Classifications

• • 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
• • 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
  • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/65—Halogen-containing esters of unsaturated acids
  • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/58—One oxygen atom, e.g. butenolide
• • 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
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/22—Oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/22—Oxygen
  • C08F212/24—Phenols or alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F220/1805—C5-(meth)acrylate, e.g. pentyl (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
  • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (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
  • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (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
  • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (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
  • C08F220/1809—C9-(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
  • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (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
  • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (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
  • 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
  • C08F220/22—Esters containing halogen
• • 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
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • 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
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
• • 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
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
• • 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
  • G03F7/20—Exposure; Apparatus therefor
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
  • C07C2603/24—Anthracenes; Hydrogenated anthracenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
  • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
  • C07C2603/74—Adamantanes

Definitions

• the present invention relates to a radiation-sensitive resin composition, a resist pattern forming method, a polymer and a compound.
• Radiation-sensitive resin compositions used for microfabrication by lithography include far ultraviolet rays such as ArF excimer laser light (wavelength 193 nm) and KrF excimer laser light (wavelength 248 nm), extreme ultraviolet rays (EUV) (wavelength 13.5 nm) and the like.
• Irradiation with radiation such as electromagnetic waves and charged particle beams such as electron beams generates acid in the exposed area, and a chemical reaction catalyzed by this acid causes a difference in the dissolution rate in the developer between the exposed area and the non-exposed area.
• a resist pattern is formed on the substrate.
• Radiation-sensitive resin compositions are required to have good sensitivity to exposure light such as extreme ultraviolet rays and electron beams, as well as excellent LWR (Line Width Roughness) performance, CDU (Critical Dimension Uniformity) performance, etc. be.
• the present invention has been made based on the circumstances as described above, and an object thereof is to form a resist pattern having good sensitivity to exposure light, excellent LWR performance and CDU performance, and a wide process window. It is an object of the present invention to provide a radiation-sensitive resin composition, a method for forming a resist pattern, a polymer, and a compound capable of
• An invention made to solve the above problems is a radiation-sensitive resin composition containing a polymer having a first structural unit represented by the following formula (1) and a radiation-sensitive acid generator.
• R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 2 , R 3 and R 4 each independently represent a hydrogen atom or a is a monovalent organic group
• R 5 is a monovalent organic group having 1 to 20 carbon atoms
• L is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• Another invention made to solve the above problems is a step of directly or indirectly coating a substrate with a radiation-sensitive resin composition, exposing the resist film formed by the coating step, and developing the exposed resist film, wherein the radiation-sensitive resin composition contains a polymer having a first structural unit represented by the following formula (1) and a radiation-sensitive acid generator. It is a resist pattern forming method for forming a resist pattern.
• R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 2 , R 3 and R 4 each independently represent a hydrogen atom or a is a monovalent organic group
• R 5 is a monovalent organic group having 1 to 20 carbon atoms
• L is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 2 , R 3 and R 4 each independently represent a hydrogen atom or a is a monovalent organic group, R 5 is a monovalent organic group having 1 to 20 carbon atoms, and L is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group
• R 2 , R 3 and R 4 each independently represent a hydrogen atom or a 20 monovalent organic group
• R 5 is a monovalent organic group having 1 to 20 carbon atoms
• L is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• the radiation-sensitive resin composition and resist pattern forming method of the present invention it is possible to form a resist pattern that has good sensitivity to exposure light, excellent LWR performance and CDU performance, and a wide process window.
• the polymer of the present invention can be suitably used as a component of the radiation-sensitive resin composition.
• the compound of the present invention can be suitably used as a monomer for synthesizing the polymer. Therefore, these materials can be suitably used in the processing of semiconductor devices, which are expected to further miniaturize in the future.
• the radiation-sensitive resin composition comprises a polymer having a first structural unit represented by the following formula (1) (hereinafter also referred to as "[A] polymer”) and a radiation-sensitive acid generator ( hereinafter also referred to as “[B] acid generator”).
• the radiation-sensitive resin composition usually contains an organic solvent (hereinafter also referred to as "[D] organic solvent”).
• the radiation-sensitive resin composition may contain an acid diffusion control agent (hereinafter also referred to as "[C] acid diffusion control agent”) as a suitable component.
• the radiation-sensitive resin composition may contain other optional components as long as the effects of the present invention are not impaired.
• the radiation-sensitive resin composition By containing the [A] polymer and [B] acid generator, the radiation-sensitive resin composition has good sensitivity to exposure light, excellent LWR performance and CDU performance, and a wide process window. A resist pattern can be formed.
• the reason why the radiation-sensitive resin composition having the above structure produces the above effects is not necessarily clear, it can be inferred, for example, as follows. That is, the first structural unit in the [A] polymer has a specific acid-dissociable group, which will be described later, so that the acid-dissociation efficiency is improved, and as a result, the sensitivity to exposure light is good, and the LWR performance and CDU performance are improved. It is considered that a resist pattern which is excellent and has a wide process window can be formed.
• the radiation-sensitive resin composition contains, for example, [A] a polymer and [B] an acid generator, and if necessary, [C] an acid diffusion controller, [D] an organic solvent and other optional components. It can be prepared by mixing in proportions and preferably filtering the resulting mixture through a membrane filter having a pore size of 0.2 ⁇ m or less.
• the polymer has a first structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (I)").
• the radiation-sensitive resin composition may contain one or more [A] polymers.
• the polymer preferably further has a second structural unit (hereinafter also referred to as “structural unit (II)”) containing a phenolic hydroxyl group.
• the polymer preferably further has a third structural unit (hereinafter also referred to as “structural unit (III)”) containing an acid-labile group other than the structural unit (I).
• the polymer may further have structural units other than the structural units (I) to (III) (hereinafter simply referred to as "other structural units”).
• the lower limit of the content of the [A] polymer in the radiation-sensitive resin composition is preferably 50% by mass with respect to all components other than the [D] organic solvent contained in the radiation-sensitive resin composition. 70% by mass is more preferred, and 80% by mass is even more preferred.
• the upper limit of the content ratio is preferably 99% by mass, more preferably 95% by mass.
• the lower limit of the polystyrene equivalent weight average molecular weight (Mw) of the polymer measured by gel permeation chromatography (GPC) is preferably 1,000, more preferably 3,000, even more preferably 5,000. 000 is even more preferred, and 7,000 is particularly preferred.
• the upper limit of Mw is preferably 50,000, more preferably 30,000, even more preferably 20,000, even more preferably 15,000, and particularly preferably 10,000.
• the Mw of the polymer can be adjusted, for example, by adjusting the type and amount of the polymerization initiator used in the synthesis.
• the upper limit of the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) of the polymer measured by GPC is preferably 2.50, and 2.00. is more preferred, and 1.75 is even more preferred.
• the lower limit of the above ratio is usually 1.00, preferably 1.10, more preferably 1.20, and even more preferably 1.30.
• Mw and Mn of the [A] polymer in the present specification are values measured using gel permeation chromatography (GPC) under the following conditions.
• GPC column 2 "G2000HXL", 1 "G3000HXL” and 1 "G4000HXL” manufactured by Tosoh Corporation Column temperature: 40°C Elution solvent: Tetrahydrofuran Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection volume: 100 ⁇ L Detector: Differential refractometer Standard material: Monodisperse polystyrene
• the polymer can be synthesized, for example, by polymerizing monomers that give each structural unit by a known method.
• Structural unit (I) is a structural unit represented by the following formula (1).
• Structural unit (I) is a structural unit having an acid-labile group.
• the term "acid-labile group” refers to a group that substitutes a hydrogen atom in a carboxyl group and is dissociated by the action of an acid to give a carboxyl group.
• the acid dissociable group (a) is dissociated by the action of the acid generated from the [B] acid generator or the like upon exposure, and the solubility of the [A] polymer in the developer between the exposed area and the non-exposed area is affected.
• a resist pattern can be formed by the difference.
• the polymer Since the polymer has the structural unit (I), it is possible to form a resist pattern that has good sensitivity to exposure light, excellent LWR performance and CDU performance, and a wide process window.
• the polymer can have one or more structural units (I).
• R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 2 , R 3 and R 4 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• R 5 is a monovalent organic group having 1 to 20 carbon atoms.
• L is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• Carbon number refers to the number of carbon atoms that make up the group.
• Organic group refers to a group containing at least one carbon atom.
• Examples of monovalent organic groups having 1 to 20 carbon atoms represented by R 2 , R 3 , R 4 or R 5 include monovalent hydrocarbon groups having 1 to 20 carbon atoms, carbon- A group containing a divalent heteroatom-containing group between carbon atoms (hereinafter also referred to as "group ( ⁇ )”), a part or all of the hydrogen atoms of the hydrocarbon group or the group ( ⁇ ) is a monovalent hetero A group substituted with an atom-containing group (hereinafter also referred to as "group ( ⁇ )”), the above hydrocarbon group, the above group ( ⁇ ), or a group in which the above group ( ⁇ ) is combined with a divalent heteroatom-containing group ( hereinafter also referred to as “group ( ⁇ )”) and the like.
• Hydrocarbon group includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. This "hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
• chain hydrocarbon group refers to a hydrocarbon group that does not contain a cyclic structure and is composed only of a chain structure, and includes both a straight chain hydrocarbon group and a branched chain hydrocarbon group.
• alicyclic hydrocarbon group refers to a hydrocarbon group that contains only an alicyclic structure as a ring structure and does not contain an aromatic ring structure, and includes monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic It contains both hydrocarbon groups.
• aromatic hydrocarbon group refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not need to be composed only of an aromatic ring structure, and may partially contain a chain structure or an alicyclic structure.
• Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include monovalent chain hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and 6 carbon atoms. to 20 monovalent aromatic hydrocarbon groups, and the like.
• Examples of monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, isobutyl group and tert-butyl.
• alkyl groups such as groups; alkenyl groups such as ethenyl group, propenyl group, butenyl group and 2-methylprop-1-en-1-yl group; and alkynyl groups such as ethynyl group, propynyl group and butynyl group.
• Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic saturated alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group, norbornyl group, adamantyl group, tricyclodecyl group, tetracyclo Polycyclic alicyclic saturated hydrocarbon groups such as dodecyl group, monocyclic alicyclic unsaturated hydrocarbon groups such as cyclopentenyl group and cyclohexenyl group, norbornenyl group, tricyclodecenyl group, tetracyclodode Examples include polycyclic alicyclic unsaturated hydrocarbon groups such as senyl group.
• Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group, benzyl group, phenethyl group, naphthylmethyl group and anthrylmethyl group. and aralkyl groups such as groups.
• heteroatom constituting the monovalent or divalent heteroatom-containing group examples include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom and the like.
• Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.
• Examples of monovalent heteroatom-containing groups include halogen atoms, hydroxy groups, alkoxy groups, carboxy groups, cyano groups, amino groups (--NR 2 ), sulfanyl groups and the like.
• R is the same or different and is a hydrogen atom or a monovalent hydrocarbon group.
• a halogen atom, a hydroxy group, an alkoxy group or an amino group is preferable, and a fluorine atom, a hydroxy group, a methoxy group or a dimethylamino group is more preferable.
• Divalent heteroatom-containing groups include, for example, -O-, -CO-, -S-, -CS-, -SO 2 -, -NR'-, and groups in which two or more of these are combined (e.g. -O-CO-, etc.).
• R' is a hydrogen atom or a monovalent hydrocarbon group.
• Examples of the divalent organic group having 1 to 20 carbon atoms represented by L include the groups exemplified as the monovalent organic groups having 1 to 20 carbon atoms represented by R 2 , R 3 , R 4 or R 5 A group obtained by removing one hydrogen atom from is mentioned.
• R 1 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of the copolymerizability of the monomer that gives the structural unit (I).
• R 2 is a monovalent organic group having 1 to 20 carbon atoms
• sensitivity to exposure light, LWR performance, CDU performance and process window are improved more than when R 2 is a hydrogen atom. can be done.
• R 2 is a monovalent organic group having 1 to 20 carbon atoms
• the acid-labile group (a) is bonded to the etheric oxygen atom of the carbonyloxy group via a secondary carbon atom.
• R 2 is a hydrogen atom
• the acid-labile group (a) is bonded to the etheric oxygen atom of the carbonyloxy group through a primary carbon atom.
• R 2 is preferably a monovalent organic group having 1 to 20 carbon atoms, such as 1 to 20 carbon atoms. or a group in which some or all of the hydrogen atoms of this hydrocarbon group are substituted with a monovalent heteroatom-containing group (group ( ⁇ )).
• R 2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms
• the hydrocarbon group is preferably a chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, an alkyl group, An alkenyl group, a monocyclic saturated alicyclic hydrocarbon group and an aryl group are more preferable, and a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a 2-methylprop-1-en-1-yl group, a cyclohexyl group or A phenyl group is more preferred.
• this group ( ⁇ ) is preferably a group in which some or all of the hydrogen atoms of the above hydrocarbon group are substituted with halogen atoms or alkoxy groups, and the above hydrocarbon group is A group in which some or all of the hydrogen atoms having are substituted with a fluorine atom or a methoxy group is more preferable, such as a trifluoromethyl group, a 4,4-difluorocyclohexyl group, a 4-fluorophenyl group, a 4-methoxyphenyl group, or 2 , 2,2-trifluoro-1,1-dimethylethyl groups are more preferred.
• R 3 is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom or an alkyl group. More preferably, a hydrogen atom or a methyl group is even more preferable.
• R 4 is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom or an alkyl group. More preferably, a hydrogen atom or a methyl group is even more preferable.
• R 5 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group in which some or all of the hydrogen atoms of this hydrocarbon group are substituted with a monovalent heteroatom-containing group (group ( ⁇ )) is preferred.
• R 5 is a monovalent hydrocarbon group having 1 to 20 carbon atoms
• the hydrocarbon group is preferably a chain hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkenyl group or an aryl group.
• -methylbut-2-en-1-yl group, phenyl group and 9-anthryl group are more preferred.
• this group ( ⁇ ) is preferably a group obtained by substituting some or all of the hydrogen atoms of the above hydrocarbon group with a halogen atom, a hydroxy group, an alkoxy group or an amino group. , more preferably a group in which some or all of the hydrogen atoms of an aromatic hydrocarbon group are substituted with a fluorine atom, a hydroxy group, a methoxy group or a dimethylamino group, a 4-fluorophenyl group, a 4-hydroxyphenyl group, a 4- A methoxyphenyl group or a 4-dimethylaminophenyl group is more preferred.
• a single bond is preferable for L.
• structural units (I) As the structural unit (I), structural units represented by the following formulas (1-1) to (1-30) (hereinafter also referred to as “structural units (I-1) to (I-30)”) are preferable. , structural units (I-2) to (I-30) are more preferred.
• the lower limit of the content of the structural unit (I) in the [A] polymer is preferably 5 mol%, more preferably 10 mol%, and 15 mol% with respect to the total structural units constituting the [A] polymer. is more preferred, and 20 mol % is even more preferred.
• the upper limit of the content ratio is preferably 80 mol %, more preferably 75 mol %, still more preferably 70 mol %, and even more preferably 65 mol %.
• Structural unit (II) is a structural unit containing a phenolic hydroxyl group.
• the “phenolic hydroxyl group” refers not only to a hydroxy group directly attached to a benzene ring but also to general hydroxy groups directly attached to an aromatic ring.
• the polymer may contain one or more structural units (II).
• the [A] polymer having the structural unit (II) can further increase the sensitivity of the radiation-sensitive resin composition to exposure light. Therefore, when the polymer [A] has the structural unit (II), the radiation-sensitive resin composition can be suitably used as a radiation-sensitive resin composition for KrF exposure, EUV exposure, or electron beam exposure. can be done.
• structural unit (II) examples include structural units represented by the following formulas (2-1) to (2-19) (hereinafter also referred to as “structural units (II-1) to (II-19)”), and the like. is mentioned.
• R P is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R P is preferably a hydrogen atom or a methyl group from the viewpoint of the copolymerizability of the monomer that gives the structural unit (II).
• the structural unit (II) includes structural units (II-1) to (II-3), (II-6) to (II-11), (II-13), (II-14), or combinations thereof. preferable. When it is a combination, a combination of two types is preferable, and the structural unit (II-1) and the structural units (II-2), (II-3), (II-6) to (II-11), (II- A combination with one of 13) and (II-14) is more preferred.
• the lower limit of the content of the structural unit (II) in the [A] polymer is 20 per all structural units constituting the [A] polymer.
• mol % is preferred, 30 mol % is more preferred, and 40 mol % is even more preferred.
• the upper limit of the content ratio is preferably 80 mol %, more preferably 70 mol %, and even more preferably 65 mol %.
• the monomer that gives the structural unit (II) for example, a monomer in which the hydrogen atom of the phenolic hydroxyl group (--OH) is substituted with an acetyl group or the like can also be used.
• the resulting polymerization reaction product is subjected to a hydrolysis reaction in the presence of a base such as an amine to synthesize the [A] polymer having the structural unit (II). can be done.
• Structural unit (III) is a structural unit other than structural unit (I) and contains an acid dissociable group.
• the acid-labile group contained in structural unit (III) (hereinafter also referred to as "acid-labile group (b)") is different from the acid-labile group (a) contained in structural unit (I).
• the polymer may contain one or more structural units (III).
• structural unit (III) examples include structural units represented by the following formulas (3-1) to (3-3) (hereinafter also referred to as “structural units (III-1) to (III-3)”), and the like. is mentioned.
• structural units (III-1) to (III-3) structural units represented by the following formulas (3-1) to (3-3) (hereinafter also referred to as "structural units (III-1) to (III-3)"), and the like. is mentioned.
• structural units (III-1) to (III-3) structural units represented by the following formulas (3-1) to (3-3)
• structural units (III-1) to (III-3) structural units represented by the following formulas (3-1) to (3-3)
• each R 1 T is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 1 X is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R Y and R Z are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a ring having 3 to It is part of 20 saturated alicyclic structures.
• R A is a hydrogen atom.
• R B and R C are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R D is a divalent hydrocarbon group having 1 to 20 carbon atoms forming an unsaturated alicyclic structure having 4 to 20 ring members together with the carbon atoms to which R A , R B and R C are respectively bonded.
• R U and R V are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms
• R W is 1 having 1 to 20 carbon atoms. or is part of a 3- to 20-membered alicyclic structure in which R U and R V are combined together and formed with the carbon atom to which they are attached, or R U and R W are part of a 4- to 20-membered aliphatic heterocyclic ring structure formed together with the carbon atom to which R 1 U is attached and the oxygen atom to which R 1 W is attached.
• number of ring members refers to the number of atoms constituting a ring structure, and in the case of a polycyclic ring, the number of atoms constituting the polycyclic ring.
• the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R X , R Y , R Z , R B , R C , R U , R V or R W includes, for example, the above formula (1) Among monovalent organic groups having 1 to 20 carbon atoms for , R 2 , R 3 or R 4 , the same groups as those exemplified as monovalent hydrocarbon groups having 1 to 20 carbon atoms can be mentioned.
• substituents that the hydrocarbon group represented by R 2 above may have include halogen atoms such as fluorine atoms, hydroxy groups, carboxy groups, cyano groups, nitro groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonyloxy groups, acyl groups, acyloxy groups, and the like.
• halogen atoms such as fluorine atoms, hydroxy groups, carboxy groups, cyano groups, nitro groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonyloxy groups, acyl groups, acyloxy groups, and the like.
• a halogen atom or an alkoxy group is preferable, and a fluorine atom or a methoxy group is more preferable.
• saturated alicyclic structures having 3 to 20 ring members in which R 1 Y and R 2 Z are combined together and formed together with the carbon atoms to which they are bonded include monocyclic structures such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, and a cyclohexane structure.
• polycyclic saturated alicyclic structures such as a saturated alicyclic structure, a norbornane structure, and an adamantane structure.
• the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R D is, for example, a monovalent organic group having 1 to 20 carbon atoms for R 2 , R 3 or R 4 in the above formula (1). Among them, groups obtained by removing one hydrogen atom from the groups exemplified as monovalent hydrocarbon groups having 1 to 20 carbon atoms can be mentioned.
• Examples of unsaturated alicyclic structures having 4 to 20 ring members in which R D is formed together with carbon atoms to which R A , R B and R C are respectively bonded include monocyclic unsaturated structures such as a cyclobutene structure, a cyclopentene structure and a cyclohexene structure. Alicyclic structures, polycyclic unsaturated alicyclic structures such as norbornene structures, and the like are included.
• the 3- to 20-membered alicyclic structure in which R U and R V are combined together and formed together with the carbon atoms to which they are bonded include, for example, monocyclic structures such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, and a cyclohexane structure.
• Polycyclic saturated alicyclic structures such as saturated alicyclic structures, norbornane structures, adamantane structures, tricyclodecane structures and tetracyclodecane structures, monocyclic unsaturated alicyclic structures such as cyclopropene structures, cyclobutene structures, cyclopentene structures and cyclohexene structures Ring structures, norbornene structures, tricyclodecene structures, polycyclic unsaturated alicyclic structures such as tetracyclododecene structures, and the like.
• Aliphatic heterocyclic structures having 4 to 20 ring members in which R 1 U and R 1 W are combined together and formed together with the carbon atom to which R 1 U is bonded and the oxygen atom to which R 1 W is bonded include, for example, an oxacyclobutane structure, oxacyclopentane, structure, a saturated oxygen-containing heterocyclic structure such as an oxacyclohexane structure, an unsaturated oxygen-containing heterocyclic structure such as an oxacyclobutene structure, an oxacyclopentene structure, an oxacyclohexene structure, and the like.
• R T is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the structural unit (II).
• R X is preferably a substituted or unsubstituted chain hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted chain hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group.
• R X is preferably a substituted or unsubstituted chain hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted chain hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group.
• preferably unsubstituted alkyl group or substituted or unsubstituted aryl group more preferably methyl group, ethyl group, i-propyl group, tert-butyl group, phenyl group, 4-methoxyphenyl group or 4-trifluoromethylphenyl groups are more preferred.
• R Y and R Z are preferably chain hydrocarbon groups, more preferably alkyl groups, and even more preferably methyl groups.
• R 2 Y and R 2 Z are also preferably part of a saturated alicyclic structure having 3 to 20 ring members formed together with the carbon atoms to which they are combined.
• a saturated alicyclic structure a cyclopentane structure, a cyclohexane structure, an adamantane structure, or a tetracyclododecane structure is preferable.
• RB is preferably a hydrogen atom.
• RC is preferably a chain hydrocarbon group, more preferably an alkyl group, and even more preferably a methyl group.
• the 4- to 20-membered unsaturated alicyclic structure in which R D is formed together with the carbon atoms to which R A , R B and R C respectively bond is preferably a monocyclic unsaturated alicyclic structure, more preferably a cyclohexene structure. .
• Structural unit (III) is preferably structural unit (III-1) or structural unit (III-2).
• structural unit (III-1) for example, structural units represented by the following formulas (3-1-1) to (3-1-13) (hereinafter referred to as “structural units (III-1-1) to (III -1-13)”) is preferred.
• RT has the same meaning as in formula (3-1) above.
• structural unit (III-2) a structural unit represented by the following formula (3-2-1) (hereinafter also referred to as “structural unit (III-2-1)”) is preferable.
• R 2 T has the same meaning as in formula (3-2) above.
• the lower limit of the content of the structural unit (III) in the [A] polymer is 5 mol % is preferred, 10 mol % is more preferred, and 15 mol % is even more preferred.
• the upper limit of the content ratio is preferably 50 mol %, more preferably 40 mol %, and even more preferably 30 mol %.
• structural unit (IV) a structural unit containing an alcoholic hydroxyl group
• structural unit (V) a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof
• structural unit (VI) a structural unit that generates an acid upon exposure described in the section ⁇ [B] acid generator> described later
• structural unit (VI) a structural unit that generates an acid upon exposure described in the section ⁇ [B] acid generator> described later
• Structural unit (IV) Structural unit (IV) is a structural unit containing an alcoholic hydroxyl group.
• Structural units (IV) include, for example, structural units represented by the following formula.
• R L2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• the lower limit of the content of the structural unit (IV) is preferably 1 mol% with respect to the total structural units constituting the [A] polymer. mol % is more preferred, and 10 mol % is even more preferred.
• the upper limit of the content ratio is preferably 40 mol %, more preferably 35 mol %, and even more preferably 30 mol %.
• Structural unit (V) is a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof.
• Structural units (V) include, for example, structural units represented by the following formula.
• R L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• Structural units (V) are preferably structural units containing a lactone structure or a cyclic carbonate structure.
• the lower limit of the content of the structural unit (V) is preferably 1 mol% with respect to the total structural units constituting the [A] polymer. mol % is more preferred, and 10 mol % is even more preferred.
• the upper limit of the content ratio is preferably 40 mol %, more preferably 35 mol %, and even more preferably 30 mol %.
• the acid generator is a substance that generates an acid upon exposure.
• Examples of the exposure light include those similar to those exemplified as the exposure light in the exposure step of the resist pattern forming method described later.
• the acid generated by exposure for example, the acid dissociable group (a) in the structural unit (I) of the [A] polymer is dissociated to generate a carboxy group, and the resist film is formed between the exposed area and the non-exposed area.
• a resist pattern can be formed by causing a difference in solubility in a developer.
• Examples of the acid generated from the acid generator include sulfonic acid and imidic acid.
• the acid generator [B] contained in the radiation-sensitive resin composition may be, for example, in the form of a low-molecular-weight compound (hereinafter also referred to as "[B] acid generator") described later, or may be in the form of a radiation-sensitive material described later. It may be in the form of a flexible acid-generating polymer (hereinafter also referred to as "[B] acid-generating polymer”), or in both of these forms.
• a "low-molecular weight compound” means a compound having a molecular weight of 1,000 or less that does not have a molecular weight distribution.
• a “radiation-sensitive acid-generating polymer” means a polymer having a structural unit (structural unit (VI)) that generates an acid upon exposure.
• the [B] radiation-sensitive acid-generating polymer can also be said to have a form in which the [B] acid generator is incorporated as a part of the polymer.
• the [B] acid-generating polymer may be a polymer different from the [A] polymer.
• the radiation-sensitive resin composition may contain one or more [B] acid generators.
• Acid generators include, for example, onium salt compounds, N-sulfonyloxyimide compounds, sulfonimide compounds, halogen-containing compounds, and diazoketone compounds.
• onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, and pyridinium salts.
• R 6 is a monovalent organic group having 1 to 30 carbon atoms.
• R7 is a divalent linking group.
• R 8 and R 9 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 10 and R 11 are each independently a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
• p is an integer from 0 to 10; q is an integer from 0 to 10; r is an integer from 0 to 10; However, p+q+r is 1 or more and 30 or less. When p is 2 or more, multiple R 7 are the same or different.
• Y + is a monovalent radiation-sensitive onium cation.
• Examples of monovalent organic groups having 1 to 30 carbon atoms represented by R 6 include monovalent organic groups having 1 to 20 carbon atoms represented by R 2 , R 3 or R 4 in formula (1) above. and the same groups as those exemplified as.
• R 6 is preferably a monovalent group containing a ring structure with 5 or more ring members.
• the monovalent group containing a ring structure having 5 or more ring members includes, for example, a monovalent group containing an alicyclic structure having 5 or more ring members, a monovalent group containing an aliphatic heterocyclic structure having 5 or more ring members, a ring Examples include a monovalent group containing an aromatic carbocyclic structure with 5 or more members, a monovalent group containing an aromatic heterocyclic structure with 5 or more ring members, and the like. These ring structures may have a substituent.
• substituents include halogen atoms such as fluorine atoms and iodine atoms, hydroxyl groups, carboxy groups, cyano groups, nitro groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonyloxy groups, acyl groups, and acyloxy groups.
• alicyclic structures having 5 or more ring members include monocyclic saturated alicyclic structures such as a cyclopentane structure, cyclohexane structure, cycloheptane structure, cyclooctane structure, cyclononane structure, cyclodecane structure, and cyclododecane structure, cyclopentene structure, and cyclohexene structure.
• monocyclic unsaturated alicyclic structures such as cycloheptene structure, cyclooctene structure and cyclodecene structure, polycyclic saturated alicyclic structures such as norbornane structure, adamantane structure, tricyclodecane structure and tetracyclododecane structure, norbornene structure,
• a polycyclic unsaturated alicyclic structure such as a tricyclodecene structure, a structure having a steroid skeleton, and the like are included.
• steroid skeleton refers to a cyclopentanoperhydrophenanthrene nucleus, a skeleton in which three cyclohexane rings and one cyclopentane ring are condensed, or one or more of the carbon-carbon bonds of this skeleton are divalent. It refers to a skeleton with double bonds.
• Steroid skeletons are generally classified into five types: cholestane structure, cholane structure, pregnane structure, androstane structure and estrane structure.
• a cholan structure is preferable as the steroid skeleton that provides R6 .
• R 6 may be a 3,7,12-trioxocolan-24-yl group or 3,12-dihydroxycolan-24-yl A 3,7,12-trihydroxycholan-24-yl group is preferred, and a 3,7,12-trioxocolan-24-yl group is more preferred.
• Examples of aliphatic heterocyclic structures having 5 or more ring members include lactone structures such as hexanolactone structure and norbornanelactone structure, sultone structures such as hexanosultone structure and norbornanesultone structure, oxacycloheptane structure, oxanorbornane structure and the like.
• Nitrogen atom-containing heterocyclic structures such as oxygen atom-containing heterocyclic structures, azacyclohexane structures and diazabicyclooctane structures, and sulfur atom-containing heterocyclic structures such as thiacyclohexane structures and thianolbornane structures are included.
• aromatic carbocyclic structures having 5 or more ring members examples include benzene structures, naphthalene structures, phenanthrene structures, and anthracene structures.
• aromatic heterocyclic structures having 5 or more ring members include oxygen atom-containing heterocyclic structures such as a furan structure, pyran structure, benzofuran structure, and benzopyran structure, and nitrogen atom-containing heterocyclic structures such as a pyridine structure, a pyrimidine structure, and an indole structure. etc.
• Examples of the divalent linking group represented by R 7 include a carbonyl group, an ether group, a carbonyloxy group, an oxycarbonyl group, an oxycarbonyloxy group, a sulfide group, a thiocarbonyl group, a sulfonyl group, and a divalent hydrocarbon group. , or a group obtained by combining these. Among these, a carbonyloxy group, a sulfonyl group, an alkanediyl group or a divalent saturated alicyclic hydrocarbon group is preferable, and a carbonyloxy group or a sulfonyl group is more preferable. When p is 2 or more, the divalent linking group other than the divalent hydrocarbon group is usually adjacent only to the divalent hydrocarbon group.
• Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 8 or R 9 include alkyl groups having 1 to 20 carbon atoms.
• R 8 or R 9 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom.
• the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R 10 or R 11 for example, at least one hydrogen atom possessed by the monovalent hydrocarbon group having 1 to 20 carbon atoms is replaced by a fluorine atom. and groups substituted with.
• R 10 or R 11 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorine atom.
• p is preferably 0 to 5, more preferably 0 to 2, and even more preferably 0 or 1.
• q is preferably 0 to 5, more preferably 0 to 2, and even more preferably 0 or 1.
• the lower limit of r is preferably 1, more preferably 2. By setting r to 1 or more, the strength of the acid generated from the [B] compound can be increased.
• the upper limit of r is preferably 4, more preferably 3, and even more preferably 2.
• the lower limit of p+q+r is preferably 2, more preferably 4.
• the upper limit of p+q+r is preferably 20, more preferably 10.
• Examples of the monovalent radiation-sensitive onium cation represented by Y + include monovalent cations represented by the following formulas (r ⁇ a) to (r ⁇ c) (hereinafter referred to as “cations (r ⁇ a) to (r ⁇ c)”) and the like.
• b1 is an integer of 0-4.
• R 1 B1 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
• the plurality of R 1 B1 are the same or different from each other and are a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or these groups are combined with each other It is part of a 4- to 20-membered ring structure composed of the carbon chain to which they are attached.
• b2 is an integer from 0 to 4;
• R 2 B2 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
• the plurality of R 2 B2 are the same or different from each other and are a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or these groups are combined with each other. It is part of a 4- to 20-membered ring structure composed of the carbon chain to which they are attached.
• R 1 B3 and R 1 B4 each independently represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or a combination of these to represent a single bond.
• b3 is an integer from 0 to 11; When b3 is 1, R B5 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
• R B5 When b3 is 2 or more, a plurality of R B5 are the same or different from each other and are a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or these groups are combined with each other. It is part of a 4- to 20-membered ring structure composed of the carbon chain to which they are attached. nb1 is an integer of 0-3.
• b4 is an integer of 0-9.
• R B6 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
• the plurality of R B6 are the same or different from each other and are a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or these groups are combined with each other It is part of a 4- to 20-membered ring structure composed of the carbon chain to which they are attached.
• b5 is an integer from 0 to 10;
• R B7 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
• the plurality of R B7 are the same or different from each other and are a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or these groups are combined with each other. It is part of a 3- to 20-membered ring structure composed of the carbon atoms or carbon chains to which they are attached.
• nb3 is an integer of 0-3.
• R B8 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• nb2 is an integer from 0 to 2;
• b6 is an integer of 0-5.
• R B9 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
• the plurality of R B9 are the same or different from each other and are a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or these groups are combined with each other It is part of a 4- to 20-membered ring structure composed of the carbon chain to which they are attached.
• b7 is an integer from 0 to 5;
• R 1 B10 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom.
• the plurality of R 1 B10 are the same or different from each other and are a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen atom, or these groups are combined with each other It is part of a 4- to 20-membered ring structure composed of the carbon chain to which they are attached.
• Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R B1 , R B2 , R B3 , R B4 , R B5 , R B6 , R B7 , R B9 or R B10 include the above formula (1) and the same groups as those exemplified as the monovalent organic group having 1 to 20 carbon atoms represented by R 2 , R 3 , R 4 or R 5 of .
• Examples of the divalent organic group represented by R B8 include the monovalent organic groups having 1 to 20 carbon atoms represented by R 2 , R 3 , R 4 or R 5 in formula (1) above. Examples include a group having one hydrogen atom removed from the group.
• R B3 and R B4 are preferably hydrogen atoms or single bonds in which they are combined with each other.
• b1 and b2 are preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
• b3 is preferably 0 to 4, more preferably 0 to 2, and even more preferably 0 or 1.
• nb1 , 0 or 1 is preferable.
• R B5 is preferably a cyclohexyl group or a cyclohexylsulfonyl group.
• R B9 and R B10 are preferably hydrocarbon groups, more preferably chain hydrocarbon groups, still more preferably alkyl groups, and even more preferably isopropyl or tert-butyl groups. .
• the monovalent radiation-sensitive onium cation represented by Y + is preferably a cation (ra) or a cation (rc).
• cation (ra) examples include cations represented by the following formulas (ra-1) to (ra-5) (hereinafter referred to as "cations (ra-1) to (ra- 5)”) and the like.
• Examples of the cation (r-c) include cations represented by the following formulas (r-c-1) to (r-c-4) (hereinafter referred to as "cations (r-c-1) to (r-c- 4)”) and the like.
• Compounds include, for example, compounds represented by the following formulas (4-1) to (4-9) (hereinafter also referred to as “compounds (B1) to (B9)").
• Y + has the same meaning as in formula (4) above.
• the lower limit of the content of the [B] acid generator in the radiation-sensitive resin composition is preferably 5 parts by mass, more preferably 10 parts by mass, and 15 parts by mass with respect to 100 parts by mass of the [A] polymer. is more preferred.
• the upper limit of the content is preferably 60 parts by mass, more preferably 55 parts by mass, and even more preferably 50 parts by mass.
• the acid-generating polymer is a polymer having a structural unit (structural unit (VI)) that generates an acid upon exposure.
• structural unit (VI) for example, a structural unit represented by the following formula (4') is preferable.
• the structural unit (VI) may be contained as a structural unit constituting the [A] polymer, or may be contained as a structural unit constituting a polymer other than the [A] polymer, [A] It is preferably contained as a structural unit constituting the polymer.
• the [A] polymer has the structural unit (VI)
• the [A] polymer also functions as a [B] acid generator.
• R 12 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 13 is a divalent linking group.
• R 14 and R 15 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 16 and R 17 are each independently a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
• s is an integer from 0 to 10; t is an integer from 0 to 10; u is an integer from 0 to 10; However, s+t+u is 1 or more and 30 or less.
• the plurality of R 13 are the same or different.
• Y + is a monovalent radiation-sensitive onium cation.
• R 12 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
• R 13 examples include groups similar to the groups exemplified as the divalent linking group represented by R 7 in the above formula (4).
• R 13 is preferably a carbonyloxy group.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 14 or R 15 include monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 8 or R 9 in the above formula (4).
• the same groups as those exemplified as the hydrogen group are included.
• R 14 or R 15 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom.
• Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R 16 or R 17 include monovalent and the same groups as those exemplified as the fluorinated hydrocarbon group of .
• R 16 or R 17 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorine atom or a trifluoromethyl group.
• s is preferably 0 to 5, more preferably 0 to 2, and even more preferably 1.
• t is preferably 0 to 5, more preferably 0 to 2, and still more preferably 0.
• the upper limit of r is preferably 4, more preferably 3, and even more preferably 2.
• the lower limit of s+t+u is preferably 2, more preferably 3.
• the upper limit of s+t+u is preferably 20, more preferably 10.
• structural unit (VI) a structural unit represented by the following formula (2'-1) (hereinafter also referred to as “structural unit (VI-1)”) is preferable.
• R 12 and Y + have the same meanings as in formula (4′) above.
• the lower limit of the content of the structural unit (VI) is preferably 1 mol% with respect to the total structural units constituting the [A] polymer. Mole % is more preferred.
• the upper limit of the content of the structural unit is preferably 20 mol %, more preferably 15 mol %, relative to the total structural units constituting the [A] polymer.
• the [C] acid diffusion control agent has the effect of controlling the diffusion phenomenon in the resist film of the acid generated from the [B] acid generator and the like upon exposure, and controlling unfavorable chemical reactions in the non-exposed regions.
• the acid diffusion controller [C] in the radiation-sensitive resin composition By containing the acid diffusion controller [C] in the radiation-sensitive resin composition, the sensitivity to exposure light, LWR performance, CDU performance and process window of the radiation-sensitive resin composition can be further improved.
• the radiation-sensitive resin composition may contain one or more [C] acid diffusion controllers.
• Acid diffusion control agents include, for example, nitrogen atom-containing compounds and compounds that generate weak acids when exposed to light (hereinafter also referred to as "photodisintegrating bases").
• photodisintegrating bases a photodegradable base is preferable. In this case, sensitivity to exposure light, LWR performance, CDU performance and process window can be further improved.
• nitrogen atom-containing compounds include amine compounds such as tripentylamine, trioctylamine and tetrabutylammonium salicylate, amide group-containing compounds such as formamide and N,N-dimethylacetamide, urea and 1,1-dimethylurea.
• Urea compounds such as pyridine, 2,4,5-triphenylimidazole, N-(undecylcarbonyloxyethyl)morpholine, 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, Nt-pentyloxycarbonyl- nitrogen-containing heterocyclic compounds such as 4-hydroxypiperidine;
• photodegradable bases include compounds containing a radiation-sensitive onium cation and an anion of a weak acid.
• the photodisintegrating base generates an acid in the exposed area to increase the solubility or insolubility of the polymer [A] in the developer, and as a result suppresses the surface roughness of the exposed area after development.
• the anion exerts a high acid scavenging function, functions as a quencher, and captures the acid diffusing from the exposed area. That is, since it functions as a quencher only in the non-exposed area, the contrast of the deprotection reaction is improved, and as a result, the resolution can be improved.
• Examples of the onium cation that decomposes upon exposure include the same as those exemplified as the monovalent radiation-sensitive onium cation in [B] the acid generator. Among them, triphenylsulfonium cation, phenyldibenzothiophenium cation, diphenyliodonium cation and phenyl(4-fluorophenyl)iodonium cation are preferred.
• anion of the weak acid examples include anions represented by the following formula.
• the photodegradable base a compound obtained by appropriately combining the onium cation decomposed by exposure to light and the anion of the weak acid can be used.
• the lower limit of the content of [C] acid diffusion controller in the radiation-sensitive resin composition is [B] acid generator 100 1 mol% is preferable, 5 mol% is more preferable, and 10 mol% is still more preferable with respect to mol%.
• the upper limit of the content is preferably 100 mol%, more preferably 60 mol%, and even more preferably 50 mol%.
• the radiation-sensitive resin composition usually contains [D] an organic solvent.
• the [D] organic solvent is a solvent capable of dissolving or dispersing at least [A] the polymer and [B] the acid generator, and [C] the acid diffusion controller and other optional components contained as necessary. is not particularly limited.
• Organic solvents include, for example, alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.
• the radiation-sensitive resin composition may contain one or more [D] organic solvents.
• alcohol solvents include aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol, and alicyclic monoalcohol solvents having 3 to 18 carbon atoms such as cyclohexanol.
• examples thereof include solvents, polyhydric alcohol solvents having 2 to 18 carbon atoms such as 1,2-propylene glycol, and polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms such as propylene glycol 1-monomethyl ether.
• ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether and diheptyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; diphenyl ether; Aromatic ring-containing ether solvents such as anisole are included.
• dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether and diheptyl ether
• cyclic ether solvents such as tetrahydrofuran and tetrahydropyran
• diphenyl ether Aromatic ring-containing ether solvents such as anisole are included.
• Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, chain ketone solvents such as di-iso-butyl ketone and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone; 2,4-pentanedione and acetonylacetone , acetophenone, and the like.
• amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N -methylacetamide, N,N-dimethylacetamide, chain amide solvents such as N-methylpropionamide, and the like.
• ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate, lactone solvents such as ⁇ -butyrolactone and valerolactone, polyhydric alcohol carboxylate solvents such as propylene glycol acetate, and propylene acetate.
• ester solvents include polyhydric alcohol partial ether carboxylate solvents such as glycol monomethyl ether, polyvalent carboxylic acid diester solvents such as diethyl oxalate, and carbonate solvents such as dimethyl carbonate and diethyl carbonate.
• hydrocarbon solvents examples include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane, and aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene and xylene. be done.
• the organic solvent is preferably an alcohol solvent and/or an ester solvent, more preferably a polyhydric alcohol partial ether solvent and/or a polyhydric alcohol partial ether carboxylate solvent having 3 to 19 carbon atoms, and propylene Glycol 1-monomethyl ether and/or propylene glycol monomethyl ether acetate are more preferred.
• the lower limit of the content of the [D] organic solvent is 50% by mass with respect to all components contained in the radiation-sensitive resin composition. is preferred, 60% by mass is more preferred, 70% by mass is even more preferred, and 80% by mass is particularly preferred.
• the upper limit of the content ratio is preferably 99.9% by mass, preferably 99.5% by mass, and more preferably 99.0% by mass.
• Other optional components include, for example, surfactants.
• the radiation-sensitive resin composition may contain one or more other optional components.
• the resist pattern forming method includes a step of directly or indirectly coating a substrate with a radiation-sensitive resin composition (hereinafter also referred to as a “coating step”), and exposing the resist film formed by the coating step. and a step of developing the exposed resist film (hereinafter also referred to as a “development step”).
• the sensitivity to exposure light is good, and the LWR performance and CDU performance are improved. It is possible to form a resist pattern which is excellent in the process window and has a wide process window.
• the substrate is directly or indirectly coated with the radiation-sensitive resin composition. Thereby, a resist film is formed directly or indirectly on the substrate.
• the radiation-sensitive resin composition described above is used as the radiation-sensitive resin composition.
• substrates include conventionally known ones such as silicon wafers, silicon dioxide, and aluminum-coated wafers. Further, the substrate may be a substrate subjected to pretreatment such as hydrophobizing treatment such as hexamethyldisilazane (hereinafter also referred to as “HMDS”) treatment.
• HMDS hexamethyldisilazane
• examples of the case of indirectly applying the radiation-sensitive resin composition to the substrate include the case of applying the radiation-sensitive resin composition onto an antireflection film formed on the substrate.
• an antireflection film include organic or inorganic antireflection films disclosed in JP-B-6-12452 and JP-A-59-93448.
• PB prebaking
• the lower limit of the temperature of PB is preferably 60°C, more preferably 80°C.
• the upper limit of the temperature is preferably 150°C, more preferably 140°C.
• the lower limit of the PB time is preferably 5 seconds, more preferably 10 seconds.
• the upper limit of the PB time is preferably 600 seconds, more preferably 300 seconds.
• the lower limit of the average thickness of the resist film to be formed is preferably 10 nm, more preferably 20 nm.
• the upper limit of the average thickness is preferably 1,000 nm, more preferably 500 nm.
• the resist film formed in the coating step is exposed.
• This exposure is performed by irradiating exposure light through a photomask (in some cases, through an immersion medium such as water).
• exposure light include electromagnetic waves such as visible light, ultraviolet rays, deep ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, and ⁇ -rays; lines, etc.
• ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV (wavelength 13.5 nm) or electron beams are more preferred, and ArF excimer laser light , EUV or electron beams are more preferred, and EUV or electron beams are particularly preferred.
• PEB post-exposure bake
• the lower limit of the PEB temperature is preferably 50°C, more preferably 80°C, and even more preferably 100°C.
• the upper limit of the temperature is preferably 180°C, more preferably 130°C.
• the lower limit of the PEB time is preferably 5 seconds, more preferably 10 seconds, and even more preferably 30 seconds.
• the upper limit of the time is preferably 600 seconds, more preferably 300 seconds, and even more preferably 100 seconds.
• the exposed resist film is developed. Thereby, a predetermined resist pattern can be formed. After development, it is common to wash with a rinsing liquid such as water or alcohol and dry.
• the developing method in the developing step may be alkali development or organic solvent development.
• the developer used for development includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n- Propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (hereinafter also referred to as "TMAH”), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0] -7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene and other alkaline compounds dissolved in at least one alkaline aqueous solution.
• TMAH tetramethylammonium hydroxide
• a TMAH aqueous solution is preferred, and a 2.38% by mass TMAH aqueous solution is more preferred.
• the developer includes organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, and solutions containing the above organic solvents.
• organic solvent include one or more of the solvents exemplified as the [D] organic solvent of the radiation-sensitive resin composition.
• an ester solvent or a ketone solvent is preferable.
• the ester solvent an acetate solvent is preferable, and n-butyl acetate is more preferable.
• the ketone solvent a chain ketone is preferred, and 2-heptanone is more preferred.
• the lower limit of the content of the organic solvent in the developer is preferably 80% by mass, more preferably 90% by mass, still more preferably 95% by mass, and particularly preferably 99% by mass.
• Components other than the organic solvent in the developer include, for example, water and silicone oil.
• Examples of the development method include a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), and a method in which the developer is piled up on the surface of the substrate by surface tension and left stationary for a certain period of time (paddle method). ), a method in which the developer is sprayed onto the surface of the substrate (spray method), and a method in which the developer dispensing nozzle scans the substrate rotating at a constant speed and continuously dispenses the developer (dynamic dispensing method). etc.
• Examples of patterns formed by the resist pattern forming method include line-and-space patterns and hole patterns.
• the polymer is described as the [A] polymer in the radiation-sensitive resin composition described above.
• the polymer can be suitably used as a component of the radiation-sensitive resin composition.
• the compound is a compound represented by the following formula (1′) (hereinafter also referred to as “[M] monomer”).
• the compound can be suitably used as the [A] polymer in the radiation-sensitive resin composition or a compound for synthesizing the polymer.
• R 1 , R 2 , R 3 , R 4 and L have the same meanings as in formula (1) above.
• the compound can be synthesized, for example, by the method described in Synthesis Examples described later.
• Mw Weight average molecular weight
• Mn number average molecular weight
• Mw/Mn degree of dispersion
• the cooled polymerization solution was put into hexane (500 parts by mass with respect to the polymerization solution), and the precipitated white powder was filtered off.
• the filtered white powder was washed twice with 100 parts by mass of hexane with respect to the polymerization solution, filtered, and dissolved in propylene glycol 1-monomethyl ether (300 parts by mass).
• methanol 500 parts by mass
• triethylamine 50 parts by mass
• ultrapure water 10 parts by mass
• Polymer (A-1) had an Mw of 7,600 and an Mw/Mn of 1.55.
• the cooled polymerization solution was put into methanol (2,000 parts by mass with respect to the polymerization solution), and the precipitated white powder was filtered off.
• the obtained solid was dissolved in acetone (100 parts by mass). It was added dropwise to 500 parts by mass of water to solidify the resin, and the obtained solid was separated by filtration. After drying at 50° C. for 12 hours, a white powdery polymer (A-66) was synthesized.
• Polymer (A-66) had an Mw of 8,500 and an Mw/Mn of 1.86.
• Table 1 shows the types and proportions of the monomers that give each structural unit of the [A] polymers obtained in Synthesis Examples 2-1 to 2-70, as well as Mw and Mw/Mn.
• "-" indicates that the corresponding monomer was not used.
• [B] acid generator] As an acid generator, compounds represented by the following formulas (B-1) to (B-10) (hereinafter also referred to as “acid generators (B-1) to (B-10)”) are used. board.
• [C] acid diffusion control agent] [C] Compounds represented by the following formulas (C-1) to (C-9) as acid diffusion control agents (hereinafter also referred to as "acid diffusion control agents (C-1) to (C-9)") Using.
• [D] organic solvent] [D] As the organic solvent, the following organic solvents (D-1) and (D-2) were used.
• D-1) Propylene glycol monomethyl ether acetate
• D-2) Propylene glycol 1-monomethyl ether
• the resist film was post-exposure baked (PEB) at 130° C. for 60 seconds.
• PEB post-exposure baked
• development was performed at 23° C. for 30 seconds to form a positive 32 nm line-and-space pattern.
• LWR performance The resist pattern was observed from above using the scanning electron microscope. The line width was measured at a total of 50 points at arbitrary points, and the 3 sigma value was obtained from the distribution of the measured values, which was defined as LWR (unit: nm). The LWR performance indicates that the smaller the LWR value, the smaller the line wobble and the better.
• the "process window” means the range of resist dimensions within which a pattern can be formed without bridging defects or collapse.
• a mask forming 32 nm lines and spaces (1L/1S) was used to form patterns from low to high exposure doses. In general, defects such as bridge formation between patterns are observed in the case of a low exposure dose, and defects such as pattern collapse are observed in the case of a high exposure dose.
• the CD (Critical Dimension) margin (unit: nm) was defined as the difference between the maximum value and the minimum value of the resist dimension at which these defects were not observed. The larger the value of the CD margin, the wider the process window and the better.
• Example 86 Preparation of radiation-sensitive resin composition (R-86) [A] polymer (A-1) 100 parts by mass, [B] acid generator (B-1) 10 parts by mass, [ C] 40 mol% of (C-1) as an acid diffusion inhibitor with respect to (B-1), and [D] 4,800 parts by mass of (D-1) and (D-2) as an organic solvent A radiation-sensitive resin composition (R-86) was prepared by blending and mixing 2,000 parts by mass and filtering through a membrane filter with a pore size of 0.20 ⁇ m.
• the resist film is developed with an organic solvent at 23° C. for 30 seconds and dried to form a negative contact hole pattern with a hole diameter of 20 nm and a pitch of 40 nm (hereinafter referred to as “20H40P (also referred to as "contact hole pattern”) was formed.
• the exposure dose for forming the 20H40P contact hole pattern was defined as the optimum exposure dose, and this optimal exposure dose was defined as Eop (unit: mJ/cm 2 ). Sensitivity is shown to be better as the value of Eop is smaller.
• CDU performance The resist pattern was observed from above using the scanning electron microscope. The hole diameter was measured at a total of 27,000 points at arbitrary points, and the 3 sigma value was obtained from the distribution of the measured values, which was defined as CDU (unit: nm). Regarding the CDU performance, the smaller the value of CDU, the smaller the dispersion of the hole diameter in the long period, indicating that the performance is good.
• a resist pattern having good sensitivity to exposure light, excellent LWR performance and CDU performance, and a wide process window can be formed.
• the polymer of the present invention can be suitably used as a component of the radiation-sensitive resin composition.
• the compound of the present invention can be suitably used as a monomer for synthesizing the polymer. Therefore, these materials can be suitably used in the processing of semiconductor devices, which are expected to further miniaturize in the future.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Emergency Medicine (AREA)
• Materials For Photolithography (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=83320047

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (2)

Family Cites Families (4)

• 2021
  • 2021-12-24 JP JP2023506765A patent/JPWO2022196024A1/ja active Pending
  • 2021-12-24 WO PCT/JP2021/048363 patent/WO2022196024A1/ja not_active Ceased
  • 2021-12-24 KR KR1020237024717A patent/KR20230157298A/ko active Pending
  • 2021-12-24 KR KR1020257024592A patent/KR20250116785A/ko active Pending
• 2022
  • 2022-02-07 TW TW114129164A patent/TW202546050A/zh unknown
  • 2022-02-07 TW TW111104224A patent/TW202237574A/zh unknown
• 2023
  • 2023-08-29 US US18/239,399 patent/US20230400767A1/en active Pending

Patent Citations (2)

Also Published As

Similar Documents

Legal Events