • Examples of the ring structure which may be formed by any two or more of R to R 9 ', R 3 ' and R9', R4' and R 5 ', R 5 ' and Rx, and Re' and Rx being bound with each other may include preferably a 5- or 6-membered ring, particularly preferably a 6-membered ring.
  • Ri' and R 2 ' is particularly preferably an alkyl group or an aryl group.
  • R 3 ' to R9' may include an alkyl group which may have a substituent or a hydrogen atom, but, in the case of using as ArF resist, a hydrogen atom is particularly preferred from the absorption strength at 193 nm.
  • Rx is particularly preferably an alkyl group or an acyl group.
  • Xf s each independently represent a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • L represents a single bond or a divalent linking group, and when a plurality of L's is present, L's may be the same or different.
  • A represents an organic group having a cyclic structure.
  • x represents an integer of 1 to 20.
  • Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom
  • the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples thereof may include a fluorine atom, CF 3 , CHF 2 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 Fn, C 6 Fi 3 , C 7 F 15 , C 8 F 17 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C4F9 and CH 2 CH 2 C 4 F9, and among them, preferably a fluorine atom, CF 3 , CHF 2 and C 2 F 5 . Particularly, it is preferred that all Xf are a fluorine atom.
  • L represents a single bond or a divalent linking group, and examples thereof may include -COO-, -OCO-, -CO-, -0-, -S-, -SO-, -S0 2 -, -N(Ri)- (in the formula, Ri represents a hydrogen atom or an alkyl group), an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group formed by combining two or more thereof, preferably -COO-, -OCO-, -CO-, -S0 2 -, -CON(Ri)-, -S0 2 N(Ri)-, -CON(Ri)-alkylene group-, -N(Ri)CO-alkylene group-, -COO-alkylene group- or -OCO-alkylene group-, and
  • alkyl group for Ri may be the same as the specific examples and preferred examples as described above as the alkyl group for Ri to R 5 .
  • the cyclic organic group of A is not particularly limited as long as the group has a cyclic structure, and examples thereof may include a alicyclic group, an aryl group, a heterocyclic group (including a group having no aromaticity, as well as a group having aromaticity, and also including a structure such as a tetrahydropyran ring, a lactone ring, a sultone ring and ⁇ , a cyclic ketone) and the like.
  • the alicyclic group may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a norbornenyl group, a tricyclodecanyl group (for example, a tricyclo[5.2.1.0(2,6)]decanyl group), a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group.
  • a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group
  • a polycyclic cycloalkyl group such as a norbornyl group, a norbornenyl group, a
  • a nitrogen-containg alicyclic group such as a piperidine group, a decahydroquinoline group and a decahydroisoquinoline group.
  • an alicyclic group having a bulky structure, which has 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group and a decahydroisoquinoline group, is preferred from the viewpoint of suppressing diffusion in film during a PEB (post-exposure baking) process and thus enhancing exposure latitude.
  • PEB post-exposure baking
  • Examples of the aryl group may include a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring. Among them, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.
  • Examples of the heterocyclic group may include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring and a pyridine ring. Among them, a furan ring, a thiophene ring and a pyridine ring are preferred.
  • the cyclic organic group may have a substituent, and examples of the substituent may include an alkyl group (which may be straight, branched or cyclic, and has preferably 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a sulfonate ester group and the like.
  • the carbon constituting the cyclic organic group may be carbonyl carbon.
  • x is preferably 1 to 8, more preferably 1 to 4, particularly preferably 1 to 3, and most preferably 1.
  • Xf is as defined in Formula (2), and preferred examples thereof are also the same.
  • two Xf s may be bound with each other to form a ring structure.
  • the disulfonylimidate anion for Z " is preferably a bis(alkylsulfonyl)imide anion.
  • the alkyl group in the bis(alkylsulfonyl)imide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • Two alkyl groups in the bis(alkylsulfonyl)imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), which may form a ring together with an imide group and two sulfonyl groups.
  • the ring structure which may be formed by the bis(alkylsulfonyl)imide anion is preferably 5- to 7-membered ring, and more preferably 6-membered ring.
  • the substituent which may be possessed by the alkyl group and the alkylene group formed by linking two alkyl groups may be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group or the like, and preferably a fluorine atom or an alkyl group substituted with a fluorine atom.
  • Z " is a sulfonate anion represented by the following Formula (B-1).
  • R b i's each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF 3 ).
  • n an integer of 0 to 4.
  • n is preferably an integer of 0 to 3, and more preferably 0 or 1.
  • X b i represents a single bond, an alkylene group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate ester bond (-OS0 2 - or -S0 3 -) or a combination thereof.
  • X bt is preferably an ester bond (-OCO- or -COO-) or a sulfonate ester bond (-OS0 2 - or -S0 3 -), and more preferably an ester bond (-OCO- or -COO-).
  • R b2 represents an organic group having 6 or more carbon atoms.
  • the organic group having 6 or more carbon atoms for 3 ⁇ 4 2 is preferably a bulky group, and examples thereof may include an alkyl group having 6 or more carbon atoms, an alicyclic group, an aryl group, a heterocyclic group and the like.
  • the alkyl group having 6 or more carbon atoms for 3 ⁇ 4, 2 may be straight or branched, and is preferably a straight or branched alkyl group having 6 to 20 carbon atoms, and examples thereof may include a straight or branched hexyl group, a straight or branched heptyl group, a straight or branched octyl group and the like. From the viewpoint of volume, a branched alkyl group is preferred.
  • the alicyclic group having 6 or more carbon atoms for 3 ⁇ 4 2 may be monocyclic or polycyclic.
  • the monocyclic aliphatic group may include a monocyclic cycloalkyl group such as a cyclohexyl group and a cyclooctyl group.
  • the polycyclic alicyclic group may include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group.
  • an alicyclic group having a bulky structure, which has 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group, is preferred from the viewpoint of suppressing diffusion in film during a PEB (post-exposure baking) process and improving the MEEF (mask error enhancement factor).
  • the aryl group having 6 or more carbon atoms for 3 ⁇ 4 2 may be monocyclic or polycyclic.
  • Examples of the aryl group may include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group. Among them, a naphthyl group having relatively low light absorbance at 193 nm is preferred.
  • the heterocyclic group having 6 or more carbon atoms for R b2 may be monocyclic or polycyclic, but a polycyclic heterocyclic group may suppress the diffusion of an acid more efficiently. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity may include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring and a pyridine ring. Examples of the heterocyclic ring having no aromaticity may include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring.
  • the substituent having 6 or more carbon atoms for 3 ⁇ 4 2 may further have a substituent.
  • the further substituent may include an alkyl group (which may be straight or branched, and has preferably 1 to 12 carbon atoms), a cycloalkyl group (which may be a monocyclic, polycyclic or spiro ring, and has preferably 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group and a sulfonate ester group.
  • the carbon constituting the alicyclic group, the aryl group or the heterocyclic group may be carbonyl carbon.
  • Z " is a sulfonate anion represented by the following Formula
  • Ri is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group or a heteroaryl group.
  • R 2 is a divalent linking group.
  • Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • ni and n 2 are each independently 0 or 1.
  • the alkyl group represented by Ri is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
  • Specific examples of the alkyl group may include a methyl group, an ethyl group, a 1 -propyl group, a 2-propyl group, a 1 -butyl group, a 2-butyl group, a 2-(2-methylpropyl) group, a 1-pentyl group, a 2-pentyl group, a 3-pentyl group, a
  • the alkyl group may have a substituent (preferably a fluorine atom), and the alkyl group having a substituent is preferably an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom, and more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.
  • a substituent preferably a fluorine atom
  • the alkyl group having a substituent is preferably an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom, and more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.
  • the alkyl group represented by Ri is preferably a methyl group, an ethyl group or a trifluoromethyl group, and more preferably a methyl group or an ethyl group.
  • the monovalent alicyclic hydrocarbon group represented by R ⁇ preferably has 5 or more carbon atoms. Further, the monovalent alicyclic hydrocarbon group preferably has 20 or less carbon atoms, and more preferably 15 or less carbon atoms.
  • the monocyclic alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms, and examples thereof may include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecanyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctadienyl group, a piperidine ring group and the like, and particularly preferably a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.
  • the polycyclic alicyclic hydrocarbon group preferably has 10 to 20 carbon atoms, and examples thereof may include a bicyclo[4.3.0]nonanyl group, a decahydronaphthalenyl group, a 1,2,3,4-tetrahydronaphthalenyl group, a tricyclo[5.2.1.0(2,6)]decanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, a borayl group, an isobornyl group, a norbornyl group, an adamantyl group, a noradamantyl group, a l,7,7-trimethyltricyclo[2.2.1.0 2 ' 6 ]heptanyl group, a 3,7,7-trimethylbicyclo[4.1.0]heptanyl group, a decahydroisoquinoline ring group and the like, and preferably a norbornyl group, an adamantyl group
  • the aryl group represented by R ⁇ preferably has 6 or more carbon atoms. Further, the aryl group preferably has 20 or less carbon atoms, and more preferably 15 or less carbon atoms.
  • the heteroaryl group represented by R ⁇ preferably has 2 or more carbon atoms. Further, the heteroaryl group preferably has 20 or less carbon atoms, and more preferably 15 or less carbon atoms.
  • the aryl group and the heteroaryl group may be a monocyclic aryl group, a monocyclic heteroaryl group, a polycyclic aryl group or a polycyclic heteroaryl group.
  • Examples of the monocyclic aryl group may include a phenyl group and the like.
  • Examples of the polycyclic aryl group may include a naphthyl group, an anthracenyl group and the like.
  • Examples of the monocyclic heteroaryl group may include a pyridyl group, a thienyl group, a furanyl group and the like.
  • Examples of the polycyclic heteroaryl group may include a quinolyl group, an isoquinolyl group and the like.
  • the monovalent alicyclic hydrocarbon group, aryl group and heteroaryl group may further have a substituent, and examples of the further substituent may include a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like), a nitro group, a cyano group, an aminde group, a sulfonamide group, an alkyl group such as a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec -butyl group, a hexyl group, a 2-ethylhexyl group and an octyl group, an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group, an alkoxycarbonyl group such as a
  • Ri is particularly preferably a cyclohexyl group or an adamantyl group.
  • Examples of the divalent linking group represented by R 2 may include, but not particularly limited thereto, -COO-, -OCO-, -CO-, -0-, -S-, -SO-, -S0 2 -, an alkylene group (preferably an alkylene group having 1 to 30 carbon atoms), a cycloalkylene group (preferably a cycloalkylene group having 3 to 30 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 30 carbon atoms), an arylene group (preferably an arylene group having 6 to 30 carbon atoms), a heteroarylene group (preferably a heteroarylene group having 2 to 30 carbon atoms) and a combination of two or more thereof.
  • the alkylene group, the cycloalkylene group, the alkenylene group, the arylene group and the heteroarylene group may further have a substituent, and specific examples of the substituent are the same as those described above with respect to the substituent which may be further possessed by the monovalent alicyclic hydrocarbon group, aryl group and heteroaryl group as Ri .
  • the divalent linking group represented by R 2 is preferably an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group or a heteroarylene group, more preferably an alkylene group, still more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 5 carbon atoms.
  • Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • the alkyl group preferably has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
  • Rf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Rf is preferably a fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , QF 9 , C 5 Fn, C 6 F 13 , C 7 F 15 , C 8 F I7 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 or CH 2 CH 2 C 4 Fc>, more preferably a fluorine atom or CF 3 .
  • ni is preferably 1.
  • n 2 is preferably 1.
  • R-208 represents an alkyl group, a cycloalkyl group or an aryl group.
  • A represents an alkylene group, an alkenylene group or an arylene group.
  • aryl group of R 208 may be the same as the specific examples of the aryl group as R 20 i to R 203 in Formula (ZI).
  • alkyl group and the cycloalkyl group of R 208 may be the same as the specific examples of the alkyl group and the cycloalkyl group as R 20 i to R 203 in Formula (ZI).
  • Examples of the alkylene group of A may include an alkylene group having 1 to 12 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group and the like), examples of the alkenylene group of A may include an alkenylene group having 2 to 12 carbon atoms (for example, a vinylene group, a propenylene group, a butenylene group and the like), and examples of the arylene group of A may include an arylene group having 6 to 10 carbon atoms (for example, a phenylene group, a tolylene group, a naphthylene group and the like).
  • the compound (B) is preferably an ionic compound represented by the compound represented by Formula (ZI) or (ZII) and the like, and it is preferred that the content of the fluorine atom contained in the anion in the ionic compound is 35% by mass based on the total amount of the atoms constituting the anion of the compound (B). Since the compound (B) is an ionic compound represented by the compound represented by Formula (ZI) or (ZII) and the like, the pattern shape becomes more rectangular.
  • the acid generator may be used either alone or in combination of two or more thereof.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invnetion contains two or more acid generators, and it is preferred that, among the two or more acid generators, at least one compound does not have an aromatic group, or has one or two aromatic groups.
  • the content of the compound capable of generating an acid upon irradiation with an actinic ray or radiation in the composition is preferably 5% by mass or more, more preferably 10%» by mass or more, still more preferably 10%> by mass to 40% by mass, and particularly preferably 10%> by mass to 30% by mass based on the total solid of the actinic ray-sensitive or radiation-sensitive resin composition.
  • Component containig at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH 3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invnetion contains a component containing at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH 3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid (hereinafter, referred to as a "component (C)").
  • component (C) a component containing at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid
  • the component (C) may be an ionic compound or a non-ionic compound, but is preferably an ionic compound.
  • the component (C) is typically a compound capturing an acid generated from the compound (B), and more specifically, the component (C) is preferably a nitrogen-containing compound or a resin having a nitrogen atom in its side chain.
  • the component (C) is a compound having at least one of a fluorine atom and a silicon atom as well as having basicity
  • any electron-withdrawing functional groups a carbonyl group, a sulfonyl group, a cyano group, a halogen atom (particularly a fluorine atom) and the like
  • all atoms adjacent to the nitrogen atom are a hydrogen atom or a carbon atoms.
  • the component (C) is a compound having at least one of a fluorine atom and a silicon atom as well as capable of increasing the basicity by the action of an acid
  • any electron-withdrawing functional groups a carbonyl group, a sulfonyl group, a cyano group, a halogen atom (particularly a fluorine atom) and the like
  • all atoms adjacent to the nitrogen atom are a hydrogen atom or a carbon atoms.
  • the component (C) does not accompany unintended change in chemical structure upon irradiation with an actinic ray or radiation in order to ensure the the action is exhibited. In other words, it is preferred that the component (C) has no photosensitivity (non-photosensitivity).
  • the component (C) is preferably a resin (C) having a repeating unit having any one or more of a fluorine atom, a silicon atom and a CH 3 partial structure in a side chain moiety of the resin.
  • the content of the repeating unit having any one or more of a fluorine atom, a silicon atom and a CH 3 partial structure in a side chain moiety of the resin is preferably 25 mol% or less, more preferably 8 mol% or less, and still more preferably 0.05 mol% to 8 mol% based on the whole repeating units of the resin (C).
  • component (C) into "a compound (C-l) having at least one of a fluorine atom and a silicon atom as well as having basicity", "a compound (C-2) having at least one of a fluorine atom and a silicon atom as well as capable of increasing the basicity by the action of an acid” and "a resin (C-3) having a CH 3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid”.
  • the compound (C-l) is not particularly limited as long as the compound has at least one of a fluorine atom and a silicon atom as well as having basicity, but, for example, a basic compound having at least one of a fluorine atom and a silicon atom and having any of the structures represented by the following Formulas (A) to (E) may be exemplified.
  • R and R are each independently a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms) or a heteroaryl group.
  • R 203 , R 204 , R 205 and R 206 each independently represent an alkyl group or a cycloalkyl group.
  • R 201 and R 202 may be bound with each other to form a ring.
  • two or more of bonding hands from carbon atoms and bonding hands from nitrogen atoms may be bound with each other to form a ring.
  • R 203 , R 204 , R 205 , R 206 , bonding hands from carbon atoms and a bonding hand from a nitrogen atom may be bound with each other to form a ring.
  • the alkyl group of R and R in Formula (A) is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-heptadecyl group, a n-octadecyl group, a n
  • the cycloalkyl group of R and R is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof may include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • alkyl group and the cycloalkyl group of R 201 and R 202 a straight alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 4 to 8 carbon atoms are preferred.
  • the aryl group of R and R is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof may include a phenyl group, a toluoyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, an anthryl group and the like.
  • the heteroaryl group of R and R is a group which contains one or more heteroatoms such as a sulfur atom, an oxygen atom and a nitrogen atom in the aryl group, and examples thereof may include a pyridyl group, an imidazolyl group, a morpholinyl group, a piperidinyl group, a pyrrolidinyl group and the like.
  • the alkyl group, the cycloalkyl group, the aryl group, the heteroaryl group of R 201 and may have a substituent, and examples of the substituent may include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an arylcarbonyl group, an alkoxyalkyl group, an aryloxyalkyl group, alkyl carbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group and the like.
  • Examples of the alkyl group as a substituent which may be further possessed by R 201 and R 202 may include a straight or branched alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group and a t-butyl group.
  • R and R may include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
  • Examples of the aryl group as a substituent which may be further possessed by R 201 and R may include an aryl group having 6 to 15 carbon atoms such as a phenyl group and a naphthyl group.
  • alkoxy group as a substituent which may be further possessed by R 201 and R may include a straight, branched or cyclic alkoxy group such as a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxy group, a n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group, a cyclopentyloxy group and a cyclohexyloxy group.
  • R may include an aryloxy group having 6 to 10 carbon atoms such as a phenyloxy group and a naphthyloxy group.
  • R may include a straight or branched acyl group having 2 to 12 carbon atoms such as an acetyl group, a propionyl group, a n-butanoyl group, an i-butanoyl group, a n-heptanoyl group, a 2-methylbutanoyl group, a 1-methylbutanoyl group and a t-heptanoyl group.
  • acyl group having 2 to 12 carbon atoms such as an acetyl group, a propionyl group, a n-butanoyl group, an i-butanoyl group, a n-heptanoyl group, a 2-methylbutanoyl group, a 1-methylbutanoyl group and a t-heptanoyl group.
  • R and R uz may include an arylcarbonyl group having 6 to 10 carbon atoms such as a phenylcarbonyl group and a naphthylcarbonyl group.
  • alkoxyalkyl group as a substituent which may be further possessed by
  • R ⁇ 1 may include a straight, branched or cyclic alkoxyalkyl group having 2 to 21 carbon atoms such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group and a 2-ethoxyethyl group.
  • R and R may include a straight, branched or cyclic alkylcarbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an i-propylcarbonyloxy group, a n-butylcarbonyloxy group, a 2-methylpropylcarbonyloxy group, an 1-methylpropylcarbonyloxy group, a t-butylcarbonyloxy group, a cyclopentylcarbonyloxy group and a cyclohexylcarbonyloxy group.
  • a straight, branched or cyclic alkylcarbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an i-propylcarbonyloxy group, a n-butylcarbonyloxy group, a 2-methylpropylcarbonyloxy
  • R and R may include an arylcarbonyloxy group having 7 to 1 1 carbon atoms such as a phenylcarbonyloxy group and a naphthylcarbonyloxy group.
  • alkoxycarbonyl group as a substituent which may be further possessed by R and R may include a straight, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an i-propoxycarbonyl group, a n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, a 1-methylpropoxycarbonyl group, a t-butoxycarbonyl group, a cyclopentyloxycarbonyl group and a cyclohexyloxycarbonyl.
  • a straight, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an i-propoxycarbonyl group, a n-butoxycarbonyl group,
  • Examples of the aryloxycarbonyl group as a substituent which may be further possessed by R and R may include an aryloxycarbonyl group having 7 to 1 1 carbon atoms such as a phenyloxycarbonyl group and a naphthyloxycarbonyl group.
  • alkoxycarbonyloxy group as a substituent which may be further possessed by R and R may include a straight, branched or cyclic alkoxycarbonyloxy group such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, a n-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy.
  • a straight, branched or cyclic alkoxycarbonyloxy group such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, a n-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cyclopentyloxy
  • R and R may include an aryloxycarbonyloxy group having 7 to 11 carbon atoms such as a phenyloxycarbonyloxy group and a naphthyloxycarbonyloxy group.
  • the compound (C-l) having a structure represented by Formula (A) may include
  • (Al) a compound having a structure represented by Formula (A) (however, R and R do not contain a fluorine atom and a silicon atom), and a "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (A),
  • (A2) a compound having a structure represented by Formula (A) (however, at least one of R 201 and R 202 is a group formed by substituting at least one hydrogen atom in the alkyl group, the cycloalkyl group, the aryl group or the heteroaryl group, which may have a substituent, by a group having a fluorine atom or silicon atom), and (A3) a compound having a structure
  • R U1 is a group formed by substituting at least one hydrogen atom in the alkyl group, the cycloalkyl group, the aryl group or the heteroaryl group, which may have a substituent, by a group having a fluorine atom or silicon atom
  • the "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (A) may be suitably exemplified by the group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent
  • the group having a silicon atom is not particularly limited as long as the group contains at least one silicon atom, and examples thereof may include a silyl group, a silyloxy group, a group having a siloxane bond, and the like.
  • the group having a silicon atom may be an alkylsilyl structure or a cyclic siloxane structure (for example, groups represented by Formulas (CS-1) to (CS-3) as described below) which may be possessed by the resin (C") as described below.
  • These groups may further have a substituent, and specific examples of the substituent are the same as the specific examples of the subsituent which may be possesse4d by R 201 and R 202 .
  • group having a silicon atom may include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group and the like.
  • the compound (C-l) having a structure represented by Formulas (B) to (D) may include a compound having a structure represented by Formulas (B) to (D), and a group having at least one of a fluorine atom and a silicon atom (for example, a group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent which may be further possessed by R and R , by a group having a fluorine atom or silicon atom).
  • a group having at least one of a fluorine atom and a silicon atom for example, a group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent which may be further possessed by R and R , by a group having a fluorine atom or silicon atom).
  • the alkyl group and the cycloalkyl group of R 203 , R 204 , R 205 and R 206 may further have a substituent, and specific examples of the substituent are the same as the specific examples of the substituent which may be further possessed by R and R .
  • the compound (C-l) having a structure represented by Formula (E) may include (El) a comound having a structure represented by Formula (E) (however, R 203 , R 204 , R2 05 and R 206 do not contain a fluorine atom and a silicon atom), and a "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (E), (E2) a compound having a structure represented by Formula (E) (however, at least one of R 203 , R 204 , R 205 and R 206 is a group formed by substituting at least one hydrogen atom in the alkyl group or the cycloalkyl group, which may have a substituent, by a group having a fluorine atom or silicon atom), and (E3) a compound having a structure represented by Formula (E) (however, at least one of R 203 , R 204 , R 205
  • the "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (E) may be suitably exemplified by the group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent which may be further possessed by R and R , by a group having a fluorine atom or silicon atom.
  • R 201 and R 202 may be bound with each other to form a ring.
  • two or more of the bonding hands from carbon atoms and the bonding hands from nitrogen atoms may be bound with eath other to form a ring.
  • two or more of R 203 , R 204 , R 205 , R 206 , bonding hands from carbon atoms and bonding hands from nitrogen atoms may be bound with each other to form a ring.
  • the ring may be an aromatic or non-aromatic nitrogen-containing heterocyclic ring.
  • the nitrogen-containing heterocyclic ring may include a 3- to 10-membered ring, preferably 4- to 8-membered ring, and more preferably 5- or 6-membered ring.
  • the ring may further have a substituent, and specific examples thereof are the same as the specific examples exemplified as as a substituent which may be further possessed by R 201 and R 202 .
  • the compound (C-l) may be suitably exemplified by a compound having a nitrogen-containing heterocyclic ring which is substituted with a fluorine atom or a group containing a fluorine atom or a silicon atom.
  • the group containing a fluorine atom or a silicon atom may include a group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent which may be further possessed by R and R , by a group having a fluorine atom or silicon atom.
  • the nitrogen-containing heterocyclic ring may be suitably exemplified by a pyrrole ring, a pyridine ring, a pyrimidine ring and the like.
  • the compound (C-2) is not particularly limited as long as the compound is a compound having at least one of a fluorine atom and a silicon atom as well as capable of increasing the basicity by the action of an acid, and examples thereof may include a comound having at least one of a fluorine atom and a silicon atom, and a carbamate group having a protecting group.
  • the protecting group constituting the carbamate group is a group represented by the following Formula (P) (the group represented by Formula (P) is bonded to a nitrogen atom at a bonding site represented by the symbol *).
  • Rbi, Rb 2 and Rb 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rbi to Rb 3 may be bound with each other to form a ring. However, all of Rbi to Rb 3 are not a hydrogen atom at the same time.
  • alkyl group, the cycloalkyl group and the aryl group of Rb 1; Rb 2 and Rb 3 are the same as the specific examples of the alkyl group, the cycloalkyl group and
  • aralkyl group of Rb l5 Rb 2 and Rb 3 may include preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylbutyl group.
  • Rb ⁇ , Rb 2 and Rb 3 preferred are a straight or branched alkyl group, cycloalkyl group and aryl group. More preferred are a straight or branched alkyl group and cycloalkyl group.
  • the ring formed by two of Rbi to Rb 3 being bound with each other is preferably a cycloalkyl group (monocyclic or polycyclic), and more specifically a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group.
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
  • Rbi, Rb 2 and Rb 3 may further have a substituent, and examples of the substituent may include a halogen atom (a fluorine atom and the like), a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), an aminoacyl group (preferably having 2 to 10 carbon atoms), a group having a silicon atom (specific examples are the same as those described in the compound (G-l)) and the like.
  • a halogen atom a fluorine atom and the like
  • an alkyl group (preferably having 1 to 10 carbon atoms) may be also exemplified as a substituent.
  • an alkyl group (preferably having 1 to 10 carbon atoms) may be also exemplified as a substituent.
  • Rb 1? Rb 2 and Rb 3 are a hydrogen atom
  • the other one is preferably an aryl group
  • examples of the aryl group may include a phenyl group, a naphthyl group and the like.
  • the compound (C-2) may be constituted by substituting at least one group connected to the nitrogen atom of the compound (C-l) by a group represented by Formula (P).
  • the compound (C-2) is not particularly limited, but a particularly preferred aspect may be a compound represented by the following Formula (1) having the group represented by Formula (P). Since the compound represented by the following Formula (1) has at least one of a fluorine atom and a silicon atom in a moiety other than the group represented by Formula (P) (a protecting group constituting a carbamate group), the compound (compound whose basicity is increased) obtained by the action of an acid on the compound represented by Formula (1) constantly has at least one of a fluorine atom and a silicon atom.
  • Ra, Rb t , Rb 2 and Rb 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rbi to Rb 3 may be bound with each other to form a ring. However, all of Rbi to Rb 3 are not a hydrogen atom at the same time.
  • Rc represents a single bond or a divalent linking group.
  • Rf represents an organic group.
  • x 0 or 1
  • y 1 or 2
  • z 1 or 2
  • x+y+z 3.
  • Ra and Rc may be bound with each other to form a nitrogen-containing heterocyclic ring.
  • the organic group as Rf contains a fluorine atom or a silicon atom.
  • At least one of two Rf s contains a fluorine atom or a silicon atom.
  • two Re's and two Rf s may be the same or different, respectively, and two Re's may be bound with each other to form a ring.
  • two R b i's, two R b2 's and two Rt, 3 's may be the same or different, respectively.
  • alkyl group, the cycloalkyl group, the aryl group or the aralkyl group as Ra, Rbi, Rb 2 and Rb 3 are the same as the specific examples of the alkyl group, the cycloalkyl group, the aryl group or the aralkyl group as Rbi, Rb 2 and Rb 3 in Formula (P).
  • Rc is preferably a divalent linking group having 2 to 12 carbon atoms (more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms), and examples thereof may include an alkylene group, a phenylene group, an ether group, an ester group, an amide group and a group formed by combining two or more thereof.
  • the organic group as Rf is preferably an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
  • alkyl group, the cycloalkyl group, the aryl group or the heteroaryl group as Rf are the same as the specific examples of the cycloalkyl group, the aryl group or the heteroaryl group as R and R in Formula (A).
  • Ra, Rbi, Rb 2 , Rb 3 , Rc and Rf may further have a substituent, respectively, and specific examples of the substituent are the same as the specific examples of the substituent which may be further possessed by Rbi, Rb 2 and Rb 3 in Formula (P).
  • Rf is preferably a group formed by substituting at least one hydrogen atom in the organic group by a group having a fluorine atom or a silicon atom.
  • specific examples of the group having a silicon atom are the same as the specific examples of the group having a silicon atom as described in the compound (C-l).
  • Rf is preferably an alkyl group in which 30% to 100% of hydrogen atoms are substituted by fluorine atoms, and examples thereof may include a perfluoroalkyl group such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group and a perfluorobutyl group.
  • example of the nitrogen-containing heterocyclic ring formed by Ra and Rc, or Re's being bound with each other may include an aromatic or non-aromatic nitrogen-containing heterocyclic ring (preferably having 3 to 20 carbon atoms).
  • examples of the nitrogen-containing heterocyclic ring may include a ring corresponding to a heterocyclic compound such as pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, lH-l,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo[l,2-a]pyridine,
  • the ring formed by two of Rbi to Rb 3 being bound with each other is preferably a monocyclic cycloalkyl such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group.
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
  • the component (C) may be a low-molecular compound or a resin (polymer compound), but is preferably a resin.
  • the molecular weight is generally 500 or less, preferably 150 to 500, and more preferably 250 to 500.
  • the compound (C-2) may be synthesized from amine, for example, by the method described in Protective Groups in Organic Synthesis 4th edition, and the like.
  • the compound represented by Formula (1) is preferably obtained by reacting dicarbonate ester or haloformate ester with amine, as shown in the following scheme.
  • X represents a halogen atom.
  • Ra, Rbi, Rb 2 , Rb 3 , Rc and Rf have the same meaing as Ra, Rbi, Rb 2 , Rb 3 , Rc and Rf in Formula (1), respectively.
  • the component (C) is a resin containing at least one of a fluorine atom and a silicon atom (hereinafter, such a resin is referred to as a resin (C")), at least one of a fluorine atom and a silicon atom may be contained in the main chain or side chain of the resin.
  • the resin (C) contains a fluorine atom
  • the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom or an aryl group containing a fluorine atom as a partial structure containing a fluorine atom.
  • the alkyl group containing a fluorine atom is a straight or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom.
  • the alkyl group has preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the alkyl group containing a fluorine atom may further have a substituent other than a fluorine atom.
  • the cycloalkyl group containing a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom.
  • the cycloalkyl group containing a fluorine atom may further have a substituent other than a fluorine atom.
  • the aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted by a fluorine atom.
  • Examples of the aryl group may include a phenyl group and a naphthyl group.
  • the aryl group containing a fluorine atom may further have a substituent other than a fluorine atom.
  • Preferred examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom and the aryl group containing a fluorine atom may include groups represented by the following Formulas (F2) to (F4).
  • R 57 to 3 ⁇ 4 8 each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R 57 to represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. At least one of 3 ⁇ 4 2 to represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. At least one of R 65 to R 68 represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom.
  • the alkyl group preferably has 1 to 4 carbon atoms.
  • R 57 to and R65 to R67 are a fluorine atom.
  • R6 2 , R6 3 and is preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Meanwhile, and R ⁇ 5 3 may be bound with each other to form a ring.
  • Examples of the group represented by Formula (F2) may include a p-fluorophenyl group, a pentafluorophenyl group and a 3,5-di(trifluoromethyl)phenyl group.
  • Examples of the group represented by Formula (F3) may include a trifluoromethyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafiuoro(2-methyl)isopropyl group, a nonafluorobutyl group, an octafluoroisobutyl group, a nonafluorohexyl group, a nonafluoro-t-butyl group, perfluoroisopentyl group, a perfluorooctyl group, a perfluoro(trimethyl)hexyl group, a 2,2,3,3-tetrafluorocyclobutyl group and a perfluorocyclohexyl group.
  • the group is more preferably a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro(2-methyl)isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group or a perfluoroisopentyl group, and more preferably a hexafluoroisopropyl group or a heptafluoroisopropyl group.
  • Examples of the group represented by Formula (F4) may include -C(CF 3 ) 2 OH, -C(C 2 F 5 ) 2 OH, -C(CF 3 )(CH 3 )OH and -CH(CF 3 )OH. Among them, -C(CF 3 ) 2 OH is particularly preferred.
  • Xi represents a hydrogen atom, -CH 3 , -F or -CF 3 .
  • X 2 represents -F or -CF 3 .
  • the resin (C) contains a silicon atom
  • the resin has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom.
  • the alkylsily structure is preferably a structure containing a trialkylsilyl group.
  • Preferred examples of the alkylsilyl structure and the cyclic siloxane structure may include roups represented by the following Formulas (CS-1) to (CS-3).
  • Ri 2 to R 26 each independently represent a straight or branched alkyl group or a cycloalkyl group.
  • the alkyl group preferably has 1 to 20 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 arbon atoms.
  • L 3 to L 5 represents a single bond or a divalent linking group.
  • the divalent linking group may include an alkylene group, a phenylene group, an ether bond, a thioether group, a carbonyl group, an ester bond, an amide bond, a urethane bond, a urea bond or a combination thereof.
  • n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.
  • Suitable examples of the resin (C) may include,
  • a resin (C"-b) having a repeating unit having at least one of a fluorine atom and a silicon atom, and a basic group or a group capable of increasing the basicity by the action of an acid and a resin (C"-b) having a repeating unit having at least one of a fluorine atom and a silicon atom, and a basic group or a group capable of increasing the basicity by the action of an acid.
  • the repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid is a repeating unit represented by the following Formula (B-I).
  • Xa represents a hydrogen atom, a methyl group which may have a substituent or a group represented by -CH 2 -Rc>.
  • R9 represents a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group may include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
  • Xa represents preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and more preferably a hydrogen atom, a methyl group or a hydroxymethyl group.
  • Ab represents a group having a basic group or a group capable of increasing the basicity by the action of an acid.
  • both of the group having basicity and the group capable of increasing the basictity by the action of an acid contain a nitrogen atom.
  • the group having a basic group as Ab is preferably a group having any of structrures rpresented by Formulas (A) to (E) or an ammonium group, and specific examples thereof may include a monovalent group formed by subtracting any one hydrogen atom from a basic compound (low-molecular compound) having any of structures represented by Formulas (A) to (E) (in this case, the basic compound may or may not have at least one of a fluorine atom and a silicon atom).
  • the group having a basic group as Ab is a group represented by the following Formula ( ⁇ - ⁇ ).
  • L representes a single bond or a divalent linking group
  • Ac represents a structure represented by Formula (A) (the bonding hand from the nitrogen atom of Formula (A) is bonded to L).
  • Examples of the divalent linking group as L may include an alkylene group, a cycloalkylene group, an ether group, a phenylene group and a group formed by combining two or more thereof, more preferably an alkylene group and cycloalkylene group, and still more preferably an alkylene group.
  • the total number of carbon atoms of the divalent linking group as L is preferably 0 to 10, more preferably 1 to 6, and still more preferably 2 or 3.
  • preferred examples of the "group capable of increasing the basicity by the action of an acid” may include "a carbamate group having a protecting group” as described in the compound (C-2).
  • the group having a group capable of increasing the basicity by the action of an acid as Ab is a group represented by the following Formula (B-II).
  • Ra, Rbi, Rb 2 and Rb 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rbi to Rb 3 may be bound with each other to form a ring. However, all of Rbi to Rb 3 are not a hydrogen atom at the same time.
  • Rc represents a single bond or a divalent linking group
  • x 0 or 1
  • y 1 or 2
  • x+y 2.
  • Ra and Rc may be bound with each other to form a nitrogen-containing heterocyclic ring.
  • two R b i's, two Rb 2 's and two Rt, 3 's may be the same or different, respectively.
  • the repeating unit having at least one of a fluorine atom and a silicon atom, and a group capable of increasing the basicity by the action of an acid is a repeating unit represented by Formula (B-1), and may include a repeating unit satisfying any of (i) Xa is a methyl group having at least one of a fluorine atom and a silicon atom (for example, a trifluoromethyl group), (ii) Ab is a group having a basic group or a group capable of increasing the basicity by the action of an acid, and also having at least one of a fluorine atom and a silicon atom, and (iii) corresponding to (i) and (ii).
  • examples of the group Ab having a basic group and also having at least one of a fluorine atom and a silicon atom may include a monovalent group formed by subtracting any one hydrogen atom from a basic compound (low-molecular compound) having any of structures represented by Formulas (A) to (E) (however, the basic compound has at least one of a fluorine atom and a silicon atom).
  • examples of the group Ab having a group capable of increasing the basicity by the action of an acid and also having at least one of a fluorine atom and a silicon atom may include a monovalent group formed by stbtracting any one hydrogen atom from any of Ra, Rc and Rf of the compound represented by Formula (1).
  • repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid in the resin (C") are shown below, but the present invention is not limited thereto.
  • X represents a hydrogen atom, -CH 3 , -CH 2 OH, -F or -CF 3 .
  • the resin (C) may further contain a repeating unit represented by the following
  • Rc 3 i represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom and the like), a cyano group or a -CH 2 -0-Rac 2 group.
  • Rac 2 represents a hydrogen atom, an alkyl group or an acyl group.
  • Rc 31 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
  • Rc 32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a silicon atom, a fluorine atom and the like.
  • L c3 represents a single bond or a divalent linking group.
  • the alkyl group of Rc 32 is preferably a straight or branched alkyl group having 3 to 20 carbon atoms.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms.
  • the alkenyl group preferably has 3 to 20 carbon atoms.
  • the cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
  • R c32 is preferably an unsubstituted alkyl group or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom.
  • L c3 represents a single bond or a divalent linking group.
  • the divalent linking group may include an ester group, an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, an ester bond (a group represented by -COO-) or a group formed by combining two or more thereof, and preferably a linking group in which the total number of carbon atoms is 1 to 12.
  • the resin (C) may further contain a repeating unit represented by the following Formula (CII-AB).
  • Rcu' and R ⁇ ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
  • Zc' represents an atomic group needed to form an alicyclic structure together with two carbon atoms (C-C) to which Rcu' and Rci 2 ' are bonded.
  • Rc 32 is a substituent for the alicyclic structure, and has the same definition as Rc 32 in Formula ( ⁇ ).
  • p represents an integer of 0 to 3, and is preferably 0 or 1.
  • Ra represents H, CH 3 , CH 2 OH, CF 3 or CN.
  • the content of the fluorine atom is preferably 5 mol% to 80 mol%, and more preferably 10 mol% to 80 mol% based on the molecular weight of the component (C).
  • the content of the repeaing unit containing a fluorine atom is preferably 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol% based on the whole repeating units of the hydrophobic resin.
  • the content of the silicon atom is preferably 2 mol% to 50 mol%, and more preferably 2 mol% to 30 mol% based on the molecular weight of the component (C).
  • the content of the repeating unit containg a silicon atom is preferably 10 mol% to 100 mol%, and more preferably 20% by mass to 100% by mass based on the whole repeating units of the resin (C").
  • the surface free energy of the component (C) may be sufficiently reduced.
  • the surface free energy of the component (C) may be sufficiently reduced.
  • the excessive acid generated from the top layer of the exposed portion may be more certainly captured, and the acid concentration may be more certainly evenly distributed in the thickness direction of the exposed portion of the resist film, it is considered that the aforementioned problems such as T-top shape or bridge defects may be more certainly suppressed.
  • the content of the "repeating unit having at least one of a fluorine atom and a silicon atom” is preferably 20 mol% to 99 mol%, more preferably 25mol% to 95 mol%, and particularly preferably 30 mol% to 90 mol% based on the whole repeating units constituting the resin (C").
  • the content of the "repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid” is preferably 15 mol%, more preferably 8 mol% or less, and particularly preferably 1 mol% to 8 mol% based on the whole repeating units constituting the resin (C").
  • the conent of the "repeating unit having at least one of a fluorine atom and a silicon atom, and a basic group or a group capable of increasing the basicity by the action of an acid” is preferably 20 mol% to 100 mol%, more preferably 25 mol% to 100 mol%, and particularly preferably 30 mol% to 100 mol% based on the whole repeating units constituting the resin (C").
  • the content of the repeating unit represented by Formula ( ⁇ ) or (CII-AB) is preferably 20 mol% to 80 mol%, more preferably 25 mol% to 70 mol%, and particularly preferably 30 mol% to 60 mol% based on the whole repeating units constituting the resin (C").
  • the weight average molecular weight of the resin (C") is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 7,500 to 15,000 in terms of polystyrene by the GPC method.
  • the polydispersity of the resin (C") is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. By doing this, it is possible to achieve more excellent resolution, pattern shape and roughness characteristics.
  • the component (C) (also including the resin (C")) may be used either alone or in combination of two or more thereof.
  • the content of the component (C) (also including the resin (C")) is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and still more preferably 0.1 % by mass to 5% by mass based on the total solid in the composition.
  • the component (C) (also including the resin (C")) may be commercially available or synthesized by a conventional method.
  • a general synthesis method of the resin (C") may be exemplified by the method as described above with respect to the resin (A).
  • the resin (C) has a small amount of impurities such as metal, but the residual amount of monomer and olygomer components is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and still more preferably 0 % by mass to 1% by mass. Accordingly, it is possible to reduce the change in sensitivity and the like over time by reducing the amount of extraneous substances in liquid.
  • C-3 Resin having a CH 3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid
  • the resin (C-3) is not particularly limited as long as the resin is a resin having a CH 3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid, buta resin having a repeating unit represented by Formula (II) as described below may be exemplified.
  • the CH 3 partial structure possessed by the side chain moiety in the resin (C-3) (hereinafter, simply referred to as a "side chain CH 3 partial structure”) includes CH 3 partial structures possessed by an ethyl group, a propyl group and the like.
  • a methyl group for example, an a-methyl group of a repeating unit having a methacrylate structure
  • a methyl group directly bonded to the main chain of the resin (C-3) makes a little contribution to surface localization of the resin (C-3) by the effect of the main chain, it is considered that such a methyl group is not included in the CH 3 partial structure in the present invention.
  • the resin (C-3) contains a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond such as, for example, a repeating unit represented by the following Formula (M), and the case where R-i i to Ri 4 are CH 3 "itself, it is considered that the CH 3 is not included in the CH 3 partial structure possessed by the side chain moiety in the present invention.
  • CH 3 partial structure present via a certain atom from the C-C main chain is included in the CH 3 partial structure in the present invention.
  • Ri i is an ethyl group (CH 2 CH 3 )
  • "one" CH 3 partial structure of the present invention is included.
  • Rn to R 14 each independently represent a side chain moiety.
  • Rn to Rj 4 of the side chain moiety may include a hydrogen atom, a monovalent organic group and the like.
  • Examples of the monovalent organic group for Rn to Ri 4 may include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group and the like, and these group may further have a substituent.
  • the resin (C-3) is a resin having a repeating unit having a CH 3 partial structure in the side chain moiety, and it is more preferred that the resin has at least one repeating unit (x) among the repeating unit represented by the following Formula (II) and the repeating unit represented by the following Formula (III).
  • XM represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom
  • R 2 represents an orgainic group having one or more CH 3 partial structures, which is stable against an acid.
  • the organic group which is stable against an acid is preferably an organic group having no "group capable of decomposing by the action of an acid to generate a polar group" described in the resin (A).
  • the alkyl group of X i is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group or the like, but a methyl group is preferred.
  • Xbi is preferably a hydrogen atom or a methyl group.
  • R 2 may include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group, each of which has one or more CH 3 partial structures.
  • the aforementioned cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.
  • R 2 is preferably an alkyl group or an alkyl-substituted cycloalkyl group, which has one or more CH 3 partial structures.
  • the organic group having one or more CH 3 partial structures, which is stable against an acid, as R 2 preferably has 2 to 10 CH 3 partial structures, and more preferably 2 to 8 CH 3 partial structures.
  • the alkyl group having one or more CH 3 partial structures in R 2 is preferably a branched alkyl group having 3 to 20 carbon atoms.
  • Specific examples of the preferred alkyl group may include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3-butyl group, a 3-hexyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5, 7-tetramethyl-4-heptyl group and the like.
  • the alkyl group is more preferably an isobutyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3 -methyl -4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l ,5-dimethyl-3-heptyl group or a 2,3 ,5 ,7-tetramethyl-4-heptyl group.
  • the cycloalkyl group having one or more CH 3 partial structures in R 2 may be monocyclic or polycyclic. Specific examples thereof may include groups having a monocyclo, bicyclo, tricyclo and tetracyclo structure having 5 or more carbon atoms. The number of carbon atoms thereof is preferably 6 to 30, and particularly preferably 7 to 25.
  • cycloalkyl group may include an adamantyl group, a noradamantyl group, a decalin residue structure, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclododecanyl group.
  • More preferred examples thereof may include an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group and a tricyclodecanyl group.
  • the cycloalkyl group is more preferably a norbornyl group, a cyclopentyl group or a cyclohexyl group.
  • the alkenyl group having one or more CH 3 partial structures in R 2 is preferably a straight or branched alkenyl group having 1 to 20 carbons, and more preferably a branched alkenyl group.
  • the aryl group having one or more CH 3 partial structures in R 2 is preferably an aryl group having 6 to 20 carbon atoms, examples thereof may include a phenyl group and a naphthyl group, and preferably a phenyl group.
  • the aralkyl group having one or more C3 ⁇ 4 partial structures in R 2 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof may include a benzyl group, a phenethyl group and a naphthylmethyl group.
  • hydrocarbon group having two or more CH 3 partial structures in R 2 may include an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2-methyl-3 -butyl group, a 3-hexyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyI group, a 3,5-dimethylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-tbutyl group,
  • the repeating unit represented by Formula (II) is preferably a repeating unit which is stable against an acid (non-acid-decomposable), and specifically, a repeating unit having no group capable of decomposing by the action of an acid to generate a polar group.
  • X 1 ⁇ 2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom
  • R 3 represents an organic group having one or more CH 3 partial structures, which is stable against an acid
  • n represents an integer of 1 to 5.
  • the alkyl group of X b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group or the like, but a hydrogen atom is preferred.
  • X b2 is preferably a hydrogen atom.
  • R 3 is an organic group which is stable against an acid, more specifically, R 3 is preferably an organic group having no "group capable of decomposing by the action of an acid to generate a polar group" described in the resin (A).
  • R 3 may include an alkyl group having one or more CH 3 partial structures.
  • the organic group having one or more CH 3 partial structures, which is stable against an acid, as R 3 preferably has 1 to 10 CH 3 partial structures, more preferably 1 to 8 CH 3 partial structures, and still more preferably 1 to 4 CH 3 partial structures.
  • the alkyl group having one or more CH 3 partial structures in R 3 is preferably a branched alkyl group having 3 to 20 carbon atoms.
  • Specific examples of the preferred alkyl group may include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3 -butyl group, a 3-hexyl group, a 2-methyl-3-pentyl group, a 3 -methyl -4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and the like.
  • the alkyl group is more preferably an isobutyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group or a 2,3,5,7-tetramethyl-4-heptyl group.
  • alkyl group having two or more CH 3 partial structures in R 3 may include an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2,3-dimethylbutyl group, a 2-methyl-3-butyl group, a 3-hexyI group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and the like.
  • the alkyl group is more preferably an alkyl group having 5 to 20 carbon atoms, such as an isopropyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and a 2,6-dimethylheptyl group.
  • an alkyl group having 5 to 20 carbon atoms such as an isopropyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexy
  • n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2
  • the repeating unit represented by Formula (III) is preferably a repeating unit which is stable against an acid (non-acid-decomposable), and specifically, a repeating unit having no group capable of decomposing by the action of an acid to generate a polar group.
  • the resin (C-3) may contain a repeating unit having at least one of a fluorine atom and a silicon atom as described above.
  • Suitable examples of the resin (C-3) may include a resin (C-3-a) having a repeating unit having a CH 3 partial structure in a side chain, and a repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid, and
  • the content of the repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid is preferably 20 mol% to 80 mol%, more preferably 25 mol% to 70 mol%, and still more preferably 30 mol% to 60 mol% based on the whole repeating units of the resin (C-3-a).
  • the content of the repeating unit having a CH 3 partial structure in a side chain, and a basic group or a group capable of increasing the basicity by the action of an acid is preferably 20 mol% to 100 mol%, more preferably 25 mol% to 100 mol%, and still more preferably 30 mol% to 100 mol% based on the whole repeating units of the resin
  • the repeating unit having a CH 3 partial structure in a side chain, and a basic group or a group capable of increasing the basicity by the action of an acid is not particularly limited as long as the hydrogen atom constituting the side chain of at least one repeating unit (x) among the repeating unit represented by Formula (II) and the repeating unit represented by Formula (III) is substituted by a basic group or a group capable of increasing the basicity by the action of an acid, and further, a CH 3 partial structure is present in the side chain.
  • repeating unit having a CH 3 partial structure in a side chain and a basic group or a group capable of increasing the basicity by the action of an acid in the resin (C- -b) are shown below.
  • the present invention is not limited thereto.
  • the content of the resin (C-3) is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and still more preferably 0.1 % by mass to 5% by mass based on the total solid of the composition.
  • the resin (C-3) may be commercially available or synthesized by a conventional method.
  • a general synthesis method of the resin (C-3) may be exemplified by the method as described above with respect to the resin (A).
  • the resin (C-3) has a small amount of impurities such as metal, but the residual amount of monomer and olygomer components is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and still more preferably 0 % by mass to 1% by mass. Accordingly, it is possible to reduce the change in sensitivity and the like over time by reducing the amount of extraneous substances in liquid.
  • the weight average molecular weight of the resin (C-3) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 7,500 to 15,000 in terms of polystyrene by the GPC method.
  • the polydispersity of the resin (C-3) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. By doing this, it is possible to achieve more excellent resolution, pattern shape and roughness characteristics.
  • the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a hydrophobic resin different from the component (C) (hereinafter, also referred to as a "hydrophobic resin (D) or simply referred to as a “resin (D)").
  • a hydrophobic resin different from the component (C) hereinafter, also referred to as a "hydrophobic resin (D) or simply referred to as a “resin (D)").
  • the hydrophobic resin (D) when the hydrophobic resin (D) is localized on the film top layer and the immersion medium is water, the static/dynamic contact angle of the resist film surface against water may be improved, thereby improving an immersion liquid follow-up property.
  • the hydrophobic resin (D) is designed to be localized at the interface as described above, but unlike a surfactant, the hydrophobic resin (D) does not necessarily have a hydrophilic group in the molecule thereof, and may not contribute to the mixing of polar/non-polar materials homogeneously.
  • the hydrophobic resin (D) has preferably one or more of "a fluorine atom", "a silicon atom” and "a CH 3 partial structure contained in a side chain moiety of a resin", and more preferably two or more thereof.
  • the hydrophobic resin (D) contains a fluorine atom and/or a silicon atom
  • the fluorine atom and/or the silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin, or may be contained in the side chain thereof.
  • the hydrophobic resin (D) contains a fluorine atom
  • the resin has an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
  • Definition and preferred ranges of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom or the aryl group having a fluorine atom are the same as those in the component (C) as described above.
  • the partial structure containing a fluorine atom may be bonded directly to the main chain or may be bonded to the main chain via a group selected from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond, or a group formed by combining two or more thereof.
  • the hydrophobic resin (D) contains a fluorine atom
  • the hydrophobic resin (D) is preferably a resin having a repeating unit having a fluorine atom, andspecific examples of the repeating unit having a fluorine atom are the same as those as described above in the component (C).
  • the hydrophobic resin (D) may contain a silicon atom. It is preferred that the resin has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
  • alkylsilyl structure or the cyclic siloxane structure is the same as the alkylsilyl structure or the cyclic siloxane structure in the component (C), and preferred ranges thereof are also the same.
  • the hydrophobic resin (D) contains a silicon atom
  • the hydrophobic resin (D) is preferably a resin having a repeating unit having a silicon atom, and specific examples of the repeating unit having a silicon atom are the same as those as described above in the component (C).
  • hydrophobic resin (D) contains a CH 3 partial structure in the side chain moiety.
  • the CH 3 partial structure (hereinafter, simply also referred to as a "side chain CH 3 partial structure") possessed by the side chain moiety in the resin (D) includes a CH 3 partial structure possessed by an ethyl group, a propyl group and the like.
  • a methyl group for example, an a-methyl group of a repeating unit having a methacrylate structure
  • a methyl group directly bonded to the main chain of the resin (D) makes a little contribution to surface localization of the resin (D) by the effect of the main chain, it is considered that such a methyl group is not included in the CH 3 partial structure in the present invention.
  • the hydrophobic resin (D) is preferably a resin having a repeating unit having a CH 3 partial structure in the side chain, and definition of the CH 3 partial structure and details of the repeating units are the same as those described above in the component (C).
  • the content of at least one repeating unit (x) among the repeating unit represented by Formula (II) and the repeating unit represented by Formula (III) is preferably 90 mol% or more, and more preferably 95 mol% or more, based on the whole repeating units of the resin (C).
  • the content is usually 100 mol% or less based on the whole repeating units of the resin (C).
  • the resin (D) contains at least one repeating unit (x) among the repeating unit represented by Formula (II) and the repeating unit represented by Formula (III) in an amount of 90 mol% or more based on all the repeating units of the resin (D), thereby increasing the surface free energy of the resin (C).
  • the hydrophobic resin (D) may have at least one group selected from the group of following (x) to (z).
  • Examples of the acid group (x) may include a phenolic hydroxyl group, a carboxylate group, a fluorinated alcohol group, a sulfonate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an
  • alkylsulfonyl)(alkylcarbonyl)imide group a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group and the like.
  • Preferred examples of the acid group may include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group and a bis(alkylcarbonyl)methylene group.
  • a fluorinated alcohol group preferably hexafluoroisopropanol
  • a sulfonimide group preferably a bis(alkylcarbonyl)methylene group.
  • the repeating unit having the acid group (x) may include a repeating unit in which the acid group is directly bonded to the main chain of the resin, such as repeating unit by an acrylic acid or a methacrylic acid, a repeating unit in which the acid group is bonded to the main chain of the resin via a linking group or the like. Further, the repeating unit may also be introduced into the end of the polymer chain by using a polymerization initiator having an acid group or a chain transfer agent at the time of polymerization, and all of these cases are preferred.
  • the repeating unit having the acid group (x) may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having the acid group (x) is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 35 mol%, and still more preferably 5 mol% to 20 mol%, based on the whole repeating units in the hydrophobic resin (D).
  • R x represents a hydrogen atom, CH 3 , CF 3 or CH 2 OH.
  • the group having a lactone structure As (y) the group having a lactone structure, the acid anhydride group or the acid imide group, a group having a lactone structure is particularly preferred.
  • the repeating unit containing these groups may include a repeating unit in which the group is directly bonded to the main chain of the resin, such as a repeating unit by an acrylate ester or a methacrylate ester.
  • the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin through a linking group.
  • the repeating unit may be introduced into the end of the resin by using a polymerization initiator or a chain transfer agent having the group at the time of polymerization.
  • repeating unit having a group having a lactone structure examples are the same as those of the repeating unit having a lactone structure described in the paragraph of acid-decomposable resin (A).
  • the content of the repeating unit having a group having a lactone structure, an acid anhydride group or an acid imide group is preferably 1 mol% to 100 mol%, more preferably 3 mol% to 98 mol%, and still more preferably 5 mol% to 95 mol%, based on the whole repeating units in the hydrophobic resin (D).
  • Examples of the repeating unit having (z) a group capable of decomposing by the action of an acid in the hydrophobic resin (D) are the same as those of the repeating unit having an acid-decomposable group exemplified in the resin (A).
  • the repeating unit having (z) a group capable of decomposing by the action of an acid may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having (z) a group capable of decomposing by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, and still more preferably 20 mol% to 60 mol%, based on the whole repeating units in the resin (D).
  • the hydrophobic resin (D) may further have a repeating unit represented by the following Formula (III).
  • Rc 31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group or a -CH 2 -0-Rac 2 group.
  • Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
  • Rc 3 i is preferably a hydrogen atom, a methyl group, a hydroxymethyl group and a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.
  • Rc 32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.
  • L c3 represents a single bond or a divalent linking group.
  • the alkyl group of Rc 32 is preferably a straight or branched alkyl group having 3 to 20 carbon atoms.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
  • the cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group or a naphthyl group, and these groups may have a substituent.
  • Rc 32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
  • the divalent linking group of L c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group or an ester bond (a group represented by
  • the content of the repeating unit represented by Formula (III) is preferably 1 mol% to 100 mol%, more preferably 10 mol% to 90 mol%, and still more preferably 30 mol% to 70 mol%, based on the whole repeating units in the hydrophobic resin.
  • hydrophobic resin (D) further has a repeating unit represented by the following Formula (CII-AB).
  • Rcii' and R d2 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
  • Z c ' represents an atomic group including two carbon atoms (C-C) bonded to form an alicyclic structure.
  • the content of the repeating unit represented by Formula (CII-AB) is preferably 1 mol% to 100 mol%, more preferably 10 mol% to 90 mol%, and still more preferably 30 mol% to 70 mol%, based on the whole repeating units in the hydrophobic resin.
  • Ra represents H, CH 3 , CH 2 OH, CF 3 or CN.
  • the content of the fluorine atom is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% by mass based on the weight average molecular weight of the hydrophobic resin (D). Further, the content of the repeating unit containing a fluorine atom is preferably 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol% based on the whole repeating units contained in the hydrophobic resin (D).
  • the content of the silicon atom is preferably 2% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass based on the weight average molecular weight of the hydrophobic resin (D). Further, the content of the repeating unit containing a silicon atom is preferably 10 mol% to 100 mol%, and more preferably 20 mol% to 100 mol%, based on the whole repeating units contained in the hydrophobic resin (D).
  • the resin (D) contains substantially no fluorine atom and silicon atom
  • the content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, and still more preferably 1 mol% or less based on the whole repeating units in the resin (D), and is ideally 0 mol%, that is, the repeating unit contains no fluorine atom and silicon atom.
  • the resin (D) substantially contains only a repeating unit composed of only atoms selected from the group consisting of a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is present in an amount of preferably 95 mol% or more, more preferably 97 mol% or more, still more preferably 99 mol% or more, and ideally 100 mol% based on the whole repeating units of the resin (D).
  • the weight average molecular weight of the hydrophobic resin (D) in terms of the standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
  • hydrophobic resin (D) may be used either alone or in combination of a plurality thereof.
  • the content of the hydrophobic resin (D) in the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and still more preferably 0.1% by mass to 5% by mass, based on the total solid in the composition of the present invention.
  • the hydrophobic resin (D) has a small amount of impurities such as metal, but the content of residual monomers or oligomer components is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, and still more preferably 0.05% by mass to 1% by mass. Accordingly, it is possible to obtain an actinic ray-sensitive or radiation-sensitive resin composition free from extraneous substances in liquid and change in sensitivity and the like over time.
  • the molecular weight distribution (Mw/Mn, also referred to as polydispersity) is in a range of preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2.
  • the hydrophobic resin (D) may be commercially available or synthesized by a conventional method.
  • Examples of a general synthesis method may include a batch polymerization method of dissolving monomer species and an initiator in a solvent and heating the solution, thereby performing the polymerization, a dropping polymerization method of adding dropwise a solution containing monomer species and an initiator to a heated solvent over 1 to 10 hours, and the like, and a dropping polymerization method is preferred.
  • reaction solvent polymerization initiator
  • reaction conditions temperature, concentration and the like
  • purification method after reaction are the same as those described in the resin (A), but in the synthesis of the hydrophobic resin (D), the reaction concentration is preferably 30% by mass to 50% by mass.
  • hydrophobic resin (D) Specific examples of the hydrophobic resin (D) are shown below. Further, the molar ratio (corresponding to each repeating unit sequentially from the left), the weight average molecular weight and the polydispersity of the repeating unit in each resin are shown in the following Table.

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Abstract

There is provided an actinic ray-sensitive or radiation-sensitive resin composition including: (A) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group; (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; and (C) a component containing at least one of: a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid, wherein a content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55% by mole or more based on a whole repeating units of the resin (A).

Description

DESCRIPTION
Title of Invention
ACTINIC RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION,
RESIST FILM USING THE SAME, PATTERN FORMING METHOD, AND METHOD FOR MANUFACTURING ELECTRONIC DEVICE AND ELECTRONIC
DEVICE USING THE SAME
Technical field
The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film using the same, a pattern forming method, and a method for manufacturing an electronic device, and an electronic device using the same. More specifically, the present invention relates to a pattern forming method suitably used for a manufacturing process of a semiconductor such as an IC, a manufacturing process of a circuit board of a liquid crystal, a thermal head or the like, and other lithography processes of photofabrication, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used in the pattern forming method, and a method for manufacturing an electronic device, and an electronic device using the same. Particularly, the present invention relates to a pattern forming method suitably used for the exposure in an ArF exposure apparatus and an ArF liquid immersion projection exposure apparatus, which use far-ultraviolet rays having a wavelength of 300 nm or less as a light source, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used in the pattern forming method, and a method for manufacturing an electronic device, and an electronic device.
Background Art
Since a resist for a KrF excimer laser (248 nm) was developed, an image forming method called chemical amplification has been used as an image forming method of a resist in order to compensate for desensitization caused by light absorption. When an image forming method of a positive type chemical amplification is exemplified and described, the method is an image forming method in which an acid-generator of an exposed portion is degraded by exposure to produce an acid, and then, by using the generated acid as a reaction catalyst in PEB (Post Exposure Bake), an alkali-insoluble group is changed to an alkali-soluble group to remove the exposed portion by alkali development. The positive type image forming method using the chemical amplification mechanism has become mainstream, and for example, a method of forming a contact hole using the method is also known (see International Publication No. WO2008/149701 and Japanese Patent Application Laid-Open No. 2004-361629).
However, in the positive type image forming method, an isolated line or dot pattern may be formed well, but the shape of the pattern easily deteriorates when an isolated space (trench pattern) or fine hole pattern is formed.
Further, in respect to the demand for further miniaturization of a pattern, a technique recently has also been known, in which an organic-based developer is used to resolve a resist film obtained by a negative type chemical amplification resist composition as well as the positive type resist composition which is a current mainstream (see, for example, Japanese Patent Application Laid-Open Nos. 2008-292975, 201 1-141494, 201 1-170316 and 2011-221513).
Among them, Japanese Patent Application Laid-Open No. 2011-141494 discloses a technique in which a resesist composition containing a polymer compound having a repeating unit having a substituted or unsubstituted naphthol group as an acid-labile group, an acid generator and an organic solvent is coated on a substrate, and after heat treatment, a developer containing an organic solvent is used to dissolve an unexposed portion, and dissolve exposed portion to obtain a negative pattern in which the exposed portion is not dissolved. According to the technique, it is said that a fine hole pattern may be efficiently formed.
By using the negative type chemical amplification resist composition according to the conventional techniques, it is possible to form a fine hole- pattern. However, there is a demand for further improvement in order to form a micro pattern in a trench pattern and the like.
The present invention has been made in consideration of the aforementioned problem, and an object thereof is to provide, in forming a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer, a pattern forming method capable of realizing small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used therein, a method for manufacturing an electronic device, and an electronic device using them.
Summary of Invention
The present invention has the following configuration, and the problem of the present invention may be accordingly solved.
[1] An actinic ray-sensitive or radiation-sensitive resin composition including: (A) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group; (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; and (C) a component containing at least one of: a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid, wherein a content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55% by mole (mol%) or more based on a whole repeating units of the resin (A).
[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the component (C) is a resin (C) having a repeating unit having at least one of a fluorine atom, a silicone atom and a CH3 partial structure contained in a side chain moiety of the resin.
[3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the component (C) is a compound capable of capturing an acid generated from the compound (B).
[4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the component (C) is an inoic compound.
[5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55% by mole to 85% by mole based on the whole repeating unit of the resin (A).
[6] The actinic ray-sensitive or radiation-sensitive resin composition of any one according to [1] to [5], wherein the group capable of decomposing by the action of an acid to generate a polar group has a structure in which the polar group is protected with a group capable of decomposing and leaving by the action of an acid, and the group capable of leaving has 5 or more carbon atoms.
[7] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] to [6], wherein the content of the compound (B) is 10% by mass (mass%) or more based on a total solid of the actinic ray-sensitive or radiation-sensitive resin composition.
[8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the compound (B) is an ionic compound, and a content of a fluorine atom containd in an anion of the ionic compound is 35% by mass or less based on a total amount of atoms constituting the anion of the compound (B).
[9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the actinic ray-sensitive or radiation-sensitive resin composition contains two or more kinds of compounds as the compound (B), and at least one of the two or more kinds of compounds is a compound having no aromatic group or having one or two aromatic groups.
[10] A resist film formed by using the actinic ray-sensitive or radiation-sensitive resin composition of any one of [1] to [9].
[1 1] A pattern forming method including: exposing the resist film according to [10]; and developing the exposed resist film with a developer containing an organic solvent to form a negative pattern.
[12] The pattern forming method according to [11], wherein the exposing is performed by liquid immersion exposure.
[13] A method for manufacturing an electronic device including the pattern forming method according to [1 1] or [12].
[14] An electronic device manufactured by the method according to [ 13] .
It is also preferred that the present invention has the following constitution.
[15] The actinic ray-sensitive or radiation-sensitive resin composition of any one of [1] to [9] further containing a hydrophobic resin (D).
[16] The actinic ray-sensitive or radiation-sensitive resin composition of any one of [2] to [9], in which the content of the repeating unit having at least one of a fluorine atom, a silicone atom and a C¾ partial structure contained in a side chain moiety of the resin is 8 mol% or less based on the whole repeating units of th resin (C).
[17] The actinic ray-sensitive or radiation-sensitive resin composition of any one of [2] to [9], in which the weight average molecular weight of the resin (C) is 7,500 to 15,000.
[18] The actinic ray-sensitive or radiation-sensitive resin composition of any one of [1] to [9], in which the resin (A) further has a repeating unit having a group havig a lactone structure or a sultone structure.
According to the present invention, it is possible to provide, in forming a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer, a pattern forming method capable of realizing small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used therein, a method for manufacturing an electronic device, and an electronic device using them.
Description of Embodiments
Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, "having" has the same meanings as "comprising".
In representing a group (atomic group) in the present specification, the representation which does not describe the substitution and unsubstitution also includes having substituents along with having no substituent. For example, "an alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (a substituted alkyl group).
The term "actinic ray" or "radiation" in the present specification refers to, for example, a bright line spectrum of a mercury lamp, far-ultraviolet rays represented by an excimer laser, extreme ultraviolet (EUV) rays, X-rays, an electron beam (EB) and the like. Further, the term "light" in the present invention refers to the actinic rays or the radiations.
In addition, unless otherwise specifically indicated, the term "exposure" in the present specification includes not only the exposure performed using a mercury lamp, far-ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, EUV rays and the like, but also drawing performed by a particle beam such as an electron beam and an ion beam.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invnetion contains:
(A) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group,
(B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and
(C) a component containing at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH3 partial structure in a side chain moiety and having basicity or capable of increasing the basicity by the action of an acid,
in which the content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55 mol% or more based on the whole repeating units of the resin (A).
By the actinic ray-sensitive or radiation-sensitive resin composition of the present invnetion, in forming a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer, it is possible to realize small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects.
The reason is unclear, but is assumed as follows.
First, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group, and the content of the repeating unit is 55 mol% or more based on the whole repeating units of the resin.
Accordingly, it is guessed that the dissolution contrast for an organic solvent between the exposed portion and unexposed portion in the resist film may be further increased, and as a result, roughness performance such as LWR may be enhanced, and reduction in development defects may be realized as well.
Further, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a component (C) containing at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH3 partial structure in a side chain moiety and having basicity or capable of increasing the basicity by the action of an acid.
Here, since the surface free energy of the component (C) is low, it is easy to be localized on the top layer portion of the resist film at high concentrations.
Accordingly, the solubility of the top layer portion of the resist film in the developer containing the organic solvent is enhanced, and as a result, the unexposed portion is remained undissolved, thereby reducing the development defects. Further, it is thought that, during the exposure, the pattern is suppressed from being reverse tapered due to the degradation of the contrast of exposure amounts in the exposed portion and the unexposed portion by diverging from the optimal point of the focus, thereby enhancing DOF.
Further, the component (C) is localized on the surface of the resist film at high concentrations, and thus, the solubility of the top layer portion of the resist film in the developer containing an organic solvent is enhanced. As a result, the resultant pattern becomes more rectangular (pattern shape becomes better), thereby reducing the pattern collapse.
Hereinafter, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention will be described.
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is used in a negative type development (development in which the solubility in a developer is decreased when exposed, and tuhs, the exposed portion is remained as a pattern, and the unexposed portion is removed), particularly in the case where a pattern having an ultrafine width (for example, 40 nm or less) is formed on the resist film. That is, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may be used as an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development, which is used for development using a developer containing an organic solvent. Here, the term, for organic solvent development refers to a use that is used in a process of developing a film using a developer containing at least an organic solvent.
It is preferred that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition and a negative type resist composition (that is, a resist composition for organic solvent development), from the viewpoint of obtaining a particularly good effect. Further, the composition according to the present invention is typically a chemical amplification resist composition.
[1] (A) Resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (A) (hereinafter, also referred to as an "acid-decomposable resin" or "resin (A)") having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group (hereinafter, also referred to as an "acid-decomposable group"). Accordingly, the resin (A) is a resin whose solubility in a developer containing an organic solvent is decreased by the action of an acid.
The acid-decomposable resin is preferably a resin in which the group generating a polar group has a structure in which the polar group is protected with a group capable of decomposing and leaving by the action of an acid (hereinafter, also referred to as an "acid-decomposable group").
Examples of the resin (A) may include a resin having acid-decomposable groups at the main chain or the side chain, or both of the main chain and the side chain.
Meanwhile, the resin (A) is also a resin capable of increasing the polarity by the action of an acid to increase the solubility in an alkali developer.
The polar group is not particularly limited as long as the polar group is a group that is sparingly soluble or insoluble in a developer containing an organic solvent, but examples thereof may include an acidic group (a group that is dissociated in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, which has been used as a developer of a tranditional resist) such as a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonate group, a sulfonamide group, a sulfonylimide, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group and a tris(alkylsulfonyl)methylene group, or an alcoholic hydroxyl group.
Meanwhile, the alcoholic hydroxyl group is a hydroxyl group that is bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) that is directly bonded to an aromatic ring, and an aliphatic alcohol (for example, a fluorinated alcohol group (a hexafluoroisopropanol group or the like)) which is substituted with an electron-withdrawing group such as a fluorine atom at the a-position is excluded as a hydroxyl group. The alcoholic hydroxyl group is preferably a hydroxyl group having a p a of 12 to 20.
Examples of a preferred polar group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) and a sulfonic acid group.
A preferred acid-decomposable group is a group obtained by substituting a hydrogen atom of the groups by a group capable of leaving by the action of an acid.
Examples of the group capable of leaving by the action of an acid may include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), -C(Roi)(Ro2)(OR39) and the like.
In the Formula, R36 to R39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R36 and R37 may be bound with each other to form a ring.
Roi and Ro2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The group capable of decomposing and leaving by the action of an acid has preferably 5 or more carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 1 1 to 20 carbon atoms. Accordingly, DOF becomes better. The reason is considered that the volume of the leaving group becomes larger by change in focus, and thus, the change in diffusion length of the acid and the compound having basicity or capable of increasing the basicity by the action of an acid becomes larger with respect to the change in exposure amount in the exposed portion, resulting in suppression of excessive diffusion of an acid into the unexposed portion, which is a factor that the pattern size is diverged from a desired width.
The alkyl group of R36 to R39, Roi and Ro2 is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a hexyl group, an octyl group and the like.
The cycloalkyl group of R36 to R39, Roi and R02 may be monocyclic or polycyclic. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof may include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an a-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, an androstanyl group and the like. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl group of R3 to 39 and R^ and Ro2 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof may include a phenyl group, a naphthyl group, an anthryl group and the like.
The aralkyl group of R36 to R3g and Roi and R02 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof may include a benzyl group, a phenethyl group, a naphthylmethyl group and the like.
The alkenyl group of R36 to R39 and Roi and R02 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof may include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like.
The ring which may be formed by R36 and R37 being bound with each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. The group is more preferably monocyclic cycloalkyl group having 5 to 6 carbon atoms, and particularly preferably a monocyclic cycloalkyl group having 5 carbon atoms.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group and the like. The group is more preferably a tertiary alkyl ester group.
It is preferred that the resin (A) has a repeating unit having an acid-decomposable group.
It is preferred that the resin (A) has a repeating unit having a repeating unit represented by the following Formula (I) as a repeating unit having an acid-decomposable group.
Figure imgf000011_0001
R1b
Ric
(I)
In Formula (I), Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom. Ria, and Ric each independently represent an alkyl group or a cycloalkyl group. Two of Rla, R^ and Ric may be bound with each other to form a ring structure.
The alkyl group of Xa may have a substituent, and examples of the substituent may include a hydroxyl group, a halogen atom (preferably, a fluorine atom).
The alkyl group of Xa is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and preferably a methyl group.
Xa is preferably a hydrogen atom or a methyl group.
The alkyl group of R] a, Rib and Ric is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group and an isobutyl group, t-butyl group.
The cycloalkyl group of Ria, Rib and Ric is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group.
The ring structure formed by two of Rja, R^ and Ric being bound with each other is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring and a cyclohexyl ring, or a polycylic cycloalkyl group such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring and an adamantane ring. The ring structure is particularly preferably a monocyclic cycloalkane ring having 5 or 6 carbon atoms.
Ria, Rib and Ric are each independently preferably an alkyl group, and more preferably a straight or branched alkyl group having 1 to 4 carbon atoms.
Each of the groups may further have a substituent, and examples of the substituent may include a halogen atom, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably a group having 8 or less carbon atoms.
Specific examples of the repeating unit represented by Formula (I) are shown below, but the present invention is not limited thereto.
In the specific examples, Rx represents a hydrogen atom, CH3, CF or CH2OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent, and when a plurality of Z's is present, Z's may be the same or different, p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and the preferable examples of a substituent that may be possessed by each group of Ri to R3.
Figure imgf000012_0001
The repeating unit represented by Formula (I) may be used either alone or in combination of two or more thereof.
Further, it is also preferred that the resin (A) has a repeating unit represented by the following Formula (AI).
Figure imgf000013_0001
In Formula (AI),
Xai represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom. T represents a divalent linking group.
Rxi to Rx3 each independently represent an alkyl group or a cycloalkyl group.
Two of Rx\ to Rx3 may be bound with each other to form a ring structure.
The divalent linking group of T may be an alkylene group, a -COO-Rt- group, a -O-Rt- group, a phenylene group or the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a -COO-Rt- group. Rt is preferably an alkylene group having lto 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group or a -(CH2)3- group.
Specific examples and preferred examples of the alkyl group of Xa! are the same as the specific examples and the preferred examples of the alkyl group of Xa in Formula (I).
Specific examples and preferred examples of the alkyl group and the cycloalkyl group of Rxi to Rx3 are the same as the specific examples and the preferred examples of the alkyl group and the cycloalkyl group of Ria to Ric in Formula (I).
Specific examples and preferred examples of the ring structure formed by two of Rxt to Rx3 being bound with each other are the same as the specific examples and the preferred examples of the ring structure formed by two of Ria to Ric in Formula (I) being bound with each other to form.
Each of the groups may have a substituent, and examples of the substituent may include an alkyl group (having 1 to 4 carbon atoms), a cycloalkyl group (having 3 to 8 carbon atoms), a halogen atom, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably a group having 8 or less carbon atoms. Among them, from the viewpoint of further enhancing the dissolution contrast for a developer containing before and after acid decomposition, the substituent is more preferably a substituent which does not have a heteroatom such as an oxygen atom, a nitrogen atom and a sulfur atom (for example, more preferably a substituent which is not an alkyl group substituted with a hydroxyl group), still more preferably a group composed only of hydrogen atoms and carbon atoms, and particularly preferably a straight or branched alkyl group or cycloalkyl group.
Specific examples of the repeating unit represented by Formula (AI) are shown below, but the present invention is not limited thereto.
In the specific examples, Xai represents a hydrogen atom, CH3, CF3 or CH2OH. Z represents a substituent, and when a plurality of Z's is present, Z's may be the same or different, p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and the preferred examples of the substituent which may be possessed by each group of Rxi to Rx3.
Figure imgf000014_0001
Figure imgf000015_0001
Further, it is also preferred that the resin (A) has a repeating unit represented by the followin Formula (rV) as a repeating unit having an acid-decomposable group.
Figure imgf000015_0002
In Formula (IV), Xb represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.
Ryi to Ry3 each independently represent an alkyl group or a cycloalkyl group. Two of Ry\ to Ry3 may be linked with each other to form a ring.
Z represents a (p+l)-valent linking group having a polycyclic hydrocarbon structure which may have a heteroatom as a ring member. It is preferred that Z does not contain an ester bond as an atomic group constituting the polycyclic ring (in other words, it is preferred that Z does not contain a lactone ring as a ring constituting the polycyclic ring).
L4 and L5 each independently represent a single bond or a divalent linking group.
p represents an integer of 1 to 3. When p is 2 or 3, L5's, Ryi 's, Ry2's and Ry3's may be the same or different, respectively.
The alkyl group of Xb may have a substituent, and examples of the substituent may include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group of Xb is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, and preferably a methyl group.
Xb is preferably a hydrogen atom or a methyl group.
Specific examples and preferred examples of the alkyl group and the cycloalkyl group of Ryi to Ry3 are the same as the specific examples and the preferred examples of the alkyl group and the cycloalkyl group of R to Rtc in Formula (I).
Specific examples and preferred examples of the ring structure formed by two of Ryi to Ry3 being bound with each other are the same as the specific examples and the preferred examples of the ring structure formed by two of R to Ric in Formula (I) being bound with each other.
Ry\ to Ry3 are each independently preferably an alkyl group, and more preferably a straight or branched alkyl group having 1 to 4 carbon atoms. Further, the sum of carbon atoms of the alkyl group as Ryi to Ry3 is preferably 5 or less.
Ryi to Ry3 may further have a substituent, and such a substituent is the same as that exemplified as a substituent which may be further possessed by Rxi to Rx3 in Formula (AI).
The linking group having a polycyclic hydrocarbon structure of Z includes a ring-assembled hydrocarbon ring group and a bridged cyclic hydrocarbon ring group, and examples thereof include a group obtained by removing any (p+1) hydrogen atoms from a ring-assembled hydrocarbon ring and a group obtained by removing any (p+1) hydrogen atoms from a bridged cyclic hydrocarbon ring, respectively.
Examples of the ring-assembled hydrocarbon ring group may include a bicyclohexane ring group, a perhydronaphthalene ring group and the like. Examples of the bridged cyclic hydrocarbon ring group may include a bicyclic hydrocarbon ring group such as a pinane ring group, a bornane ring group, a norpinane ring group, a norbornane ring group and a bicyclooctane ring group (a bicyclo[2.2.2]octane ring group, a bicyclo[3.2.1]octane ring group and the like), a tricyclic hydrocarbon ring group such as a homobledane ring group, an adamantane ring group, a tricyclo[5.2.1.0 ' Jdecane ring group and a
2 5
tricyclo[4.3.1.1 ' Jundecane ring group, a tetracyclic hydrocarbon ring group such as a tetracyclo[4.4.0.12'5. l7'10ldodecane ring group and a perhydro- 1 ,4-methano 5,8-methanonaphthalene ring group, and the like. Further, the bridged cyclic hydrocarbon ring group also includes a condensed cyclic hydrocarbon ring group, for example, a condensed ring group obtained by condensing a plurality of 5- to 8-membered cycloalkane ring groups, such as a perhydronaphthalene (decalin) ring group, a perhydroanthracene ring group, a perhydrophenanthrene ring group, a perhydroacenaphthene ring group, a perhydrofluorene ring group, a perhydroindene ring group and a perhydrophenalene ring group.
Preferred examples of the bridged cyclic hydrocarbon ring group may include a norbornane ring group, an adamantane ring group, a bicyclooctane ring group, a
2 6
tricyclo[5,2,l,0 ' Jdecane ring group and the like. More preferred examples of the bridged cyclic hydrocarbon ring group may include a norbornane ring group and an adamantane ring group.
The linking group having a polycyclic hydrocarbon structure represented by Z may have a substituent. Examples of the substituent which may be possessed by Z may include a substituent such as an alkyl group, a hydroxyl group, a cyano group, a keto group (an alkylcarbonyl group and the like), an acyloxy group, -COOR, -CON(R)2, -S02R, -S03R and -S02N(R)2. Herein, R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
The alkyl group, the alkylcarbonyl group, the acyloxy group, -COR, -COOR, -CON(R)2, -S02R, -SO3R and -S02N(R)2 as the substituent which may be possessed by Z may further have a substituent, and examples of the substituent may include a halogen atom (preferably, fluorine atom).
In the linking group having a polycyclic hydrocarbon structure represented by Z, the carbon constituting the polycyclic ring (the carbon contributing to ring formation) may be carbonyl carbon. Further, as described above, the polycyclic ring may have a heteroatom such as an oxygen atom and a sulfur atom as a ring member. However, as described above, Z does not contain an ester bond as an atomic group constituting the polycyclic ring.
Examples of the linking group represented by L4 and L5 may include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -0-, -S-, -SO-, -S02-, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a linking group formed by combining a plurality of these groups and the like, and a linking group having a total carbon number of 12 or less is preferred.
L4 is preferably a single bond, an alkylene group, -COO-, -OCO-, -CONH-, -NHCO-, -alkylene group-COO-, -alkylene group-OCO-, -alkylene group-CONH-, -alkylene group-NHCO-, -CO-, -0-, -S02- or -alkylene group-O-, and more preferably a single bond, an alkylene group, -alkylene group-COO- or -alkylene group-O-.
L5 is preferably a single bond, an alkylene group, -COO-, -OCO-, -CONH-, -NHCO-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, -NHCO-alkylene group-, -CO-, -0-, -S02-, -O-alkylene group- or -O-cycloalkylene group-, and more preferably a single bond, an alkylene group, -COO-alkylene group-, -O-alkylene group- or -O-cycloalkylene group-.
In the aforementioned method, the bonding hand "-" at the left side means connecting to the ester bond on the main chain side in L and connecting to Z in L5, and the bonding hand "-" at the right side means bonding to Z in L and bonding to the ester bond connected to the group represented by (Ry1)(Ry2)(Ry3)C- in L5.
Meanwile, L4 and L5 may be bonded to the same atom constituting the polycylic ring in Z.
p is preferably 1 or 2, and more preferably 1.
Secific examples of the repeating unit represented by Formula (IV) are shown below, but the present invention is not limited thereto. In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.
Figure imgf000019_0001
Further, it is also preferred that the resin (A) is a resin capable of generating an alcoholic hydroxyl group and increasing the polarity by the action of an acid to increase the solubility in an alkali developer containing an organic solvent. The structure in which the polar group is protected with a group capable of decomposing and leaving by the action of an acid is preferably (i) a structure represented by the following Formula (b), capable of decomposing by the action of an acid to generate one alcoholic hydroxyl group, or (ii) a structure represented by the following Formula (c), capable of decomposing by the action of an acid to generate two or three alcoholic hydroxyl groups.
* O— P2 {* °¾"p3
(b) (c)
In the formula, P2 represents a monovalent group capable of decomposing and leaving by the action of an acid.
P3 represents a z-valent group capable of decomposing and leaving by the action of an acid, z represents 2 or 3.
* represents a bonding hand linked to the main chain or the side chain of the resin.
The structure (i) is preferably a group represented by the following Formula (b-1), (b-2 (b-3) or (b-4), and more preferably a group re resented by the following Formula (b-1).
Figure imgf000020_0001
In Formula (b-1),
Rx4's each independently represent a hydrogen atom or a monovalent organic group. Rx4's may be bound with each other to form a ring.
Rx5 represents a monovalent organic group. One of Rx4's and Rx5 may be bound with each other to form a ring.
In Formula (b-2),
Rx4' represents a hydrogen atom or a monovalent organic group.
Rx5"s each independently represent a monovalent organic group. Rx5"s may be bound with each other to form a ring. Further, one of Rx5"s and Rx4' may be bound with each other to form a ring.
In Formula (b-3),
Rx6's each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. Two Rx6's may be bound with each other to form a ring. However, in the case where one or two of Rx6's are a hydrogen atom, at least one of the remaining Rx6's represents an aryl group, an alkenyl group or an alkynyl group.
In Formula (b-4),
Rx6"s each independently represent a monovalent organic group. Two Rx6"s may be bound with each other to form a ring.
In Formulas (b-1) to (b-4), * represents a bonding hand linked to the main chain or the side chain of the resin.
As described above, Rx4 and Rx4' each independently represent a hydrogen atom or a monovalent organic group. Rx4 and Rx4' are each independently preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.
The alkyl group of Rx4 and Rx4' may be straight or branched. The alkyl group has preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the alkyl group of Rx4 may include a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a n-butyl group.
The cycloalkyl group of Rx4, Rx4' may be monocyclic or polycyclic. The cycloalkyl group has preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. Examples of the cycloalkyl group of Rx4 may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.
Further, in Formula (b-1), at least one of Rx4's is preferably a monovalent organic group. By adopting such a configuration, particularly high sensitivity may be achieved.
The alkyl group and the cycloalkyl group as Rx4 and Rx4 may further have a substituent, and examples of the substituent may include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), an aryl group (having 6 to 10 carbon atoms) and the like, and preferably a substituent having 8 or less carbon atoms.
As described above, Rx5 and Rx5' each independently represent a monovalent organic group. Rx5 and Rx5' are each independently preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. The alkyl group and the cycloalkyl group may further have a substituent, and examples of the substituent may include the groups as described in the substituent which may be possessed by the alkyl group and the cycloalkyl group as Rx4 and Rx4'.
The alkyl group of Rx5 and Rx5' may have no substituent or have one or more aryl groups and/or one or more silyl groups as a substituent. The unsubstituted alkyl group has preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyhl group moiety in the alkyl group substituted with one or more aryl groups has preferably 1 to 25 carbon atoms.
Specific examples of the alkyl group of Rx5, Rx5' may also be exemplified by those described as specific examples of the alkyl group of Rx4 and Rx . Further, the aryl group in the alkyl group substituted with one or more aryl groups has prererably 6 to 10 carbon atoms, and specific examples thereof may include a phenyl group and a naphthyl group.
The alkyl group moiety in the alkyl group substituted with one or more silyl groups has preferably 1 to 30 carbon atoms. Further, in the case wehre the cycloalkyl group of Rx5 and Rx5' has no substituent, the cycloalkyl group has preferably 3 to 20 carbon atoms, and more preferably 3 to 15 carbon atoms.
Specific examples of the cycloalkyl group of Rx5 and Rx5' may also be exemplified by those as described as specific examples of the cycloalkyl group of Rx4 and Rx '.
Rx6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group. However, in the case where one or two of three Rx6's are a hydrogen atom, at least one of the remaining Rx6's represents an aryl group, an alkenyl group or an alkynyl group. Rx6 is preferably a hydrogen atom or an alkyl group.
The alkyl group, the cycloalkyl group, the aryl group, the alkenyl group and the alkynyl group as Rx6 may further have a substituent, and examples of the substituent may be exemplified by those as described in the substituent which may be possessed by Rxi to Rx3.
Examples of the alkyl group and the cycloalkyl group of Rx6 may also be exemplified by those as described in the alkyl group and the cycloalkyl group of Rx4 and Rx4'. Particularly, in the case where the alkyl group has no substituent, the alkyhl group has preferably 1 to 6 carbon atoms, and more preferably 1 to 3.
Examples of the aryl group of Rx6 may include an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.
Examples of the alkenyl group of Rx6 may include an alkenyl group having 2 to 5 carbon atoms such as a vinyl group, a propenyl group and an allyl group.
Examples of the alkynyl group of Rx6 may include an alkynyl group having 2 to 5 carbon atoms such as a ethynyl group, a propynyl group and a butynyl group.
Rx6"s are each independently preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or a cycloalkyl group, and still more preferably an alkyl group.
Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for Rx6' may be exemplified by alkyl group and the cycloalkyl group described for Rx4 and Rx ' and the aryl group described for Rx6.
The alkyl group, the cycloalkyl group and the aryl group may further have a substituent, and examples of the substituent may include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms), an aryl group (having 6 to 10 carbon atoms) and the like, and preferably a group having 8 or less carbon atoms.
The structure (ii) is preferably a group represented by the following Formula (c-1), (c-2) or (c-3).
Figure imgf000023_0001
(c-1) (c-2) (c-3)
In Formula (c-1), Rx7's each independently represent a hydrogen atom or a monovalent organic group.
Rx7's may be bound with each other to form a ring.
In Formula (c-2), Rx8's each independently represent a monovalent organic group.
Rx8's may be bound with each other to form a ring.
In Formula (c-3), Rx8' represents a monovalent organic group.
In Formulas (c-1) to (c-3), * represents a bonding hand linked to the main chain or the side chain of the resin.
As described above, Rx7 represents a hydrogen atom or a monovalent organic group. Rx7 is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom or an alkyl group having no substituent.
Rx7 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.
The alkyl group and the cycloalkyl group as Rx7 may further have a substituent, and examples of the substituent may be exemplified by the groups as described in the substituent which may be possessed by Rxi to Rx3.
Specific examples of the alkyl group and the cycloalkyl group of Rx7 may also be exemplified as those described as specific examples of the alkyl group and the cycloalkyl group of Rx4 and Rx4'.
As described above, Rx8 and Rx8' represent a hydrogen atom or a monovalent organic group. Rx8 and Rx8' are each independently preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.
Examples of the alkyl group and the cycloalkyl group of Rx8 and Rx8' may also be exemplified by those described in the alkyl group and the cycloalkyl group of Rx and Rx4'.
The resin (A) has preferably a repeating unit in which the polar group is protected with the leaving group capable of decomposing and leaving by the action of an acid (hereinaftger, also referred to as an acid-decomposable repeating unit (a)), and more preferable a repeating unit having the structure (i) or (ii).
The repeating unit having any one of the structures (i) and (ii) may be exemplified by a repeating unit represented by the following Formula (1-1) or (1-2).
Figure imgf000024_0001
(1-1 ) (I-2)
In the formula,
Ra's each independently represent a hydrogen atom, an alkyl group or a group represented by -CH2-0-Ra2. Herein, Ra2 represents a hydrogen atom, an alkyl group or an acyl group.
P represents the structcture (i). When a plurality of P's is present, P's may be the same or different, and may be bound with each other to form a ring. In the case where a plurality of P's are bound with each other to form a ring, the bound P's may be represented by the structure (ii), and in this case, * in Formula (c) in the structure (ii) represents a bonding hand linked to R\.
Ri represents a (n+l)-valent organic group.
Rn represents a divalent organic group. In the case where a plurality of Rn's is present, Rn's may be the same or different,
n represents an integer of 1 or more.
represents a linking group represented by -COO-, -OCO-, -CONH-, -0-, -Ar-, -S03- or -S02NH-. Herein, Ar represents a divalent aromatic group. In the case wehre a plurality of Li's is present, Li's may be the same or different.
q represents a repeating number of the group represented by -Ru-Li-, and an integer of 0 to 3.
Ra represents a hydrogen atom, an alkyl group or a group represented by -CH2-0-Ra2.
The alkyl group of Ra has preferably 6 or less carbon atoms, and the alkyl group and the acyl group of Ra2 has preferably 5 or less carbon atoms. The alkyl group of Ra, and the alkyl group and the acyl group of Ra2 may have a substituent.
Ra is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 1 to 10 carbon atoms, and specifically, preferably a hydrogen atom, a methyl group, a trifluoromethyl group or hydroxymethyl group, and more preferably a hydrogen atom or a methyl group.
Ri represents a (n+l)-valent organic group. Ri is preferably a non-aromatic hydrocarbon group. In this case, Ri may be a chained hydrocarbon group or an alicyclic hydrocarbon group. Ri is more preferably an alicyclic hydrocarbon.
The chained hydrocarbon as Ri may be straight or branched. Further, the chained hydrocarbon has preferably 1 to 8 carbon atoms. For example, in the case where the chained hydrocarbon group is an alkylene group, the alkylene group is preferably a methylene group, an ethylene group, a n-propylene group, an isopropylene group, a n-butylene group, an isobutylene group or a sec-butylene group.
The alicyclic hydrocarbon as Ri may be monocyclic or polycyclic. The alicyclic hydrocarbon has, for example a monocyclo, bicyclo, tricyclo or tetracyclo structure. The alicyclic hydrocarbon group has generally 5 or more carbon atoms, preferably 6 to 30 carbon atoms, and 7 to 25 carbon atoms.
Examples of the alicyclic hydrocarbon may include those having partial structures as listed below. Each of the partial structures may have a substituent. Further, in each of the partial structures, a methylene group(-CH2-) may be substituted with an oxygen atom(-O-), a sulfur atom(-S-), a carbonyl group [-C(=0)-], a sulfonyl group [-S(=0)2-], a sulfinyl group [-S(=0)-] or an imino group [-N(R)-] (wherein R is a hydrogen atom or an alkyl group).
Figure imgf000026_0001
For example, in the case where Ri is a cycloalkylene group, R\ is preferably an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododecanylene group, a norbornylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclodecanylene group or a cyclododecanylene group, and more preferably an adamantylene group, a norbornylene group, a cyclohexylene group, a cyclopentylene group, a tetracyclododecanylene group or a tricyclodecanylene group.
The non-aromatic hydrocarbon group of Ri may have a substituent. Examples of the substituent may include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group and an alkoxycarbonyl group having 2 to 6 carbon atoms. The aforementiond alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent. Examples of the substituent may include a hydroxyl group, a halogen atom and an alkoxy group.
Details of the divalent organic group of Rn are the same as the case where n=l in the (n+l)-valent organic group as Rt, that is, the case where Ri is a divalent organic group, and specific examples thereof are also the same.
Li represents a linking group represented by -COO-, -OCO-, -CONH-, -0-, -Ar-, -S03- or -S02NH- ("-" at the left side of these linking groups means connecting to the main chain of the resin). Herein, Ar represents a divalent aromatic ring group, and is preferably a divalent aromatic ring group having 6 to 10 carbon atoms, such as, for example, a phenylene group and a naphthylene group. Li is preferably a linking group represented by -COO-, -CONH- or -Ar-, and more preferably a linking group represented by -COO- or -CONH-.
n is an integer of 1 or more, n is preferably an integer of 1 to 3, and more preferably 1 or 2. Further, when n is an integer of 2 or more, it is possible to further enhance the dissolution contrast for a developer containing an organic solvent. Accordingly, the resolution may be further enhanced, and at the same time, LWR may be further reduced.
q represents a repeating number of a group represented by -R1-L1-, and represents an integer of 0 to 3. q is preferably an integer of 0 to 2, and more preferably 0 or 1.
Specific examples of the acid-decomposable repeating unit (a) are shown below. Meanwhile, in the specific examples, Ra and P have the same meaning as Ra and P in Formula (1-1) or (1-2). Pi has the same meaning as Pi in Formula (a). P3 has the same meaning as P3 when z is 2 in Formula (c).
Figure imgf000028_0001
In the group capable of leaving by the action of an acid in the acid-decomposable repeating unit (a), appropriate examples thereof may also include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), -C(Roi)(Ro2)(OR39) and the like.
In the Formula, R36 to R3g each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R36 and R3 may be bound with each other to form a ring.
Roi and Ro2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. The group is more preferably a tertiary alkyl ester group. It is also preferred that the acid-decomposable repeating unit (a) that may be contained in the resin (A) is a repeating unit represented by the following Formula (a2).
Figure imgf000029_0001
In Formula (a2), Ra"s each independently represent a hydrogen atom, an alkyl group or a group represented by -CH2-0-Ra2'. Herein, Ra2' represents a hydrogen atom, an alkyl group or an acyl group.
Ri' represents a (n'+l)-valent organic group.
Rn' represents a divalent organic group. In the case where a plurality of Rn"s is present, Rn"s may be the same or different.
Li' represents a linking gropu represented by -COO-, -OCO-, -CONH-, -0-, -Ar'-, -S03- or -S02NH-. Herein, Ar' represents a divalent aromatic ring group. In the case where a plurality of LV's is present, L^'s may be the same or different.
q' represents a repeating number of a group represented by -Rn'-Li', and represents an integer of 0 to 3.
n represents an ingeger of 1 or more.
Rx4'"s each independently represent a hydrogen atom or a monovalent organic group. Rx4"'s may be bound with each other to form a ring.
Rx5" represents a monovalent organic group. One of Rx4"'s and Rx5" may be bound with each other to form a ring.
Details of Ra', Ra2', Ri', Rn', L|', Ar', Rx4", and Rx5" are the same as those described in Ra, Ra2, Rls Rn, Li, and Ar in Formula (1-1), and Rx4 and Rx5 in the (b-1), respectively. In addition, preferred ranges of n and q' in Formula (a2) are the same as the preferred ranges of n and q in Formula (1-1), respectively.
Preferred specific examples of the repeating unit (a) having an acid-decomposable group will be shown below, but the present invention is not limited thereto.
In the specific examples, R1, R10 and Xa represent a hydrogen atom, CH3, CF3 or CH2OH. Me represents a methyl group.
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
33
Figure imgf000034_0001

Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
The repeating unit having an acid-decomposable group may be used either alone or in combination of two or more thereof.
The content of the repeating unit having an acid-decomposable group contained in the resin (A) (or the sum in the case where a plurality of repeating units having an acid-decomposable group is present) is preferably 55 mol% or more, more preferably 55 mol% to 85 mol%, still more preferably 55 mol% to 70 mol%, and particularly preferably 55 mol% to 65 mol% based on the whole repeating units of the resin (A).
Within the range, LWR is reduced, and development defects are decreased. The resin (A) may contain a repeating unit having a lactone structure or a sultone structure.
Although any structure may be used as long as a lactone structure or a sultone structure is possessed, the lactone structure or the sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure, and more preferably a 5- to 7-membered ring lactone structure to which another ring structure is condensed to form a bicyclo or spiro structure, or a 5- to 7-membered ring sultone structure to which another ring structure is condensed to form a bicyclo or spiro structure. It is still more preferred to have a lactone structure represented by any one of the following Formulas (LCl-1) to (LCI -21) or a sultone structure represented by any one of the following Formulas (SLl-1) to (SL1-3). Further, the lactone structure or the sultone structure may be bonded directly to the main chain. A preferred lactone structure is (LCl-1), (LCl-4), (LCl-5), (LCl-6), (LCl-13), (LCl-14) and (LCI- 17), and a particularly preferred lactone structure is (LCl-4). By using such a specific lactone structure, LWR and development defects are improved.
Figure imgf000040_0001
n2
Figure imgf000040_0002
LC1-7 LC1 -8 LC1-9 LC1-10
LC1-12
Figure imgf000040_0003
The lactone structure or the sultone structure moiety may or may not have a substituent (Rb2). Preferred examples of the substituent (Rb2) may include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group and the like. The substituent is more preferably an alkyl group having 1 to 4 carbon atoms, a cyano group and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, the substituents (Rb2's) may be the same as or different. In addition, the substituents (Rb2's) may be bound with each other to form a ring.
The repeating unit having a lactone group or a sultone structure usually has an optical isomer, but any optical isomer may be used. Further, the optical isomer may be used either alone or as a mixture of two or more thereof. When one kind of the optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, and more preferably 95% or more.
It is preferred that the repeating unit having a lactone structure or a sultone structure is a repeatin unit represented by the following Formula (III).
Figure imgf000041_0001
In Formula (III),
A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).
When a plurality of Ro's is present, Ro's each independently represent an alkylene group, a cycloalkylene group or a combination thereof.
When a plurality of Z's is present, Z's each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond
(a group represented by—
Figure imgf000041_0002
or a urea bond
9
(a group represented by—
Herein, R's each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.
R8 represents a monovalent organic group having a lactone structure or a sultone structure.
n is a repeating number of a structure represented by -Ro-Z-, represents an integer of 0 to 5, and is preferably 0 or 1, and more preferably 0. When n is 0, -Ro-Z- is not present, and the structure becomes a single bond.
R7 represents a hydrogen atom, a halogen atom or an alkyl group.
The alkylene group and the cycloalkylene group of Ro may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond. The alkyl group of R7 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and particularly preferably a methyl group.
Each of the alkylene group and the cycloalkylene group of Ro and the alkyl group of R7 may be substituted, and examples of the substituent may include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group and a benzyloxy group, and an acyloxy group such as an acetyloxy group and a propionyloxy group.
R7 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
A preferred chain alkylene group in Ro is preferably a chain alkylene having 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, and examples thereof may include a methylene group, an ethylene group, a propylene group and the like. A preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof may include a cyclohexylene group, a cyclopentylene group, a norbornylene group, an adamantylene group and the like. In order to exhibit effects of the present invention, a chain alkylene group is more preferred, and a methylene group is particularly preferred.
The monovalent organic group having a lactone structure or a sultone structure represented by R8 is not limited as long as the organic group has a lactone structure or a sultone structure, specific examples thereof may include a lactone structure or a sultone structure represented by any one of Formulas (LCl-1) to (LCl-21) and (SLl-1) to (SL1-3), and among them, a structure represented by (LCI -4) is particularly preferred. Further, n2 in (LCl-1) to (LCl-21) is more preferably 2 or less.
Further, R8 is preferably a monovalent organic group having an unsubstituted lactone structure or a sultone structure, or a monovalent organic group having a lactone structure or a sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent, and more preferably a monovalent organic group having a lactone structure having a cyano group as a substituent (cyanolactone).
Specific examples of the repeating unit having a group having a lactone structure or a sultone structure will be shown below, but the present is not limited thereto.
Figure imgf000043_0001
Figure imgf000044_0001
(In the formulas, Rx represents H, CH3,
Figure imgf000045_0001
In order to improve the effects of the present invention, two or more kinds of the repeating units having a lactone structure or a sultone structure may be used in combination as well.
In the case where the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 55 mol%, and still more preferably 10 mol% to 50 mol% based on the whole repeating units of the resin (A).
Further, the resin (A) may have a repeating unit having a cyclic carbonate ester structure.
It is preferred that the repeating unit having a cyclic carbonate ester is a repeating unit represented by the following Formula (A-l).
Figure imgf000046_0001
In Formula (A-l), RA' represents a hydrogen atom or an alkyl group.
When n is 2 or more, RA 's each independently represent a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic or polycyclic structure together with a group represented by -0-C(=0)-0- in the formula,
n is an integer of 0 or more.
Formula (A-l) will be described in detail.
The alkyl group represented by RA1 may have a substituent such as a fluorine atom. RA1 represents preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably a methyl group.
The substituent represented by RA 2 is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, an alkoxycarbonyl amino group. The substituent is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof may include a straight alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group; a branced alkyl group having 3 to 5 carbon atoms such as an isopropyl group, an isobutyl group and t-butyl group, and the like. The alkyl group may have a substituent such as a hydroxyl group.
n is an integer of 0 or more, which represents the number of substituents. n is, for example, preferably 0 to 4, and more preferably 0.
Examples of the divalent linking group represented by A may include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond or a combination thereof. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof may include a methylene group, an ethylene group, a propylene group and the like.
In an aspect of the present invention, A is preferably a single bond or an alkylene group. Examples of the monocyclic ring containing -0-C(=0)-0-, represented by Z, may include a 5- to 7-membered ring in which nA=2 to 4 in the cyclic carbonate ester represented by the following Formula (a), and preferably 5- or 6-memberd ring (nA=2 or 3), and more preferably 5-membered ring (nA=2).
Examples of the polycyclic ring containing -0-C(=0)-0-, represented by Z, may include a structure in which the cyclic carbonate ester represented by the following Formula (a) forms a condensed ring or a spiro ring together with one or two or more other ring structures. The "other ring structures" which may form a condensed ring or a spiro ring may be an alic clic hydrocarbon group, an aromatic hydrocarbon group or heterocyclic ring.
Figure imgf000047_0001
The monomer corresponding to the repeating unit represented by Formula (A-1) may be synthesized by a conventionally known method as described, for example, in Tetrahedron Letters, Vol. 27, No. 32 p. 3741(1986), Organic Letters, Vol. 4, No.15 p. 2561(2002) and the like.
In the resin (A), the repeating unit represented by Formula (A-1) may be contained either alone or in combination of two or more thereof. In the resin (A), the content of the repeating unit having a cyclic carbonate ester structure (preferably, a repeating unit represented by Formula (A-1)) is preferably 3 mol% to 80 mol%, more preferably 3 mol% to 60 mol%, particularly preferably 3 mol% to 30 mol%, and most preferably 10 mol% to 15 mol% based on the whole repeating units constituting the resin (A). By setting the content to the range, it is possible to enhance the developability as a resist, low defects, low LWR, low PEB temperature dependency, profile and the like.
Specific examples of the repeating unit represented by Formula (A-1) (repeating units (A-la) to (A-lw)) are shown below, but the present invention is not limited thereto.
Meanwhile, RA' in the following specific examples have the same meaning as RA' in Formula (A-1).
Figure imgf000048_0001
In the case where the resin (A) contains a repeating unit having a cyclic carbonate ester structure, the content of the repeating unit having cyclic carbonate ester structure is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 55 mol%, and still more preferably 10 mol% to 50 mol% based on the whole repeating unit.
The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. As a result, the adhesion to a substrate and the affinity for a developer are enhanced. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group.
Further, it is preferred that the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is different from the repeating unit having an acid-decomposable group (That is, preferably a repeating unit which is stable to an acid).
The alicyclic hydrocarbon structure in the alicyclic hydrocarbon strucuture substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diadamantyl group or a norbornane group.
The repeating unit is more preferably a repeating unit represented by any one of the following formulas (Alia) to (AIIc).
Figure imgf000049_0001
(Alia) (Allb) (AIIc)
In the formulas, Rx represents a hydrogen atom, a methyl group, hydroxymethyl group or a trifluoromethyl group.
Ab represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by Ab may include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond or a combination thereof. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and examples thereof may include a methylene group, an ethylene group, a propylene group and the like.
In an aspect of the present invention, Ab is preferably a single bond or an alkylene group.
Rp represents a hydrogen atom, a hydroxyl group or hydroxyalkyl group. A plurality of Rp's may be the same or different, but at least one of Rp's represents a hydroxyl group or hydroxyalkyl group.
The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but, in the case where the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, the content of the repeating unit having a hydroxyl group or a cyano group is preferably 1 mol% to 40 mol%, more preferably 3 mol% to 30 mol%, and still more preferably 5 mol% to 25 mol% based on the whole repeating units in the resin (A). Specific examples of the repeating unit having a hydroxyl group or a cyano group will be shown below but the present invention is not limited thereto.
Figure imgf000050_0001
Figure imgf000050_0002
Besides, the monomer described after [0011] of the specification of International Publication WO2011/122336 and the corresponding repeating unit may be suitably used.
The resin (A) may have a repeating unit having an acid group. Examples of the acid group may include a carboxyl group, a sulfonamide group, a sulfonylimide, a bissulfonylimide, a naphthoic structure, and an aliphatic alcohol group substituted with an electron-withdrawing group at the a-position (for example, a hexafluoroisopropanol group), and it is more preferred to have a repeating unit having a carboxyl group. By containing the repeating unit having an acid group, the resolution increases in the usage of contact holes. As for the repeating unit having an acid group, a repeating unit in which the acid group is directly bonded to the main chain of the resin, such as repeating unit by an acrylic acid or a methacrylic acid or a repeating unit in which the acid group is bonded to the main chain of the resin through a linking group, and a repeating unit which is introduced into the end of the polymer chain by using a polymerization initiator having an acid group or a chain transfer agent at the time of polymerization are all preferred, and the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. A repeating unit by an acrylic acid or a methacrylic acid is particularly preferred.
The resin (A) may or may not contain a repeating unit having an acid group, but in the case of containing a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 25 mol% or less, and more preferably 20 mol% or less, based on the whole repeating units in the resin (A). When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.
Specific examples of the repeating unit having an acid group will be described below, but the present invention is not limited thereto.
In the s ecific examples, Rx represents H, CH3, CH2OH or CF3.
Figure imgf000051_0001
The resin (A) of the present invention may have a repeating unit having an alicyclic hydrocarbon structure having no polar group (for example, the acid group, the hydroxyl group, and the cyano group) and not exhibiting acid decomposability. Accordingly, elution of low molecular components from the resist film into the liquid for liquid immersion during the liquid immersion exposure may be reduced, and further, the solubility of the resin during the development using a developer containing an organic solvent may be appropriately adjusted. Examples of the repeating unit may include a repeating unit represented by Formula (IV).
Figure imgf000052_0001
In Formula (IV), R5 represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group or a -CH2-0-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group and a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.
The cyclic structure possessed by R5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group may include a cycloalkyl group having 3 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group, and a cycloalkenyl group having 3 to 12 carbon atoms, such as a cyclohexenyl group. The monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group.
The polycyclic hydrocarbon group includes a ring-assembled hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring-assembled hydrocarbon group may include a bicyclohexyl group, a perhydronaphthalenyl group and the like. Examples of the bridged cyclic hydrocarbon ring may include a bicyclic hydrocarbon ring such as a pinane ring, a bornane ring, a norpinane ring, a norboraane ring and a bicyclooctane ring (a bicyclo[2.2.2]octane ring, a bicyclo[3.2.1]octane ring and the like), a tricyclic ydrocarbon ring such as a homobledane ring, an adamantine ring, a tricyclo[5.2.1.02'6]decane ring and a
2 5
tricyclo[4.3.1.1 ' Jundecane ring, a tetracyclic hydrocarbon ring such as a tetracyclo[4.4.0.12'5. l7'10ldodecane ring and a perhydro-l,4-methano-5,8-methanonaphthalene ring, and the like. Further, the bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, for example, a condensed ring obtained by condensing a plurality of 5- to 8-membered cycloalkane rings, such as a perhydronaphthalene (decalin) ring, a perhydroanthracene ring, a perhydrophenanthrene ring, a perhydroacenaphthene ring, a perhydrofluorene ring, a perhydroindene ring and a perhydrophenalene ring.
Preferred examples of the bridged cyclic hydrocarbon ring may include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo[5,2,l,02'6]decanyl group and the like. More preferred examples of the bridged cyclic hydrocarbon ring may include a norbornyl group and an adamantyl group.
The alicyclic hydrocarbon groups may have a substituent, and preferred examples of the substituent may include a halogen atom, an alkyl group, a hydroxyl group whose hydrogen atom is substituted, an amino group whose hydrogen atom is substituted and the like. Preferred examples of the halogen atom may include a bromine atom, a chlorine atom and a fluorine atom, and preferred examples of the alkyl group may include a methyl group, an ethyl group, a n-butyl group and a t-butyl group. The aforementioned alkyl group may further have a substituent, and examples of the substituent which may be further possessed by the alkyl group may include a halogen atom, an alkyl group, a hydroxyl group whose hydrogen atom is substituted, and an amino group whose hydrogen atom is substituted.
Examples of the substituent for the hydrogen atom may include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred examples of the alkyl group may include an alkyl group having 1 to 4 carbon atoms, preferred examples of the substituted methyl group may include a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group, and a 2-methoxyethoxymethyl group, examples of the substituted ethyl group may include a 1 -ethoxy ethyl group and a 1 -methyl- 1-methoxyethyl group, preferred examples of the acyl group may include an aliphatic acyl group having 1 to 6 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group and a pivaloyl group, and examples of the alkoxycarbonyl group may include an alkoxycarbonyl group having 1 to 4 carbon atoms and the like.
The resin (A) may or may not contain a repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability, but in the case of containing the repeating unit, the content ratio of the repeating unit is preferably 1 mol% to 50 mol%, and more preferably 10 mol% to 50 mol%, based on the whole repeating units in the resin (A).
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability will be described below, but the present invention is not limited thereto. In the formula, Ra represents H, CH3, CH2OH or
Figure imgf000054_0001
The resin (A) used in the composition of the present invention may have, in addition to the aforementioned repeating structural units, various repeating structural units for the purpose of controlling the dry etching resistance, suitability for a standard developer, adhesion to a substrate and resist profile, and further, resolution, heat resistance, sensitivity and the like, which are properties generally required for an actinic ray-sensitive or radiation-sensitive resin composition.
Examples of the repeating structural units may include repeating structural units corresponding to the monomers described below, but are not limited thereto.
Accordingly, the performance required for the resin used in the composition of the present invention, particularly
(1) solubility in a coating solvent,
(2) film-forming property (glass transition temperature),
(3) alkali developability,
(4) film reduction (selection of a hydrophilic, hydrophobic or alkali-soluble group),
(5) adhesion of unexposed portion to substrate, and
(6) dry etching resistance, and the like may be finely adjusted.
Examples of the monomer may include a compound having one addition-polymerizable unsaturated bond selected from acrylate esters, me hacrylate esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.
Besides, an addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the aforementioned various repeating structural units may be copolymerized.
In the resin (A) used in the composition of the present invention, the molar ratio of respective repeating structural units contained is appropriately set in order to control dry etching resistance, suitability for a standard developer, adhesion to a substrate and resist profile of the actinic ray-sensitive or radiation-sensitive resin composition, and further, resolution, heat resistance, sensitivity and the like which are performances generally required for the actinic ray-sensitive or radiation-sensitive resin composition.
When the composition of the present invention is for ArF exposure, from the viewpoint of transparency to ArF light, the resin (A) used in the composition of the present invention preferably has substantially no aromatic ring (specifically, the ratio of a repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%, that is, the resin does not have an aromatic group), and the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
The form of the resin (A) in the present invention may be any form of a random type, a block type, a comb type, and a star type. The resin (A) may be synthesized, for example, by polymerization of radicals, cations, or anions of an unsaturated monomer, corresponding to each structure. Further, it is also possible to obtain a target resin by using an unsaturated monomer corresponding to a precursor of each structure to perform polymerization, and then performing a polymer reaction.
When the composition of the present invention is for ArF exposure, from the viewpoint of transparency to ArF light, the resin (A) used in the composition of the present invention preferably has substantially no aromatic ring (specifically, the ratio of a repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%, that is, the resin does not have an aromatic group), and the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
It is preferred that the resin (A) contains no fluorine atom and no silicon atom from the viewpoint of compatibility with the resin (D) as describe below.
The resin (A) used in the composition of the present invention is preferably a resin in which all the repeating units are a (meth)acrylate-based repeating unit. In this case, it is possible to use any of a resin in which all the repeating units are methacrylate-based repeating units, a resin in which all the repeating units are an acrylate-based repeating unit, and a resin in which all the repeating units are methacrylate-based repeating units or acrylate-based repeating units, but it is preferred that the acrylate-based repeating unit is present in an amount of 50 mol% or less based on the whole repeating units.
In the case where KrF excimer laser light, electron beam, X-ray or high-energy beam having a wavelength of 50 nm or less (EUV and the like) is irradiated on the composition of the present invention, it is preferred that the resin (A) further has a hydroxystyrene-based repeating unit. The resin (A) has more preferably a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group and an acid-decomposable repeating unit such as tertiary alkyl (meth)acrylate ester.
Preferred examples of the hydroxystyrene-based repeating unit having an acid-decomposable group may include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, tertiary alkyl (meth)acrylate ester and the like, and more preferably 2-alkyl-2-adamantyl(meth)acrylate and dialkyl(l-adamantyl)methyl (meth)acrylate.
The resin (A) in the present invention may be synthesized by a conventional method (for example, radical polymerization). Examples of a general synthesis method may include a batch polymerization method of dissolving monomer species and an initiator in a solvent and heating the solution to perform the polymerization, a dropping polymerization method of adding dropwise a solution containing monomer species and an initiator to a heated solvent over 1 to 10 hours, and the like, and a dropping polymerization method is preferred. Examples of a reaction solvent may include tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, an ester solvent such as ethyl acetate, an amide solvent such as dimethylformamide, dimethylacetamide, and a solvent capable of dissolving the composition of the present invention described below, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and cyclohexanone. The polymerization is more preferably performed by using the same solvent as the solvent used in the photosensitive composition of the present invention. Accordingly, generation of particles during storage may be suppressed.
The polymerization reaction is preferably performed under an inert gas atmosphere such as nitrogen and argon. As for the polymerization initiator, the polymerization is initiated by using a commercially available radical initiator (azo-based initiator, peroxide and the like). The radical initiator is preferably an azo-based initiator, and an azo-based initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator may include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate) and the like. The initiator is added additionally or in parts, if desired, and after the completion of reaction, the reaction product is poured in a solvent, and a desired polymer is recovered by a powder or solid recovery method, or the like. The reaction concentration is 5% by mass to 50% by mass, and preferably 10% by mass to 30% by mass. The reaction temperature is usually 10°C to 150°C, preferably 30°C to 120°C, and more preferably 60°C to 100°C.
After the reaction is completed, the reaction solution is allowed to cool to room temperature and purified. The purification may be performed by a typical method, such as a liquid-liquid extraction method of applying water-washing or combining water-washing with an appropriate solvent to remove residual monomers or oligomer components, a purification method in a solution state, such as ultrafiltration of removing only polymers having a molecular weight not more than a specific molecular weight by virtue of extraction, a reprecipitation method of adding dropwise a resin solution in a poor solvent to solidify the resin in the poor solvent to remove residual monomers and the like, a purification method in a solid state, such as washing of the resin slurry separated by filtration with a poor solvent and the like, and the like.
For example, the resin is precipitated as a solid by contacting the reaction solution with a solvent (poor solvent) in which the resin is sparingly soluble or insoluble and which is in a volumetric amount of 10 times or less and preferably 10 to 5 times the reaction solution.
The solvent (precipitation or reprecipitation solvent) used at the time of operation of precipitation or reprecipitation from the polymer solution may be sufficient if the solvent is a poor solvent for the polymer, and the solvent may be appropriately selected from hydrocarbon, halogenated hydrocarbon, a nitro compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, and a mixed solvent including these solvents, depending on the kind of the polymer. Among these solvents, a solvent containing at least alcohol (particularly, methanol or the like) or water is preferred as the precipitation or reprecipitation solvent.
The amount of the precipitation or reprecipitation solvent used may be appropriately selected by considering the efficiency, yield and the like, but in general, the amount is 100 parts by mass to 10,000 parts by mass, preferably 200 by parts by mass to 2,000 parts by mass, and more preferably 300 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the polymer solution.
The temperature during the precipitation or reprecipitation may be appropriately selected in consideration of the efficiency or operability, but is usually 0 to 50°C, and preferably in the vicinity of room temperature (for example, approximately 20°C to 35°C). The precipitation or reprecipitation operation may be performed by a known method such as batch system and continuous system using a commonly employed mixing vessel such as stirring tank.
The precipitated or reprecipitated polymer is usually subjected to commonly employed solid-liquid separation such as filtration and centrifugation, then dried and used. The filtration is performed by using a solvent-resistant filter element, and preferably under pressure. The drying is performed under atmospheric pressure or reduced pressure (preferably under reduced pressure) at a temperature of approximately 30°C to 100°C and preferably at a temperature of approximately 30°C to 50°C.
Meanwhile, after the resin is once precipitated and separated, the resin may be dissolved in a solvent again and then brought into contact with a solvent in which the resin is sparingly soluble or insoluble. That is, there may be used a method including, after the completion of radical polymerization reaction, bringing the polymer into contact with a solvent in which the polymer is sparingly soluble or insoluble, to precipitate a resin (process a), separating the resin from the solution (process b), dissolving the resin in a solvent again to prepare a resin solution A (process c), and then bringing the resin solution A into contact with a solvent in which the resin is sparingly soluble or insoluble and which is in a volumetric amount of less than 10 times (volumetric amount of preferably 5 times or less) the resin solution A, to precipitate a resin solid (process d), and separating the precipitated resin (process e).
In addition, for suppressing the resin after preparation of the composition from aggregation or the like, as described in, for example, Japanese Patent Application Laid-Open No. 2009-037108, a process of dissolving the synthesized resin in a solvent to prepare a solution, and heating the solution at approximately 30°C to 90°C for approximately 30 minutes to 4 hours may be added.
The weight average molecular weight of the resin (A) in the present invention is 7,000 or more as described above, preferably 7,000 to 200,000, more preferably 7,000 to 50,000, still more preferably 7,000 to 40,000, and particularly preferably 7,000 to 30,000, in terms of polystyrene by the GPC method. If the weight average molecular weight is less than 7,000, the solubility in an organic-based developer becomes higher, and thus, there is a concern that a fine pattern may not be formed.
The polydispersity (molecular weight distribution) is usually in a range of 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution is, the better the resolution and resist shape are, and the smoother the side wall of the resist pattern is, and thus roughness is excellent.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending ratio of the resin (A) in the entire composition is preferably 30% by mass to 99% by mass, and more preferably 60% by mass to 95% by mass, based on the total solid of the composition of the resin (A).
Further, in the present invention, the resin (A) may be used either alone or in combination of two or more thereof. [2] (B) Compound capable of generating an acid upon irradiation with an actinic ray or radiation
The composition in the present invention contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation (hereinafter, also referred to as an "acid generator" or a "compound (B)).
The acid generator is particularly limited as long as the acid generator is known, but is preferably a compound represented by the following Formula (ZI), (ZII) or (ZIII).
Figure imgf000059_0001
(ZI) (ZII) (ZIII)
In Formula (ZI),
R2oi> R202 and R203 each independently represent an organic group.
The organic group as R20i , R202 and R203 has generally 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
Further, two of R20i to R203 may be bound with each other to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group therein. Examples of the group in which two of R20i to R203 are bound to form may include an alkylene group (for example, a butylene group and a pentylene group).
Meanwhile, the acid generator may be a compound having a plurality of structures represented by Formula (ZI). For example, the acid generator may be a compound having a structure in which at least one of R201 to R203 of a compound represented by Formula (ZI) is bound via a single bond or a linking group to at least one of R201 to R203 of another compound represented by Formula (ZI).
Z" represents a non-nucleophilic anion (an anion having an extremely low ability of causing a nucleophilic reaction).
Examples of Z" may include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion and the like), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkylcarboxylate anion and the like), a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, a tris(alkylsulfonyl)methide anion and the like.
The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, and examples thereof may include preferably a straight or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.
Examples of the aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion may include preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group and a naphthyl group.
The alkyl group, the cycloalkyl group and the aryl group as exemplified above may have a substituent. Specific examples thereof may include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkylaminosulfonyl group (preferably having 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), a cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms) and the like. The aryl group and the ring structure possessed by each group may further have an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent.
Examples of the aralkyl group in the aralkylcarboxylate anion may include preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylbutyl group.
Examples of the sulfonylimide anion may include a saccharin anion.
The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of the alkyl group may include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group and the like, and preferably a fluorine atom or an alkyl group substituted with a fluorine atom.
Examples of the other Z may include fluorinated phosphate (for example, PF6 "), fluorinated boron (for example, BF4 "), fluorinated antimony (for example, SbF6 ") and the like.
Z is preferably an aliphatic sulfonate anion substituted with a fluorine atom at least at the a-position of sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably having 4 to 8 carbon atoms) and a benzenesulfonate anion having a fluorine atom, and still more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion and a 3,5-bis(trifluoromethyl)benzenesulfonate anion.
From the viewpoint of the acid strength, it is preferred that pKa of the generated acid is -1 or less in order to enhance the sensitivity.
Examples of the organic group of R201, R202 and R203 may include an aryl group (preferably having 6 to 15 carbon atoms), a straight or branched alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15) and the like.
It is preferred that at least one of R201, R202 and R203 is an aryl group, and it is more preferred that all three are an aryl group. The aryl group may be a heteroaryl group such as an indole residue structure and a pyrrole residue structure, in addition to a phenyl group, a naphthyl group and the like.
The aryl group, the alkyl group and the cycloalkyl group as R20i, R202 and R203 may have a substituent. Examples of the substituent may include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms) and the like, but not limited thereto.
Further, two groups selected from R201, R202 and R203 may be bound via a single bond or a linking group. Examples of the linking group may include an alkylene group (preferably having 1 to 3 carbon atoms), -0-, -S-, -CO-, -S02- and the like, but not limited thereto.
Preferred structures in the case where at least one of R20i, R202 and R203 is not an aryl group may include a cation structure such as compounds exemplified in paragraphs 0046 and 0047 of Japanese Patent Application Laid-Open No. 2004-233661 and paragraphs 0040 to 0046 of Japanese Patent Application Laid-Open No. 2003-35948, compounds exemplified as Formula (1-1) to Formual (1-70) in U.S. Patent Application Laid-Open No. 2003/0224288 Al, and compounds exemplified as Formula (IA-1) to Formula (IA-54) and Formula (IB-1) to Formula (IB-24) of U.S. Patent Application Laid-Open No. 2003/0077540A1. More preferred examples of the compound represented by (ZI) may include a compound represented by Formula (ZI-3) or (ZI-4) as described below. First, a compound repres
Figure imgf000062_0001
In Formula (ZI-3),
Ri represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group,
R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R2 and R3 may be bound with each other to form a ring,
Ri and R2 may be bound with each other to form a ring,
Rx and Ry each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, Rx and Ry may be bound with each other to form a ring, and the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond or an amide bond.
Z" represents a non-nucleophilic anion.
The alkyl group as
Figure imgf000062_0002
is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specific examples thereof may include a straight alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-an octyl group, a n-dodecyl group, a n-tetradecyl group and a n-octadecyl group, and a branched alkyl group such as an isopropyl group, an isobutyl group, t-butyl group, a neopentyl group and a 2-ethylhexyl group. The alkyl group of may have a substituent, and examples of the alkyl group having a substituent may include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group and the like.
The cycloalkyl group as Ri is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. Specific examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like. The cycloalkyl group of Rt may have a substituent, and examples of the substituent may include an alkyl group and an alkoxy group. The alkoxy group as Ri is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples thereof may include a methoxy group, an ethoxy group, an isopropyloxy group, a t-butyloxy group, a t-amyloxy group and a n-butyloxy group. The alkoxy group of Ri may have a substituent, and examples of the substituent may include an alkyl group and a cycloalkyl group.
The cycloalkoxy group as R\ is a cycloalkoxy group having 3 to 20 carbon atoms, and examples thereof may include a cyclohexyloxy group, a norbornyloxy group, an adamantyloxy group and the like. The cycloalkoxy group of Ri may have a substituent, and examples of the substituent may include an alkyl group and a cycloalkyl group.
The aryl group as Ri is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof may include a phenyl group, a naphthyl group, a biphenyl group and the like. The aryl group of R\ may have a substituent, and preferred examples of the substituent may include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkylthio group and an arylthio group. In the case where the substituent is an alkyl group, a cycloalkyl group, an alkoxy group or cycloalkoxy group, The alkyl group of Ri as described above may be a cycloalkyl group, an alkoxy group or a cycloalkoxy group.
The alkenyl group as Ri may be a vinyl group or an allyl group.
R2 and R3 represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R2 and R3 may be bound with each other to form a ring. However, at least one of R2 and R3 represents an alkyl group, a cycloalkyl group or an aryl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for R2 and R3 may be the same as the specific examples and preferred examples for Rt as described above. In the case where R2 and R3 are bound with each other to form a ring, the sum of the number of carbon atoms contributing to formation of the ring included in R2 and R3 is preferably 4 to 7, and particularly preferably 4 or 5.
R] and R2 may be bound with each other to form a ring. In the case where Ri and R2 are bound with each other to form a ring, it is preferred that R\ is an aryl group (preferably a phenyl group or a naphthyl group, which may have a substituent) and R2 is an alkylene group having 1 to 4 carbon atoms (preferably a methylene group or an ethylene group), and preferred examples of the substituent may include a substituent which may be possessed by the aryl group as R\ as described above. As another aspect in the case where Ri and R2 are bound with each other to form a ring, it is also preferred that R\ is a vinyl group and R2 is an alkylene group having 1 to 4 carbon atoms.
The alkyl group represented by Rx and Ry is preferably an alkyl group having 1 to 15 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group.
The cycloalkyl group represented by R and Ry is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.
The alkenyl group represented by Rx and Ry is preferably an alkenyl group having 2 to 30 carbon atoms, and examples thereof may include a vinyl group, an allyl group and a styryl group.
The aryl group represented by Rx and Ry is preferably, for example, an aryl group having 6 to 20 carbon atoms, and specific examples thereof may include a phenyl group, a naphthyl group, an azulenyl group, an acenaphthylenyl group, a phenanthrenyl group, a phenalenyl group, a phenanthracenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, a benzopyrenyl group and the like. The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
The alkyl group moiety of the 2-oxoalkyl group and the alkoxycarbonylalkyl group represented by Rx and Ry may be exemplified by those listed above as Rx and Ry.
The cycloalkyl group moiety of the 2-oxocycloalkyl group and the alkoxycarbonylcycloalkyl group represented by Rx and Ry may be exemplified by those listed above as Rx and Ry.
Z" may be exemplified by those listed above as Z" in Formula (ZI).
The compound represented by Formula (ZI-3) is preferably a compound represented by the following Formulas (ZI-3a) and (ZI-3b).
Figure imgf000064_0001
In Formulas (ZI-3a) and (ZI-3b), Ri, R2 and R3 are the same as those defined in Formula (ZI-3).
Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom, m, n, p and q mean an integer, and are preferably 0 to 3, more preferably 1 to 2, and particularly 1. The alkylene group which links S+ and Y may have a substituent, and preferred examples of the substituent may include an alkyl group.
When Y is a nitrogen atom, R5 represents a monovalent organic group, and when Y is an oxygen atom or a sulfur atom, R5 does not exist. R5 is preferably a group containing an electron-withdrawing group, and particularly preferably a group represented by the following Formulas (ZI-3a-l) to (ZI-3a-4).
Figure imgf000065_0001
( ZI - 3a - l ) ( ZI - 3a - 2 ) ( ZI - 3a - 3 ) ( ZI - 3a - 4 )
In Formulas (ZI-3a-l) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for R may be the same as the specific examples and preferred examples as described above for Rt in Formula (ZI-3).
In Formulas (ZI-3a-l) to (ZI-3a-4), * represents a bonding hand connected to a nitrogen atom as Y in the compound represented by Formula (ZI-3 a).
When Y is a nitrogen atom, R5 is particularly preferably a group represented by -S0 -R . R4 represents an alkyl group, a cycloalkyl group or an aryl group, and is preferably an alkyl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group for R4 may be the same as the specific examples and preferred examples as described above for Ri.
Z" may be exemplified by those listed above as Z" in Formula (ZI).
The compound represented by Formula (ZI-3) is particularly preferably a compound represented by the following Formulas (ZI-3a') and (ZI-3b').
Figure imgf000065_0002
In Formula (ZI-3a') and (ZI-3b'), Rl s R , R3, Y and R5 are the same as those defined in Formulas (ZI-3a) and (ZI-3b).
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000068_0002
Subsequently, a compound represented by Formula (ZI-4) will be described.
Figure imgf000069_0001
In Formula (ZI-4),
Ri3 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a cycloalkyl group. These groups may have a substituent.
When a plurality of R14's is present, Rn'seach independently represent a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a cycloalkyl group. These groups may have a substituent.
Ri5's each independently represent an alkyl group, a cycloalkyl group or a naphthyl group. Two R15's may be bound with each other to form a ring, and may contain a heteroatom such as an oxygen atom, a sulfur atom and a nitrogen atom as an atom constituting the ring. These groups may have a substituent.
1 represents an integer of 0 to 2.
r represents an integer of 0 to 8.
Z" represents a non-nucleophilic anion, and may be exemplified by the same non-nucleophilic anion as Z" in Formula (ZI).
In Formula (ZI-4), the alkyl group of Ri3, R14 and R15 is straight or branched, and preferably has 1 to 10 carbon atoms.
The cycloalkyl group of R13, R14 and R]5 may be a monocyclic or polycyclic cycloalkyl group.
The alkoxy group of R13 and Ri4 is straight or branched, and preferably has 1 to 10 carbon atoms.
The alkoxycarbonyl group of Ri3 and Ri4 is straight or branched, and preferably has 2 to 1 1 carbon atoms.
The group having a cycloalkyl group of i3 and R] may be a monocyclic or polycyclic group having a cycloalkyl group. These groups may further have a substituent.
The alkyl group in the alkylcarbonyl group of R14 may be exemplified by the specific examples of the alkyl group as Ri3 to Ri5 as described above. The alkylsulfonyl group and the cycloalkylsulfonyl group of Ri4 are straight, branched or cyclic, and preferably have 1 to 10 carbon atoms.
Examples of the substituent which may be possessed by each of the groups may include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group and the like.
Examples of the ring structure which may be formed by two Ri5's being bound with each other may include a 5- or 6-membered ring formed by two R]5's together with the sulfur atom in Formula (ZI-4), particularly preferably 5-membered ring (that is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. The divalent Ri5 may have a substituent, and examples of the substituent may include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group and the like. A plurality of substituents for the ring structure may exist, and these may be bound with each other to form a ring.
R15 in Formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent gropu in which two R15's are bound with each other to form a tetrahydrothiophene ring structure together with a sulfur atom, or the like, and particularly preferably a divalent gropu in which two R15's are bound with each other to form a tetrahydrothiophene ring structure together with a sulfur atom.
The substituent which may be possessed by Ri3 and Ri4 is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group or a halogen atom (particularly, a fluorine atom).
1 is preferably 0 or 1, and more preferably 1.
r is preferably 0 to 2.
Specific examples of the cation structure possessed by the compound represented by Formula (ZI-3) or (ZI-4) as described above may include, in addition to the cation structure such as compounds exemplified in Japanese Patent Application Laid-Open No. 2004-233661, Japanese Patent Application Laid-Open No. 2003-35948, U.S. Patent Application Laid-Open No. 2003/0224288 A 1 and U.S. Patent Application Laid-Open No. 2003/0077540A1 as described above, for example, a cation structure in chemical structures exemplified in paragraphs 0046, 0047, 0072 to 0077 and 0107 to 0110 of Japanese Patent Application Laid-Open No. 2011-53360, a cation structure in chemical structures exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 of Japanese Patent Application Laid-Open No. 201 1-53430, and the like. In Formulas (ZII) and (ZIII),
R204 to R207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, the alkyl group and the cycloalkyl group of R204 to R207 are the same as the aryl group, the alkyl group and the cycloalkyl group of R201 to R203 in the compound (ZI) as described above.
The aryl group, the alkyl group and the cycloalkyl group of R204 to R207 may have a substituent. Examples of the substituent may also include those which may be possessed by the aryl group, the alkyl group and the cycloalkyl group of R201 to R203 in the compound (ZI) as described above.
Z" may be exemplified by those listed above as Z" in Formula (ZI).
Further, in addition to the compound represented by Formula (ZI-3) or (ZI-4), the compound represented by the following Formula (Γ) is also preferred as an acid generator. By using the compound represented by the following Formula (Γ), the permeability of exposure light is enhanced, and thus, LWR and DOF become better.
Figure imgf000071_0001
In Formula (Γ),
X' represents an oxygen atom, a sulfur atom or -N(Rx)-.
Ri' and R2' each independently represent an alkyl group, a cycloalkyl group or an aryl group.
R3' to R9' each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylcarbonyloxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group or an arylcarbonyloxy group.
Rx represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an alkoxycarbonyl group, an aryl group, an arylcarbonyl group or an aryloxycarbonyl group.
Ri and R2' may be bound with each other to form a ring. Further, any two or more of Re' to R9 , R3' and R9 , R and R5', R5' and Rx, and R^ and Rx each may be bound with each other to form a ring.
X' is preferably a sulfur atom or -N(Rx)- from the viewpoint of suppressing the abso tivity(for example, absorbance at a wavelength of 193 run) to a low level.
Z" may be exemplified by those listed above as Z" in Formula (ZI).
The alkyl group as R\ to R9' and Rx may have a substituent, is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specific examples thereof may include a straight alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-an octyl group, a n-dodecyl group, a n-tetradecyl group and a n-octadecyl group, and a branched alkyl group such as an isopropyl group, an isobutyl group, a t-butyl group, a neopentyl group and a 2-ethylhexyl group.
Meanwhile, examples of the alkyl group having a substituent with respect to Rx may include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group and the like.
Examples of the alkyl group having a substituent with respect to Ri' and R2' may include a methoxyethyl group and the like.
Further, examples thereof may also include particularly a group in which a straight or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue structure and the like) and the like.
The cycloalkyl group as R\ to R9' and Rx may have a substituent, is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring. Specific examples thereof may include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like.
The acyl group as R3' to R9' and Rx may have a substituent, and is preferably an acyl group having 1 to 10 carbon atoms. Specific examples thereof may include an acetyl group, a propionyl group, an isobutyryl group and the like.
The alkenyl group as Rx is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof may include a vinyl group, an allyl group, a butenyl group and the like.
The alkoxy group as R3' to R9' may have a substituent, and is preferably an alkoxy group having 1 to 20 carbon atoms. Specific examples thereof may include a methoxy group, an ethoxy group, an isopropyloxy group, a cyclohexyloxy group and the like.
The alkoxycarbonyl group as R3' to R9' may have a substituent, and is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Specific examples thereof may include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a cyclohexyloxycarbonyl group and the like. The alkylcarbonyloxy group as R3' to R9' may have a substituent, and is preferably an alkylcarbonyloxy group having 2 to 20 carbon atoms. Specific examples thereof may include a methylcarbonyloxy group, an ethylcarbonyloxy group, an isopropylcarbonyloxy group, a cyclohexylcarbonyloxy group and the like.
The aryl group as R\ to R9' and Rx may have a substituent, is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof may include a phenyl group, a naphthyl group and the like.
The aryloxy group as R3' to R91 may have a substituent, is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof may include a phenyloxy group, a naphthyloxy group and the like.
The aryloxycarbonyl group as R3' to R9' and Rx may have a substituent, is preferably an aryloxycarbonyl group having 7 to 15 carbon atoms, and examples thereof may include a phenyloxycarbonyl group, a naphthyloxycarbonyl group and the like.
The arylcarbonyloxy group as R3' to R9' may have a substituent, is preferably an arylcarbonyloxy group having 7 to 15 carbon atoms, and examples thereof may include a phenylcarbonyloxy group, a naphthylcarbonyloxy group and the like.
The arylcarbonyl group as Rx may have a substituent, is preferably an arylcarbonyl group having 7 to 15 carbon atoms, and examples thereof may include a phenyl carbonyl group, a naphthylcarbonyl group and the like.
Examples of the substituent which may be possessed by the alkyl group as R3' to R9', the cycloalkyl group as Rj' to R and Rx, the acyl group as R3' to R9' and Rx, the alkoxy group as R3' to R9, the alkoxycarbonyl group as R3' to R9', the alkylcarbonyloxy group as R3' to R9', the aryl group as Ri' to R9' and Rx, the aryloxy group as R3' to R9', the aryloxycarbonyl group as R3' to R9' and Rx, the arylcarbonyloxy group as R3' to R9', and the arylcarbonyl group as Rx, respectively, may include an alkyl group (which may be straight, branched or cyclic, and preferably has 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms) and the like.
Examples of the ring structure which may be formed by R^ and R2' being bound with each other may include a 5- or 6-membered ring formed by divalent Ri' and R2' (for example, an ethylene group, a propylene group, a 1,2-cyclohexylene group and the like) together with a sulfur atom in Formula (Γ), particularly preferably 5-membered ring (that is, a tetrahydrothiophene ring). However, from the viewpoint of the decomposition efficiency of acid anion generation, it is preferred that R ' and R2' are not bound with each other to form a ring.
Examples of the ring structure which may be formed by any two or more of R to R9', R3' and R9', R4' and R5', R5' and Rx, and Re' and Rx being bound with each other may include preferably a 5- or 6-membered ring, particularly preferably a 6-membered ring.
Ri' and R2' is particularly preferably an alkyl group or an aryl group.
Particularly preferred examples of R3' to R9' may include an alkyl group which may have a substituent or a hydrogen atom, but, in the case of using as ArF resist, a hydrogen atom is particularly preferred from the absorption strength at 193 nm.
Rx is particularly preferably an alkyl group or an acyl group.
Subsequently, description will be made with respect to Formula (2) and Formula (2'), which are preferred structures of the non-nucleophilic anion Z".
First, a sulfonate anion represented by Formula (2) will be described.
Figure imgf000074_0001
In Formula (2),
Xf s each independently represent a fluorine atom or an alkyl group substituted with at least one fluorine atom.
L represents a single bond or a divalent linking group, and when a plurality of L's is present, L's may be the same or different.
A represents an organic group having a cyclic structure.
x represents an integer of 1 to 20.
The anion of Formula (2) will be described in detail.
Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples thereof may include a fluorine atom, CF3, CHF2, C2F5, C3F7, C4F9, C5Fn, C6Fi3, C7F15, C8F17, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9 and CH2CH2C4F9, and among them, preferably a fluorine atom, CF3, CHF2 and C2F5. Particularly, it is preferred that all Xf are a fluorine atom.
L represents a single bond or a divalent linking group, and examples thereof may include -COO-, -OCO-, -CO-, -0-, -S-, -SO-, -S02-, -N(Ri)- (in the formula, Ri represents a hydrogen atom or an alkyl group), an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group formed by combining two or more thereof, preferably -COO-, -OCO-, -CO-, -S02-, -CON(Ri)-, -S02N(Ri)-, -CON(Ri)-alkylene group-, -N(Ri)CO-alkylene group-, -COO-alkylene group- or -OCO-alkylene group-, and more preferably -COO-, -OCO-, -S02-, -CON(Ri)- or -S02N(Ri)-. When a plurality of L's is present, L's may be the same or different.
Specific examples and preferred examples of the alkyl group for Ri may be the same as the specific examples and preferred examples as described above as the alkyl group for Ri to R5.
The cyclic organic group of A is not particularly limited as long as the group has a cyclic structure, and examples thereof may include a alicyclic group, an aryl group, a heterocyclic group (including a group having no aromaticity, as well as a group having aromaticity, and also including a structure such as a tetrahydropyran ring, a lactone ring, a sultone ring and\, a cyclic ketone) and the like.
The alicyclic group may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a norbornenyl group, a tricyclodecanyl group (for example, a tricyclo[5.2.1.0(2,6)]decanyl group), a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Further, also preferred is a nitrogen-containg alicyclic group such as a piperidine group, a decahydroquinoline group and a decahydroisoquinoline group. Among them, an alicyclic group having a bulky structure, which has 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group and a decahydroisoquinoline group, is preferred from the viewpoint of suppressing diffusion in film during a PEB (post-exposure baking) process and thus enhancing exposure latitude.
Examples of the aryl group may include a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring. Among them, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm. Examples of the heterocyclic group may include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring and a pyridine ring. Among them, a furan ring, a thiophene ring and a pyridine ring are preferred.
The cyclic organic group may have a substituent, and examples of the substituent may include an alkyl group (which may be straight, branched or cyclic, and has preferably 1 to 12 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a sulfonate ester group and the like.
Meanwhile, the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon.
x is preferably 1 to 8, more preferably 1 to 4, particularly preferably 1 to 3, and most preferably 1.
Subsequently, a disulfonylimidate anion will be described.
SC¾-Xf
"N (2 ' ) xso2-xf
In Formula (2'),
Xf is as defined in Formula (2), and preferred examples thereof are also the same. In Formula (2'), two Xf s may be bound with each other to form a ring structure.
The disulfonylimidate anion for Z" is preferably a bis(alkylsulfonyl)imide anion.
The alkyl group in the bis(alkylsulfonyl)imide anion is preferably an alkyl group having 1 to 5 carbon atoms.
Two alkyl groups in the bis(alkylsulfonyl)imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), which may form a ring together with an imide group and two sulfonyl groups. The ring structure which may be formed by the bis(alkylsulfonyl)imide anion is preferably 5- to 7-membered ring, and more preferably 6-membered ring.
The substituent which may be possessed by the alkyl group and the alkylene group formed by linking two alkyl groups may be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group or the like, and preferably a fluorine atom or an alkyl group substituted with a fluorine atom.
It is also preferred that Z" is a sulfonate anion represented by the following Formula (B-1).
Figure imgf000077_0001
In Formula (B-1),
Rbi's each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF3).
n represents an integer of 0 to 4.
n is preferably an integer of 0 to 3, and more preferably 0 or 1.
Xbi represents a single bond, an alkylene group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate ester bond (-OS02- or -S03-) or a combination thereof.
Xbt is preferably an ester bond (-OCO- or -COO-) or a sulfonate ester bond (-OS02- or -S03-), and more preferably an ester bond (-OCO- or -COO-).
Rb2 represents an organic group having 6 or more carbon atoms.
The organic group having 6 or more carbon atoms for ¾2 is preferably a bulky group, and examples thereof may include an alkyl group having 6 or more carbon atoms, an alicyclic group, an aryl group, a heterocyclic group and the like.
The alkyl group having 6 or more carbon atoms for ¾,2 may be straight or branched, and is preferably a straight or branched alkyl group having 6 to 20 carbon atoms, and examples thereof may include a straight or branched hexyl group, a straight or branched heptyl group, a straight or branched octyl group and the like. From the viewpoint of volume, a branched alkyl group is preferred.
The alicyclic group having 6 or more carbon atoms for ¾2 may be monocyclic or polycyclic. Examples of the monocyclic aliphatic group may include a monocyclic cycloalkyl group such as a cyclohexyl group and a cyclooctyl group. Examples of the polycyclic alicyclic group may include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Among them, an alicyclic group having a bulky structure, which has 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group, is preferred from the viewpoint of suppressing diffusion in film during a PEB (post-exposure baking) process and improving the MEEF (mask error enhancement factor).
The aryl group having 6 or more carbon atoms for ¾2 may be monocyclic or polycyclic. Examples of the aryl group may include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group. Among them, a naphthyl group having relatively low light absorbance at 193 nm is preferred.
The heterocyclic group having 6 or more carbon atoms for Rb2 may be monocyclic or polycyclic, but a polycyclic heterocyclic group may suppress the diffusion of an acid more efficiently. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity may include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring and a pyridine ring. Examples of the heterocyclic ring having no aromaticity may include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring.
The substituent having 6 or more carbon atoms for ¾2 may further have a substituent. Examples of the further substituent may include an alkyl group (which may be straight or branched, and has preferably 1 to 12 carbon atoms), a cycloalkyl group (which may be a monocyclic, polycyclic or spiro ring, and has preferably 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group and a sulfonate ester group. Meanwhile, the carbon constituting the alicyclic group, the aryl group or the heterocyclic group (the carbon contributing to ring formation) may be carbonyl carbon.
Specific examples of the sulfonate anion structure represented by Formula (B-l) are shown below, but the present invention is not limited thereto.
Figure imgf000079_0001
Figure imgf000079_0002
Figure imgf000079_0003
Figure imgf000079_0004
It is also preferred that Z" is a sulfonate anion represented by the following Formula
(A-I).
Figure imgf000079_0005
In Formula (A-I),
Ri is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group or a heteroaryl group.
R2 is a divalent linking group.
Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. ni and n2 are each independently 0 or 1.
The alkyl group represented by Ri is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group may include a methyl group, an ethyl group, a 1 -propyl group, a 2-propyl group, a 1 -butyl group, a 2-butyl group, a 2-(2-methylpropyl) group, a 1-pentyl group, a 2-pentyl group, a 3-pentyl group, a
1- (2-methylbutyl) group, a l-(3-methylbutyl) group, a 2-(2-methylbutyl) group, a
2- (3-methylbutyl) group, a neopentyl group, a 1-hexyl group, a 2-hexyl group, a 3-hexyl group, a l-(2-methylpentyl) group, a l-(3-methylpentyl) group, a l-(4-methylpentyl) group, a
2- (2-methylpentyl) group, a 2-(3-methylpentyl) group, a 2-(4-methylpentyl) group, a
3- (2-methylpentyl) group, a 3-(3-methylpentyl) group and the like.
Further, the alkyl group may have a substituent (preferably a fluorine atom), and the alkyl group having a substituent is preferably an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom, and more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.
The alkyl group represented by Ri is preferably a methyl group, an ethyl group or a trifluoromethyl group, and more preferably a methyl group or an ethyl group.
The monovalent alicyclic hydrocarbon group represented by R\ preferably has 5 or more carbon atoms. Further, the monovalent alicyclic hydrocarbon group preferably has 20 or less carbon atoms, and more preferably 15 or less carbon atoms. The monovalent alicyclic hydrocarbon group may be a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group. A part of -CH2- of the alicyclic hydrocarbon group may be substituted by -O- or -C(=0)-.
The monocyclic alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms, and examples thereof may include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecanyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctadienyl group, a piperidine ring group and the like, and particularly preferably a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.
The polycyclic alicyclic hydrocarbon group preferably has 10 to 20 carbon atoms, and examples thereof may include a bicyclo[4.3.0]nonanyl group, a decahydronaphthalenyl group, a 1,2,3,4-tetrahydronaphthalenyl group, a tricyclo[5.2.1.0(2,6)]decanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, a borayl group, an isobornyl group, a norbornyl group, an adamantyl group, a noradamantyl group, a l,7,7-trimethyltricyclo[2.2.1.02'6]heptanyl group, a 3,7,7-trimethylbicyclo[4.1.0]heptanyl group, a decahydroisoquinoline ring group and the like, and preferably a norbornyl group, an adamantyl group, a noradamantyl group.
The aryl group represented by R\ preferably has 6 or more carbon atoms. Further, the aryl group preferably has 20 or less carbon atoms, and more preferably 15 or less carbon atoms.
The heteroaryl group represented by R\ preferably has 2 or more carbon atoms. Further, the heteroaryl group preferably has 20 or less carbon atoms, and more preferably 15 or less carbon atoms.
The aryl group and the heteroaryl group may be a monocyclic aryl group, a monocyclic heteroaryl group, a polycyclic aryl group or a polycyclic heteroaryl group.
Examples of the monocyclic aryl group may include a phenyl group and the like.
Examples of the polycyclic aryl group may include a naphthyl group, an anthracenyl group and the like.
Examples of the monocyclic heteroaryl group may include a pyridyl group, a thienyl group, a furanyl group and the like.
Examples of the polycyclic heteroaryl group may include a quinolyl group, an isoquinolyl group and the like.
The monovalent alicyclic hydrocarbon group, aryl group and heteroaryl group may further have a substituent, and examples of the further substituent may include a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like), a nitro group, a cyano group, an aminde group, a sulfonamide group, an alkyl group such as a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec -butyl group, a hexyl group, a 2-ethylhexyl group and an octyl group, an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group, an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group and a benzoyl group , an acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxyl group.
Ri is particularly preferably a cyclohexyl group or an adamantyl group.
Examples of the divalent linking group represented by R2 may include, but not particularly limited thereto, -COO-, -OCO-, -CO-, -0-, -S-, -SO-, -S02-, an alkylene group (preferably an alkylene group having 1 to 30 carbon atoms), a cycloalkylene group (preferably a cycloalkylene group having 3 to 30 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 30 carbon atoms), an arylene group (preferably an arylene group having 6 to 30 carbon atoms), a heteroarylene group (preferably a heteroarylene group having 2 to 30 carbon atoms) and a combination of two or more thereof. The alkylene group, the cycloalkylene group, the alkenylene group, the arylene group and the heteroarylene group may further have a substituent, and specific examples of the substituent are the same as those described above with respect to the substituent which may be further possessed by the monovalent alicyclic hydrocarbon group, aryl group and heteroaryl group as Ri .
The divalent linking group represented by R2 is preferably an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group or a heteroarylene group, more preferably an alkylene group, still more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 5 carbon atoms.
Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Rf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Rf is preferably a fluorine atom, CF3, C2F5, C3F7, QF9, C5Fn, C6F13, C7F15, C8FI7, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9 or CH2CH2C4Fc>, more preferably a fluorine atom or CF3.
ni is preferably 1.
n2 is preferably 1.
Preferred specific examples of the sulfonate anion represented by Formula (A-I) are shown below, but the present invention is not limited thereto.
[Sulfonate anion represented by Formula (A-I)]
H F, H ?
C-0-C2H -C— C-SO3- -C2H4-C-C-SO3
I I O CF3 F F F
Figure imgf000083_0001
H ί H F\
Me-C-O— C2H4-C— C-S03- Et-C-O— C2H4-C-C-SO3-
11 II I
] I I
O CF3 F O F F
Figure imgf000083_0002
Further, the compound represented by the following Formula (ZV) may also be exemplified as an acid generator.
Figure imgf000084_0001
In Formula (ZV),
R-208 represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group of R208 may be the same as the specific examples of the aryl group as R20i to R203 in Formula (ZI).
Specific examples of the alkyl group and the cycloalkyl group of R208 may be the same as the specific examples of the alkyl group and the cycloalkyl group as R20i to R203 in Formula (ZI).
Examples of the alkylene group of A may include an alkylene group having 1 to 12 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group and the like), examples of the alkenylene group of A may include an alkenylene group having 2 to 12 carbon atoms (for example, a vinylene group, a propenylene group, a butenylene group and the like), and examples of the arylene group of A may include an arylene group having 6 to 10 carbon atoms (for example, a phenylene group, a tolylene group, a naphthylene group and the like).
Among acid generators, particularly preferred examples are shown below.
84
Figure imgf000085_0001
85
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
ĨZ75)
Figure imgf000090_0001
Ĩ280)
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000092_0002
Figure imgf000092_0003
Figure imgf000093_0001
(zl08)
The compound (B) is preferably an ionic compound represented by the compound represented by Formula (ZI) or (ZII) and the like, and it is preferred that the content of the fluorine atom contained in the anion in the ionic compound is 35% by mass based on the total amount of the atoms constituting the anion of the compound (B). Since the compound (B) is an ionic compound represented by the compound represented by Formula (ZI) or (ZII) and the like, the pattern shape becomes more rectangular.
The acid generator may be used either alone or in combination of two or more thereof.
It is preferred that the actinic ray-sensitive or radiation-sensitive resin composition according to the present invnetion contains two or more acid generators, and it is preferred that, among the two or more acid generators, at least one compound does not have an aromatic group, or has one or two aromatic groups.
The content of the compound capable of generating an acid upon irradiation with an actinic ray or radiation in the composition is preferably 5% by mass or more, more preferably 10%» by mass or more, still more preferably 10%> by mass to 40% by mass, and particularly preferably 10%> by mass to 30% by mass based on the total solid of the actinic ray-sensitive or radiation-sensitive resin composition.
[3] (C) Component containig at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invnetion contains a component containing at least one of a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and a resin having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid (hereinafter, referred to as a "component (C)").
When exposing a resist film containing (C), since a compound having basicity or a compound capable of increasing the basicity by the action of an acid is present on the top layer sruface of the resist film at a high concentration, it is possible to capture an excessive acid generated on the top layer of the exposed portion. That is, the aicd concentration may be evenly distributed in the thickness direction of the exposed portion of the resist film. Accordingly, since an insolulization or sparing solubilization reaction of the resist film in an developer containing an organic solvent may be performed evenly with acid catalyst in the thickness direction of the resist film, in forming a resist pattern, it is possible to suppress a T-top shape or bridge defects of the formed pattern. The component (C) may be an ionic compound or a non-ionic compound, but is preferably an ionic compound.
The component (C) is typically a compound capturing an acid generated from the compound (B), and more specifically, the component (C) is preferably a nitrogen-containing compound or a resin having a nitrogen atom in its side chain.
Here, in the case where the component (C) is a compound having at least one of a fluorine atom and a silicon atom as well as having basicity, in order that the component (C) has sufficient basicity, it is preferred that any electron-withdrawing functional groups (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom (particularly a fluorine atom) and the like) are not bonded directly to the nitrogen atom, and it is more preferred that all atoms adjacent to the nitrogen atom are a hydrogen atom or a carbon atoms.
Further, in the case where the component (C) is a compound having at least one of a fluorine atom and a silicon atom as well as capable of increasing the basicity by the action of an acid, in order that the compound capable of increasing the basicity by the action of an acid has sufficient basicity, it is preferred that any electron-withdrawing functional groups (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom (particularly a fluorine atom) and the like) are not bonded directly to the nitrogen atom of the compound capable of increasing the basicity by the action of an acid, and it is more preferred that all atoms adjacent to the nitrogen atom are a hydrogen atom or a carbon atoms.
Meanwhile, it is preferred that the component (C) does not accompany unintended change in chemical structure upon irradiation with an actinic ray or radiation in order to ensure the the action is exhibited. In other words, it is preferred that the component (C) has no photosensitivity (non-photosensitivity).
The component (C) is preferably a resin (C) having a repeating unit having any one or more of a fluorine atom, a silicon atom and a CH3 partial structure in a side chain moiety of the resin.
The content of the repeating unit having any one or more of a fluorine atom, a silicon atom and a CH3 partial structure in a side chain moiety of the resin is preferably 25 mol% or less, more preferably 8 mol% or less, and still more preferably 0.05 mol% to 8 mol% based on the whole repeating units of the resin (C).
Hereinafter, description will be made by dividing the component (C) into "a compound (C-l) having at least one of a fluorine atom and a silicon atom as well as having basicity", "a compound (C-2) having at least one of a fluorine atom and a silicon atom as well as capable of increasing the basicity by the action of an acid" and "a resin (C-3) having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid".
[3-1] (C-l) Compound having at least one of a fluorine atom and a silicon atom as well as having basicity
The compound (C-l) is not particularly limited as long as the compound has at least one of a fluorine atom and a silicon atom as well as having basicity, but, for example, a basic compound having at least one of a fluorine atom and a silicon atom and having any of the structures represented by the following Formulas (A) to (E) may be exemplified.
R 201 ■ ^ ^ ^ R 204 R205 N— R202 — N— C— N— =C— N=C— — C— N— R203-C— N— C-R206
I I
(A) (B) (C) (D) (E)
In Formula (A), R and R are each independently a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms) or a heteroaryl group.
In Formula (E), R203, R204, R205 and R206 each independently represent an alkyl group or a cycloalkyl group.
In the structure represented by Formula (A), R201 and R202 may be bound with each other to form a ring.
In the structures represented by Formulas (B) to (D), two or more of bonding hands from carbon atoms and bonding hands from nitrogen atoms may be bound with each other to form a ring.
In the structure represented by Formula (E), two or more of R203, R204, R205, R206, bonding hands from carbon atoms and a bonding hand from a nitrogen atom may be bound with each other to form a ring.
The alkyl group of R and R in Formula (A) is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-heptadecyl group, a n-octadecyl group, a n-nonadecyl group, a n-eicosyl, an i-propyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a t-dodecyl group and the like.
The cycloalkyl group of R and R is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof may include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
Among the alkyl group and the cycloalkyl group of R201 and R202, a straight alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 4 to 8 carbon atoms are preferred.
The aryl group of R and R is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof may include a phenyl group, a toluoyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, an anthryl group and the like.
The heteroaryl group of R and R is a group which contains one or more heteroatoms such as a sulfur atom, an oxygen atom and a nitrogen atom in the aryl group, and examples thereof may include a pyridyl group, an imidazolyl group, a morpholinyl group, a piperidinyl group, a pyrrolidinyl group and the like.
The alkyl group, the cycloalkyl group, the aryl group, the heteroaryl group of R201 and may have a substituent, and examples of the substituent may include a halogen atom, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an arylcarbonyl group, an alkoxyalkyl group, an aryloxyalkyl group, alkyl carbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group and the like.
Examples of the alkyl group as a substituent which may be further possessed by R201 and R202 may include a straight or branched alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group and a t-butyl group.
Examples of the cycloalkyl group as a substituent which may be further possessed by
201 202
R and R may include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
Examples of the aryl group as a substituent which may be further possessed by R201 and R may include an aryl group having 6 to 15 carbon atoms such as a phenyl group and a naphthyl group.
Examples of the alkoxy group as a substituent which may be further possessed by R201 and R may include a straight, branched or cyclic alkoxy group such as a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxy group, a n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a t-butoxy group, a cyclopentyloxy group and a cyclohexyloxy group.
Examples of the aryloxy group as a substituent which may be further possessed by R201
202
and R may include an aryloxy group having 6 to 10 carbon atoms such as a phenyloxy group and a naphthyloxy group.
Examples of the acyl group as a substituent which may be further possessed by R201
202
and R may include a straight or branched acyl group having 2 to 12 carbon atoms such as an acetyl group, a propionyl group, a n-butanoyl group, an i-butanoyl group, a n-heptanoyl group, a 2-methylbutanoyl group, a 1-methylbutanoyl group and a t-heptanoyl group.
Examples of the arylcarbonyl group as a substituent which may be further possessed by
201 202
R and R uz may include an arylcarbonyl group having 6 to 10 carbon atoms such as a phenylcarbonyl group and a naphthylcarbonyl group.
Examples of the alkoxyalkyl group as a substituent which may be further possessed by
201 202
R^1 and may include a straight, branched or cyclic alkoxyalkyl group having 2 to 21 carbon atoms such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group and a 2-ethoxyethyl group.
Examples of the aryloxyalkyl group as a substituent which may be further possessed by
201 202
R in and may include an aryloxyalkyl group having 7 to 12 carbon atoms such as a phenyloxymethyl group, a phenyloxyethyl group, a naphthyloxymethyl group and a naphthyloxyethyl group.
Examples of the alkylcarbonyloxy group as a substituent which may be further
201 202
possessed by R and R may include a straight, branched or cyclic alkylcarbonyloxy group such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an i-propylcarbonyloxy group, a n-butylcarbonyloxy group, a 2-methylpropylcarbonyloxy group, an 1-methylpropylcarbonyloxy group, a t-butylcarbonyloxy group, a cyclopentylcarbonyloxy group and a cyclohexylcarbonyloxy group.
Examples of the arylcarbonyloxy group as a substituent which may be further
201 202
possessed by R and R may include an arylcarbonyloxy group having 7 to 1 1 carbon atoms such as a phenylcarbonyloxy group and a naphthylcarbonyloxy group.
Examples of the alkoxycarbonyl group as a substituent which may be further possessed by R and R may include a straight, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an i-propoxycarbonyl group, a n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, a 1-methylpropoxycarbonyl group, a t-butoxycarbonyl group, a cyclopentyloxycarbonyl group and a cyclohexyloxycarbonyl. Examples of the aryloxycarbonyl group as a substituent which may be further possessed by R and R may include an aryloxycarbonyl group having 7 to 1 1 carbon atoms such as a phenyloxycarbonyl group and a naphthyloxycarbonyl group.
Examples of the alkoxycarbonyloxy group as a substituent which may be further possessed by R and R may include a straight, branched or cyclic alkoxycarbonyloxy group such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, a n-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy.
Examples of the aryloxycarbonyloxy group as a substituent which may be further
201 202
possessed by R and R may include an aryloxycarbonyloxy group having 7 to 11 carbon atoms such as a phenyloxycarbonyloxy group and a naphthyloxycarbonyloxy group.
The compound (C-l) having a structure represented by Formula (A) may include
201 202
(Al) a compound having a structure represented by Formula (A) (however, R and R do not contain a fluorine atom and a silicon atom), and a "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (A), (A2) a compound having a structure represented by Formula (A) (however, at least one of R201 and R202 is a group formed by substituting at least one hydrogen atom in the alkyl group, the cycloalkyl group, the aryl group or the heteroaryl group, which may have a substituent, by a group having a fluorine atom or silicon atom), and (A3) a compound having a structure
201 202
represented by Formula (A) (however, at least one of R U1 and is a group formed by substituting at least one hydrogen atom in the alkyl group, the cycloalkyl group, the aryl group or the heteroaryl group, which may have a substituent, by a group having a fluorine atom or silicon atom), and a "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (A).
In (Al) and (A3), the "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (A) may be suitably exemplified by the group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent
201 202
which may be further possessed by R and R , by a group having a fluorine atom or silicon atom.
Here, the group having a silicon atom is not particularly limited as long as the group contains at least one silicon atom, and examples thereof may include a silyl group, a silyloxy group, a group having a siloxane bond, and the like. Further, the group having a silicon atom may be an alkylsilyl structure or a cyclic siloxane structure (for example, groups represented by Formulas (CS-1) to (CS-3) as described below) which may be possessed by the resin (C") as described below. These groups may further have a substituent, and specific examples of the substituent are the same as the specific examples of the subsituent which may be possesse4d by R201 and R202.
Specific examples of the group having a silicon atom may include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group and the like.
The compound (C-l) having a structure represented by Formulas (B) to (D) may include a compound having a structure represented by Formulas (B) to (D), and a group having at least one of a fluorine atom and a silicon atom (for example, a group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent which may be further possessed by R and R , by a group having a fluorine atom or silicon atom).
Here, specific examples of the group having a silicon atom are the same as those described above.
In Formula (E), specific examples of the alkyl group and the cycloalkyl group of R203, R204, R205 and R206 are the same as the specific examples of the alkyl group and the cycloalkyl group of R201 and R202.
The alkyl group and the cycloalkyl group of R203, R204, R205 and R206 may further have a substituent, and specific examples of the substituent are the same as the specific examples of the substituent which may be further possessed by R and R .
The compound (C-l) having a structure represented by Formula (E) may include (El) a comound having a structure represented by Formula (E) (however, R203, R204, R205 and R206 do not contain a fluorine atom and a silicon atom), and a "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (E), (E2) a compound having a structure represented by Formula (E) (however, at least one of R203, R204, R205 and R206 is a group formed by substituting at least one hydrogen atom in the alkyl group or the cycloalkyl group, which may have a substituent, by a group having a fluorine atom or silicon atom), and (E3) a compound having a structure represented by Formula (E) (however, at least one of R203, R204, R205 and R206 is a group formed by substituting at least one hydrogen atom in the alkyl group or the cycloalkyl group, which may have a substituent, by a group having a fluorine atom or silicon atom), and a "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (E).
In (El) and (E3), the "group having at least one of a fluorine atom and a silicon atom" at a position other than the structure reprseneted by Formula (E) may be suitably exemplified by the group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent which may be further possessed by R and R , by a group having a fluorine atom or silicon atom.
Here, specific examples of the group having a silicon atom are the same as those described above.
In the structures represented by Formulas (A) to (E), the bonding hands from carbon atoms and/or a nitrogen atom are connected to other atoms constituting the comound (C-l).
Further, as described above, in the structure represented by Formula (A), R201 and R202 may be bound with each other to form a ring. In the structures represented by Formulas (B) to (D), two or more of the bonding hands from carbon atoms and the bonding hands from nitrogen atoms may be bound with eath other to form a ring. In the structure represented by Formula (E), two or more of R203, R204, R205, R206, bonding hands from carbon atoms and bonding hands from nitrogen atoms may be bound with each other to form a ring.
The ring may be an aromatic or non-aromatic nitrogen-containing heterocyclic ring. Examples of the nitrogen-containing heterocyclic ring may include a 3- to 10-membered ring, preferably 4- to 8-membered ring, and more preferably 5- or 6-membered ring. The ring may further have a substituent, and specific examples thereof are the same as the specific examples exemplified as as a substituent which may be further possessed by R201 and R202.
In other words, the compound (C-l) may be suitably exemplified by a compound having a nitrogen-containing heterocyclic ring which is substituted with a fluorine atom or a group containing a fluorine atom or a silicon atom. The group containing a fluorine atom or a silicon atom may include a group formed by substituting at least one hydrogen atom in the specific examples (however, a halogen atom and a hydroxyl group are excluded) exemplified as as a substituent which may be further possessed by R and R , by a group having a fluorine atom or silicon atom.
The nitrogen-containing heterocyclic ring may be suitably exemplified by a pyrrole ring, a pyridine ring, a pyrimidine ring and the like.
In the case where the compound (C-l) is a low-molecular compound (described below), in the structures represented by Formulas (A) to (E), it is preferred that the bonding hands from carbon atoms and/or nitrogen atoms are bonded to a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, respectively, and specific examples of these groups are the same s those described in R and R . [3-2] (C-2) Compound having at least one of a fluorine atom and a silicon atom as well as capable of increasing the basicity by the action of an acid
The compound (C-2) is not particularly limited as long as the compound is a compound having at least one of a fluorine atom and a silicon atom as well as capable of increasing the basicity by the action of an acid, and examples thereof may include a comound having at least one of a fluorine atom and a silicon atom, and a carbamate group having a protecting group.
It is preferred that the protecting group constituting the carbamate group is a group represented by the following Formula (P) (the group represented by Formula (P) is bonded to a nitrogen atom at a bonding site represented by the symbol *).
Figure imgf000102_0001
In Formula (P),
Rbi, Rb2 and Rb3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rbi to Rb3 may be bound with each other to form a ring. However, all of Rbi to Rb3 are not a hydrogen atom at the same time.
Specific examples of the alkyl group, the cycloalkyl group and the aryl group of Rb1; Rb2 and Rb3 are the same as the specific examples of the alkyl group, the cycloalkyl group and
201 202
the aryl group of R and R in the group represented by Formula (P).
Specific examples of the aralkyl group of Rbl5 Rb2 and Rb3 may include preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylbutyl group.
As Rb\, Rb2 and Rb3, preferred are a straight or branched alkyl group, cycloalkyl group and aryl group. More preferred are a straight or branched alkyl group and cycloalkyl group.
The ring formed by two of Rbi to Rb3 being bound with each other is preferably a cycloalkyl group (monocyclic or polycyclic), and more specifically a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
Rbi, Rb2 and Rb3 may further have a substituent, and examples of the substituent may include a halogen atom (a fluorine atom and the like), a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), an aminoacyl group (preferably having 2 to 10 carbon atoms), a group having a silicon atom (specific examples are the same as those described in the compound (G-l)) and the like. For the cyclic structure in the aryl group, the cycloalkyl group and the like, an alkyl group (preferably having 1 to 10 carbon atoms) may be also exemplified as a substituent. For the aminoacyl group, an alkyl group (preferably having 1 to 10 carbon atoms) may be also exemplified as a substituent.
In the case where two of Rb1? Rb2 and Rb3 are a hydrogen atom, the other one is preferably an aryl group, and examples of the aryl group may include a phenyl group, a naphthyl group and the like.
The compound (C-2) may be constituted by substituting at least one group connected to the nitrogen atom of the compound (C-l) by a group represented by Formula (P).
The compound (C-2) is not particularly limited, but a particularly preferred aspect may be a compound represented by the following Formula (1) having the group represented by Formula (P). Since the compound represented by the following Formula (1) has at least one of a fluorine atom and a silicon atom in a moiety other than the group represented by Formula (P) (a protecting group constituting a carbamate group), the compound (compound whose basicity is increased) obtained by the action of an acid on the compound represented by Formula (1) constantly has at least one of a fluorine atom and a silicon atom. Accordingly, even in the post-exposure baking (PEB) process as described below, since the compound whose basicity is increased is not diffused into the internal direction of the resist film, but is present at a desired position, "capturing an excessive acid generated on the top layer of the exposed portion" as described above may be more certainly performed, and thus, the aicd concentration may be more evenly distributed in the thickness direction of the exposed portion of the resist film.
Figure imgf000104_0001
In Formula (1),
Ra, Rbt, Rb2 and Rb3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rbi to Rb3 may be bound with each other to form a ring. However, all of Rbi to Rb3 are not a hydrogen atom at the same time.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x+y+z=3.
When x=z=l, Ra and Rc may be bound with each other to form a nitrogen-containing heterocyclic ring.
When z=l, the organic group as Rf contains a fluorine atom or a silicon atom.
When z=2, at least one of two Rf s contains a fluorine atom or a silicon atom.
Further, when z=2, two Re's and two Rf s may be the same or different, respectively, and two Re's may be bound with each other to form a ring.
When y=2, two Rbi's, two Rb2's and two Rt,3's may be the same or different, respectively.
Specific examples of the alkyl group, the cycloalkyl group, the aryl group or the aralkyl group as Ra, Rbi, Rb2 and Rb3 are the same as the specific examples of the alkyl group, the cycloalkyl group, the aryl group or the aralkyl group as Rbi, Rb2 and Rb3 in Formula (P).
Rc is preferably a divalent linking group having 2 to 12 carbon atoms (more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms), and examples thereof may include an alkylene group, a phenylene group, an ether group, an ester group, an amide group and a group formed by combining two or more thereof.
The organic group as Rf is preferably an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.
Specific examples of the alkyl group, the cycloalkyl group, the aryl group or the heteroaryl group as Rf are the same as the specific examples of the cycloalkyl group, the aryl group or the heteroaryl group as R and R in Formula (A). Ra, Rbi, Rb2, Rb3, Rc and Rf may further have a substituent, respectively, and specific examples of the substituent are the same as the specific examples of the substituent which may be further possessed by Rbi, Rb2 and Rb3 in Formula (P).
In the case where the organic group as Rf contains a fluorine atom or a silicon atom, Rf is preferably a group formed by substituting at least one hydrogen atom in the organic group by a group having a fluorine atom or a silicon atom. Here, specific examples of the group having a silicon atom are the same as the specific examples of the group having a silicon atom as described in the compound (C-l).
In the case where the organic group as Rf contains a fluorine atom or a silicon atom, particularly, Rf is preferably an alkyl group in which 30% to 100% of hydrogen atoms are substituted by fluorine atoms, and examples thereof may include a perfluoroalkyl group such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group and a perfluorobutyl group.
Further, example of the nitrogen-containing heterocyclic ring formed by Ra and Rc, or Re's being bound with each other may include an aromatic or non-aromatic nitrogen-containing heterocyclic ring (preferably having 3 to 20 carbon atoms). Examples of the nitrogen-containing heterocyclic ring may include a ring corresponding to a heterocyclic compound such as pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, lH-l,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo[l,2-a]pyridine,
(1 S,4S)-(+)-2,5-diazabicyclo[2.2. l]heptane, 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene, indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline and 1,5,9-triazacyclododecane. These rings may further have one or more kind of, or one or more substituents, and specific examples of the substituent are the same as the specific examples of the substituent wich may be further possessed by Rbi, Rb2 and Rb3 of Formula (P).
The ring formed by two of Rbi to Rb3 being bound with each other is preferably a monocyclic cycloalkyl such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
The component (C) may be a low-molecular compound or a resin (polymer compound), but is preferably a resin.
In the case where the component (C) is a low-molecular compound, the molecular weight is generally 500 or less, preferably 150 to 500, and more preferably 250 to 500.
Further, the compound (C-2) may be synthesized from amine, for example, by the method described in Protective Groups in Organic Synthesis 4th edition, and the like. For example, the compound represented by Formula (1) is preferably obtained by reacting dicarbonate ester or haloformate ester with amine, as shown in the following scheme. In the formulas, X represents a halogen atom. Ra, Rbi, Rb2, Rb3, Rc and Rf have the same meaing as Ra, Rbi, Rb2, Rb3, Rc and Rf in Formula (1), respectively.
Figure imgf000106_0001
Specific examples of the compounds (C-1) and (C-2) are shown below, but the present invention is not limited thereto.
Figure imgf000106_0002
In the case where the component (C) is a resin containing at least one of a fluorine atom and a silicon atom (hereinafter, such a resin is referred to as a resin (C")), at least one of a fluorine atom and a silicon atom may be contained in the main chain or side chain of the resin.
In the case where the resin (C") contains a fluorine atom, it is preferred that the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom or an aryl group containing a fluorine atom as a partial structure containing a fluorine atom.
The alkyl group containing a fluorine atom is a straight or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. The alkyl group has preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than a fluorine atom.
The cycloalkyl group containing a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom. The cycloalkyl group containing a fluorine atom may further have a substituent other than a fluorine atom.
The aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted by a fluorine atom. Examples of the aryl group may include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than a fluorine atom.
Preferred examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom and the aryl group containing a fluorine atom may include groups represented by the following Formulas (F2) to (F4).
Figure imgf000107_0001
(F2> (F3) (F4)
In Formula (F2) to (F4), R57 to ¾8 each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R57 to represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. At least one of ¾2 to represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. At least one of R65 to R68 represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. The alkyl group preferably has 1 to 4 carbon atoms.
It is preferred that all of R57 to and R65 to R67 are a fluorine atom.
R62, R63 and is preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Meanwhile, and R<53 may be bound with each other to form a ring.
Examples of the group represented by Formula (F2) may include a p-fluorophenyl group, a pentafluorophenyl group and a 3,5-di(trifluoromethyl)phenyl group.
Examples of the group represented by Formula (F3) may include a trifluoromethyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafiuoro(2-methyl)isopropyl group, a nonafluorobutyl group, an octafluoroisobutyl group, a nonafluorohexyl group, a nonafluoro-t-butyl group, perfluoroisopentyl group, a perfluorooctyl group, a perfluoro(trimethyl)hexyl group, a 2,2,3,3-tetrafluorocyclobutyl group and a perfluorocyclohexyl group. Among them, the group is more preferably a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro(2-methyl)isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group or a perfluoroisopentyl group, and more preferably a hexafluoroisopropyl group or a heptafluoroisopropyl group.
Examples of the group represented by Formula (F4) may include -C(CF3)2OH, -C(C2F5)2OH, -C(CF3)(CH3)OH and -CH(CF3)OH. Among them, -C(CF3)2OH is particularly preferred.
Specific examples of the repeating unit containing a fluorine atom are shown below. In the specific examples, Xi represents a hydrogen atom, -CH3, -F or -CF3. X2 represents -F or -CF3.
Figure imgf000109_0001
Figure imgf000110_0001
In the case where the resin (C") contains a silicon atom, it is preferred that the resin has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. The alkylsily structure is preferably a structure containing a trialkylsilyl group.
Preferred examples of the alkylsilyl structure and the cyclic siloxane structure may include roups represented by the following Formulas (CS-1) to (CS-3).
Figure imgf000110_0002
(CS-1) (CS-2) (CS-3)
In Formulas (CS-1) to (CS-3), Ri2 to R26 each independently represent a straight or branched alkyl group or a cycloalkyl group. The alkyl group preferably has 1 to 20 carbon atoms. The cycloalkyl group preferably has 3 to 20 arbon atoms.
L3 to L5 represents a single bond or a divalent linking group. Examples of the divalent linking group may include an alkylene group, a phenylene group, an ether bond, a thioether group, a carbonyl group, an ester bond, an amide bond, a urethane bond, a urea bond or a combination thereof.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.
Specific examples of the repeating unit having a group represented by Formulas (CS-1)
Figure imgf000111_0001
=CH3, C2H5, C3H7, C^Hg
Suitable examples of the resin (C") may include,
a resin (C"-a) having a repeating unit having at least one of a fluorine atom and a silicon atom, and a repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid, and a resin (C"-b) having a repeating unit having at least one of a fluorine atom and a silicon atom, and a basic group or a group capable of increasing the basicity by the action of an acid.
In the resin (C"-a), specific examples of the repeating unit having at least one of a fluorine atom and a silicon atom may be as exemplified above.
In the resin (C"-a), it is preferred that the repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid is a repeating unit represented by the following Formula (B-I).
Figure imgf000112_0001
In Formula (B-I), Xa represents a hydrogen atom, a methyl group which may have a substituent or a group represented by -CH2-Rc>. R9 represents a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group may include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa represents preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and more preferably a hydrogen atom, a methyl group or a hydroxymethyl group.
Ab represents a group having a basic group or a group capable of increasing the basicity by the action of an acid.
In Ab, it is preferred that both of the group having basicity and the group capable of increasing the basictity by the action of an acid contain a nitrogen atom.
The group having a basic group as Ab is preferably a group having any of structrures rpresented by Formulas (A) to (E) or an ammonium group, and specific examples thereof may include a monovalent group formed by subtracting any one hydrogen atom from a basic compound (low-molecular compound) having any of structures represented by Formulas (A) to (E) (in this case, the basic compound may or may not have at least one of a fluorine atom and a silicon atom).
It is more preferred that the group having a basic group as Ab is a group represented by the following Formula (Β-Γ).
-L-Ac (Β-Γ)
In Formula (Β-Γ), L representes a single bond or a divalent linking group, and Ac represents a structure represented by Formula (A) (the bonding hand from the nitrogen atom of Formula (A) is bonded to L).
Examples of the divalent linking group as L may include an alkylene group, a cycloalkylene group, an ether group, a phenylene group and a group formed by combining two or more thereof, more preferably an alkylene group and cycloalkylene group, and still more preferably an alkylene group. The total number of carbon atoms of the divalent linking group as L is preferably 0 to 10, more preferably 1 to 6, and still more preferably 2 or 3.
In the group having a group capable of increasing the basicity by the action of an acid as Ab, preferred examples of the "group capable of increasing the basicity by the action of an acid" may include "a carbamate group having a protecting group" as described in the compound (C-2).
It is more preferred that the group having a group capable of increasing the basicity by the action of an acid as Ab is a group represented by the following Formula (B-II).
Figure imgf000113_0001
In Formula (B-II),
Ra, Rbi, Rb2 and Rb3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rbi to Rb3 may be bound with each other to form a ring. However, all of Rbi to Rb3 are not a hydrogen atom at the same time.
Rc represents a single bond or a divalent linking group,
x represents 0 or 1, y represents 1 or 2, and x+y=2.
When x=l, Ra and Rc may be bound with each other to form a nitrogen-containing heterocyclic ring.
When y=2, two Rbi's, two Rb2's and two Rt,3's may be the same or different, respectively.
In Formula (B-II), specific examples of each of the groups in Ra, Rbi, Rb2, Rb3 and Rc, the ring which may be formed by two of Rbi to Rb3 being bound with each other, and the nitrogen-containing heterocyclic ring which may be formed by Ra and Rc being bound with each other are the same as those described in Formula (1).
In the resin (C"-b), the repeating unit having at least one of a fluorine atom and a silicon atom, and a group capable of increasing the basicity by the action of an acid is a repeating unit represented by Formula (B-1), and may include a repeating unit satisfying any of (i) Xa is a methyl group having at least one of a fluorine atom and a silicon atom (for example, a trifluoromethyl group), (ii) Ab is a group having a basic group or a group capable of increasing the basicity by the action of an acid, and also having at least one of a fluorine atom and a silicon atom, and (iii) corresponding to (i) and (ii).
With respect to (ii), examples of the group Ab having a basic group and also having at least one of a fluorine atom and a silicon atom may include a monovalent group formed by subtracting any one hydrogen atom from a basic compound (low-molecular compound) having any of structures represented by Formulas (A) to (E) (however, the basic compound has at least one of a fluorine atom and a silicon atom).
Further, with respect to (ii), examples of the group Ab having a group capable of increasing the basicity by the action of an acid and also having at least one of a fluorine atom and a silicon atom may include a monovalent group formed by stbtracting any one hydrogen atom from any of Ra, Rc and Rf of the compound represented by Formula (1).
Specific examples of the repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid in the resin (C") are shown below, but the present invention is not limited thereto. In the specific examples, X represents a hydrogen atom, -CH3, -CH2OH, -F or -CF3.
Figure imgf000115_0001
The resin (C") may further contain a repeating unit represented by the following
Formula (ΙΙΓ).
Figure imgf000116_0001
Rc3i represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom and the like), a cyano group or a -CH2-0-Rac2 group. In the formula, Rac2 represents a hydrogen atom, an alkyl group or an acyl group.
Rc31 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.
Rc32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a silicon atom, a fluorine atom and the like.
Lc3 represents a single bond or a divalent linking group.
The alkyl group of Rc32 is preferably a straight or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group preferably has 3 to 20 carbon atoms.
The alkenyl group preferably has 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
Rc32 is preferably an unsubstituted alkyl group or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom.
Lc3 represents a single bond or a divalent linking group. Examples of the divalent linking group may include an ester group, an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, an ester bond (a group represented by -COO-) or a group formed by combining two or more thereof, and preferably a linking group in which the total number of carbon atoms is 1 to 12.
The resin (C") may further contain a repeating unit represented by the following Formula (CII-AB).
Figure imgf000117_0001
(C I I -AB)
In Formula (CII-AB),
Rcu' and R^' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group. Zc' represents an atomic group needed to form an alicyclic structure together with two carbon atoms (C-C) to which Rcu' and Rci2' are bonded.
Rc32 is a substituent for the alicyclic structure, and has the same definition as Rc32 in Formula (ΙΙΓ).
p represents an integer of 0 to 3, and is preferably 0 or 1.
Specific examples of the repeating unit represented by Formula (ΙΙΓ) or (CII-AB) are shown below. In the specific examples, Ra represents H, CH3, CH2OH, CF3 or CN.
Figure imgf000117_0002
Specific examples of the resin (C") are shown below, but the present invention is not limited thereto.
Figure imgf000118_0001
In the case where the component (C) (also including the resin (C")) contains a fluorine atom, the content of the fluorine atom is preferably 5 mol% to 80 mol%, and more preferably 10 mol% to 80 mol% based on the molecular weight of the component (C). In the case where the component (C) is the resin (C"), the content of the repeaing unit containing a fluorine atom is preferably 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol% based on the whole repeating units of the hydrophobic resin.
In the case where the component (C) (also including the resin (C")) contains a silicon atom, the content of the silicon atom is preferably 2 mol% to 50 mol%, and more preferably 2 mol% to 30 mol% based on the molecular weight of the component (C). In the case where the component (C) is the resin (C"), the content of the repeating unit containg a silicon atom is preferably 10 mol% to 100 mol%, and more preferably 20% by mass to 100% by mass based on the whole repeating units of the resin (C").
By setting the content of the fluorine atom or the silicon atom based on the molecular weight of the component (C) within the aforementioned range, since sufficient fluorine atoms or silicon atoms are contained in the component (C), the surface free energy of the component (C) may be sufficiently reduced. As a result, it is possible to localize the component (C) on the top layer portion of the resist film more certainly. Accordingly, since the excessive acid generated from the top layer of the exposed portion may be more certainly captured, and the acid concentration may be more certainly evenly distributed in the thickness direction of the exposed portion of the resist film, it is considered that the aforementioned problems such as T-top shape or bridge defects may be more certainly suppressed.
In the resin (C-a), the content of the "repeating unit having at least one of a fluorine atom and a silicon atom" is preferably 20 mol% to 99 mol%, more preferably 25mol% to 95 mol%, and particularly preferably 30 mol% to 90 mol% based on the whole repeating units constituting the resin (C").
In the resin (C-a), the content of the "repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid" is preferably 15 mol%, more preferably 8 mol% or less, and particularly preferably 1 mol% to 8 mol% based on the whole repeating units constituting the resin (C").
In the resin (C-b), the conent of the "repeating unit having at least one of a fluorine atom and a silicon atom, and a basic group or a group capable of increasing the basicity by the action of an acid" is preferably 20 mol% to 100 mol%, more preferably 25 mol% to 100 mol%, and particularly preferably 30 mol% to 100 mol% based on the whole repeating units constituting the resin (C").
In the resin (C"), the content of the repeating unit represented by Formula (ΙΙΓ) or (CII-AB) is preferably 20 mol% to 80 mol%, more preferably 25 mol% to 70 mol%, and particularly preferably 30 mol% to 60 mol% based on the whole repeating units constituting the resin (C").
The weight average molecular weight of the resin (C") is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 7,500 to 15,000 in terms of polystyrene by the GPC method.
The polydispersity of the resin (C") is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. By doing this, it is possible to achieve more excellent resolution, pattern shape and roughness characteristics.
The component (C) (also including the resin (C")) may be used either alone or in combination of two or more thereof.
The content of the component (C) (also including the resin (C")) is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and still more preferably 0.1 % by mass to 5% by mass based on the total solid in the composition.
The component (C) (also including the resin (C")) may be commercially available or synthesized by a conventional method. A general synthesis method of the resin (C") may be exemplified by the method as described above with respect to the resin (A).
It is natural that the resin (C") has a small amount of impurities such as metal, but the residual amount of monomer and olygomer components is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and still more preferably 0 % by mass to 1% by mass. Accordingly, it is possible to reduce the change in sensitivity and the like over time by reducing the amount of extraneous substances in liquid. [3-3] (C-3) Resin having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid
The resin (C-3) is not particularly limited as long as the resin is a resin having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid, buta resin having a repeating unit represented by Formula (II) as described below may be exemplified.
The CH3 partial structure possessed by the side chain moiety in the resin (C-3) (hereinafter, simply referred to as a "side chain CH3 partial structure") includes CH3 partial structures possessed by an ethyl group, a propyl group and the like.
Meanwhile, since a methyl group (for example, an a-methyl group of a repeating unit having a methacrylate structure) directly bonded to the main chain of the resin (C-3) makes a little contribution to surface localization of the resin (C-3) by the effect of the main chain, it is considered that such a methyl group is not included in the CH3 partial structure in the present invention.
More specifically, in the case where the resin (C-3) contains a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond such as, for example, a repeating unit represented by the following Formula (M), and the case where R-i i to Ri4 are CH3 "itself, it is considered that the CH3 is not included in the CH3 partial structure possessed by the side chain moiety in the present invention.
Meanwhile, it is considered that a CH3 partial structure present via a certain atom from the C-C main chain is included in the CH3 partial structure in the present invention. For example, in the case where Ri i is an ethyl group (CH2CH3), it is considered that "one" CH3 partial structure of the present invention is included.
Figure imgf000120_0001
In Formula (M),
Rn to R14 each independently represent a side chain moiety.
Examples of Rn to Rj4 of the side chain moiety may include a hydrogen atom, a monovalent organic group and the like.
Examples of the monovalent organic group for Rn to Ri4 may include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group and the like, and these group may further have a substituent.
It is preferred that the resin (C-3) is a resin having a repeating unit having a CH3 partial structure in the side chain moiety, and it is more preferred that the resin has at least one repeating unit (x) among the repeating unit represented by the following Formula (II) and the repeating unit represented by the following Formula (III).
Hereinafter, the repeating unit represented by Formula (II) will be describide in detail.
Figure imgf000121_0001
(I I)
In Formula (II), XM represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R2 represents an orgainic group having one or more CH3 partial structures, which is stable against an acid. Here, more specifically, the organic group which is stable against an acid is preferably an organic group having no "group capable of decomposing by the action of an acid to generate a polar group" described in the resin (A).
The alkyl group of X i is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group or the like, but a methyl group is preferred.
Xbi is preferably a hydrogen atom or a methyl group.
Examples of R2 may include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group, each of which has one or more CH3 partial structures. The aforementioned cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.
R2 is preferably an alkyl group or an alkyl-substituted cycloalkyl group, which has one or more CH3 partial structures.
The organic group having one or more CH3 partial structures, which is stable against an acid, as R2, preferably has 2 to 10 CH3 partial structures, and more preferably 2 to 8 CH3 partial structures.
The alkyl group having one or more CH3 partial structures in R2 is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of the preferred alkyl group may include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3-butyl group, a 3-hexyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5, 7-tetramethyl-4-heptyl group and the like. The alkyl group is more preferably an isobutyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3 -methyl -4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l ,5-dimethyl-3-heptyl group or a 2,3 ,5 ,7-tetramethyl-4-heptyl group.
The cycloalkyl group having one or more CH3 partial structures in R2 may be monocyclic or polycyclic. Specific examples thereof may include groups having a monocyclo, bicyclo, tricyclo and tetracyclo structure having 5 or more carbon atoms. The number of carbon atoms thereof is preferably 6 to 30, and particularly preferably 7 to 25. Preferred examples of the cycloalkyl group may include an adamantyl group, a noradamantyl group, a decalin residue structure, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a cyclododecanyl group. More preferred examples thereof may include an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group and a tricyclodecanyl group. The cycloalkyl group is more preferably a norbornyl group, a cyclopentyl group or a cyclohexyl group.
The alkenyl group having one or more CH3 partial structures in R2 is preferably a straight or branched alkenyl group having 1 to 20 carbons, and more preferably a branched alkenyl group.
The aryl group having one or more CH3 partial structures in R2 is preferably an aryl group having 6 to 20 carbon atoms, examples thereof may include a phenyl group and a naphthyl group, and preferably a phenyl group.
The aralkyl group having one or more C¾ partial structures in R2 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof may include a benzyl group, a phenethyl group and a naphthylmethyl group.
Specific examples of the hydrocarbon group having two or more CH3 partial structures in R2 may include an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2-methyl-3 -butyl group, a 3-hexyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyI group, a 3,5-dimethylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-tbutylcyclohexyl group, an isobornyl group and the like. The hydrocarbon group is more preferably an isobutyl group, a t-butyl group, a
2- methyl-3 -butyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a
3- methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group, a 3,5-dimethylcyclohexyl group, a 3,5-di-tert-butylcyclohexyl group, a 4-isopropylcyclohexyl group, a 4-t-butylcyclohexyl group or an isobornyl group.
Preferred specific examples of the repeating unit represented by Formula (II) are shown below. However, the present invention is not limited thereto.
Figure imgf000124_0001
Figure imgf000124_0002
It is preferred that the repeating unit represented by Formula (II) is preferably a repeating unit which is stable against an acid (non-acid-decomposable), and specifically, a repeating unit having no group capable of decomposing by the action of an acid to generate a polar group.
Hereinafter, the repeating unit represented by Formula (III) will be described in detail.
Figure imgf000125_0001
(III)
In Formula (III), X½ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R3 represents an organic group having one or more CH3 partial structures, which is stable against an acid, and n represents an integer of 1 to 5.
The alkyl group of Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group or the like, but a hydrogen atom is preferred.
Xb2 is preferably a hydrogen atom.
Since R3 is an organic group which is stable against an acid, more specifically, R3 is preferably an organic group having no "group capable of decomposing by the action of an acid to generate a polar group" described in the resin (A).
Examples of R3 may include an alkyl group having one or more CH3 partial structures.
The organic group having one or more CH3 partial structures, which is stable against an acid, as R3, preferably has 1 to 10 CH3 partial structures, more preferably 1 to 8 CH3 partial structures, and still more preferably 1 to 4 CH3 partial structures.
The alkyl group having one or more CH3 partial structures in R3 is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of the preferred alkyl group may include an isopropyl group, an isobutyl group, a 3-pentyl group, a 2-methyl-3 -butyl group, a 3-hexyl group, a 2-methyl-3-pentyl group, a 3 -methyl -4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and the like. The alkyl group is more preferably an isobutyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group or a 2,3,5,7-tetramethyl-4-heptyl group.
Specific examples of the alkyl group having two or more CH3 partial structures in R3 may include an isopropyl group, an isobutyl group, a t-butyl group, a 3-pentyl group, a 2,3-dimethylbutyl group, a 2-methyl-3-butyl group, a 3-hexyI group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, an isooctyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and the like. More preferably, the alkyl group is more preferably an alkyl group having 5 to 20 carbon atoms, such as an isopropyl group, a t-butyl group, a 2-methyl-3 -butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, a 2,4,4-trimethylpentyl group, a 2-ethylhexyl group, a 2,6-dimethylheptyl group, a l,5-dimethyl-3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group and a 2,6-dimethylheptyl group.
n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2
Preferred specific examples of the repeating unit represented by Formula (III) are shown below. However, the present invention is not limited thereto.
Figure imgf000126_0001
It is preferred that the repeating unit represented by Formula (III) is preferably a repeating unit which is stable against an acid (non-acid-decomposable), and specifically, a repeating unit having no group capable of decomposing by the action of an acid to generate a polar group.
The resin (C-3) may contain a repeating unit having at least one of a fluorine atom and a silicon atom as described above.
Suitable examples of the resin (C-3) may include a resin (C-3-a) having a repeating unit having a CH3 partial structure in a side chain, and a repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid, and
a resin (C-3-b) having a repeating unit having a CH3 partial structure in a side chain, and a basic group or a group capable of increasing the basicity by the action of an acid.
In the resin (C-3-a), specific examples and preferred range of the repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid may be exemplified by those described above.
In the resin (C-3 -a), the content of the repeating unit having a basic group or a group capable of increasing the basicity by the action of an acid is preferably 20 mol% to 80 mol%, more preferably 25 mol% to 70 mol%, and still more preferably 30 mol% to 60 mol% based on the whole repeating units of the resin (C-3-a).
In the resin (C-3-b), the content of the repeating unit having a CH3 partial structure in a side chain, and a basic group or a group capable of increasing the basicity by the action of an acid is preferably 20 mol% to 100 mol%, more preferably 25 mol% to 100 mol%, and still more preferably 30 mol% to 100 mol% based on the whole repeating units of the resin
(C-3-b).
In the resin (C-3-b), the repeating unit having a CH3 partial structure in a side chain, and a basic group or a group capable of increasing the basicity by the action of an acid is not particularly limited as long as the hydrogen atom constituting the side chain of at least one repeating unit (x) among the repeating unit represented by Formula (II) and the repeating unit represented by Formula (III) is substituted by a basic group or a group capable of increasing the basicity by the action of an acid, and further, a CH3 partial structure is present in the side chain.
Specific examples of the repeating unit having a CH3 partial structure in a side chain, and a basic group or a group capable of increasing the basicity by the action of an acid in the resin (C- -b) are shown below. However, the present invention is not limited thereto.
Figure imgf000127_0001
The content of the resin (C-3) is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and still more preferably 0.1 % by mass to 5% by mass based on the total solid of the composition.
The resin (C-3) may be commercially available or synthesized by a conventional method. A general synthesis method of the resin (C-3) may be exemplified by the method as described above with respect to the resin (A).
It is natural that the resin (C-3) has a small amount of impurities such as metal, but the residual amount of monomer and olygomer components is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and still more preferably 0 % by mass to 1% by mass. Accordingly, it is possible to reduce the change in sensitivity and the like over time by reducing the amount of extraneous substances in liquid.
The weight average molecular weight of the resin (C-3) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 7,500 to 15,000 in terms of polystyrene by the GPC method.
The polydispersity of the resin (C-3) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. By doing this, it is possible to achieve more excellent resolution, pattern shape and roughness characteristics.
[4] (D) Hydrophobic resin
Particularly when applied to liquid immersion exposure, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain a hydrophobic resin different from the component (C) (hereinafter, also referred to as a "hydrophobic resin (D) or simply referred to as a "resin (D)").
Accordingly, when the hydrophobic resin (D) is localized on the film top layer and the immersion medium is water, the static/dynamic contact angle of the resist film surface against water may be improved, thereby improving an immersion liquid follow-up property.
It is preferred that the hydrophobic resin (D) is designed to be localized at the interface as described above, but unlike a surfactant, the hydrophobic resin (D) does not necessarily have a hydrophilic group in the molecule thereof, and may not contribute to the mixing of polar/non-polar materials homogeneously.
From the viewpoint of the localization on the film top layer, the hydrophobic resin (D) has preferably one or more of "a fluorine atom", "a silicon atom" and "a CH3 partial structure contained in a side chain moiety of a resin", and more preferably two or more thereof.
In the case where the hydrophobic resin (D) contains a fluorine atom and/or a silicon atom, the fluorine atom and/or the silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin, or may be contained in the side chain thereof.
In the case where the hydrophobic resin (D) contains a fluorine atom, it is preferred that the resin has an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. Definition and preferred ranges of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom or the aryl group having a fluorine atom are the same as those in the component (C) as described above.
The partial structure containing a fluorine atom may be bonded directly to the main chain or may be bonded to the main chain via a group selected from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond, or a group formed by combining two or more thereof.
In the case where the hydrophobic resin (D) contains a fluorine atom, the hydrophobic resin (D) is preferably a resin having a repeating unit having a fluorine atom, andspecific examples of the repeating unit having a fluorine atom are the same as those as described above in the component (C).
The hydrophobic resin (D) may contain a silicon atom. It is preferred that the resin has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
Definition of the alkylsilyl structure or the cyclic siloxane structure is the same as the alkylsilyl structure or the cyclic siloxane structure in the component (C), and preferred ranges thereof are also the same.
In the case where the hydrophobic resin (D) contains a silicon atom, the hydrophobic resin (D) is preferably a resin having a repeating unit having a silicon atom, and specific examples of the repeating unit having a silicon atom are the same as those as described above in the component (C).
Further, as described above, it is also preferred that the hydrophobic resin (D) contains a CH3 partial structure in the side chain moiety.
Here, the CH3 partial structure (hereinafter, simply also referred to as a "side chain CH3 partial structure") possessed by the side chain moiety in the resin (D) includes a CH3 partial structure possessed by an ethyl group, a propyl group and the like.
Meanwhile, since a methyl group (for example, an a-methyl group of a repeating unit having a methacrylate structure) directly bonded to the main chain of the resin (D) makes a little contribution to surface localization of the resin (D) by the effect of the main chain, it is considered that such a methyl group is not included in the CH3 partial structure in the present invention.
The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH3 partial structure in the side chain, and definition of the CH3 partial structure and details of the repeating units are the same as those described above in the component (C).
In the case where the resin (D) contains a CH3 partial structure in the side chain moiety and particularly has no fluorine atom and silicon atom, the content of at least one repeating unit (x) among the repeating unit represented by Formula (II) and the repeating unit represented by Formula (III) is preferably 90 mol% or more, and more preferably 95 mol% or more, based on the whole repeating units of the resin (C). The content is usually 100 mol% or less based on the whole repeating units of the resin (C).
The resin (D) contains at least one repeating unit (x) among the repeating unit represented by Formula (II) and the repeating unit represented by Formula (III) in an amount of 90 mol% or more based on all the repeating units of the resin (D), thereby increasing the surface free energy of the resin (C). As a result, it is difficult for the resin (D) to be localized on the surface of the resist film, and thus the static/dynamic contact angle of the resist film against water may be certainly improved, thereby improving an immersion liquid follow-up property.
Further, even in the case where the hydrophobic resin (D) contains (i) a fluorine atom and/or a silicon atom and the case where the hydrophobic resin (D) includes (ii) a CH3 partial structure in the side chain moiety, the hydrophobic resin (D) may have at least one group selected from the group of following (x) to (z).
(x) an acid group
(y) a group having a lactone structure, an acid anhydride group or an acid imide group, and
(z) a group capable of decomposing by the action of an acid
Examples of the acid group (x) may include a phenolic hydroxyl group, a carboxylate group, a fluorinated alcohol group, a sulfonate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an
(alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group and the like.
Preferred examples of the acid group may include a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group and a bis(alkylcarbonyl)methylene group.
Examples of the repeating unit having the acid group (x) may include a repeating unit in which the acid group is directly bonded to the main chain of the resin, such as repeating unit by an acrylic acid or a methacrylic acid, a repeating unit in which the acid group is bonded to the main chain of the resin via a linking group or the like. Further, the repeating unit may also be introduced into the end of the polymer chain by using a polymerization initiator having an acid group or a chain transfer agent at the time of polymerization, and all of these cases are preferred. The repeating unit having the acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having the acid group (x) is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 35 mol%, and still more preferably 5 mol% to 20 mol%, based on the whole repeating units in the hydrophobic resin (D).
Specific examples of the repeating unit having the acid group (x) are shown below, but the present invention is not limited thereto. In the formulas, Rx represents a hydrogen atom, CH3, CF3 or CH2OH.
131
Figure imgf000132_0001
Figure imgf000133_0001
As (y) the group having a lactone structure, the acid anhydride group or the acid imide group, a group having a lactone structure is particularly preferred.
Examples of the repeating unit containing these groups may include a repeating unit in which the group is directly bonded to the main chain of the resin, such as a repeating unit by an acrylate ester or a methacrylate ester. Or, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin through a linking group. Or, the repeating unit may be introduced into the end of the resin by using a polymerization initiator or a chain transfer agent having the group at the time of polymerization.
Examples of the repeating unit having a group having a lactone structure are the same as those of the repeating unit having a lactone structure described in the paragraph of acid-decomposable resin (A).
The content of the repeating unit having a group having a lactone structure, an acid anhydride group or an acid imide group is preferably 1 mol% to 100 mol%, more preferably 3 mol% to 98 mol%, and still more preferably 5 mol% to 95 mol%, based on the whole repeating units in the hydrophobic resin (D).
Examples of the repeating unit having (z) a group capable of decomposing by the action of an acid in the hydrophobic resin (D) are the same as those of the repeating unit having an acid-decomposable group exemplified in the resin (A). The repeating unit having (z) a group capable of decomposing by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (D), the content of the repeating unit having (z) a group capable of decomposing by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, and still more preferably 20 mol% to 60 mol%, based on the whole repeating units in the resin (D).
The hydrophobic resin (D) may further have a repeating unit represented by the following Formula (III).
Figure imgf000134_0001
In Formula (III),
Rc31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group or a -CH2-0-Rac2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group or an acyl group. Rc3i is preferably a hydrogen atom, a methyl group, a hydroxymethyl group and a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.
Rc32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.
Lc3 represents a single bond or a divalent linking group.
In Formula (III), the alkyl group of Rc32 is preferably a straight or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group or a naphthyl group, and these groups may have a substituent.
Rc32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of Lc3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group or an ester bond (a group represented by
-COO-).
The content of the repeating unit represented by Formula (III) is preferably 1 mol% to 100 mol%, more preferably 10 mol% to 90 mol%, and still more preferably 30 mol% to 70 mol%, based on the whole repeating units in the hydrophobic resin.
It is also preferred that the hydrophobic resin (D) further has a repeating unit represented by the following Formula (CII-AB).
Figure imgf000135_0001
( C I I - A B )
In Formula (CII-AB),
Rcii' and Rd2' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc' represents an atomic group including two carbon atoms (C-C) bonded to form an alicyclic structure.
The content of the repeating unit represented by Formula (CII-AB) is preferably 1 mol% to 100 mol%, more preferably 10 mol% to 90 mol%, and still more preferably 30 mol% to 70 mol%, based on the whole repeating units in the hydrophobic resin.
Specific examples of the repeating units represented by Formulas (III) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formulas, Ra represents H, CH3, CH2OH, CF3 or CN.
Figure imgf000135_0002
In the case where the hydrophobic resin (D) has a fluorine atom, the content of the fluorine atom is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% by mass based on the weight average molecular weight of the hydrophobic resin (D). Further, the content of the repeating unit containing a fluorine atom is preferably 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol% based on the whole repeating units contained in the hydrophobic resin (D).
In the case where the hydrophobic resin (D) has a silicon atom, the content of the silicon atom is preferably 2% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass based on the weight average molecular weight of the hydrophobic resin (D). Further, the content of the repeating unit containing a silicon atom is preferably 10 mol% to 100 mol%, and more preferably 20 mol% to 100 mol%, based on the whole repeating units contained in the hydrophobic resin (D).
Meanwhile, particularly in the case where the resin (D) contains a CH3 partial structure in the side chain moiety, it is also preferred that the resin (D) contains substantially no fluorine atom and silicon atom, and in this case, specifically, the content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, and still more preferably 1 mol% or less based on the whole repeating units in the resin (D), and is ideally 0 mol%, that is, the repeating unit contains no fluorine atom and silicon atom. Further, it is preferred that the resin (D) substantially contains only a repeating unit composed of only atoms selected from the group consisting of a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is present in an amount of preferably 95 mol% or more, more preferably 97 mol% or more, still more preferably 99 mol% or more, and ideally 100 mol% based on the whole repeating units of the resin (D).
The weight average molecular weight of the hydrophobic resin (D) in terms of the standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
Further, the hydrophobic resin (D) may be used either alone or in combination of a plurality thereof.
The content of the hydrophobic resin (D) in the composition is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, and still more preferably 0.1% by mass to 5% by mass, based on the total solid in the composition of the present invention.
Similarly to the resin (A), It is natural that the hydrophobic resin (D) has a small amount of impurities such as metal, but the content of residual monomers or oligomer components is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, and still more preferably 0.05% by mass to 1% by mass. Accordingly, it is possible to obtain an actinic ray-sensitive or radiation-sensitive resin composition free from extraneous substances in liquid and change in sensitivity and the like over time. Further, from the viewpoint of resolution, resist shape, side wall of resist pattern, roughness and the like, the molecular weight distribution (Mw/Mn, also referred to as polydispersity) is in a range of preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2.
The hydrophobic resin (D) may be commercially available or synthesized by a conventional method. Examples of a general synthesis method may include a batch polymerization method of dissolving monomer species and an initiator in a solvent and heating the solution, thereby performing the polymerization, a dropping polymerization method of adding dropwise a solution containing monomer species and an initiator to a heated solvent over 1 to 10 hours, and the like, and a dropping polymerization method is preferred.
The reaction solvent, polymerization initiator, reaction conditions (temperature, concentration and the like) and purification method after reaction are the same as those described in the resin (A), but in the synthesis of the hydrophobic resin (D), the reaction concentration is preferably 30% by mass to 50% by mass.
Specific examples of the hydrophobic resin (D) are shown below. Further, the molar ratio (corresponding to each repeating unit sequentially from the left), the weight average molecular weight and the polydispersity of the repeating unit in each resin are shown in the following Table.
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000139_0002
(HR-45) (HR-46) (HR-47) (HR-48)
Figure imgf000140_0001
(HR-49) (Hf,.^, (HR-51) (HR-52)
Figure imgf000140_0002
(HR-64) (HR.85)
Table 1
Resin Composition Mw Mw/Mn
HR-1 50/50 4900 1.4
HR-2 50/50 5100 1.6
HR-3 50/50 4800 1.5
HR-4 50/50 5300 1.6
HR-5 50/50 4500 1.4
HR-6 100 5500 1.6
HR-7 50/50 5800 1.9
HR-8 50/50 4200 1.3
HR-9 50/50 5500 1.8
HR-10 40/60 7500 1.6
HR-11 70/30 6600 1.8
HR-12 40/60 3900 1.3
HR-13 50/50 9500 1.8
HR-14 50/50 5300 1.6
HR-15 100 6200 1.2
HR-16 100 5600 1.6
HR-17 100 4400 1.3
HR-18 50/50 4300 1.3
HR-19 50/50 6500 1.6
HR-20 30/70 6500 1.5
HR-21 50/50 6000 1.6
HR-22 50/50 3000 1.2
HR-23 50/50 5000 1.5
HR-24 50/50 4500 1.4
HR-25 30/70 5000 1.4
HR-26 50/50 5500 1.6
HR-27 50/50 3500 1.3
HR-28 50/50 6200 1.4
HR-29 50/50 6500 1.6
HR-30 50/50 6500 1.6
Figure imgf000141_0001
HR-31 50/50 4500 1.4
HR-32 30/70 5000 1.6
HR-33 30/30/40 6500 1.8
HR-34 50/50 4000 1.3
HR-35 50/50 6500 1.7
Figure imgf000142_0001
Figure imgf000143_0001
(C-22) (C-23) (C-24)
Figure imgf000143_0002
Figure imgf000144_0001
(D-2)
Figure imgf000144_0002
(D-3) (D-4)
Figure imgf000144_0003
(D-5) (D-6)
Figure imgf000144_0004
(D-7) (D-8)
Figure imgf000144_0005
(D-9) (D-10)
Figure imgf000145_0001
(D-13)
Figure imgf000145_0002
(D-15)
Table 2
Resin Composition Mw Mw/Mn
C-l 50/50 9600 1.74
C-2 60/40 34500 1.43
C-3 30/70 19300 1.69
C-4 90/10 26400 1.41
C-5 100 27600 1.87
C-6 80/2 4400 1.96
C-l 100 16300 1.83
C-8 5/95 24500 1.79
C-9 20/80 15400 1.68
C-10 50/50 23800 1.46
C-l l 100 22400 1.57
C-12 10/90 21600 1.52
C-13 100 28400 1.58
C-14 50/50 16700 1.82
C-15 100 23400 1.73
C-16 60/40 18600 1.44
C-17 80/20 12300 1.78
C-18 40/60 18400 1.58
C-19 70/30 12400 1.49
C-20 50/50 23500 1.94
C-21 10/90 7600 1.75
C-22 5/95 14100 1.39
C-23 50/50 17900 1.61
C-24 10/90 24600 1.72
C-25 50/40/10 23500 1.65
C-26 60/30/10 13100 1.51
C-27 50/50 21200 1.84
C-28 10/90 19500 1.66 Table 3
Figure imgf000147_0001
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin containing at least one of a fluorine atom and a silicon atom. Accordingly, the hydrophobic resin is localized on the film top layer formed of the actinic ray-sensitive or radiation-sensitive resin composition, and thus, when the immersion medium is water, the receding contact angle of the film surface against water after baking and before exposing may be improved, thereby improving an immersion liquid follow-up property.
The receding contact angle after baking the coating film formed of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and befor exposing the coating film is preferably 60° to 90°, more preferably 65° or more, still more preferably 70°, and particularly preferably 75° at an exposure temperature, usually at a temperature of 23±3°C and a humidity of 45±5%.
The hydrophobic resin is localized at the interface as described above, but unlike a surfactant, the hydrophobic resin does not necessarily have a hydrophilic group in the molecule thereof, and may not contribute to the mixing of polar/non-polar materials homogeneously.
In the liquid immersion exposure process, the liquid for liquid immersion needs to move on a wafer following the movement of an exposure head that scans on the wafer at a high speed and forms an exposure pattern, and thus the contact angle of the liquid for liquid immersion for the resist film in a dynamic state is important, and a performance of allowing the exposure head to follow the high-speed scanning is required for the resist while a liquid droplet no longer remains.
Since the hydrophobic resin is hydrophobic, the development scum and BLOB defect are prone to deteriorate after alkali development, but by virtue of having three or more polymer chains through at least one brance part, the alkali dissolution rate is enhanced as compared with a straight resin, thereby improving the development scum and BLO defect performances.
In the case where the hydrophobic resin has a fluorine atom, the content of the fluorine atom is preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 80% by mass based on the weight molecular weight of the hydrophobic resin. Further, the repeating unit containing a fluorine atom is preferably in an amount of 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol% based on the whole repeating units of the hydrophobic resin.
In the case where the hydrophobic resin has a silicon atom, the content of the silicon atom is preferably 2% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass based on the weight molecular weight of the hydrophobic resin. Further, the repeating unit containing a silicon atom is preferably in an amount of 10 mol% to 90 mol%, and more prerferably 20 to 80 mol% based on the whole repeating units of the hydrophobic resin.
The weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 35,000. Here, the weight average molecular weight of the resin represents a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).
The hydrophobic resin may be used by appropriately adjusting its content in the actinic ray-sensitive or radiation-sensitive resin composition such that the receding contact angle of the resist film is within the above range, but the content thereof is preferably 0.01% by mass to 20% by mass, more preferably 0.1 % by mass to 15% by mass, still more preferably 0.1 % by mass to 10%) by mass, and particlurly preferably 0.2% by mass to 8% by mass based on the total solid of the actinic ray-sensitive or radiation-sensitive resin composition.
The hydrophobic resin may be used either alone or in combination of two or more thereof.
[5-1] (N) Basic compound or ammonium salt compound whose basicity decreases upon irradiation with an actinic ray or radiation
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may contain a basic compound or an ammonium salt compound (hereinafter, also referred to as a "compound (N)") whose basicity decreases upon irradiation with an actinic ray or radiation.
The compound (N) is preferably a compound (N-1) having a basic functional group or an ammonium group and a group capable of generating an acidic functional group upon irradiation with an actinic ray or radiation. That is, the compound (N) is preferably a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with an actinic ray or radiation, or an ammonium salt compound having an ammonium group and a group capable of generating an acidic functional group upon irradiation with an actinic ray or radiation.
Examples of the compounds which is generated by decomposing the compound (N) or (N-1) upon irradiation with an actinic ray or radiation and whose basicity decreases may include compounds represented by the following Formulas (PA-I), (PA-II) or (PA-III), and from the viewpoint of enhancing excellent effects relating to LWR, uniformity of a local pattern dimension and DOF to a high level, the compounds represented by Formula (PA-II) or (PA-III) are particularly preferred.
First, the compounds represented by Formula (PA-I) will be described.
Q-A,-(X)n-B-R (PA-I)
In Formula (PA-I),
Ai represents a single bond or a divalent linking group.
Q represents -SO3H, or -C02H. Q corresponds to an acidic functional group generated upon irradiation with an actinic ray or radiation.
X represents -S02- or -CO-.
B represents a single bond, an oxygen atom or -N(Rx)-.
Rx represents a hydrogen atom, or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.
The divalent linking group in Ai is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof may include an alkylene group, a phenylene group and the like. The divalent linking group is more preferably an alkylene group having at least one fluorine atom, and has preferably 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. The alkylene chain may have a linking group such as an oxygen atom and sulfur atom. The alkylene group is preferably an alkylene group in which 30% to 100% of the number of the hydrogen atom is substituted by a fluorine atom, and more preferably an alkylene group in which the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferred, and a perfiuoroethylene group, a perf uoropropylene group and a perfluorobutylene group are more preferred.
The monovalent organic group in Rx preferably has 4 to 30 carbon atoms, and examples thereof may include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like.
The alkyl group in Rx may have a substituent, is preferably a straight or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain.
Meanwhile, examples of the alkyl group having a substituent may particularly include a group in which a straight or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue structure and the like).
The cycloalkyl group in Rx may have a substituent, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.
The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group in Rx may have a substituent and is preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group in Rx may have a substituent, and examples thereof may include a group having a double bond at an arbitrary position of the alkyl group exemplified as Rx.
Examples of a preferred partial structure of the basic functional group may include a structure such as crown ether, primary to tertiary amine, and a nitrogen-containing heterocyclic ring (pyridine, imidazole, pyrazine and the like).
Examples of the preferred partial structure of the ammonium group may include a primary to tertiary ammonium structure, a pyridinium structure, an imidazolinium structure, a pyrazinium structure and the like.
Meanwhile, the basic functional group is preferably a functional group having a nitrogen atom, and more preferably a structure having a primary to tertiary amino group, or a nitrogen-containing heterocyclic structure. In these structures, from the viewpoint of improving basicity, it is preferred that all atoms adjacent to the nitrogen atom contained in the structure are a carbon atom or a hydrogen atom. In addition, from the viewpoint of improving basicity, it is preferred that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom and the like) is not directly bonded to the nitrogen atom.
The monovalent organic group in the monovalent organic group (group R) containing the structure preferably has 4 to 30 carbon atoms, examples thereof may include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like, and each group may have a substituent.
The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group in the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group containing a basic functional group or an ammonium group in R are the same as the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group, respectively, exemplified as Rx.
Examples of the substituent which may be possessed by each group may include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like. For the cyclic structure in the aryl group, the cycloalkyl group and the like, examples of the substituent thereof may also include an alkyl group (preferably having 1 to 20 carbon atoms). For the aminoacyl group, examples of the substituent thereof may also include one or two alkyl groups (preferably having 1 to 20 carbon atoms).
When B is -N(Rx)-, R and Rx preferably are bound with each other to form a ring. By forming a ring structure, the stability is improved, and thus, the storage stability of the composition using the same is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and the ring may be monocyclic or polycyclic and may contain an oxygen atom, a sulfur atom or a nitrogen atom therein.
Examples of the monocyclic structure may include a 4- to 8-membered ring including a nitrogen atom and the like. Examples of the polycyclic structure may include a structure having a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent, and preferred examples of the substituent may include a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 15 carbon atoms), an acyloxy group (preferably having 2 to 15 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 15 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like. For the cyclic structure in the aryl group, the cycloalkyl group and the like, examples of the substituent thereof may also include an alkyl group (preferably having 1 to 15 carbon atoms). For the aminoacyl group, examples of the substituent thereof may include one or two alkyl groups (preferably having 1 to 15 carbon atoms).
Among the compounds represented by Formula (PA-I), a compound in which the Q site is a sulfonic acid may be synthesized by using a general sulfonamidation reaction. For example, the compound may be obtained by a method of selectively reacting one sulfonyl halide moiety of a bis-sulfonyl halide compound with an amine compound to form a sulfonamide bond and then hydrolyzing the other sulfonyl halide moiety, or a method of ring-opening a cyclic sulfonic acid anhydride through reaction with an amine compound.
Subsequently, compounds represented by Formula (PA-II) will be described.
Q,-Xi-NH-X2-Q2 (PA-II)
In Formula (PA-II),
Q] and Q2 each independently represent a monovalent organic group. However, any one of Qi and Q2 has a basic functional group. Qj and Q2 may be bound with each other to form a ring, and the ring formed may have a basic functional group.
Xi and X2 each independently represent -CO- or -S02-.
Meanwhile, -NH- corresponds to an acidic functional group generated upon irradiation with an actinic ray or radiation.
The monovalent organic group as Qj and Q2 in Formula (PA-II) preferably has 1 to 40 carbon atoms, and examples thereof may include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like.
The alkyl group in Q\ and Q2 may have a substituent and is preferably a straight or branched alkyl group having 1 to 30 carbon atoms, and the alkyl chain may have an oxygen atom, a sulfur atom or a nitrogen atom.
The cycloalkyl group in Qj and Q2 may have a substituent, is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom and a nitrogen atom in the ring.
The aryl group in Qi and Q2 may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group in Qj and Q2 may have a substituent, and is preferably an aralkyl group having 7 to 20 carbon atoms. The alkenyl group in Qi and Q2 may have a substituent, and examples thereof may include a group having a double bond at an arbitrary position of the alkyl group.
Examples of the substituent which may be possessed by each group may include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), an aminoacyl group (preferably having 2 to 10 carbon atoms) and the like. For the cyclic structure in the aryl group, the cycloalkyl group and the like, examples of the substituent thereof may also include an alkyl group (preferably having 1 to 10 carbon atoms). For the aminoacyl group, examples of the substituent thereof may aslo have an alkyl group (preferably having 1 to 10 carbon atoms). Examples of the alkyl group having a substituent may include a perfluoroalkyl group such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group and a perfluorobutyl group.
Preferred partial structures of the basic functional group possessed by at least one of Qi and Q2 has are the same as those described as the basic functional group possessed by R of Formula (PA-I).
Examples of the structure in which Qi and Q2 are bound with each other to form a ring and the ring formed has a basic functional group may include a structure in which the organic groups of Qi and Q2 are further bonded with an alkylene group, an oxy group, an imino group or the like.
In Formula (PA-II), at least one of Xi and X2 is preferably -S02-.
Subsequently, compounds represented by Formula (PA-III) will be described.
Q1-X1-NH-X2-A2-(X3)m-B-Q3 (PA-III)
In Formula (PA-III),
Qi and Q3 each independently represent a monovalent organic group. However, any one of Q\ and Q3 has a basic functional group. Q\ and Q3 may be bound with each other to form a ring, and the ring formed may have a basic functional group.
Xi, X2 and X3 each independently represent -CO- or -S02-.
A2 represents a divalent linking group.
B represents a single bond, an oxygen atom or -N(Qx)-.
Qx represents a hydrogen atom, or a monovalent organic group.
When B is -N(Qx)-, Q3 and Qx may be bound with each other to form a ring. m represents 0 or 1.
Meanwhile, -NH- corresponds to an acidic functional group generated upon irradiation with an actinic ray or radiation.
Qi has the same meaning as Q\ in Formula (PA-II).
Examples of the organic group of Q3 are the same as those of the organic groups of Qi and Q2 in Formula (PA-II).
Further, examples of the structure in which Q\ and Q3 are bound with each other to form a ring and the ring formed has a basic functional group may include a structure in which the organic groups of Qi and Q3 are further bound with an alkylene group, an oxy group, an imino group or the like.
The divalent linking group in A2 is preferably a divalent linking group having 1 to 8 carbon atoms and having a fluorine atom, and examples thereof may include an alkylene group having 1 to 8 carbon atoms and having a fluorine atom, a phenylene group having a fluorine atom and the like. The divalent linking group is more preferably an alkylene group having a fluorine atom, and has preferably 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms. The alkylene chain may have a linking group such as an oxygen atom and a sulfur atom. The alkylene group is preferably an alkylene group in which 30% to 100% of the number of the hydrogen atoms is substituted by a fluorine atom, preferably a perfluoroalkylene group, and particularly preferably a perfluoroalkylene group having 2 to 4 carbon atoms.
The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof may include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. Examples of the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group are the same as those for PX in Formula (PA-I).
In Formula (PA-III), Xls X2 and X3 are preferably -S02-.
The compound (N) is preferably a sulfonium salt compound of the compound represented by Formula (PA-I), (PA-II) or (PA-III), or an iodonium salt compound of the compound represented by Formula (PA-I), (PA-II) or (PA-III), and more preferably a compound represented by the following Formula (PA1) or (PA2).
Figure imgf000155_0001
In Formula (PA1),
R'20i , R'202 and R'203 each independently represent an organic group, and specific examples thereof are the same as those for R201, R202 and R203 of Formula ZI in the component
(B).
X" represents a sulfonate anion or a carboxylate anion in which a hydrogen atom is elimitated in the -S03H moiety or -COOH moiety of the compound represented by Formula (PA-I), or an anion in which a hydrogen atom is eliminated from the -NH- moiety of the compound represented by Formula (PA- II) or (PA-III).
In Formula (PA2),
R'204 and R'205 each independently represent an aryl group, an alkyl group or a cycloalkyl group, and specific examples thereof are the same as those for R204 and R205 of Formula ZII in the component (B).
X" represents a sulfonate anion or a carboxylate anion in which a hydrogen atom is eliminated in the -S03H moiety or -COOH moiety of the compound represented by Formula (PA-I), or an anion in which a hydrogen atom is eliminated from the -NH- moiety of the compound represented by Formula (PA- II) or (PA-III).
The compound (N) decomposes upon irradiation with an actinic ray or radiation to generate, for example, a compound represented by Formula (PA-I), (PA- II) or (PA-III).
The compound represented by Formula (PA-I) is a compound which is reduced in or deprived of the basicity, or is changed from the basicity to acidity by having a sulfonic acid group or a carboxylic acid group together with a basic functional group or an ammonium group, as compared to the compound (N).
The compound represented by Formula (PA-II) or (PA-III) is a compound which is reduced in or deprived of the basicity or is changed from the basicity to acidity by having an organic sulfonylimino group or an organic carbonylimino group together with a basic functional group, as compared to the compound (N).
In the present invention, decrease in the basicity upon irradiation with an actinic ray or radiation means that the acceptor property for a proton (an acid generated upon irradiation with an actinic ray or radiation) of the compound (N) decreases upon the irradiation with an actinic ray or radiation. The decrease in the acceptor property means that when an equilibrium reaction of producing a non-covalent bond complex as a proton adduct takes place from a basic functional group-containing compound and a proton or when an equilibrium reaction of letting the counter cation of the ammonium group-containing compound be exchanged with a proton takes place, the equilibrium constant in the chemical equilibrium decreases.
In this manner, the compound (N) whose basicity decreases upon irradiation with an actinic ray or radiation is contained in the resist film, so that in the unexposed portion, the acceptor property of the compound (N) may be sufficiently expressed, and thus an unintended reaction of an acid diffused from the exposed portion or the like with the resin (A) may be suppressed, and simultaneously in the exposed portion, the acceptor property of the compound (N) decreases, and thus the intended reaction of an acid with the resin (A) more certainly occurs, and in the degree of contribution of the operation mechanism, it is assumed that a pattern excellent in terms of line width roughness (LWR), uniformity of local pattern dimension, depth of focus (DOF) and pattern shape may be obtained.
Meanwhile, the basicity may be confirmed by measuring the pH, and a calculated value may be calculated by commercially available software.
Hereinafter, specific examples of the compound (N) capable of generating a compound represented by Formula (PA-I) upon irradiation with an actinic ray or radiation will be described, but the present invention is not limited thereto.
Figure imgf000157_0001
Figure imgf000158_0001
These compounds may be easily synthesized from a compound represented by Formula (P A-I) or a lithium, sodium or potassium salt thereof and a hydroxide, bromide, chloride or the like of iodonium or sulfonium, by using the salt exchange method described in Japanese Patent Application Publication No. HI 1-501909 or Japanese Patent Application Laid-Open No. 2003-246786. Further, the synthesis may also be performed in accordance with the synthesis method described in Japanese Patent Application Laid-Open No. H7-333851.
Hereinafter, specific examples of the compound (N) capable of generating a compound represented by Formula (PA-II) or (PA-III) upon irradiation with an actinic ray or radiation will be described, but the present invention is not limited thereto.

Figure imgf000159_0001
Figure imgf000160_0001
These compounds may be easily synthesized by using a general sulfonate esterification reaction or sulfonamidation reaction. For example, the compound may be obtained by a method of selectively reacting one sulfonyl halide moiety of a bis-sulfonyl halide compound with an amine, alcohol or the like including a partial structure represented by Formula (PA-II) or (PA-III) to form a sulfonamide bond or a sulfonate ester bond and then hydrolyzing the other sulfonyl halide moiety, or a method of ring-opening a cyclic sulfonic acid anhydride by an amine or alcohol including a partial structure represented by Formula (PA-II). The amine or alcohol including a partial structure represented by Formula (PA-II) or (PA-III) may be synthesized by reacting an amine or an alcohol with an anhydride such as (R'02C)20, (R'S02)20 and the like or an acid chloride compound such as R'02CC1 and R'S02C1 (R' is a methyl group, a n-octyl group or a trifluoromethyl group) under basicity conditions. In particular, the synthesis may be performed in accordance with synthesis examples and the like in Japanese Patent Application Laid-Open No. 2006-330098.
The molecular weight of the compound (N) is preferably 500 to 1,000.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain the compound (N), but in the case of containing the compound (N), the content of the compound (N) is preferably 0.1% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass, based on the solid of the actinic ray-sensitive or radiation-sensitive resin composition.
[5-2] (Ν') Basic Compound
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may contain a basic compound (Ν') different from the resin (A) in order to reduce the change in performance over time from exposure to heating.
Preferred examples of the basic compound (Ν') may include compounds having a structure represented by the following Formulas (Α') to (Ε').
RA20' I I RA20 | RA205 RA200_N _RA202 — N— C =N - =c_N— c— =o— Nl— RA2 D3 -C N C-RA206
(Α') (B"> (O (D-) ( Ε')
In Formulas (Α') to (Ε'),
RA 's, RA 's and RA 's may be the same as or different, and represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having 6 to 20 carbon), and RA201 and RA202 may be bound with each other to form a ring. RA203's, RA204's, RA205's and RA 's may be the same as or different, and represent an alkyl group (preferably having 1 to 20 carbon atoms). The alkyl group may have a substituent, and the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl group in Formulas (Α') to (Ε') is more preferably unsubstituted.
Preferred specific examples of the basic compound (Ν') may include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred specific examples thereof may include a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond and the like.
Examples of the compound having an imidazole structure may include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Examples of the compound having a diazabicyclo structure may include l,4-diazabicyclo[2,2,2]octane,
1.5- diazabicyclo[4,3,0]non-5-ene, l,8-diazabicyclo[5,4,0]undec-7-ene and the like. Examples of the compound having an onium hydroxide structure may include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, a sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like. Examples of the compound having an onium carboxylate structure may include a compound, in which the anion moiety of a compound having an onium hydroxide structure has been converted into carboxylate, such as acetate, adamantane-1 -carboxylate and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure may include tri(n-butyl)amine, tri(n-octyl)amine and the like. Examples of the compound having an aniline structure may include
2.6- diisopropylaniline, Ν,Ν-dimethylaniline, N,N-dibutylaniline, Ν,Ν-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond may include ethanolamine, diethanolamine, triethanolamine, tris(memoxyethoxyethyl)amine and the like. Examples of the aniline derivative having a hydroxyl group and/or an ether bond may include N,N-bis(hydroxyethyl)aniline and the like.
Examples of the preferred basic compound may further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate ester group, and an ammonium salt compound having a sulfonate ester group. It is preferred that the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate ester group, and the ammonium salt compound having a sulfonate ester group have at least one alkyl group bonded to a nitrogen atom. Further, it is preferred that the alkyl chain has an oxygen atom therein to form an oxyalkylene group. The number of the oxyalkylene groups is one or more, preferably 3 to 9, and more preferably 4 to 6, in the molecule. Among the oxyalkylene groups, the structures of -CH2CH20-, CH(CH3)CH20- or -CH2CH2CH20- are preferred.
Specific examples of the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate ester group, and the ammonium salt compound having a sulfonate ester group may include compounds (C 1 - 1 ) to (C3-3) as exemplified in paragraph [0066] of U.S. Patent Application Laid-Open No. 2007/0224539, but are not limited thereto.
Further, a nitrogen-containing organic compound having a group capable of leaving by the action of an acid may also be used as a kind of the basic compound. Examples of the compound may include a compound represented by the following Formula (F). Meanwhile, the compound represented by the following Formula (F) exhibits an effective basicity in the system as a result of leaving of the group capable of leaving by the action of an acid.
Figure imgf000163_0001
In Formula (F), Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Further, when n=2, two Ra's may be the same as or different, and two Ra's may be bound with each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof.
Rb's independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. However, in -C(Rb)(Rb)(R ), when one or more Rb's are a hydrogen atom, at least one of remaining RbS is a cyclopropyl group or a 1-alkoxy alkyl group.
At least two Rb's may be bound with each other to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n+m=3.
In Formula (F), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group represented by Ra and Rb may be substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group and an oxo group, an alkoxy group or a halogen atom.
Examples of the alkyl group, the cycloalkyl group, the aryl group or the aralkyl group (the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group may be substituted with the functional group, an alkoxy group or a halogen atom) of the R may include
a group derived from a straight or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane and dodecane, a group in which the group derived from the alkane is substituted with one or more kinds of or one or more of cycloalkyl groups such as, for example, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group,
a group derived from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane and noradamantane, a group in which the group derived from the cycloalkane is substituted with one or more kinds of or one or more of straight or branched alkyl groups such as, for example, a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group and a t-butyl group,
a group derived from an aromatic compound such as benzene, naphthalene and anthracene, a group in which the group derived from the aromatic compound is substituted with one or more kinds of or one or more of straight or branched alkyl groups such as, for example, a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group and a t-butyl group, and
a group derived from a heterocyclic compound such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole and benzimidazole, a group in which the group derived from the heterocyclic compound is substituted with one or more kinds of or one or more of straight or branched alkyl groups or groups derived from aromatic compounds, a group in which the group derived from a straight or branched alkane or the group derived from a cycloalkane is substituted with one or more kinds of or one or more of groups derived from aromatic compounds, such as a phenyl group, a naphthyl group and an anthracenyl group, a group in which the aforementioned substituent is substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group and an oxo group, and the like.
Further, examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) in which Ra's are bound with each other to form or a derivative thereof may include a group derived from a heterocyclic compound such as pyrrolidine, piperidine, morpholine, 1 ,4,5, 6-tetrahydropyrimi dine, 1 ,2,3,4-tetrahydroquinoline,
1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, lH-l,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo[l,2-a]pyridine, (lS,4S)-(+)-2,5-diazabicyclo[2.2.1]heptane, l,5,7-triazabicyclo[4.4.0]dec-5-ene, indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline and 1,5,9-triazacyclododecane, a group in which the group derived from the heterocyclic compound is substituted with one or more kinds of or one or more of straight or branched groups derived from alkane, groups derived from cycloalkane, groups derived from aromatic compounds, groups derived from heterocyclic compounds and functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group and an oxo group, and the like.
Specific examples of the compound represented by Formula (F) will be described below.
Figure imgf000166_0001
Figure imgf000167_0001
(D-52) (D-53) (D-54) (D-55)
The compound represented by Formula (F) may be commercially available or synthesized from a commercially available amine by the method described in Protective Groups in Organic Synthesis, 4th Edition and the like. The compound may be synthesized in accordance with the method described in, for example, Japanese Patent Application Laid-Open No. 2009-199021, as the most general method.
Further, a compound having an amine oxide structure may also be used as the basic compound (Ν'). Specific examples of the compound may include triethylamine pyridine N-oxide, tributylamine N-oxide, triethanolamine N-oxide, tris(methoxyethyl)amine N-oxide, tris(2-(methoxymethoxy)ethyl)amine=oxide, 2,2',2"-nitrilotriethylpropionate N-oxide, N-2-(2-methoxyethoxy)methoxyethylmorpholine N-oxide, and an amine oxide compound exemplified in Japanese Patent Application Laid-Open No. 2008-102383. Further, as the basic compound (Ν'), a sulfonic acid compound having no fluorine atom, a compound capable of generating a sulfonic acid compound having no fluorine atom upon irradiation with an actinic ray or radiation, a carboxylic acid compound, a compound capable of generating a carboxylic acid compound upon irradiation with an actinic ray or radiation may be used. The reason is that, if the compound has a relatively weaker acidic functional group than the acid generated from the aforementioned acid generator (compound (B)), the compound can capure a proton derived from the acid generator which generates a relatively strong acid, thereby functioning as a "basic compound".
The molecular weight of the basic compound (Ν') is preferably 250 to 2,000, and more preferably 400 to 1,000. From the viewpoint of more reduction in LWR and uniformity of local pattern dimension, the molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more.
These basic compounds (Ν') may be used in combination with the compound (N), and are used either alone or in combination of two or more thereof.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain the basic compound (Ν'), but in the case of containing the basic compound (Ν'), the amount of the basic compound (Ν') used is usually 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 5% by mass, based on the solid of the actinic ray-sensitive or radiation-sensitive resin composition.
[6] (E) Solvent
The actinic ray-sensitive or radiation-sensitive resin composition usually contains a solvent (E).
Examples of the solvent which may be used at the time of preparing the actinic ray-sensitive or radiation-sensitive resin composition in the present invention may include an organic solvent such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl ester lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate and alkyl pyruvate.
Specific examples of these solvents may include those described in paragraphs [0441] to [0455] of U.S. Patent Application Publication No. 2008/0187860.
In the present invention, a mixed solvent in which a solvent containing a hydroxyl group and a solvent containing no hydroxyl group in the structure thereof are mixed may be used as an organic solvent.
As the solvent containing a hydroxyl group and the solvent containing no hydroxyl group, the aforementioned exemplary compound may be appropriately selected, and the solvent containing a hydroxyl group is preferably alkylene glycol monoalkyl ether, alkyl lactate or the like, and more preferably propylene glycol monomethyl ether (PGME, another name l-methoxy-2-propanol) or ethyl lactate. Further, the solvent containing no hydroxyl group is preferably alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, a monoketone compound which may contain a ring, a cyclic lactone, alkyl acetate or the like, and among them, particularly preferably propylene glycol monomethyl ether acetate (PGMEA, another name l-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone or butyl acetate, and most preferably propylene glycol monomethyl ether acetate, ethyl ethoxypropionate or 2-heptanone.
The mixing ratio (by mass) of the solvent containing a hydroxyl group to the solvent containing no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent in which the solvent containing no hydroxyl group is contained in an amount of 50% by mass or more is particularly preferred from the viewpoint of coating uniformity.
The solvent preferably includes propylene glycol monomethyl ether acetate, and a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate is preferred.
[7] (F) Surfactant
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not further contain a surfactant, but in the case of containing a surfactant, it is more preferred that the composition contains any one of fluorine and/or silicon-based surfactants (a fluorine-based surfactant, a silicon-based surfactant and a surfactant having both a fluorine atom and a silicon atom), or two or more thereof.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a surfactant, thereby imparting a resist pattern with adhesion and reduced development defects due to improved sensitivity and resolution when using an exposure light source with a wavelength of 250 nm or less, particularly 220 nm or less.
Examples of the fluorine-based and/or silicon-based surfactants may include surfactants described in paragraph [0276] of U.S. Patent Application Publication No. 2008/0248425, such as Eftop EF301 and EF303 (manufactured by Shin-Akita Chemical Co., Ltd.), Fluorad FC430, 431 and 4430 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F176, F189, F113, F110, F177, F120 and R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105 and 106 and KH-20 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Industries, Inc.), GF-300 and GF-150 (manufactured by Toagosei Chemical Industry Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 and EF601 (manufactured by JEMCO Co., Ltd.), PF636, PF656, PF6320 and PF6520 (manufactured by OMNOVA Solutions, Inc.), and FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D and 222D (manufactured by NEOS Co., Ltd.). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicon-based surfactant.
Further, other than those known surfactants described above, it is possible to use a surfactant using a polymer having a fluoro-aliphatic group derived from a fluoro-aliphatic compound which is prepared by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) as the surfactant. The fluoro-aliphatic compound may be synthesized by the method described in Japanese Patent Application Laid-Open No. 2002-90991.
Examples of a surfactant corresponding to the aforementioned surfactant may include Megafac F178, F-470, F-473, F-475, F-476 and F-472 (manufactured by DIC Corporation), a copolymer of an acrylate having a C Fi3 group (or methacrylate) with a (poly(oxyalkylene))acrylate (or methacrylate), a copolymer of an acrylate having a C3F7 group (or methacrylate) with a (poly(oxyethylene))acrylate (or methacrylate) and a (poly(oxypropylene))acrylate (or methacrylate), and the like.
Further, in the present invention, it is also possible to use a surfactant other than the fluorine-based and/or silicon-based surfactant, described in paragraph [0280] of U.S. Patent Application Publication No. 2008/0248425.
These surfactants may be used either alone or in combination of several thereof.
When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is preferably 0.0001% by mass to 2% by mass, and more preferably 0.0005% by mole to 1% by mole, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent).
Meanwhile, by adjusting the amount of the surfactant added to 10 ppm or less based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface uneven distribution of the hydrophobic resin is increased, and accordingly, the surface of the resist film may be made to be more hydrophobic, thereby improving the water follow-up property at the time of liquid immersion exposure.
[8] (G) Other additives The actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain an onium carboxylate salt. Examples of the onium carboxylate salt may include those described in paragraphs [0605] to [0606] of U.S. Patent Application Laid-Open No. 2008/0187860.
The onium carboxylate salt may be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in an appropriate solvent.
In the case of the actinic ray-sensitive or radiation-sensitive resin composition contains an onium carboxylate salt, the content thereof is generally 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 7% by mass, based on the total solid of the composition.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a compound for accelerating solubility in a developer (for example, a phenol compound having a molecular weight of 1 ,000 or less, or an alicyclic or aliphatic compound having a carboxyl group) and the like, if necessary.
The phenol compound having a molecular weight of 1,000 or less may be easily synthesized by a person skilled in the art by referring to the methods described in, for example, Japanese Patent Application Laid-Open No. H4-122938, Japanese Patent Application Laid-Open No. H2-28531, U.S. Patent No. 4,916,210, European Patent No. 219294 and the like.
Specific examples of the alicyclic or aliphatic compound having a carboxyl group may include a carboxylic acid derivative having a steroid structure, such as cholic acid, deoxycholic acid, lithocholic acid and the like, an adamantanecarboxylic acid derivative, adamantanedicarboxylic acid, cyclohexanecarboxylic acid and cyclohexanedicarboxylic acid, but are not limited thereto.
From the viewpoint of improving the resolution, the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used in a film thickness of 30 nm to 250 nm, and more preferably in a film thickness of 30 nm to 200 nm. Such a film thickness may be achieved by setting a solid concentration in the composition to an adequate range to have an appropriate viscosity, thereby improving coatability and film- formation property.
The solid concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0% by mass to 10% by mass, preferably 2.0% by mass to 5.7% by mass, and more preferably 2.0% by mass to 5.3% by mass. By setting the solid concentration to the aforementioned range, the resist solution may be uniformly applied on a substrate and a resist pattern having excellent LWR may be formed. The reason is not clear, but it is thought that by setting the solid content concentration to 10% by mass or less and preferably 5.7% by mass or less, aggregation of materials, particularly, a photo-acid generator, in the resist solution is suppressed, and as a result, a uniform resist film may be formed.
The solid concentration is a weight percentage of the weight of other resist components excluding the solvent, based on the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is used by dissolving the aforementioned components in a predetermined organic solvent, preferably in the mixed solvent, filtering the solution through a filter, and then applying the filtered solution on a predetermined support (substrate). The filter used for filtration is preferably a polytetrafluoroethylene-, polyethylene- or nylon-made filter having a pore size of 0.1 μηι or less, more preferably 0.05 μηι or less, and still more preferably 0.03 μηι or less. In the filtration through a filter, as described in, for example, Japanese Patent Application Laid-Open No. 2002-62667, circulating filtration may be performed, or the filtration may be performed by connecting a plurality of kinds of filters in series or in parallel. In addition, the composition may be filtered a plurality of times. Further, a deaeration treatment or the like may be applied to the composition before or after filtration.
[9] Pattern forming method
The pattern forming method (negative pattern forming method) of the present invention at least includes
(a) forming a film (resist film) by the aforementioned actinic ray-sensitive or radiation-sensitive resin composition,
(b) exposing the film, and
(c) performing development using a developer containing an organic solvent to form a negative pattern.
The exposure in the process (b) may be liquid immersion exposure.
It is preferred that the pattern forming method of the present invention includes (d) a heating process after (b) the exposure process.
The pattern forming method of the present invention may further include (e) performing development using an alkali developer. The pattern forming method of the present invention may include several times of (b) the exposure process.
The pattern forming method of the present invention may include several times of (e) the heating process.
The resist film of the present invention is formed of the aforementioned actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and more specifically, it is preferred that the resist film is formed on a substrate. In the pattern forming method of the present invention, the process of forming a film by an actinic ray-sensitive or radiation-sensitive resin composition on a substrate, the process of exposing the film, and the process of performing development may be performed by a generally known method.
It is also preferred that the method includes, after film formation, a pre-baking process (PB) before the exposure process.
Further, it is also preferred that the method includes a post-exposure baking process (PEB) after the exposure process but before the development process.
As for the heating temperature, both PB and PEB are performed preferably at 70°C to 130°C, and more preferably at 80°C to 120°C.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
The heating may be performed using a means equipped with a typical exposure/developing machine or may be performed using a hot plate or the like.
By means of baking, the reaction in the exposed portion is accelerated, and thus the sensitivity or pattern profile is improved.
The light source wavelength used in the exposure apparatus in the present invention is not limited, but examples thereof may include an infrared light, visible light, ultraviolet light, far ultraviolet light, an extreme-ultraviolet light, X-ray, an electron beam and the like, but the light source wavelength is preferably far ultraviolet light at a wavelength of preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 nm to 200 nm. Specific examples thereof may include a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), a F2 excimer laser (157 nm), an X-ray, an EUV (13 nm), an electron beam and the like, and a KrF excimer laser, an ArF excimer laser, an EUV or an electron beam is preferred, and an ArF excimer laser is more preferred.
Further, in the process of performing exposure of the present invention, a liquid immersion exposure method may be applied.
The liquid immersion exposure method is, as the technique to increase the resolution, a technique of performing the exposure by filling a high refractive-index liquid (hereinafter, also referred to as a "liquid for liquid immersion") between a projection lens and a sample.
As described above, for the "effect of liquid immersion", assuming that λο is the wavelength of exposure light in air, n is the refractive index of the liquid for liquid immersion for air, Θ is the convergence half-angle of beam and NA0 = sinG, the resolution and the depth of focus in liquid immersion may be expressed by the following equations. Here, kt and k2 are coefficients related to the process.
(Resolution) = kr(Xo/n)/NAo
(Depth of focus) = ±k2-(¾o /n)/NA0 2
That is, the effect of liquid immersion is equivalent to the use of an exposure wavelength having a wavelength of 1/n. In other words, in the case of a projection optical system having the same NA, the depth of focus may be made n times larger by the liquid immersion. This is effective for all pattern shapes and may be combined with the super-resolution technology that is now being currently studied, such as a phase-shift method and a modified illumination method.
In the case of performing liquid immersion exposure, a process of washing the surface of the film with an aqueous chemical liquid may be performed (1) after forming the film on a substrate and before the process of performing exposure and/or (2) after the process of exposing the film through a liquid for liquid immersion but before the process of heating the film.
The liquid for liquid immersion is preferably a liquid which is transparent to light at the exposure wavelength and has a temperature coefficient of refractive index as small as possible in order to minimize the distortion of an optical image projected on the film, but particularly, when the exposure light source is an ArF excimer laser (wavelength; 193 nm), water is preferably used from the viewpoint of easy availability and easy handleability in addition to the aforementioned viewpoint.
When water is used, an additive (liquid) capable of decreasing the surface tension of water and increasing the interfacial activity may be added in a small ratio. It is preferred that the additive does not dissolve the resist layer on the wafer and has only a negligible effect on the optical coat at the undersurface of the lens element.
Such an additive is preferably an aliphatic alcohol having a refractive index almost equal to that of, for example, water, and specific examples thereof may include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index almost equal to that of water, even when the alcohol component in water is evaporated and the content concentration thereof is changed, it is possible to obtain an advantage in that the change in the refractive index of the liquid as a whole may be made very small.
Meanwhile, when a substance opaque to light at 193 nm or an impurity greatly differing from water in the refractive index is incorporated, the incorporation incurs distortion of the optical image projected on the resist, and thus, the water used is preferably distilled water. Further, pure water filtered through an ion exchange filter or the like may also be used.
The electrical resistance of water used as the liquid for liquid immersion is preferably 18.3 MQcm or more, and TOC (organic concentration) is preferably 20 ppb or less and the water is preferably subjected to deaeration treatment.
Further, the lithography performance may be enhanced by raising the refractive index of the liquid for liquid immersion. From this viewpoint, an additive for rising the refractive index may be added to water, or heavy water (D20) may be used in place of water.
When a film formed by using the composition of the present invention is exposed through a liquid immersion medium, the aforementioned hydrophobic resin (D) may be further added if necessary. The hydrophobic resin (D) is added, thereby improving the receding contact angle of the surface. The receding contact angle of the film is preferably 60° to 90°, and more preferably 70° or more.
In the liquid immersion exposure process, the liquid for liquid immersion needs to move on a wafer following the movement of an exposure head that scans on the wafer at a high speed and forms an exposure pattern, and thus the contact angle of the liquid for liquid immersion for the resist film in a dynamic state is important, and a performance of allowing the exposure head to follow the high-speed scanning is required for the resist while a liquid droplet no longer remains.
In order not to cause the film to directly contact the liquid for liquid immersion, a film (hereinafter, also referred to as a "topcoat") that is sparingly soluble in a liquid for liquid immersion may be formed between the film formed using the composition of the present invention and the liquid for liquid immersion. Examples of a function required for the topcoat may include coating suitability to the upper layer portion of the resist, transparency to radiation, particularly to radiation having a wavelength of 193 nm, and poor solubility in the liquid for liquid immersion. It is preferred that the topcoat may be uniformly coated onto the upper layer of the resist without being mixed with the resist.
The topcoat is preferably a polymer not containing an aromatic group from the viewpoint of the transparency to 193 nm. Specific examples of the polymer may include a hydrocarbon polymer, an acrylate ester polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, a silicon-containing polymer, a fluorine-containing polymer and the like. The described-above hydrophobic resin (D) is also suitable as the topcoat. If impurities are eluted from the topcoat to the liquid for liquid immersion, the optical lens is contaminated, and thus it is preferred that the amounts of residual monomer components of the polymer included in the topcoat are small.
When the topcoat is peeled off, a developer may be used, or another peeling agent may be used. As the peeling agent, a solvent that rarely penetrates the film is preferred. From the viewpoint that the peeling process may be performed simultaneously with the developing treatment process of the film, it is preferred that the topcoat may be peeled off by an alkali developer. From the viewpoint of peeling off the topcoat with an alkali developer, the topcoat is preferably acidic, but from the viewpoint of a non-intermixture property with respect to the film, the topcoat may be neutral or alkaline.
It is preferred that there is no difference or a small difference in the refractive index between the topcoat and the liquid for liquid immersion. In this case, the resolution may be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferred that water is used as the liquid for liquid immersion, and thus the topcoat for AxF liquid immersion exposure preferably has a refractive index close to the refractive index (1.44) of water. Further, from the viewpoint of transparency and refractive index, the topcoat is preferably a thin film.
It is preferred that the topcoat is not mixed with the film and the liquid for liquid immersion. From this viewpoint, when the liquid for liquid immersion is water, it is preferred that the solvent used for the topcoat is sparingly soluble in the solvent used for the composition of the present invention and is a water-insoluble medium. Further, when the liquid for liquid immersion is an organic solvent, the topcoat may be water-soluble or water-insoluble.
In the present invention, the substrate on which the film is formed is not particularly limited, and it is possible to use an inorganic substrate such as silicon, SiN, Si02 or SiN, a coating-type inorganic substrate such as SOG, or a substrate generally used in the process of manufacturing a semiconductor such as IC or manufacturing a liquid crystal device or a circuit board such as a thermal head or in the lithography process of other photo-fabrication processes. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.
When the pattern forming method of the present invention further includes performing development using an alkali developer, it is possible to use an alkaline aqueous solution of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia and the like, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and piperidine, and the like, as the alkali developer.
Further, alcohols and a surfactant may be added to the alkaline aqueous solution each in an appropriate amount and the mixture may be used.
The alkali concentration of the alkali developer is usually 0.1% by mass to 20% by mass.
The pH of the alkali developer is usually 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is preferred.
As for the rinse solution in the rinse treatment performed after the alkali development, pure water is used, and an appropriate amount of a surfactant may be added thereto to use the mixture.
Further, after the development treatment or rinse treatment, a treatment of removing the developer or rinse solution adhering on the pattern by a supercritical fluid may be performed.
In the pattern forming method of the present invention, as the developer (hereinafter, also referred to as an organic-based developer) in the process of performing developing using a developer containing an organic solvent to form a negative pattern, a polar solvent such as a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent and an ether-based solvent, and a hydrocarbon-based solvent may be used.
Examples of the ketone-based solvent may include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate and the like.
Examples of the ester-based solvent may include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like.
Examples of the alcohol-based solvent may include an alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol and the like, a glycol-based solvent such as ethylene glycol, diethylene glycol and tnethylene glycol, a glycol ether-based solvent such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, tnethylene glycol monoethyl ether and methoxymethyl butanol, and the like.
Examples of the ether-based solvent may include, in addition to the glycol ether-based solvents, dioxane, tetrahydrofuran, phenetol, dibutyl ether and the like.
Exampless of the amide-based solvent may include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, Ν,Ν-dimethylformamide, hexamethylphosphoric triamide, l,3-dimethyl-2-imidazolidinone and the like.
Examples of the hydrocarbon-based solvent may include an aromatic hydrocarbon-based solvent such as toluene and xylene, and an aliphatic hydrocarbon-based solvent such as pentane, hexane, octane and decane.
A plurality of the aforementioned solvents may be mixed, or the solvents may be used by being mixing with a solvent other than those described above or with water. However, in order to sufficiently exhibit the effects of the present invention, it is preferred that the water content ratio of the entire developer is less than 10% by mass, and it is more prefened that the developer contains substantially no moisture.
That is, the amount of the organic solvent used in the organic-based developer is preferably 90% by mass to 100% by mass, and preferably 95% by mass to 100% by mass, based on the total amount of the developer.
In particular, the organic-based developer is preferably a developer containing at least one of organic solvents selected from the group consisting of a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent and an ether-based solvent.
The vapor pressure of the organic-based developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less, at 20°C. By adjusting the vapor pressure of the organic-based developer to 5 kPa or less, evaporation of the developer on a substrate or in a development cup is suppressed so that temperature uniformity in the wafer plane is improved, and as a result, the dimensional uniformity in the wafer plane is improved.
Specific examples of the solvent having a vapor pressure of 5 kPa or less may include a ketone-based solvent such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone and methyl isobutyl ketone, an ester-based solvent such as butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate, an alcohol-based solvent such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol, a glycol-based solvent such as ethylene glycol, diethylene glycol and triethylene glycol, a glycol ether-based solvent such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethylbutanol, an ether-based solvent such as tetrahydrofuran, phenetol and dibutyl ether, an amide-based solvent such as N-methyl-2-pyrrolidone, Ν,Ν-dimethylacetamide and Ν,Ν-dimethylformamide, an aromatic hydrocarbon-based solvent such as toluene and xylene, and an aliphatic hydrocarbon-based solvent such as octane and decane.
Specific examples of the solvent having a vapor pressure of 2 kPa or less that is in a particularly preferred range may include a ketone-based solvent such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone and phenylacetone, an ester-based solvent such as butyl acetate, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, an alcohol-based solvent such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol, a glycol-based solvent such as ethylene glycol, diethylene glycol and triethylene glycol, a glycol ether-based solvent such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethylbutanol, an ether-based solvent such as phenetol and dibutyl ether, an amide-based solvent such as N-methyl-2-pyrrolidone, Ν,Ν-dimethylacetamide and N,N-dimethylformamide, an aromatic hydrocarbon-based solvent such as xylene, and an aliphatic hydrocarbon-based solvent such as octane and decane.
To the organic-based developer, a surfactant may be added in an appropriate amount, if necessary.
The surfactant is not particularly limited but, for example, ionic or nonionic fluorine-based and/or silicon-based surfactant and the like may be used. Examples of the fluorine and/or silicon-based surfactants may include surfactants described in Japanese Patent Application Laid-Open Nos. S62-36663, S61-226746, S61-226745, S62-170950, S63-34540, H7-230165, H8-62834, H9-54432, and H9-5988 and U.S. Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451, and a nonionic surfactant is preferred. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a silicon-based surfactant is more preferably used.
The amount of the surfactant used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, and more preferably 0.01% by mass to 0.5% by mass based on the total amount of the developer.
As for the developing method, it is possible to apply, for example, a method of dipping a substrate in a bath filled with a developer for a predetermined time (a dipping method), a method of raising a developer on a substrate surface sufficiently by the effect of a surface tension and keeping the substrate still for a predetermined time, thereby performing development (a puddle method), a method of spraying a developer on a substrate surface (a spray method), a method of continuously ejecting a developer on a substrate spinning at a constant speed while scanning a developer ejecting nozzle at a constant rate (a dynamic dispense method) and the like.
When the aforementioned various developing methods include ejecting a developer toward a resist film from a development nozzle of a developing apparatus, the ejection pressure of the developer ejected (the flow velocity per unit area of the developer ejected) is preferably 2 mL/sec/mm2 or less, more preferably 1.5 mL/sec/mm2 or less, and still more preferably 1 mL/sec/mm2 or less. The flow velocity has no particular lower limit, but is preferably 0.2 mL/sec/mm2 or more in consideration of throughput.
By setting the ejection pressure of the ejected developer to the aforementioned range, pattern defects resulting from the resist scum after development may be significantly reduced.
Details on the mechanism are not clear, but it is thought that it is because the resist film-resist pattern is suppressed from being inadvertently cut or collapsing by setting the ejection pressure to the above-described range, the pressure imposed on the resist film by the developer is decreased.
Meanwhile, the ejection pressure (mL/sec/mm2) of the developer is the value at the outlet of the development nozzle in the developing apparatus.
Examples of the method for adjusting the ejection pressure of the developer may include a method of adjusting the ejection pressure by a pump or the like, a method of supplying a developer from a pressurized tank and adjusting the pressure to change the ejection pressure and the like.
In addition, after the process of performing development using a developer containing an organic solvent, a process of stopping the development while replacing the solvent with another solvent may be performed.
A process of rinsing a film using a rinse solution is preferably included after the process of performing development using a developer containing an organic solvent.
The rinse solution used in the rinse process after the process of performing development using a developer containing an organic solvent is not particularly limited as long as the rinse solution does not dissolve the resist pattern, and a solution including a general organic solvent may be used. As for the rinse solution, a rinse solution containing at least one of organic solvents selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent and an ether-based solvent is preferably used.
Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amide-based solvent and the ether-based solvent are the same as those described above for the developer containing an organic solvent.
After the process of performing development using a developer containing an organic solvent, a process of performing rinsing using a rinse solution containing at least one of organic solvents selected from the group consisting of a ketone-based solvent, an ester-based solvent, an alcohol-based solvent and an amide-based solvent is more preferably performed, a process of performing rinsing using a rinse solution containing an alcohol-based solvent or an ester-based solvent is still more preferably performed, a process of performing rinsing using a rinse solution containing a monohydric alcohol is particularly preferably performed, and a process of performing rinsing using a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is most preferably performed.
Here, examples of the monohydric alcohol used in the rinsing process may includes a straight, branched or cyclic monohydric alcohol, and specifically, it is possible to use 1-butanol, 2-butanol, 3-methyl-l-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol,
3- hexanol, 3-heptanol, 3-octanol, 4-octanol and the like, and as the particularly preferred monohydric alcohol having 5 or more carbon atoms, it is possible to use 1-hexanol, 2-hexanol,
4- methyl-2-pentanol, 1-pentanol, 3-methyl-l-butanol and the like.
A plurality of the components may be mixed, or the solvent may be used by being mixed with an organic solvent other than those described above.
The water content ratio in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content ratio to 10% by mass or less, good development characteristics may be obtained.
The vapor pressure of the rinse solution used after the process of performing development using a developer containing an organic solvent is preferably 0.05 kPa to 5 kPa, still more preferably 0.1 kPa to 5 kPa, and most preferably 0.12 kPa to 3 kPa, at 20°C. By setting the vapor pressure of the rinse solution to 0.05 kPa to 5 kPa, the temperature uniformity in the wafer plane is improved. Further, swelling caused by permeation of the rinse solution is suppressed. As a result, the dimensional uniformity in the wafer plane is improved.
The rinse solution may also be used by adding an appropriate amount of a surfactant thereto.
In the rinsing process, the wafer subjected to development using a developer containing an organic solvent is rinsed by using the above-described rinse solution including an organic solvent. The method of rinse treatment is not particularly limited, but it is possible to apply, for example, a method of continuously ejecting a rinse solution on a substrate spinning at a constant speed (spin coating method), a method of dipping a substrate in a bath filled with a rinse solution for a predetermined time (dipping method), a method of spraying a rinse solution on a substrate surface (spraying method), and the like, and among them, it is preferred that the rinse treatment is performed by the spin coating method and after the rinsing, the substrate is spun at a rotational speed of 2,000 rpm to 4,000 rpm to remove the rinse solution from the substrate. Further, it is also preferred that a heating process (post bake) is included after the rinsing process. The developer and rinse solution remaining between patterns and in the inside of the pattern are removed by the bake. The heating process after the rinsing process is performed at usually 40°C to 160°C, and preferably 70°C to 95°C, for usually 10 seconds to 3 minutes, and preferably 30 to 90 seconds.
Further, the present invention also relates to a method for manufacturing an electronic device, including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electric electronic devices (such as home appliances, OA-media-related devices, optical devices and communication devices).
Example
(Synthesis of Resin (P- 1 ))
27.9 g of cyclohexanone was placed in a 3-neck flask, and heated at 80°C under nitrogen flow. Subsequently, the following monomer 1 (1 1.8 g) and monomer 2 (15.1 g) were dissolved in cyclohexanone (51.9 g) to prepare a monomer solution, and a solution prepared by adding 0.55 g (2.0 mol% based on the total amount of the monomers) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) thereto was added dropwise to the flask over 6 hours. After the completion of dropwise addition, the solution was also allowed to react at 80°C for 2 hours. The reaction solution was allowed to cool, and then added dropwise to a mixed solvent of 670 g of heptane/74.5 g of ethyl acetate, and a precipitated powder was obtained by filtration and dried to obtain 22.6 g of Resin (P-l). The weight average molecular weight obtained from the GPC (carrier: tetrahydrofuran (THF)) of the obtained Resin (P-l) was 21,500, the polydispersity Mw/Mn was 1.
Figure imgf000183_0001
Monomer 1 Monomer 2 (P-1)
Hereinafter, Resins (P-2) to (P-l 4) were synthesized in the same manner as in Resin
(P-l).
The structure of the synthesized resin, the composition ratio (molar ratio), and the mass average molecular weight and the polydispersity of the repeating unit will be described below.
Figure imgf000184_0001
Figure imgf000185_0001
Figure imgf000185_0002
<Acid generator> The acid generators used in the examples and the content (MnF) of the fluorine atoms contained in the anion in the acid generators are shown below.
Figure imgf000186_0001
Figure imgf000186_0002
PAG"4 MnF = 11 5wt% PAG-5 MnF = 9.81wt%
Figure imgf000186_0003
PAG-10 PAG-11 MnF = 30.35wt%
MnF = 12.13wt%
<Basic Compound (N) whose basicity decreases upon irradiation with actinic ray or radiation, and basic compound (N')>
The following compounds were used as the basic compound whose basicity decreases upon irradiation with an actinic ray or radiation, or the basic compound.
Figure imgf000187_0001
Figure imgf000187_0002
Figure imgf000187_0003
<Hydrophobic resin>
A hydrophobic resin was appropriately selected from Resins (HR-1) to (HR-84), (C-1) to (C-28), and (D-l) to (D-16) previously exemplified.
<Component (C)>
The following compounds were used as the component (C). The compositin ratio (molar ratio), the weight molecular weight and the polydispersity of the repeating unit of the component (C) are shown below.
Figure imgf000188_0001
D-10
<Surfactant>
The followings were prepared as the surfactant.
W-1 : Megafac F176 (manufactured by DIC Corporation; fluorine-based)
W-2: Megafac R08 (manufactured by DIC Corporation; fluorine- and silicon-based) W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicon-based)
W-4: Troysol S-366 (manufactured by Troy Chemical Industries, Inc.)
W-5: KH-20 (manufactured by Asahi Glass Co., Ltd.) W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based) <Solvent>
The followings were prepared as the solvent.
(Group a)
SL-1 : Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether propionate
SL-3: 2-Heptanone
(Group b)
SL-4: Ethyl lactate
SL-5: Propylene glycol monomethyl ether (PGME)
SL-6: Cyclohexanone
(Group c)
SL-7: γ-Butyrolactone
SL-8: Propylene carbonate
<Developer>
The followings were prepared as the developer.
SG-1 : Butyl acetate
SG-2: Methyl amyl ketone
SG-3: Ethyl-3-ethoxypropionate
SG-4: Pentyl acetate
SG-5: Isopentyl acetate
SG-6: Propylene glycol monomethyl ether acetate (PGMEA)
SG-7: Cyclohexanone
<Rinse solution>
The followings are used as the rinse solution.
SR-1 : 4-methyl-2-pentanol
SR-2: 1-hexanol
SR-3: Butyl acetate
SR-4: Methyl amyl ketone
SR-5: Ethyl-3-ethoxypropionate
<ArF Liquid Immersion Exposure>
(Preparation of Resist)
The components shown in the following Table 4 were dissolved in the solvent showname Table to have a total solid content of 3.5% by mass, and each was filtered through a polyethylene filter having a pore size of 0.03 μηι to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition). An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer and baked at 205°C for 60 seconds to form an antireflection film having a thickness of 95 nm. The actinic ray-sensitive or radiation-sensitive resin composition was applied thereon and baked (PB: prebake) at 100°C over 60 seconds to form a resist film having a thickness of 100 nm.
The obtained wafer was subjected to pattern exposure by using an ArF excimer laser liquid immersion scanner (manufactured by ASML Co., Ltd.; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) through a halftone mask in which a mask portion is 35 nm and a pitch between trenches was 90 nm (here, a portion corresponding to the trench was light-shielded in order to form a negative image). As the liquid for liquid immersion, ultrapure water was used. Thereafter, heating (PEB: post exposure bake) was performed at 100°C for 60 seconds. Subsequently, the wafer was developed by performing puddling using the organic solvent-based developer shown in the following table for 30 seconds, and then rinsed by performing puddling using the rinse solution shown in the following table for 30 seconds. Subsequently, a trench pattern having a space width of 35 nm was obtained by spinning the wafer at a rotational speed of 4,000 rpm for 30 seconds.
(LWR)
In observation of a trench pattern having a space width of 35 nm resolved in the optimal exposure amount, the width was observed at an arbitrary point when observed at the top of the pattern with a Critical Dimension scanning electron microscope (SEM: S9380, manufactured by Hitachi, Ltd.) and the change in measurement was evaluated as 3σ. A smaller value indicates better performance.
(DOF)
Considering the exposure amount and the focus forming the trench pattern having a space width of 35 nm were regarded as the optimal exposure amount and the optimal focus, respectively, when the focus was changed (defocused) while maintaining the exposure amount at a level of the optimal exposure amount, the width of the foucus allowing the pattern size of 35 nm± 10% was calculated. A larger value indicates better depth of focus (DOF).
(Collapse)
In the trench pattern having a space width of 35 nm in the optimal focus, the maximum spapce dimension was observed, in which collapse does not occur when changing the exposure amount was observed. A lager value indicates better performance because collapse hardly occurs.
(Pattern shape)
The side wall of the trench pattern having a space width of 35 nm resolved in the optimal exposure amount was observed with a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.), and the value of (top dimension of the pattern/bottom dimension of the pattern) was evaluated. A smaller value indicates more excellent pattern shape.
(Development defects)
Using a defect inspection apparatus (KLA2360 (trade name), manufactured by KLA-Tencor Corporation), the pixel size of the defect inspection apparatus was set to 0.16 m, the critical value ws set to 20, and measurement was performed in a random mode to detect the development defects extracted from the difference occurred by overlap between a comparative image and a pixcel unit. The number of development defects per unit area was calculated, and the development defect performance was evaluated in accordance with the following criteria.
A (good) ... D.D. (defect density) value is less than 0.5
B (poor) ... D.D. (defect density) value is 0.5 or more
The evaluation results are shown in Table 4 below.
Table 4
Figure imgf000192_0001
Table 4 (continued)
Figure imgf000193_0001
From Table 4, it is understood that a micro pattern with high precision which is excellent in LWR, DOF, pattern shape collapse and defect performance may be stably formed by developing the resist composition of the present invention with a developer containing an organic solvent.
Further, Examples 7 to 17 using the actinic ray-sensitive or radiation-sensitive resin composition in which the content of the compound (B) is 10% by mass or more based on the total solide of the actinic ray-sensitive or radiation-sensitive resin composition, showed a particularly excellent result in the LWR evaluation.
Further, Examples 13 to 17 in which the actinic ray-sensitive or radiation-sensitive resin composition contains two or more compounds as the compound (B) and at least one of the two or more compounds has no aromatic group or has one or two aromatic groups, showed particularly excellent results in the LWR and collapse evaluations.
Industrial Applicability
According to the present invention, it is possible to provide, in forming a micro pattern such as a trench pattern whose pattern size represented by a line width or space with is 40 nm or less by an organic-based developer, a pattern forming method capable of realizing small line width roughness (LWR), excellent depth of focus (DOF), excellent pattern shape, suppression of pattern collapse and reduction in development defects, an actinic ray-sensitive or radiation-sensitive resin composition and a resist film used therein, a method for manufacturing an electronic device, and an electronic device using them.
This application is based on Japanese patent application No. 2012-167813 filed on July 27, 2012, the entire content of which is hereby incorporated by reference, the same as if set forth at length.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising:
(A) a resin having a repeating unit having a group capable of decomposing by the action of an acid to generate a polar group;
(B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; and
(C) a component containing at least one of:
a compound having at least one of a fluorine atom and a silicon atom and having basicity or capable of increasing the basicity by the action of an acid, and
a resin having a CH3 partial structure in a side chain moiety and having a basicity or capable of increasing the basicity by the action of an acid,
wherein a content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55% by mole or more based on a whole repeating units of the resin (A).
2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein
the component (C) is a resin (C) having a repeating unit having at least one of a fluorine atom, a silicone atom and a CH3 partial structure contained in a side chain moiety of the resin.
3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein
the component (C) is a compound capable of capturing an acid generated from the compound (B).
4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein
the component (C) is an inoic compound.
5. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein
the content of the repeating unit having a group capable of decomposing by the action of an acid to generate a polar group is 55% by mole to 85% by mole based on the whole repeating unit of the resin (A).
6. The actinic ray-sensitive or radiation-sensitive resin composition of any one according to claims 1 to 5, wherein
the group capable of decomposing by the action of an acid to generate a polar group has a structure in which the polar group is protected with a group capable of decomposing and leaving by the action of an acid, and
the group capable of leaving has 5 or more carbon atoms.
7. The actinic ray-sensitive or radiation-sensitive resin composition according to claims 1 to 6, wherein
the content of the compound (B) is 10% by mass or more based on a total solid of the actinic ray-sensitive or radiation-sensitive resin composition.
8. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein
the compound (B) is an ionic compound, and
a content of a fluorine atom containd in an anion of the ionic compound is 35% by mass or less based on a total amount of atoms constituting the anion of the compound (B).
9. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein
the actinic ray-sensitive or radiation-sensitive resin composition contains two or more kinds of compounds as the compound (B), and
at least one of the two or more kinds of compounds is a compound having no aromatic group or having one or two aromatic groups.
10. A resist film formed by using the actinic ray-sensitive or radiation-sensitive resin composition of any one of claims 1 to 9.
1 1. A pattern forming method comprising:
exposing the resist film according to claim 10;
and developing the exposed resist film with a developer containing an organic solvent to form a negative pattern.
12. The pattern forming method according to claim 11,
wherein the exposing is performed by liquid immersion exposure.
13. A method for manufacturing an electronic device comprising the pattern forming method according to claim 11 or 12.
14. An electronic device manufactured by the method according to claim 13.
15. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9, further comprising a hydrophobic resin (D).
16. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 2 to 9,
wherein a content of the repeating unit having at least one of a fluorine atom, a silicone atom and a CH3 partial structure contained in a side chain moiety of the resin is 8% by mole or less based on a whole repeating units of th resin (C).
17. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 2 to 9,
wherein a weight average molecular weight of the resin (C) is 7,500 to 15,000.
18. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9,
wherein the resin (A) further contains a repeating unit having a group with a lactone structure or a sultone structure.
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