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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
  • C08F12/30—Sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F212/30—Sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
  • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • 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
• • 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
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
  • G03F7/322—Aqueous alkaline compositions
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
  • H10P76/2042—Photolithographic processes using lasers
• • 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
  • C08F120/00—Homopolymers 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
  • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F120/10—Esters
  • C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F120/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings 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
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3218—Carbocyclic compounds

Definitions

• the present invention relates to a method for manufacturing a semiconductor substrate and a composition for forming a resist underlayer film.
• a multilayer resist process is used in which a resist pattern is formed by exposing and developing a resist film laminated on a substrate via a resist underlayer film such as an organic underlayer film or a silicon-containing film. It is In this process, the resist underlayer film is etched using this resist pattern as a mask, and the substrate is further etched using the obtained resist underlayer film pattern as a mask, thereby forming a desired pattern on the semiconductor substrate.
• a resist underlayer film such as an organic underlayer film or a silicon-containing film.
• the resist underlayer film is required to have solvent resistance against the solvent of the resist composition, and resist pattern rectangularity to suppress skirting of the resist pattern and ensure the rectangularity of the resist pattern.
• the present invention has been made based on the above circumstances, and an object thereof is to provide a semiconductor substrate using a composition for forming a resist underlayer film capable of forming a resist underlayer film having excellent solvent resistance and resist pattern rectangularity.
• An object of the present invention is to provide a production method and a composition for forming a resist underlayer film.
• the present invention in one embodiment, a step of directly or indirectly applying a composition for forming a resist underlayer film onto a substrate; a step of applying a composition for forming a resist film to the resist underlayer film formed by the step of applying the composition for forming a resist underlayer film; a step of exposing the resist film formed by the step of applying the composition for forming a resist film to radiation; and developing at least the exposed resist film,
• the composition for forming a resist underlayer film is a polymer having a partial structure represented by the following formula (i) (hereinafter also referred to as "[A] polymer”);
• the present invention relates to a method for manufacturing a semiconductor substrate containing a solvent (hereinafter also referred to as "[C] solvent”).
• Y 1 is a divalent group selected from the group consisting of a sulfonyl group, a carbonyl group and an alkanediyl group.
• Y 2 is selected from the group consisting of a sulfonyl group, a carbonyl group and a single bond. However, when Y 1 is an alkanediyl group, Y 2 is a sulfonyl group or a carbonyl group, and when Y 2 is a single bond, Y 1 is a sulfonyl group or a carbonyl group.
• .R 1 is a monovalent organic group having 1 to 20 carbon atoms.
• X + is a monovalent onium cation.* is a bond with another structure in the polymer.
• the present invention in another embodiment, a polymer having a partial structure represented by the following formula (i);
• the present invention relates to a composition for forming a resist underlayer film containing a solvent and
• Y 1 is a divalent group selected from the group consisting of a sulfonyl group, a carbonyl group and an alkanediyl group.
• Y 2 is selected from the group consisting of a sulfonyl group, a carbonyl group and a single bond.
• Y 1 is an alkanediyl group
• Y 2 is a sulfonyl group or a carbonyl group
• Y 1 is a sulfonyl group or a carbonyl group
• .R 1 is a monovalent organic group having 1 to 20 carbon atoms.
• X + is a monovalent onium cation.* is a bond with another structure in the polymer.
• a semiconductor substrate can be efficiently manufactured because a composition for forming a resist underlayer film capable of forming a resist underlayer film having excellent solvent resistance and resist pattern rectangularity is used.
• a composition for forming a resist underlayer film a film having excellent solvent resistance and resist pattern rectangularity can be formed. Therefore, these can be suitably used for manufacturing semiconductor devices and the like.
• the method for producing a semiconductor substrate includes a step of directly or indirectly coating a substrate with a composition for forming a resist underlayer film (hereinafter also referred to as “coating step (I)”), and the composition for forming a resist underlayer film.
• a step of applying a resist film-forming composition to the resist underlayer film formed by the product coating step (hereinafter also referred to as “coating step (II)”), and the resist film-forming composition coating step A step of exposing the resist film formed by using radiation (hereinafter also referred to as an “exposure step”) and a step of developing at least the exposed resist film (hereinafter also referred to as a “developing step”). .
• a resist underlayer film having excellent solvent resistance and resist pattern rectangularity is formed by using a predetermined composition for forming a resist underlayer film in the coating step (I). Therefore, a semiconductor substrate having a favorable pattern shape can be manufactured.
• the method for manufacturing a semiconductor substrate includes, before the coating step (II), a step of heating the resist underlayer film formed by the resist underlayer film-forming composition coating step at 200° C. or higher (hereinafter referred to as “ (also referred to as “heating step”).
• the method for manufacturing a semiconductor substrate may optionally include a step of directly or indirectly forming a silicon-containing film on the substrate prior to the coating step (I) (hereinafter also referred to as a “silicon-containing film forming step”. ) may be further provided.
• composition for forming a resist underlayer film used in the method for manufacturing a semiconductor substrate and each step in the case of including a heating step, which is a preferred step, and a silicon-containing film forming step, which is an optional step, will be described below.
• composition for forming a resist underlayer film contains [A] polymer and [C] solvent.
• the composition may contain optional ingredients as long as the effects of the present invention are not impaired.
• the composition for forming a resist underlayer film can form a resist underlayer film excellent in solvent resistance and resist pattern rectangularity.
• an organic solvent can reduce the solubility for
• the acid generated from the above partial structure in the resist underlayer film supplies the acid to the bottom of the resist film in the exposed portion in the exposure process, increasing the solubility in the developer at the bottom of the resist film and exhibiting the rectangularity of the resist pattern. can do.
• the polymer has a partial structure represented by the following formula (i).
• the composition may contain one or more [A] polymers.
• Y 1 is a divalent group selected from the group consisting of a sulfonyl group, a carbonyl group and an alkanediyl group.
• Y 2 is selected from the group consisting of a sulfonyl group, a carbonyl group and a single bond. However, when Y 1 is an alkanediyl group, Y 2 is a sulfonyl group or a carbonyl group, and when Y 2 is a single bond, Y 1 is a sulfonyl group or a carbonyl group.
• .R 1 is a monovalent organic group having 1 to 20 carbon atoms.
• X + is a monovalent onium cation.* is a bond with another structure in the polymer.
• alkanediyl group represented by Y 1 examples include linear or branched alkanediyl groups having 1 to 10 carbon atoms such as methanediyl, ethanediyl, propanediyl and butanediyl groups. Among them, the alkanediyl group represented by Y1 is preferably a methanediyl group.
• the monovalent organic group having 1 to 20 carbon atoms represented by R 1 includes, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon-carbon A group having a divalent heteroatom-containing group therebetween, a group obtained by substituting a part or all of the hydrogen atoms of the above hydrocarbon group with a monovalent heteroatom-containing group, or a combination thereof.
• an "organic group” is a group having at least one carbon atom.
• Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include monovalent linear hydrocarbon groups having 1 to 20 carbon atoms, monovalent alicyclic hydrocarbon groups having 4 to 20 carbon atoms, and 6 to 20 monovalent aromatic hydrocarbon groups or combinations thereof.
• hydrocarbon group includes chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. This "hydrocarbon group” includes a saturated hydrocarbon group and an unsaturated hydrocarbon group.
• a “chain hydrocarbon group” means a hydrocarbon group composed only of a chain structure without a ring structure, and includes both a straight chain hydrocarbon group and a branched chain hydrocarbon group.
• alicyclic hydrocarbon group means 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 (However, it does not have to consist only of an alicyclic structure, and a part of it may contain a chain structure.).
• Aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure as a ring structure (however, it need not consist only of an aromatic ring structure; structure).
• 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 and tert-butyl group.
• Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl group and cyclohexyl group; cycloalkenyl groups such as cyclopropenyl group, cyclopentenyl group and cyclohexenyl group; norbornyl group; bridging ring saturated hydrocarbon groups such as adamantyl group and tricyclodecyl group; and bridging ring unsaturated hydrocarbon groups such as norbornenyl group and tricyclodecenyl group.
• Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl group, tolyl group, naphthyl group, anthracenyl group, pyrenyl group, and benzyl group.
• heteroatom constituting the divalent or monovalent 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, for example, fluorine, chlorine, bromine and iodine atoms.
• the divalent heteroatom-containing group includes, for example, -CO-, -CS-, -NH-, -O-, -S-, groups in which these are combined, and the like.
• Examples of monovalent heteroatom-containing groups include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, and a halogen atom.
• R 1 may have a substituent other than the above monovalent heteroatom-containing group.
• R 1 above is preferably a monovalent organic group having 1 to 20 carbon atoms in which a fluorine atom or a fluorinated hydrocarbon group is bonded to the carbon atom adjacent to Y 2 in formula (i) above.
• R 1 is preferably a C 1-20 monovalent fluorinated alkyl group in which a fluorine atom or a fluorinated hydrocarbon group is bonded to the carbon atom adjacent to Y 2 in the above formula (i).
• R 1 is more preferably a C 1-5 perfluoroalkyl group, particularly preferably a trifluoromethyl group.
• R 1 is more preferably a fluoroalkyl group having 1 to 5 carbon atoms or a perfluoroalkyl group having 1 to 5 carbon atoms, and a 2,2,2-trifluoroethyl group. or a perfluoroethyl group is particularly preferred.
• R C3 , R C4 and R C5 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, a substituted or unsubstituted an aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen atom, —OSO 2 —R CC1 or —SO 2 —R CC2 , or a ring formed by combining two or more of these groups Represent structure.
• R CC1 and R CC2 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, a substituted or unsubstituted C 5-25 alicyclic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
• c1, c2 and c3 are each independently an integer of 0-5.
• the plurality of R C3 to R C5 and R CC1 and R CC2 may be the same or different.
• R C6 is a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms. or a halogen atom.
• c4 is an integer of 0-7.
• the plurality of R 1 C6 may be the same or different, and the plurality of R 1 C6 may represent a ring structure formed by being combined with each other.
• R C7 is a substituted or unsubstituted C 1-7 linear or branched alkyl group, a substituted or unsubstituted C 6 or 7 aromatic hydrocarbon group, or a halogen atom.
• c5 is an integer of 0-6.
• the plurality of R 7 may be the same or different, and the plurality of R 7 may represent a ring structure formed by being combined with each other.
• n c2 is an integer of 0-3.
• R C8 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• n c1 is an integer of 0-2.
• R 1 C9 and R 10 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, a substituted or unsubstituted C 6 12 aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, —OSO 2 —R CC3 or —SO 2 —R CC4 , or two or more of these groups combined together.
• R CC3 and R CC4 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, a substituted or unsubstituted C 5-25 alicyclic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
• c6 and c7 are each independently an integer of 0-5.
• the plurality of R C9 , R C10 , R CC3 and R CC4 may be the same or different.
• Examples of unsubstituted linear alkyl groups represented by R C3 , R C4 , R C5 , R C6 , R C7 , R C9 and R C10 include methyl group, ethyl group, n-propyl group, n- A butyl group and the like can be mentioned.
• Examples of unsubstituted branched alkyl groups represented by R C3 , R C4 , R C5 , R C6 , R C7 , R C9 and R C10 include isopropyl group, isobutyl group, sec-butyl group, t-butyl and the like.
• Examples of unsubstituted aromatic hydrocarbon groups represented by R C3 , R C4 , R C5 , R C9 and R C10 include aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group and naphthyl group; Examples include aralkyl groups such as benzyl group and phenethyl group.
• Examples of the unsubstituted aromatic hydrocarbon group represented by R 6 C6 and R 6 C7 include phenyl group, tolyl group, benzyl group and the like.
• Examples of the divalent organic group represented by R 1 C8 include a group obtained by removing one hydrogen atom from the monovalent organic group represented by R 1 above.
• substituents that may substitute hydrogen atoms of the alkyl groups and aromatic hydrocarbon groups represented by R C3 , R C4 , R C5 , R C6 , R C7 , R C9 and R C10 include carbon monovalent chain hydrocarbon groups of number 1 to 10, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and propoxy group, methoxycarbonyl group and ethoxycarbonyl group alkoxycarbonyloxy groups such as alkoxycarbonyloxy group, methoxycarbonyloxy group and ethoxycarbonyloxy group, acyl groups such as formyl group, acetyl group, propionyl group and butyryl group, cyano group and nitro group.
• halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom
• alkoxy groups such as methoxy
• R C3 , R C4 , R C5 , R C6 , R C7 , R C9 and R C10 are unsubstituted linear or branched alkyl groups, halogen atoms, fluorinated alkyl groups, unsubstituted monovalent Aromatic hydrocarbon groups, —OSO 2 —R BB5 and —SO 2 —R BB5 are preferred, and branched alkyl groups, halogen atoms, fluorinated alkyl groups and unsubstituted monovalent aromatic hydrocarbon groups are more preferred. A t-butyl group and a fluorine atom are more preferred.
• RBB5 is an unsubstituted monovalent alicyclic hydrocarbon group or an unsubstituted monovalent aromatic hydrocarbon group.
• C1, c2 and c3 in formula (ca) are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• c4 in formula (cb) is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 1.
• c5 is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
• nc2 is preferably 2 or 3, more preferably 2.
• nc1 is preferably 0 or 1, more preferably 0.
• cations (ca) and cations (cc) are preferred as X + . More preferred cations (ca) are triphenylsulfonium cations and tris(4-fluorophenyl)sulfonium cations.
• the cations (cc) include diphenyliodonium cation, bis(4-t-butylphenyl)iodonium cation, bis(4-fluorophenyl)iodonium cation, bis(4-bromophenyl)iodonium cation, bis(4-cyano Phenyl)iodonium cation and bis(4-nitrophenyl)iodonium cation are more preferable.
• the polymer preferably has a repeating unit represented by the following formula (1) (hereinafter also referred to as "repeating unit (1)").
• the partial structure represented by the above formula (i) in the [A] polymer i.e., a sulfonimide salt structure, a sulfonamide salt structure, an imide salt structure, etc. acid-generating structure
• the partial structure represented by the above formula (i) in the [A] polymer i.e., a sulfonimide salt structure, a sulfonamide salt structure, an imide salt structure, etc. acid-generating structure
• R a is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• L 1 is a single bond or a divalent link other than an alkanediyl group. is a group, and Y 1 , Y 2 , R 1 and X + have the same meanings as in formula (i) above.
• the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R a is a monovalent hydrocarbon group having 1 to 20 carbon atoms in R 1 of the above formula (i). It can be preferably adopted.
• R a has a substituent, the substituent is represented by R C3 , R C4 , R C5 , R C6 , R C7 , R C9 and R C10 in the above formulas (ca) to (c-c).
• R a is preferably a hydrogen atom.
• the divalent linking group represented by L 1 is a divalent group other than an alkanediyl group, which is a monovalent organic group having 1 to 20 carbon atoms represented by R 1 in formula (i) above.
• a group obtained by removing one hydrogen atom from is mentioned.
• L 1 is preferably a divalent hydrocarbon group.
• Examples of the divalent hydrocarbon group for L 1 include a group obtained by removing one hydrogen atom from the monovalent hydrocarbon group having 1 to 20 carbon atoms for R 1 in formula (i) above.
• L 1 is preferably a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a benzenediyl group.
• repeating unit (1) include repeating units represented by the following formulas (1-1) to (1-18).
• R a has the same meaning as in formula (1) above. Among them, repeating units represented by the above formulas (1-1) to (1-3) and (1-10) to (1-18) are preferred.
• the lower limit of the content ratio of the repeating unit (1) in all repeating units constituting the polymer is preferably 1 mol%, more preferably 5 mol%. , 10 mol % is more preferred, and 20 mol % is particularly preferred.
• the upper limit of the content is preferably 100 mol%, more preferably 70 mol%, still more preferably 60 mol%, and particularly preferably 50 mol%.
• the polymer further has a repeating unit represented by the following formula (2) (excluding the repeating unit (1) above) (hereinafter also referred to as "repeating unit (2)”): is preferred.
• the polymer may have one or more repeating units (2).
• R 3 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• L3 is a single bond or a divalent linking group.
• R 4 is a monovalent organic group having 1 to 20 carbon atoms.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 3 include the groups exemplified as the monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R a in the above formula (1). can be preferably employed.
• examples of the substituent include the groups exemplified as the substituent of R a in formula (1) above.
• Examples of the divalent linking group represented by L 3 include the groups exemplified as the divalent linking group represented by L 1 in formula (1) above.
• L 3 is a single bond or -COO-. preferable.
• Examples of monovalent organic groups having 1 to 20 carbon atoms represented by R 4 include monovalent organic groups having 1 to 20 carbon atoms represented by R 1 in formula (i) above.
• R 4 includes a substituted or unsubstituted monovalent hydrocarbon group represented by R a in the above formula (1), a substituted or unsubstituted monovalent heterocyclic group, and carbon- A group containing —CO—, —CS—, —O—, —S—, —SO 2 — or —NR′—, or a combination of two or more of these, between carbon atoms or at the carbon terminus, and the like are preferred.
• R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• R 4 above is preferably a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent chain hydrocarbon group or a substituted or unsubstituted monovalent heterocyclic group.
• heterocyclic group examples include a group obtained by removing one hydrogen atom from an aromatic heterocyclic ring structure and a group obtained by removing one hydrogen atom from an alicyclic heterocyclic ring structure.
• the heterocyclic structure also includes a 5-membered ring aromatic structure having aromaticity by introducing a heteroatom.
• Heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and the like.
• aromatic heterocyclic structures examples include oxygen atom-containing aromatic heterocyclic structures such as furan, pyran, benzofuran, and benzopyran; nitrogen atom-containing aromatic heterocyclic structures such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, acridine, phenazine, carbazole; sulfur atom-containing aromatic heterocyclic structures such as thiophene; Examples include aromatic heterocyclic structures containing multiple heteroatoms such as thiazole, benzothiazole, thiazine, and oxazine.
• alicyclic heterocyclic structures include oxygen atom-containing alicyclic heterocyclic structures such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane; nitrogen atom-containing alicyclic heterocyclic structures such as aziridine, pyrrolidine, pyrazolidine, piperidine, piperazine; Sulfur atom-containing alicyclic heterocyclic structures such as thietane, thiolane, and thiane; Alicyclic heterocyclic structures containing a plurality of heteroatoms such as oxazoline, morpholine, oxathiolane, oxazine and thiomorpholine, structures in which an alicyclic heterocyclic structure such as benzoxazine and an aromatic ring structure are combined, and the like can be mentioned.
• oxygen atom-containing alicyclic heterocyclic structures such as oxirane, ox
• the cyclic structures also include structures containing lactone structures, cyclic carbonate structures, sultone structures and cyclic acetals.
• repeating unit (2) include repeating units represented by the following formulas (2-1) to (2-20).
• R 3 has the same definition as in formula (2) above. Among them, repeating units represented by the above formulas (2-1) to (2-8) are preferable.
• the lower limit of the content ratio of the repeating unit (2) in all repeating units constituting the [A] polymer is preferably 5 mol %, more preferably 10 mol %, still more preferably 15 mol %, and particularly preferably 20 mol %.
• the upper limit of the content ratio is preferably 95 mol%, more preferably 90 mol%, still more preferably 85 mol%, and particularly preferably 80 mol%.
• the polymer may further have a repeating unit (W) represented by the following formula (W-1) or (W-2). [A] The polymer may have one or more repeating units (W).
• R w1 represents a ring structure with 6 to 20 ring members formed with two carbon atoms in the formula.
• R w2 represents It represents a ring structure with 4 to 20 ring members formed with one carbon atom.
• the ring structure having 6 to 20 ring members represented by R w1 includes a structure corresponding to a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms in R 1 of the above formula (1), the above formula (1 ), a structure corresponding to a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in R 1 of the above formula (2), a structure corresponding to a monovalent heterocyclic group in R 4 of the above formula (2), a lactone structure, a cyclic carbonate structure , a sultone structure, a cyclic acetal, or a combination thereof.
• the ring structure may have a fused ring structure.
• a fused ring is a ring structure in which adjacent rings share an edge (two adjacent atoms).
• Examples of the ring structure with 4 to 20 ring members represented by R w2 include groups obtained by expanding the ring structure with 6 to 20 ring members represented by R w1 to 4 to 20 ring members.
• R w1 and R w2 have a substituent
• substituents include the groups exemplified as the substituent for R 1 in formula (i) above.
• repeating unit (W) include repeating units represented by the following formulas (W-1-1) to (W-1-2) and (W-2-1) to (W-2-2) A unit etc. are mentioned.
• the lower limit of the content ratio of the repeating unit (W) in all repeating units constituting the [A] polymer is preferably 10 mol %, more preferably 20 mol %, even more preferably 30 mol %.
• the upper limit of the content ratio is preferably 80 mol%, more preferably 70 mol%, and even more preferably 60 mol%.
• the lower limit of the weight average molecular weight of the polymer is preferably 1,000, more preferably 2,000, even more preferably 3,000, and particularly preferably 5,000.
• the upper limit of the molecular weight is preferably 22,000, more preferably 20,000, still more preferably 19,000, and particularly preferably 18,000.
• the method for measuring the weight average molecular weight is described in Examples.
• the lower limit of the content of the [A] polymer in the components other than the [C] solvent in the composition for forming a resist underlayer film is preferably 10% by mass, more preferably 20% by mass, and even more preferably 30% by mass.
• the upper limit of the content ratio is preferably 100% by mass, more preferably 90% by mass, and even more preferably 80% by mass.
• [[A] polymer synthesis method] [A] The polymer can be synthesized by performing radical polymerization, ionic polymerization, polycondensation, polyaddition, addition condensation, etc. depending on the type of monomer. For example, when synthesizing the [A] polymer by radical polymerization, it can be synthesized by polymerizing monomers that give each structural unit in an appropriate solvent using a radical polymerization initiator or the like.
• radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-cyclopropylpropyl pionitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis isobutyrate, dimethyl-2,2′-azobis(2-methylpropionate), etc.
• azo-based radical initiators peroxide-based radical initiators such as benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide; These radical initiators can be used individually by 1 type or in mixture of 2 or more types.
• the [C] solvent described later can be suitably employed.
• the solvents used for these polymerizations may be used singly or in combination of two or more.
• the reaction temperature in the above polymerization is usually 40°C to 150°C, preferably 50°C to 120°C.
• the reaction time is generally 1 hour to 48 hours, preferably 1 hour to 24 hours.
• the composition for forming a resist underlayer film may contain other polymer (hereinafter also referred to as "[B] polymer”) in addition to the [A] polymer.
• the [B] polymer may include, for example, a polymer obtained by radical polymerization that does not contain the repeating unit (1) (hereinafter also referred to as "[B1] polymer”). It may also contain a polymer obtained by addition condensation (hereinafter also referred to as "[B2] polymer”).
• the composition may contain one or more of the [B1] polymer and [B2] polymer.
• the [B1] polymer may have the following repeating unit together with or in place of the repeating unit (2) in the [A] polymer.
• the polymer may have a repeating unit represented by the following formula (3) (hereinafter also referred to as "repeating unit (3)").
• R 42 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• L 42 is a single bond or a divalent linking group.
• the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 42 includes the substituted or unsubstituted R a of the above formula (1).
• a group shown as a monovalent hydrocarbon group having 1 to 20 carbon atoms can be preferably employed.
• L42 is a single bond, an alkanediyl group obtained by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms, or a cycloalkylene group obtained by removing one hydrogen atom from a cycloalkyl group having 5 to 10 carbon atoms.
• an arylene group obtained by removing one hydrogen atom from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a carbonyl group, an oxygen atom, or a combination thereof, a single bond, and an alkanediyl having 1 to 5 carbon atoms.
• a group, a cycloalkylene group having 5 to 7 carbon atoms, a phenylene group, a carbonyl group, an oxygen atom, or a combination thereof is more preferred.
• repeating unit (3) include repeating units represented by the following formulas (3-1) to (3-8).
• R 42 has the same definition as in formula (3) above.
• the lower limit of the content of the repeating unit (3) in the total repeating units constituting the [B1] polymer is preferably 30 mol%, and 40 mol%. More preferably, 50 mol % is even more preferable.
• the upper limit of the content is preferably 99 mol%, more preferably 90 mol%, and even more preferably 85 mol%.
• the polymer has a repeating unit represented by the following formula (4) (excluding the case of the above formula (3)) (hereinafter also referred to as "repeating unit (4)"). good too.
• R 53 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• L 53 is a single bond or a divalent linking group.
• R 54 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• the substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 53 and R 54 are respectively substituted groups represented by R a in the above formula (1).
• R 53 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the repeating unit (4).
• R 54 is preferably a monovalent chain hydrocarbon group having 1 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent branched chain alkyl group having 1 to 10 carbon atoms or carbon Aromatic hydrocarbon groups of numbers 6 to 10 are more preferred.
• R 53 and R 54 have a substituent, preferred examples of the substituent include the substituents that R a in the above formula (1) can have.
• L 53 is a single bond, an alkanediyl group obtained by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms, or a cycloalkylene group obtained by removing one hydrogen atom from a cycloalkyl group having 5 to 10 carbon atoms.
• a carbonyl group, an oxygen atom or a combination thereof are preferred, a single bond, an alkanediyl group having 1 to 5 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, a carbonyl group, an oxygen atom or a combination thereof are more preferred, and a single Bonding is even more preferred.
• preferred examples of the substituent include the substituents that R a of the above formula (1) can have.
• repeating unit (4) include repeating units represented by the following formulas (4-1) to (4-17).
• R 53 has the same definition as in formula (4) above.
• the lower limit of the content of the repeating unit (4) in the total repeating units constituting the [B1] polymer is preferably 1 mol%, and 5 mol%. More preferably, 10 mol % is even more preferable.
• the upper limit of the content may be 100 mol%, preferably 50 mol%, more preferably 40 mol%, and even more preferably 30 mol%.
• the polymer is a repeating unit represented by the following formula (5) (excluding the case of the above formula (3) and the above formula (4)) (hereinafter also referred to as "repeating unit (5)". ).
• R 65 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• L 64 is a single bond or a divalent linking group.
• Ar 1 is a monovalent group having an aromatic ring with 6 to 20 ring members.
• the term "number of ring members” refers to the number of atoms forming a ring.
• the biphenyl ring has 12 ring members
• the naphthalene ring has 10 ring members
• the fluorene ring has 13 ring members.
• the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 65 includes the substituted or unsubstituted R a of the above formula (1).
• a group shown as a monovalent hydrocarbon group having 1 to 20 carbon atoms can be preferably employed.
• R 65 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the repeating unit (5).
• R 65 has a substituent
• preferred examples of the substituent include the substituents that R a of the above formula (1) can have.
• L 64 is a single bond, an alkanediyl group obtained by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms, or a cycloalkylene group obtained by removing one hydrogen atom from a cycloalkyl group having 5 to 10 carbon atoms.
• a carbonyl group, an oxygen atom or a combination thereof are preferred, a single bond, an alkanediyl group having 1 to 5 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, a carbonyl group, an oxygen atom or a combination thereof are more preferred, and a single Bonding is even more preferred.
• the aromatic ring having 6 to 20 ring members in Ar 1 includes, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, indene ring and pyrene ring, pyridine ring, pyrazine ring, An aromatic heterocyclic ring such as a pyrimidine ring, a pyridazine ring, a triazine ring, or a combination thereof can be used.
• the aromatic ring of Ar 1 is at least one aromatic hydrocarbon ring selected from the group consisting of benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring, perylene ring and coronene ring. is preferred, and a benzene ring, naphthalene ring or pyrene ring is more preferred.
• the monovalent group having an aromatic ring with 6 to 20 ring members represented by Ar 1 is the aromatic ring with 6 to 20 ring members in Ar 1 above, with one hydrogen atom removed. and the like are preferably mentioned.
• Ar 1 has a substituent
• preferred examples of the substituent include the substituents that R a of the above formula (1) can have.
• repeating unit (5) examples include repeating units represented by the following formulas (5-1) to (5-10).
• R 65 has the same meaning as in formula (5) above. Among them, repeating units represented by the above formula (5-1) are preferable.
• the lower limit of the content of the repeating unit (5) in the total repeating units constituting the [B1] polymer is preferably 5 mol%, and 10 mol%. More preferably, 20 mol % is even more preferable.
• the upper limit of the content is preferably 70 mol%, more preferably 60 mol%, and even more preferably 40 mol%.
• the lower limit of the weight average molecular weight of the polymer is preferably 500, more preferably 1000, even more preferably 2000, and particularly preferably 3000.
• the upper limit of the molecular weight is preferably 10,000, more preferably 9,000, even more preferably 8,000, and particularly preferably 7,000.
• the lower limit of the content of the [B1] polymer is 10% by mass in the total mass of the [A] polymer and [B1] polymer. is preferred, 20% by mass is more preferred, and 30% by mass is even more preferred.
• the upper limit of the content ratio is preferably 80% by mass, more preferably 70% by mass, and even more preferably 60% by mass in the total mass of the [A] polymer and [B1] polymer.
• the polymer can be synthesized by radical polymerization.
• monomers that give each structural unit can be synthesized by polymerizing in a suitable solvent using a radical polymerization initiator or the like.
• the polymer has a repeating unit represented by the following formula ( ⁇ ).
• the polymer may have two or more repeating units represented by the following formula ( ⁇ ).
• the composition may contain one or more [B2] polymers.
• Ar a is a divalent group having an aromatic ring with 5 to 40 ring members.
• Ar b is a hydrogen atom or a divalent group having an aromatic ring with 5 to 40 ring members. be.
• the aromatic rings having 5 to 40 ring members in Ar a and Ar b include, for example, benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring, perylene ring, coronene ring
• Aromatic hydrocarbon rings such as rings, furan rings, pyrrole rings, thiophene rings, phosphor rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, triazine rings, etc.
• a heteroaromatic ring, or a combination thereof, or the like can be mentioned.
• the aromatic ring of Ar a and Ar b is at least one aromatic hydrocarbon selected from the group consisting of benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring, perylene ring and coronene ring.
• a ring is preferred.
• the aromatic ring of Ar a and Ar b is more preferably a benzene ring, a naphthalene ring or a pyrene ring.
• the divalent group having an aromatic ring with 5 to 40 ring members represented by Ar a and Ar b includes two hydrogen atoms from the aromatic ring with 5 to 40 ring members in Ar a .
• Groups excluding atoms are preferred.
• At least one of Ar a and Ar b has at least one group selected from the group consisting of a group represented by the following formula ( ⁇ -1) and a group represented by the following formula ( ⁇ -2) is preferred.
• R 7 is each independently a divalent organic group having 1 to 20 carbon atoms or a single bond. * is a carbon atom in the aromatic ring. It is a bond.
• the divalent organic group having 1 to 20 carbon atoms represented by R 7 includes, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms, A group having a divalent heteroatom-containing group between the carbon-carbon atoms of the hydrocarbon group, a group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with a monovalent heteroatom-containing group, or a combination thereof etc.
• divalent hydrocarbon group having 1 to 20 carbon atoms examples include a chain divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and a divalent hydrocarbon group having 4 to 20 carbon atoms. 6 to 20 divalent aromatic hydrocarbon groups or combinations thereof.
• Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include methanediyl group, ethanediyl group, propanediyl group, butanediyl group, hexanediyl group, octanediyl group and the like. Among them, an alkanediyl group having 1 to 8 carbon atoms is preferred.
• the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms includes, for example, a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group; a cycloalkenediyl group such as a cyclopentenediyl group and a cyclohexenediyl group; adamantanediyl group, tricyclodecanediyl group, and other bridged ring saturated hydrocarbon groups; and bridged ring unsaturated hydrocarbon groups, such as norbornenediyl group and tricyclodecenediyl group.
• a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group
• a cycloalkenediyl group such as a cyclopentenediyl group and a cyclohex
• Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group, naphthalenediyl group, anthracenediyl group, pyrenediyl group, toluenediyl group, and xylenediyl group.
• heteroatom constituting the divalent or monovalent 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, for example, fluorine, chlorine, bromine and iodine atoms.
• the divalent heteroatom-containing group includes, for example, -CO-, -CS-, -NH-, -O-, -S-, groups in which these are combined, and the like.
• Examples of monovalent heteroatom-containing groups include a hydroxy group, a sulfanyl group, a cyano group, a nitro group, and a halogen atom.
• R 7 is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms such as a methanediyl group, an ethanediyl group, a phenylene group, -O-, or a combination thereof, and a methanediyl group or a combination of a methanediyl group and -O- is more preferred.
• Ar a has a group represented by the above formula ( ⁇ -1), and the group is preferably represented by the following formula ( ⁇ -1-1).
• Ar a and Ar b may have a substituent other than the group represented by the above formula ( ⁇ -1) and the group represented by the above formula ( ⁇ -2).
• substituents include monovalent chain hydrocarbon groups having 1 to 10 carbon atoms; halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy, ethoxy and propoxy; phenoxy group, aryloxy group such as naphthyloxy group, alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group, alkoxycarbonyloxy group such as methoxycarbonyloxy group and ethoxycarbonyloxy group, formyl group, acetyl group, propionyl group, Examples include acyl groups such as butyryl groups, cyano groups, nitro groups, and hydroxy groups.
• repeating unit represented by the above formula ( ⁇ ) examples include repeating units represented by the following formulas ( ⁇ -1) to ( ⁇ -7).
• resole polymer is a polymer obtained by reacting a phenolic compound with an aldehyde using an alkaline catalyst.
• phenolic compounds include Phenols such as phenol, cresol, xylenol, resorcinol, bisphenol A; Naphthols such as 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9-bis(6-hydroxynaphthyl)fluorene; 9-anthrol, such as anthrol; and hydroxypyrenes such as 1-hydroxypyrene and 2-hydroxypyrene.
• Phenols such as phenol, cresol, xylenol, resorcinol, bisphenol A
• Naphthols such as 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9-bis(6-hydroxynaphthyl)fluorene
• 9-anthrol such as anthrol
• aldehydes examples include aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, and 1-pyrenecarboxaldehyde; Aldehyde sources such as paraformaldehyde, trioxane, paraldehyde, and the like are included.
• a polyarylene-based polymer is a polymer having structural units derived from a compound containing an arylene skeleton.
• the arylene skeleton includes, for example, a phenylene skeleton, a naphthylene skeleton, a biphenylene skeleton and the like.
• polyarylene-based polymers examples include polyarylene ether, polyarylene sulfide, polyarylene ether sulfone, polyarylene ether ketone, and polymers having structural units containing a biphenylene skeleton and structural units derived from a compound containing an acenaphthylene skeleton. is mentioned.
• Triazine-based polymer A triazine-based polymer is a polymer having structural units derived from a compound having a triazine skeleton. Examples of compounds having a triazine skeleton include melamine compounds and cyanuric acid compounds.
• a calixarene-based polymer is a cyclic oligomer in which a plurality of aromatic rings to which a hydroxy group is bonded is cyclically bonded via a hydrocarbon group, or a part or all of the hydrogen atoms possessed by the hydroxy group, the aromatic ring and the hydrocarbon group are It is a substituted compound.
• the lower limit of the weight average molecular weight of the polymer is preferably 500, more preferably 1000, even more preferably 1500, and particularly preferably 2000.
• the upper limit of the molecular weight is preferably 8,000, more preferably 7,000, still more preferably 6,000, and particularly preferably 5,000.
• the lower limit of the content of the [B2] polymer is 10% by mass in the total mass of the [A] polymer and [B2] polymer. is preferred, 20% by mass is more preferred, and 30% by mass is even more preferred.
• the upper limit of the content ratio is preferably 80% by mass, more preferably 70% by mass, and even more preferably 60% by mass in the total mass of the [A] polymer and [B2] polymer.
• the polymer is typically produced by acid addition condensation of an aromatic ring compound as a precursor having a phenolic hydroxyl group that gives A a of the above formula ( ⁇ ) and an aldehyde derivative as a precursor, followed by the above It can be synthesized by a nucleophilic substitution reaction with a phenolic hydroxyl group on a halogenated hydrocarbon corresponding to the group represented by formula ( ⁇ -1) or ( ⁇ -2).
• the [C] solvent is not particularly limited as long as it can dissolve or disperse the [A] polymer and optionally contained optional components.
• Solvents include, for example, hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, nitrogen-containing solvents, and the like.
• a solvent can be used individually by 1 type or in combination of 2 or more types.
• hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as n-pentane, n-hexane and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene and xylene.
• ester solvents include carbonate solvents such as diethyl carbonate, acetic acid monoester solvents such as methyl acetate and ethyl acetate, lactone solvents such as ⁇ -butyrolactone, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate.
• carbonate solvents such as diethyl carbonate
• acetic acid monoester solvents such as methyl acetate and ethyl acetate
• lactone solvents such as ⁇ -butyrolactone
• diethylene glycol monomethyl ether acetate diethylene glycol monomethyl ether acetate
• propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate.
• Valued alcohol partial ether carboxylate solvents such as methyl lactate and ethyl lactate, and the like are included.
• alcohol solvents examples include monoalcohol solvents such as methanol, ethanol, n-propanol and 4-methyl-2-pentanol, and polyhydric alcohol solvents such as ethylene glycol and 1,2-propylene glycol. .
• ketone solvents include chain ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone, and cyclic ketone solvents such as cyclohexanone.
• ether solvents examples include linear ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran, and polyhydric alcohol partial ether solvents such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether. Solvents and the like are included.
• nitrogen-containing solvents examples include linear nitrogen-containing solvents such as N,N-dimethylacetamide and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
• the solvent is preferably an alcohol solvent, an ether solvent or an ester solvent, more preferably a monoalcohol solvent, a polyhydric alcohol partial ether solvent, a polyhydric alcohol partial ether carboxylate solvent or a lactate ester solvent.
• Preferred are 4-methyl-2-pentanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethyl lactate.
• the lower limit of the content of the [C] solvent in the composition for forming a resist underlayer film is preferably 50% by mass, more preferably 60% by mass, and even more preferably 70% by mass.
• the upper limit of the content ratio is preferably 99.9% by mass, more preferably 99% by mass, and even more preferably 95% by mass.
• composition for forming a resist underlayer film may contain arbitrary components as long as the effects of the present invention are not impaired.
• optional components include the above [B] polymer, as well as a cross-linking agent, an acid generator, a dehydrating agent, an acid diffusion control agent, and a surfactant.
• An arbitrary component can be used individually by 1 type or in combination of 2 or more types.
• cross-linking agent is not particularly limited, and a known cross-linking agent can be freely selected and used.
• a known cross-linking agent can be freely selected and used.
• At least one or more is preferably used as a cross-linking agent.
• the polyfunctional (meth)acrylates are not particularly limited as long as they are compounds having two or more (meth)acryloyl groups.
• an aliphatic polyhydroxy compound and (meth)acrylic acid are reacted. obtained by reacting polyfunctional (meth)acrylates, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, hydroxyl group-containing (meth)acrylates and polyfunctional isocyanates
• trimethylolpropane tri(meth)acrylate ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate , 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate,
• Cyclic ether-containing compounds include, for example, 1,6-hexanediol diglycidyl ether, 3′,4′-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexene carboxylate, vinylcyclohexene monoxide 1,2- Oxiranyl group-containing compounds such as epoxy-4-vinylcyclohexene, 1,2:8,9 diepoxylimonene; 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylenebisoxetane, 3-ethyl-3 ⁇
• Examples include oxetanyl group-containing compounds such as [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane.
• Glycolurils include, for example, tetramethylolglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, compounds in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or mixtures thereof, tetramethylol Compounds in which 1 to 4 methylol groups of glycoluril are acyloxymethylated, glycidylglycolurils, and the like can be mentioned.
• Glycidyl glycolurils include, for example, 1-glycidyl glycoluril, 1,3-diglycidyl glycoluril, 1,4-diglycidyl glycoluril, 1,6-diglycidyl glycoluril, 1,3,4-tri glycidyl glycoluril, 1,3,4,6-tetraglycidyl glycoluril, 1-glycidyl-3a-methylglycoluril, 1-glycidyl-6a-methyl-glycoluril, 1,3-diglycidyl-3a-methylglycoluril, 1,4-diglycidyl-3a-methylglycoluril, 1,6-diglycidyl-3a-methylglycoluril, 1,3,4-triglycidyl-3a-methylglycoluril, 1,3,4-triglycidyl-6a- methyl glycol uril, 1,3,4,6-tetraglycidyl-3a-methyl glycol uril, 1-glycidyl-3
• diisocyanates examples include 2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 3,4-tolylene diisocyanate, 3,5-tolylene diisocyanate, 4,4′- diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate and the like.
• Melamines include, for example, melamine, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine, monobutyromelamine, dibutyromelamine, tributyromelamine, tetrabutyrole Examples include melamine, pentabutyromelamine, hexabutyromelamine, and alkylated derivatives of these methylolmelamines or butyromelamines. These melamines can be used alone or in combination of two or more.
• Benzoguanamines include, for example, benzoguanamines in which the amino group is modified with four alkoxymethyl groups (alkoxymethylol groups) (tetraalkoxymethylbenzoguanamines (tetraalkoxymethylolbenzoguanamines)), such as tetramethoxymethylbenzoguanamine; benzoguanamines whose amino groups are modified with a total of four alkoxymethyl groups (particularly methoxymethyl groups) and hydroxymethyl groups (methylol groups); benzoguanamines whose amino groups are modified with up to 3 alkoxymethyl groups (especially methoxymethyl groups); benzoguanamine in which amino groups are modified with alkoxymethyl groups (especially methoxymethyl groups) and hydroxymethyl groups of 3 or less in total; and the like. These benzoguanamines can be used individually or in mixture of 2 or more types.
• polynuclear phenols examples include dinuclear phenols such as 4,4'-biphenyldiol, 4,4'-methylenebisphenol, 4,4'-ethylidenebisphenol and bisphenol A; Redentrisphenol, 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol, 4,4'-(1-(4-(1- Trinuclear phenols such as (4-hydroxy-3,5-bis(methoxymethyl)phenyl)-1-methylethyl)phenyl)ethylidene)bis(2,6-bis(methoxymethyl)phenol); polyphenols such as novolak etc. These polynuclear phenols can be used alone or in combination of two or more.
• the polyfunctional thiol compound is a compound having two or more mercapto groups in one molecule, and specific examples include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2 ,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 2,3 -dimercaptosuccinic acid, 1,2-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedithiol, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 3,4 -dimercaptotoluene, 4-chloro-1,3-benzenedithiol, 2,4,6-trimethyl-1
• mercapto compounds such as 1,2,6-hexanetriol trithioglycolate, 1,3,5-trithiocyanuric acid, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate compounds having groups, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptopropionate) pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1 , 3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and the like compounds having four or more mercapto groups mentioned.
• These polyfunctional thiol compounds can be used individually or in mixture of
• the lower limit of the content of [D] cross-linking agent is 100 parts by mass of [A] polymer, or [A] polymer and [B ] 10 parts by mass is preferable, 20 parts by mass is more preferable, and 30 parts by mass is still more preferable with respect to a total of 100 parts by mass of the polymer.
• the upper limit of the content is preferably 100 parts by mass, more preferably 90 parts by mass, and even more preferably 80 parts by mass.
• composition for forming a resist underlayer film is prepared by mixing [A] a polymer, [C] a solvent, and optionally optional components in a predetermined ratio, and preferably applying the resulting mixture to a membrane having a pore size of 0.5 ⁇ m or less. It can be prepared by filtering with a filter or the like.
• Silicon-containing film forming step In this step performed prior to the coating step (I), a silicon-containing film is formed directly or indirectly on the substrate.
• the substrate examples include metal or semi-metal substrates such as silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, and titanium substrates, among which silicon substrates are preferred.
• the substrate may be a substrate on which a silicon nitride film, an alumina film, a silicon dioxide film, a tantalum nitride film, a titanium nitride film, or the like is formed.
• a silicon-containing film can be formed by coating a silicon-containing film-forming composition, chemical vapor deposition (CVD), atomic layer deposition (ALD), or the like.
• CVD chemical vapor deposition
• ALD atomic layer deposition
• a method for forming a silicon-containing film by coating a silicon-containing film-forming composition for example, a coating film formed by directly or indirectly coating a substrate with a silicon-containing film-forming composition is subjected to exposure and / Or the method of hardening by heating, etc. are mentioned.
• Commercially available products of the silicon-containing film-forming composition include, for example, "NFC SOG01", “NFC SOG04", and "NFC SOG080" (manufactured by JSR Corporation).
• Silicon oxide films, silicon nitride films, silicon oxynitride films, and amorphous silicon films can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
• Examples of the radiation used for the exposure include visible light, ultraviolet rays, far ultraviolet rays, X-rays, electromagnetic waves such as ⁇ -rays, and particle beams such as electron beams, molecular beams, and ion beams.
• the lower limit of the temperature when heating the coating film is preferably 90°C, more preferably 150°C, and even more preferably 200°C.
• the upper limit of the temperature is preferably 550°C, more preferably 450°C, and even more preferably 300°C.
• the lower limit of the average thickness of the silicon-containing film is preferably 1 nm, more preferably 10 nm, and even more preferably 15 nm.
• the upper limit is preferably 20,000 nm, more preferably 1,000 nm, even more preferably 100 nm.
• the average thickness of the silicon-containing film can be measured in the same manner as the average thickness of the resist underlayer film.
• Forming a silicon-containing film indirectly on a substrate includes, for example, forming a silicon-containing film on a low dielectric insulating film or an organic underlayer film formed on a substrate.
• the composition for forming a resist underlayer film is applied onto the silicon-containing film formed on the substrate.
• the method of coating the composition for forming a resist underlayer film is not particularly limited, and can be carried out by an appropriate method such as spin coating, casting coating, roll coating, or the like. As a result, a coating film is formed, and [C] a resist underlayer film is formed by volatilization of the solvent.
• the lower limit to the average thickness of the resist underlayer film to be formed is preferably 0.5 nm, more preferably 1 nm, and even more preferably 2 nm.
• the upper limit of the average thickness is preferably 50 nm, more preferably 20 nm, still more preferably 10 nm, and particularly preferably 7 nm.
• the method for measuring the average thickness is described in Examples.
• the silicon-containing film forming step may be omitted.
• the resist underlayer film formed by the coating step (I) is heated at 200° C. or higher. Heating the resist underlayer film promotes decomposition of the sulfonimide salt structure in the [A] polymer. This step is performed before the coating step (II).
• the coating film may be heated in an air atmosphere or in a nitrogen atmosphere.
• the lower limit of the heating temperature is preferably 200°C, preferably 210°C, more preferably 220°C, and even more preferably 230°C.
• the upper limit of the heating temperature is preferably 400°C, more preferably 350°C, and even more preferably 280°C.
• the lower limit of the heating time is preferably 30 seconds, more preferably 40 seconds, and even more preferably 60 seconds.
• the upper limit of the time is preferably 800 seconds, more preferably 400 seconds, and even more preferably 200 seconds.
• step (II) the composition for forming a resist film is applied to the resist underlayer film formed in the step of applying the composition for forming a resist underlayer film.
• the method of applying the composition for forming a resist film is not particularly limited, and examples thereof include a spin coating method.
• pre-baking (hereinafter also referred to as “PB”) is performed.
• a resist film is formed by volatilizing the solvent.
• the PB temperature and PB time can be appropriately determined according to the type of resist film forming composition used.
• the lower limit of the PB temperature is preferably 30°C, more preferably 50°C.
• the upper limit of the PB temperature is preferably 200°C, more preferably 150°C.
• the lower limit of the PB time is preferably 10 seconds, more preferably 30 seconds.
• the upper limit of the PB time is preferably 600 seconds, more preferably 300 seconds.
• the composition for forming a resist film used in this step includes, for example, a positive-type or negative-type chemically amplified resist composition containing a radiation-sensitive acid generator, and a positive composition containing an alkali-soluble resin and a quinonediazide-based photosensitive agent.
• resist compositions, negative resist compositions containing an alkali-soluble resin and a cross-linking agent, and metal-containing resist compositions containing metals such as tin and zirconium As the resist film-forming composition used in this step, it is preferable to use a so-called positive resist film-forming composition for alkali development.
• Such a composition for forming a resist film contains, for example, a resin having an acid-labile group and a radiation-sensitive acid generator, and is used for exposure with ArF excimer laser light (for ArF exposure) or exposure with extreme ultraviolet rays.
• a composition for forming a positive resist film for EUV exposure is preferred.
• the resist film formed in the resist film-forming composition coating step is exposed to radiation.
• This step causes a difference in solubility in a basic liquid, which is a developer, between an exposed portion and an unexposed portion of the resist film. More specifically, the solubility of the exposed portion of the resist film in a basic liquid increases.
• the radiation used for exposure can be appropriately selected depending on the type of resist film-forming composition used.
• Examples thereof include electromagnetic waves such as visible light, ultraviolet rays, deep ultraviolet rays, X-rays and ⁇ -rays, and particle beams such as electron beams, molecular beams and ion beams.
• far ultraviolet rays are preferable, and KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm), F2 excimer laser light (wavelength 157 nm), Kr2 excimer laser light (wavelength 147 nm), ArKr excimer laser.
• Exposure conditions can be appropriately determined according to the type of the resist film-forming composition to be used.
• PEB post-exposure bake
• the PEB temperature and PEB time can be appropriately determined according to the type of resist film-forming composition used.
• the lower limit of the PEB temperature is preferably 50°C, more preferably 70°C.
• the upper limit of the PEB temperature is preferably 200°C, more preferably 150°C.
• the lower limit of the PEB time is preferably 10 seconds, more preferably 30 seconds.
• the upper limit of the PEB time is preferably 600 seconds, more preferably 300 seconds.
• This step is preferably alkali development in which the developer used is a basic liquid. Due to the above exposure process, a difference in solubility in a basic liquid, which is a developer, occurs between the exposed area and the unexposed area of the resist film. A resist pattern is formed by removing the exposed portion where the resistance is relatively high.
• the resist underlayer film contains a polymer containing a sulfonic acid group, the solubility in a basic liquid, which is a developer, is increased, and the polymer can be removed together with the resist film in the developing step of the resist film.
• the resist underlayer film may be partially developed in the thickness direction from the outermost surface of the resist underlayer film, the entire thickness direction is developed (that is, the resist underlayer film is completely removed in the exposed portion). is more preferable.
• a part of the resist underlayer film in the plane direction may be used, and the etching process of the resist underlayer film, which is conventionally required, can be omitted by continuously developing the resist underlayer film following the resist film with a basic solution. It is possible to efficiently form a good resist pattern by reducing the number of steps and suppressing the influence on other films.
• the basic liquid for alkaline development is not particularly limited, and known basic liquids can be used.
• Basic solutions for alkali development include, 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 (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-
• TMAH aqueous solution in which at least one alkaline compound such as diazabicyclo-[4.3.0]-5-nonene is dissolved can be mentioned.
• a TMAH aqueous solution is preferable, and a 2.38% by mass TMAH aque
• Examples of the developer used for organic solvent development include the same ones as those exemplified as the [C] solvent described above.
• washing and/or drying may be performed after the development.
• etching is performed using the resist pattern (and the resist underlayer film pattern) as a mask. Etching may be performed once or multiple times, that is, etching may be performed sequentially using a pattern obtained by etching as a mask. Multiple times are preferable from the viewpoint of obtaining a pattern with a better shape. When etching is performed multiple times, for example, the silicon-containing film and the substrate are sequentially etched. Etching methods include dry etching, wet etching, and the like. Dry etching is preferable from the viewpoint of improving the pattern shape of the substrate. For this dry etching, gas plasma such as oxygen plasma is used. A semiconductor substrate having a predetermined pattern is obtained by the etching.
• Dry etching can be performed using, for example, a known dry etching apparatus.
• the etching gas used for dry etching can be appropriately selected according to the mask pattern, the elemental composition of the film to be etched, etc. Examples include CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 and SF 6 .
• Fluorine-based gases chlorine-based gases such as Cl 2 and BCl 3 , oxygen-based gases such as O 2 , O 3 and H 2 O, H 2 , NH 3 , CO, CO 2 , CH 4 , C 2 H 2 , C 2H4 , C2H6 , C3H4 , C3H6 , C3H8 , HF , HI, HBr, HCl, NO, NH3 , reducing gases such as BCl3 , He, N2 , Inert gas, such as Ar, etc. are mentioned. These gases can also be mixed and used. When etching a substrate using the pattern of the resist underlayer film as a mask, a fluorine-based gas is usually used.
• composition for forming a resist underlayer film contains [A] polymer and [C] solvent.
• a composition for forming a resist underlayer film used in the method for manufacturing a semiconductor substrate can be suitably employed.
• Mw Weight average molecular weight
• Average thickness of film The average thickness of the film is measured using a spectroscopic ellipsometer ("M2000D" by JA WOOLLAM) at arbitrary 9 points at intervals of 5 cm including the center of the resist underlayer film. The average thickness was obtained as a calculated value.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of diisopropyl ether to obtain 1.8 g of a white solid (yield: 45%).
• the obtained polymer (A-4) represented by the following formula (A-4) had an Mw of 10092, an Mn of 6288, and a molecular weight dispersity of 1.60.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of diisopropyl ether to obtain 2.8 g of a white solid (yield: 70%).
• the resulting polymer (A-5) represented by the following formula (A-5) had an Mw of 17340, an Mn of 10632, and a molecular weight dispersity of 1.63.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of diisopropyl ether to obtain 2.9 g of a white solid (yield: 72%).
• the obtained polymer (A-6) represented by the following formula (A-6) had Mw of 15600, Mn of 9760 and a molecular weight dispersity of 1.60.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the volume of diisopropyl ether to obtain 3.2 g of a white solid (yield: 80%).
• the obtained polymer (A-7) represented by the following formula (A-7) had Mw of 17,320, Mn of 10,654, and a molecular weight dispersity of 1.63.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 6.67 g of a white solid (yield: 80%).
• the resulting polymer (A-8) had an Mw of 12200, an Mn of 6777, and a molecular weight dispersity of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 7.62 g of a white solid (yield: 80%).
• the resulting polymer (A-9) had an Mw of 12200, an Mn of 6777, and a molecular weight dispersity of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 2.57 g of a white solid (yield: 80%).
• the resulting polymer (A-10) had Mw of 8400, Mn of 4670, and a molecular weight distribution of 1.8.
• the obtained polymer (A-11) had Mw of 9800, Mn of 5440, and molecular weight dispersity of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 11.84 g of a white solid (yield: 80%).
• the resulting polymer (A-12) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 11.05 g of a white solid (yield: 80%).
• the resulting polymer (A-13) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 11.86 g of a white solid (yield: 80%).
• the resulting polymer (A-14) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 12.77 g of a white solid (yield: 80%).
• the resulting polymer (A-15) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 10.59 g of a white solid (yield: 80%).
• the resulting polymer (A-16) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 8.59 g of a white solid (yield: 80%).
• the resulting polymer (A-17) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymer (A-18) had Mw of 9800, Mn of 5440 and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 9.02 g of a white solid (yield: 80%).
• the resulting polymer (A-19) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 11.18 g of a white solid (yield: 80%).
• the resulting polymer (A-20) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 12.77 g of a white solid (yield: 80%).
• the obtained polymer (A-21) had Mw of 9800, Mn of 5440, and molecular weight dispersity of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 12.51 g of a white solid (yield: 80%).
• the resulting polymer (A-22) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the obtained polymer (A-23) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 13.22 g of a white solid (yield: 80%).
• the resulting polymer (A-24) had Mw of 9800, Mn of 5440, and a molecular weight distribution of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 12.9 g of a white solid (yield: 80%).
• the obtained polymer (A-25) had Mw of 12200, Mn of 6777, and molecular weight dispersity of 1.8.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 12.9 g of a white solid (yield: 80%).
• the obtained polymer (A-26) had Mw of 12200, Mn of 6777, and molecular weight dispersity of 1.8.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (b-3) represented by the following formula (b-3).
• the Mw of polymer (b-3) was 3,400.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (B-3).
• the Mw of polymer (B-3) was 4,500.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (B-4). Mw of the polymer (B-4) was 5,400.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (B-5). Mw of the polymer (B-5) was 3,400.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (b-6) represented by the following formula (b-6).
• the Mw of polymer (b-6) was 7,200.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (B-7).
• the Mw of polymer (B-7) was 6,400.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (b-8) represented by the following formula (b-8).
• the Mw of polymer (b-8) was 3,400.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (B-8). Mw of the polymer (B-8) was 4,500.
• the obtained organic phase was concentrated by an evaporator, and the residue was dropped into 500 g of methanol to obtain a precipitate.
• the precipitate was collected by suction filtration and washed several times with 100 g of methanol. Then, it was dried at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (B-9). Mw of the polymer (B-9) was 6,200.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 3.15 g of a white solid (yield: 80%). Mw of the resulting polymer (B-10) was 12,200.
• the resulting polymerization liquid was concentrated by an evaporator and then purified by precipitation with 10 times the amount of methyl isobutyl ketone to obtain 2.84 g of a white solid (yield: 80%). Mw of the obtained polymer (B-11) was 8,200.
• D-1 compound represented by the following formula (D-1)
• D-2 compound represented by the following formula (D-2)
• composition (J-1) [A] 50 parts by weight of (A-1) as a polymer, [D] 50 parts by weight of (D-2) as a cross-linking agent, [C] 1100 parts by weight of (C-1) as a solvent and (C -2) Dissolved in 200 parts by mass.
• the resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 0.45 ⁇ m to prepare composition (J-1).
• PTFE polytetrafluoroethylene
• Example 2 to 57 and Comparative Examples 1 to 3 Compositions (J-2) to (J-57) and (CJ-1) to (CJ-3) in the same manner as in Example 1 except that the types and contents of each component shown in Table 1 below were used. ) was prepared. "-" in the column “A, B, D” in Table 1 indicates that the corresponding component was not used.
• the absolute value of the numerical value obtained by (X ⁇ X0) ⁇ 100/X0 is calculated, and the film thickness change rate ( %).
• the solvent resistance is "A” (good) when the film thickness change rate is less than 1%, "B” (slightly good) when it is 1% or more and less than 10%, and "C” when it is 10% or more. (bad).
• An organic underlayer film forming material (“HM8006” from JSR Corporation) was applied onto a 12-inch silicon wafer by a spin coating method using a spin coater (“CLEAN TRACK ACT12” from Tokyo Electron Ltd.). C. for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• a composition for forming a silicon-containing film (“NFC SOG080” manufactured by JSR Corporation) was applied onto the organic underlayer film, heated at 220°C for 60 seconds, and then cooled at 23°C for 30 seconds to obtain an average thickness. A 20 nm silicon-containing film was formed. The composition prepared above was applied onto the silicon-containing film formed above to form a resist underlayer film.
• the resist underlayer film thus formed was heated at 250° C. for 180 seconds and then cooled at 23° C. for 30 seconds to obtain a resist underlayer film having an average thickness of 5 nm.
• the resist composition (R-1) was applied onto the resist underlayer film formed above, heated at 130° C. for 60 seconds, and then cooled at 23° C. for 30 seconds to form a resist film with an average thickness of 50 nm.
• an EUV scanner ASML "TWINSCAN NXE: 3300B" (NA 0.3, sigma 0.9, quadruple pole illumination, 1:1 line and space mask with a line width of 16 nm on the wafer) was used to create a resist film. After the extreme ultraviolet irradiation, the substrate was heated at 110° C.
• An organic underlayer film forming material (“HM8006” from JSR Corporation) was applied onto a 12-inch silicon wafer by a spin coating method using a spin coater (“CLEAN TRACK ACT12” from Tokyo Electron Ltd.). C. for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• a composition for forming a silicon-containing film (“NFC SOG800” manufactured by JSR Corporation) was applied onto this organic underlayer film, heated at 220°C for 60 seconds, and then cooled at 23°C for 30 seconds to obtain an average thickness. A 20 nm silicon-containing film was formed. The composition prepared above was applied onto the silicon-containing film formed above to form a resist underlayer film.
• the resist underlayer film thus formed was heated at 250° C. for 180 seconds and then cooled at 23° C. for 30 seconds to obtain a resist underlayer film having an average thickness of 5 nm.
• the resist composition (R-1) was applied onto the resist underlayer film, heated at 130° C. for 60 seconds, and then cooled at 23° C. for 30 seconds to form a resist film having an average thickness of 50 nm.
• HM8006 organic underlayer film forming material
• CLEAN TRACK ACT12 spin coater
• C. for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• a composition for forming a silicon-containing film (“NFC SOG800” manufactured by JSR Corporation) was applied onto this organic underlayer film, heated at 220°C for 60 seconds, and then cooled at 23°C for 30 seconds to obtain an average thickness.
• a 20 nm silicon-containing film was formed.
• the composition prepared above was applied onto the silicon-containing film formed above to form a resist underlayer film.
• the resist underlayer film thus formed was heated at 250° C. for 180 seconds and then cooled at 23° C. for 30 seconds to obtain a resist underlayer film having an average thickness of 5 nm.
• the resist composition (R-1) was applied onto the resist underlayer film, heated at 130° C. for 60 seconds, and then cooled at 23° C. for 30 seconds to form a resist film having an average thickness of 50 nm.
• the resist film was exposed using an EB scanner (electron beam drawing apparatus (manufactured by Elionix; ELS-F150, current 1 pA, voltage 150 kV, pattern size 200 nm). After the electron beam irradiation, the substrate was exposed at 110 ° C. for 60 seconds.
• the compound (S-1) used for the preparation of the EUV exposure resist composition (R-2) was synthesized by the procedure shown below.
• a reaction vessel 6.5 parts by mass of isopropyltin trichloride was added while stirring 150 mL of 0.5 N sodium hydroxide aqueous solution, and the reaction was carried out for 2 hours.
• the deposited precipitate was collected by filtration, washed twice with 50 parts by mass of water, and dried to obtain compound (S-1).
• the compound (S-1) has the structure of the hydroxide oxide product (i-PrSnO (3/2-x/2) (OH) x (0 ⁇ x ⁇ 3)) of the hydrolyzate of isopropyltin trichloride. unit).
• An organic underlayer film forming material (“HM8006” from JSR Corporation) was applied onto a 12-inch silicon wafer by a spin coating method using a spin coater (“CLEAN TRACK ACT12” from Tokyo Electron Ltd.). C. for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• the composition for forming a resist underlayer film prepared above was applied, heated at 220° C. for 60 seconds, and then cooled at 23° C. for 30 seconds to form a resist underlayer film having an average thickness of 5 nm. .
• the EUV exposure resist composition (R-2) is applied by the spin coating method using the above spin coater, and after a predetermined time has elapsed, after heating at 90 ° C. for 60 seconds, A resist film having an average thickness of 35 nm was formed by cooling at 23° C. for 30 seconds.
• EUV scanner ASML "TWINSCAN NXE: 3300B" (NA 0.3, sigma 0.9, quadruple pole illumination, 1:1 line and space mask with a line width of 16 nm on the wafer) is used to expose the resist film. After exposure, the substrate was heated at 110° C. for 60 seconds and then cooled at 23° C.
• the resist underlayer films formed from the compositions of Examples had better solvent resistance and resist pattern rectangularity than the resist underlayer films formed from the compositions of Comparative Examples. was excellent.
• a composition for forming a resist underlayer film capable of forming a resist underlayer film having excellent solvent resistance and resist pattern rectangularity is used, it is possible to efficiently manufacture a semiconductor substrate. can.
• a film excellent in solvent resistance and resist pattern rectangularity can be formed. Therefore, these can be suitably used for manufacturing semiconductor devices and the like.

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