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
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic 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
  • G03F7/09—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
  • C08F12/22—Oxygen
  • C08F12/24—Phenols or alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/56—Acrylamide; Methacrylamide
• • 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
  • C09D141/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur; Coating compositions based on derivatives of such polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—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
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
• • 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
  • G03F7/70—Microphotolithographic exposure; Apparatus therefor
  • G03F7/70008—Production of exposure light, i.e. light sources
  • G03F7/70033—Production of exposure light, i.e. light sources by plasma extreme ultraviolet [EUV] sources
• • 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
• • 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

Definitions

• the present invention relates to a method for manufacturing a semiconductor substrate and a composition for forming a resist underlayer film.
• a multi-layer resist process in which a resist pattern is formed by exposing and developing a resist film that is laminated on a substrate via a resist underlayer film such as an organic underlayer film or a silicon-containing film.
• a resist underlayer film such as an organic underlayer film or a silicon-containing film.
• the resist underlayer film is etched using this resist pattern as a mask, and the substrate is further etched using the resulting resist underlayer film pattern as a mask, thereby forming a desired pattern on the semiconductor substrate.
• the resist underlayer film is required to have resistance to the solvent in the resist composition, and pattern rectangularity that suppresses pattern tailing at the bottom of the resist film and ensures the rectangularity of the resist pattern.
• the present invention was made based on the above circumstances, and its purpose is to provide a composition for forming a resist underlayer film that can form a resist underlayer film that has excellent solvent resistance and pattern rectangularity, and a method for manufacturing a semiconductor substrate.
• the present invention comprises: A polymer having a repeating unit represented by the following formula (1) (hereinafter also referred to as “polymer (A)”),
• the present invention relates to a composition for forming a resist underlayer film, comprising:
• R 1 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 linking group.
• Ar 1 is a monovalent group having an aromatic ring having 6 to 20 ring members. The aromatic ring is substituted with at least one halogen atom.
• Ar 1 has at least one group (hereinafter also referred to as "specific group") selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), a group represented by the following formula (2-4), a group represented by the following formula (2-5), a group represented by the following formula (2-6), a group represented by the following formula (2-7), and a group represented by the following formula (2-8).
• group represented by the following formula (2-1) to (2-8) * represents a bond to an atom constituting Ar 1
• R 7 represents a divalent organic group having 1 to 20 carbon atoms or a single bond.
• R 8 , R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• ** is a bond to an atom constituting Cy. Cy is a ring structure formed together with the two carbon atoms in the formula and having 3 to 20 ring members.
• R 11 is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, or a bond to **.
• R 12 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• R 13 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• the present invention provides a method for producing a pharmaceutical composition comprising the steps of: A step of directly or indirectly applying a composition for forming a resist underlayer film to a substrate; a step of applying a composition for forming a resist film to the resist underlayer film formed by the above-mentioned step of applying a composition for forming a resist film; a step of exposing the resist film formed by the resist film-forming composition application step to radiation; and developing at least the exposed resist film.
• the composition for forming a resist underlayer film A polymer having a repeating unit represented by the following formula (1): and a solvent.
• R 1 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 linking group.
• Ar 1 is a monovalent group having an aromatic ring having 6 to 20 ring members. The aromatic ring is substituted with at least one halogen atom.
• Ar 1 has at least one group selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), a group represented by the following formula (2-4), a group represented by the following formula (2-5), a group represented by the following formula (2-6), a group represented by the following formula (2-7), and a group represented by the following formula (2-8).
• * represents a bond to an atom constituting Ar 1
• R 7 represents a divalent organic group having 1 to 20 carbon atoms or a single bond.
• R 8 , R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• ** is a bond to an atom constituting Cy. Cy is a ring structure formed together with the two carbon atoms in the formula and having 3 to 20 ring members.
• R 11 is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, or a bond to **.
• R 12 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• R 13 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• the composition for forming a resist underlayer film can form a film that is excellent in solvent resistance and pattern rectangularity.
• the method for manufacturing a semiconductor substrate uses a composition for forming a resist underlayer film that can form a resist underlayer film that is excellent in solvent resistance and pattern rectangularity, so that semiconductor substrates can be manufactured efficiently. Therefore, these can be suitably used for manufacturing semiconductor devices, etc.
• resist underlayer film forming composition and the method for manufacturing a semiconductor substrate according to each embodiment of the present invention will be described in detail below. Combinations of preferred aspects in the embodiments are also preferred.
• composition for forming a resist underlayer film contains a polymer (A) and a solvent (B).
• the composition may contain any optional components within a range that does not impair the effects of the present invention.
• compositions for forming a resist film include a positive or negative chemically amplified resist composition containing a radiation-sensitive acid generator, a positive resist composition containing an alkali-soluble resin and a quinone diazide-based photosensitizer, a negative resist composition containing an alkali-soluble resin and a crosslinking agent, and a metal-containing resist composition containing metals such as tin, zirconium, and hafnium.
• the underlayer film formed by the composition contains halogen atoms derived from the polymer [A], so that the efficiency of generating secondary electrons due to absorption of extreme ultraviolet rays is high.
• halogen atoms derived from the polymer [A] so that the efficiency of generating secondary electrons due to absorption of extreme ultraviolet rays is high.
• a sufficient difference in solubility occurs in the interface region on the underlayer film side of the organic resist film during exposure to extreme ultraviolet rays, and the insolubilization of the metal-containing resist film is promoted, thereby suppressing the tailing of the pattern at the bottom of the resist film and ensuring the rectangularity of the resist pattern.
• the polymer [A] since the polymer [A] has a specific group, a crosslinked structure is formed in the resulting resist underlayer film, and the solubility in organic solvents can be reduced.
• the lower limit of the content of the metal or metal compound in the components other than the solvent in the metal-containing resist composition is preferably 50% by mass, more preferably 70% by mass, even more preferably 80% by mass, and particularly preferably 85% by mass.
• the upper limit of the content is, for example, 100% by mass or 95% by mass.
• the polymer [A] has a repeating unit represented by the following formula (1) (hereinafter also referred to as "repeating unit (1)").
• the polymer [A] can contain one or more types of repeating unit (1).
• the polymer [A] may have a repeating unit other than the repeating unit (1).
• the composition can contain one or more types of polymer [A].
• R 1 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 linking group.
• Ar 1 is a monovalent group having an aromatic ring having 6 to 20 ring members. The aromatic ring is substituted with at least one halogen atom.
• Ar 1 has at least one group selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), a group represented by the following formula (2-4), a group represented by the following formula (2-5), a group represented by the following formula (2-6), a group represented by the following formula (2-7), and a group represented by the following formula (2-8).
• * represents a bond to an atom constituting Ar 1
• R 7 represents a divalent organic group having 1 to 20 carbon atoms or a single bond.
• R 8 , R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• ** is a bond to an atom constituting Cy. Cy is a ring structure formed together with the two carbon atoms in the formula and having 3 to 20 ring members.
• R 11 is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, or a bond to **.
• R 12 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• R 13 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R1 is not particularly limited, and examples thereof include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof.
• Examples of monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and neopentyl; alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.
• Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups such as cyclopropenyl, cyclopentenyl and cyclohexenyl groups; bridged ring saturated hydrocarbon groups such as norbornyl, adamantyl and tricyclodecyl groups; and bridged ring unsaturated hydrocarbon groups such as norbornenyl and tricyclodecenyl groups.
• Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, tolyl, naphthyl, anthracenyl, pyrenyl, fluorenyl, and 9-methylidenefluorenyl groups.
• R1 has a substituent
• substituents include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; an alkoxycarbonyloxy group such as a methoxycarbonyloxy group or an ethoxycarbonyloxy group; an acyl group such as a formyl group, an acetyl group, a propionyl group, or a butyryl group; a cyano group; and a nitro group.
• a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
• R 1 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the repeating unit (1).
• examples of the divalent linking group represented by L1 include a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent heteroatom-containing group, a group having the above divalent heteroatom-containing group between carbon-carbon atoms of the above divalent hydrocarbon group having 1 to 20 carbon atoms, a group in which some or all of the hydrogen atoms of the above hydrocarbon group have been substituted with monovalent heteroatom-containing groups, and combinations thereof.
• the divalent hydrocarbon group having 1 to 20 carbon atoms a group in which one hydrogen atom has been removed from the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 above can be suitably used, and a group in which one hydrogen atom has been removed from a phenyl group or a group in which one hydrogen atom has been removed from a 9-methylidenefluorenyl group is preferred.
• Heteroatoms constituting a divalent or monovalent heteroatom-containing group include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, halogen atoms, etc.
• halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
• divalent heteroatom-containing group examples include -CO-, -CS-, -NR'-, -O-, -S-, -SO 2 -, and combinations of these.
• R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
• Preferred divalent heteroatom-containing groups are -CO-O-, -CO-NH-, and -O-.
• Examples of monovalent heteroatom-containing groups include hydroxyl groups, sulfanyl groups, cyano groups, nitro groups, carboxy groups, amino groups, and halogen atoms.
• examples of the aromatic ring having 6 to 20 ring members in Ar 1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, an indene ring, and a pyrene ring, aromatic heterocycles such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring, and combinations thereof.
• aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, an indene ring, and a pyrene ring
• aromatic heterocycles such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring, and combinations thereof.
• the aromatic ring in Ar 1 is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.
• the aromatic ring is substituted with at least one halogen atom. It is preferable that the aromatic ring is substituted with at least two halogen atoms. In this case, the multiple halogen atoms may be the same or different. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. It is preferable that the halogen atom is an iodine atom.
• the divalent organic group having 1 to 20 carbon atoms represented by R 7 can be suitably selected from the divalent linking group represented by L 1 in the above formula (1).
• a combination of a divalent hydrocarbon group having 1 to 10 carbon atoms and a divalent heteroatom-containing group is preferable, and a combination of a methanediyl group, an ethanediyl group, a propanediyl group, a benzenediyl group, or a combination thereof with -O-, -CO-, or a combination thereof is more preferable.
• examples of the monovalent organic group having 1 to 20 carbon atoms represented by R 8 , R 9 , R 10 , R 11 , R 12 and R 13 include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group having a divalent heteroatom-containing group between the carbon atoms of this hydrocarbon group or at the terminal of the hydrocarbon group, a group in which some or all of the hydrogen atoms of the hydrocarbon group have been substituted with a monovalent heteroatom-containing group, or a combination of these.
• an "organic group” is a group having at least one carbon atom.
• a monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 in the above formula (1) can be suitably used.
• the divalent heteroatom-containing group and the monovalent heteroatom-containing group for R 8 to R 13 the divalent heteroatom-containing group and the monovalent heteroatom-containing group for L 1 in the above formula (1) can be suitably adopted.
• R 8 to R 13 are all hydrogen atoms.
• the ring structure having 3 to 20 ring members formed together with the two carbon atoms in the formula represented by Cy can be suitably a ring structure corresponding to the monovalent alicyclic hydrocarbon having 3 to 20 carbon atoms in R 1 of the above formula (1).
• Cy is preferably a cycloalkane ring having 5 to 10 carbon atoms, more preferably a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring.
• repeating unit (1) include repeating units represented by the following formulas (1-1) to (1-15).
• R 1 has the same meaning as in the above formula (1).
• the lower limit of the content of repeating unit (1) in all repeating units constituting polymer [A] is preferably 10 mol%, more preferably 30 mol%, and even more preferably 75 mol%.
• the upper limit of the content may be 100 mol%, i.e., polymer [A] may be a homopolymer of repeating unit (1).
• polymer [A] is a copolymer
• the upper limit of the content of repeating unit (1) may be 99 mol% or 95 mol%.
• the polymer [A] may further have a repeating unit represented by the following formula (3) (excluding the case of the above formula (1)) (hereinafter also referred to as "repeating unit (2)").
• the polymer [A] may have one or more types of repeating unit (2).
• R 31 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• L 31 is a single bond or a divalent linking group.
• R 41 is a monovalent organic group having 1 to 20 carbon atoms.
• R 31 As the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 31 , a monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 in the above formula (1) can be suitably adopted.
• R 31 has a substituent
• R 1 in the above formula (1) can be suitably adopted.
• L 31 a divalent linking group represented by L 1 in the above formula (1) can be suitably adopted.
• L 31 is preferably a single bond.
• monovalent organic groups having 1 to 20 carbon atoms represented by R 41 monovalent organic groups having 1 to 20 carbon atoms represented by R 8 to R 13 in the above formulas (2-1), (2-2) and (2-3) can be suitably used.
• this monovalent organic group a substituted or unsubstituted monovalent heterocyclic group is also suitable.
• heterocyclic groups include groups in which one hydrogen atom has been removed from an aromatic heterocyclic structure and groups in which one hydrogen atom has been removed from an aliphatic heterocyclic structure.
• Five-membered aromatic structures that have aromaticity due to the introduction of heteroatoms are also included in the heterocyclic structure.
• heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.
• aromatic heterocyclic structure 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, and carbazole; Sulfur-containing aromatic heterocyclic structures such as thiophene;
• heterocyclic ring examples include aromatic heterocyclic structures containing a plurality of heteroatoms, such as thiazole, benzothiazole, thiazine, and oxazine.
• Examples of the aliphatic heterocyclic structure include oxygen atom-containing aliphatic heterocyclic structures such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane; Nitrogen-containing aliphatic heterocyclic structures such as aziridine, pyrrolidine, pyrazolidine, piperidine, and piperazine; Sulfur-containing aliphatic heterocyclic structures such as thietane, thiolane, and thiane;
• Examples of the heterocyclic structure include aliphatic heterocyclic structures containing a plurality of heteroatoms, such as oxazoline, morpholine, oxathiolane, oxazine, and thiomorpholine, and structures in which an aliphatic heterocyclic structure and an aromatic ring structure are combined, such as benzoxazine.
• Cyclic structures include lactone structures, cyclic carbonate structures, sultone structures, and structures containing cyclic acetals.
• repeating unit (2) include repeating units represented by the following formulas (3-1) to (3-20).
• R 31 has the same meaning as in the above formula (3).
• the lower limit of the content of repeating unit (2) in all repeating units constituting the polymer [A] is preferably 5 mol%, more preferably 10 mol%, and even more preferably 15 mol%.
• the upper limit of the content is preferably 90 mol%, more preferably 85 mol%, and even more preferably 80 mol%.
• the polymer [A] may have, as other repeating units, repeating units containing a sulfonate ester structure, repeating units derived from maleic acid, maleic anhydride, maleimide derivatives, etc., and repeating units containing a structure that generates acid upon exposure, such as a sulfonimide salt structure, a sulfonamide salt structure, or an imide salt structure.
• the lower limit of the content ratio of the other repeating units (total content ratio when multiple types are present) in all repeating units constituting the polymer [A] is preferably 1 mol%, more preferably 5 mol%, and even more preferably 10 mol%.
• the upper limit of the above content is preferably 90 mol%, more preferably 85 mol%, and even more preferably 80 mol%.
• the lower limit of the weight average molecular weight of the polymer [A] is preferably 1000, more preferably 1500, even more preferably 2000, and particularly preferably 2500.
• the upper limit of the above molecular weight is preferably 10000, more preferably 8000, even more preferably 6000, and particularly preferably 5000.
• the method for measuring the weight average molecular weight is described in the Examples.
• the lower limit of the content of the polymer [A] in the composition for forming a resist underlayer film is preferably 0.05 mass%, more preferably 0.1 mass%, even more preferably 0.15 mass%, and particularly preferably 0.2 mass%, based on the total mass of the polymer [A] and the solvent [B].
• the upper limit of the content is preferably 1 mass%, more preferably 0.8 mass%, even more preferably 0.6 mass%, and particularly preferably 0.4 mass%, based on the total mass of the polymer [A] and the solvent [B].
• the lower limit of the content of the polymer [A] in the components other than the solvent [B] in the composition for forming the 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 is preferably 100% by mass, but may be 90% by mass or 85% by mass.
• the polymer (A) can be synthesized by radical polymerization, ionic polymerization, polycondensation, polyaddition, addition condensation, etc., depending on the type of monomer.
• the monomers that provide each structural unit can be polymerized in an appropriate solvent using a radical polymerization initiator, etc.
• the radical polymerization initiator may be, for example, azo radical initiators such as azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, and dimethyl-2,2'-azobis(2-methylpropionate); or peroxide radical initiators such as benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. These radical initiators may be used alone or in combination of two or more.
• azo radical initiators such as azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,
• the solvent used in the above polymerization the solvent [B] described below can be suitably used. These solvents used in the polymerization may be used alone or in combination of two or more kinds.
• the reaction temperature in the above polymerization is usually 40°C to 150°C, preferably 50°C to 120°C.
• the reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.
• the solvent (B) is not particularly limited as long as it can dissolve or disperse the polymer (A) and any optional components contained as necessary.
• Solvents include, for example, hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, nitrogen-containing solvents, water, etc. [B] Solvents can be used alone or in combination of two or more.
• 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 and propylene carbonate, acetate monoester solvents such as methyl acetate and ethyl acetate, acetate diester solvents such as 1,6-diacetoxyhexane, lactone solvents such as ⁇ -butyrolactone, polyhydric alcohol partial ether carboxylate solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and lactate ester solvents such as methyl lactate and ethyl lactate.
• carbonate solvents such as diethyl carbonate and propylene carbonate
• acetate monoester solvents such as methyl acetate and ethyl acetate
• acetate diester solvents such as 1,6-diacetoxyhexane
• lactone solvents such as ⁇ -butyrolactone
• polyhydric alcohol partial ether carboxylate solvents such as diethylene glycol monomethyl
• alcohol-based solvents examples include monoalcohol-based solvents such as methanol, ethanol, n-propanol, 4-methyl-2-pentanol, and 2,2-dimethyl-1-propanol, and polyhydric alcohol-based solvents such as ethylene glycol and 1,2-propylene glycol.
• Ketone solvents include, for example, chain ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone, and cyclic ketone solvents such as cyclohexanone.
• ether solvents include chain 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.
• nitrogen-containing solvents examples include chain nitrogen-containing solvents such as N,N-dimethylacetamide, and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
• ketone solvents As the solvent, ketone solvents, ether solvents, or ester solvents are preferred, cyclic ketone solvents, polyhydric alcohol partial ether solvents, or polyhydric alcohol partial ether carboxylate solvents are more preferred, and cyclohexanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are even more preferred.
• the resist underlayer film forming composition may contain optional components within a range that does not impair the effects of the present invention.
• the optional components include a crosslinking agent, an acid generator, a dehydrating agent, an acid diffusion control agent, a surfactant, etc.
• the optional components may be used alone or in combination of two or more.
• the content of the optional components in the total mass of the polymer [A] and the optional components is preferably 30 mass% or less, and more preferably 20 mass% or less.
• composition for forming a resist underlayer film can be prepared by mixing the polymer [A], the solvent [B], and, if necessary, any optional components in a predetermined ratio, and filtering the resulting mixture preferably through a membrane filter or the like having a pore size of 0.5 ⁇ m or less.
• the method for manufacturing a semiconductor substrate includes a step of directly or indirectly applying a composition for forming a resist underlayer film to a substrate (hereinafter also referred to as a “coating step (I)”), a step of applying a composition for forming a resist film to the resist underlayer film formed by the above-mentioned coating step of the composition for forming a resist film (hereinafter also referred to as a “coating step (II)”), a step of exposing the resist film formed by the above-mentioned coating step of the composition for forming a resist film to 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 "development step”).
• a resist underlayer film having excellent solvent resistance and pattern rectangularity can be formed by using a specific composition for forming a resist underlayer film in the coating step (I), and thus a semiconductor substrate having a good pattern shape can be manufactured.
• the method for manufacturing a semiconductor substrate preferably further includes a step of heating the resist underlayer film formed by the resist underlayer film forming composition application step at 200°C or higher (hereinafter also referred to as the "heating step") prior to the application step (II).
• the method for manufacturing the semiconductor substrate may further include, as necessary, a step of forming a silicon-containing film directly or indirectly on the substrate prior to the coating step (I) (hereinafter also referred to as the "silicon-containing film forming step").
• the method includes the heating step, which is a preferred step, and the silicon-containing film formation step, which is an optional step.
• Silicon-containing film formation process In this step, which is carried out prior to the above coating step (I), a silicon-containing film is formed directly or indirectly on a substrate.
• the substrate may be, for example, a metal or semimetal substrate such as a silicon substrate, an aluminum substrate, a nickel substrate, a chromium substrate, a molybdenum substrate, a tungsten substrate, a copper substrate, a tantalum substrate, or a titanium substrate, and among these, a silicon substrate is 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.
• the 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.
• methods for forming a silicon-containing film by coating a silicon-containing film-forming composition include a method in which the silicon-containing film-forming composition is directly or indirectly coated on a substrate, and the coated film is then cured by exposure and/or heating.
• Examples of commercially available silicon-containing film-forming compositions include "NFC SOG01", “NFC SOG04", and "NFC SOG080” (all from 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).
• Radiation used for the above-mentioned exposure includes, for example, electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, and gamma rays, as well as 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 above 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, and 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.
• Examples of forming a silicon-containing film indirectly on a substrate include forming a silicon-containing film on a low dielectric insulating film or an organic underlayer film formed on a substrate.
• the composition for forming resist underlayer film is coated on the silicon-containing film formed on the substrate.
• the coating method of the composition for forming resist underlayer film is not particularly limited, and can be carried out by suitable methods such as spin coating, casting coating, roll coating, etc.This forms a coating film, and the solvent [B] volatilizes, etc., to form a resist underlayer film.
• the lower limit of the average thickness of the resist underlayer film 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, even more preferably 10 nm, and particularly preferably 7 nm.
• the method for measuring the average thickness is as described in the Examples.
• the silicon-containing film forming step can be omitted.
• the resist underlayer film formed in the coating step (I) is heated. Heating the resist underlayer film promotes the formation of a crosslinked structure by the specific group in the polymer (A). This step is carried out 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 may be 180°C, but 200°C is preferred, 210°C is more preferred, and 220°C is even more preferred.
• the upper limit of the heating temperature is preferably 400°C, 350°C is more preferred, and 280°C is even more preferred.
• the lower limit of the heating time is preferably 15 seconds, and 30 seconds is more preferred.
• the upper limit of the heating time is preferably 800 seconds, 400 seconds is more preferred, and 200 seconds is even more preferred.
• a composition for forming a resist film is applied to the resist underlayer film formed in the above-mentioned step of applying the composition for forming a resist film.
• the method for applying the composition for forming a resist film is not particularly limited, and examples thereof include a rotational coating method.
• a resist composition is applied so that the resist film to be formed has a predetermined thickness, and then the resist film is formed by volatilizing the solvent in the applied film through pre-baking (hereinafter also referred to as "PB").
• the PB temperature and PB time can be appropriately determined depending on the type of resist film forming composition used, etc.
• the lower limit of the PB temperature is preferably 30°C, and more preferably 50°C.
• the upper limit of the PB temperature is preferably 200°C, and more preferably 150°C.
• the lower limit of the PB time is preferably 10 seconds, and more preferably 30 seconds.
• the upper limit of the PB time is preferably 600 seconds, and more preferably 300 seconds.
• the resist film-forming composition used in this process is preferably a composition that is exposed to extreme ultraviolet rays, and examples of such compositions include positive or negative chemically amplified resist compositions that contain a radiation-sensitive acid generator, and metal-containing resist compositions that contain metals such as tin, zirconium, and hafnium.
• the resist film formed in the resist film-forming composition application process is exposed to radiation.
• This process causes a difference in solubility in a basic liquid, which is a developer, or in an organic solvent 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, or the solubility of the exposed portion in an organic solvent decreases.
• the radiation used for exposure can be appropriately selected depending on the type of the resist film-forming composition used.
• visible light, ultraviolet light, far ultraviolet light, electromagnetic waves such as X-rays and gamma rays, electron beams, molecular beams, particle beams such as ion beams, etc. can be mentioned.
• 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 light (wavelength 134 nm) or extreme ultraviolet light (wavelength 13.5 nm, etc., also referred to as "EUV”) is more preferred, and ArF excimer laser light or EUV is even more preferred.
• the exposure conditions can be appropriately determined depending on the type of the resist film-forming composition used, etc.
• PEB post-exposure baking
• the PEB temperature and PEB time can be appropriately determined depending on the type of resist film-forming composition used.
• the lower limit of the PEB temperature is preferably 50°C, and more preferably 70°C.
• the upper limit of the PEB temperature is preferably 200°C, and more preferably 150°C.
• the lower limit of the PEB time is preferably 10 seconds, and more preferably 30 seconds.
• the upper limit of the PEB time is preferably 600 seconds, and more preferably 300 seconds.
• the exposed resist film is developed. At this time, a part of the resist underlayer film may be further developed.
• the developer used in this development include an alkaline aqueous solution (alkaline developer), an organic solvent-containing liquid (organic solvent developer), and the like.
• the basic liquid for alkaline development is not particularly limited, and any known basic liquid can be used.
• Examples of basic liquids for alkaline development include aqueous alkaline solutions in which at least one of the following alkaline compounds is dissolved: 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-diazabicyclo-[4.3.0]-5-nonene, etc.
• TMAH tetramethylammonium hydroxide
• TMAH tetramethylammonium hydrox
• washing and/or drying may be performed after the development.
• etching is performed using the resist pattern (and resist underlayer film pattern) as a mask.
• the number of times of etching may be one or more, that is, etching may be performed sequentially using the pattern obtained by etching as a mask. From the viewpoint of obtaining a pattern with a better shape, multiple times are preferable.
• etching is performed sequentially in the order of the silicon-containing film and the substrate.
• the etching method include dry etching and wet etching. From the viewpoint of obtaining a better shape of the pattern of the substrate, dry etching is preferable. For this dry etching, for example, gas plasma such as oxygen plasma is used.
• reducing gases such as He, N2 , Ar , etc.
• inert gases such as He, N2 , Ar , etc.
• gases can also be used in mixture.
• a fluorine-based gas is usually used.
• the silicon-containing film can be removed by carrying out a removal process.
• Mw Weight average molecular weight
• Mn number average molecular weight
• PDI polydispersity index
• Polymer [A] was synthesized according to the procedure shown below.
• the numbers attached to each repeating unit indicate the content (mol %) of that repeating unit.
• the content of that repeating unit is 100 mol %.
• the composition ratio was confirmed by 13 C-NMR.
• d-1 Epichlorohydrin d-2: 3,4-Epoxycyclohexylmethanol d-3: 3-Oxetanemethanol d-4: Propargyl bromide d-5: 4-Ethynylbenzoyl chloride d-6: Propargyl alcohol d-7: Propiolic acid d-8: Ultrapure water d-9: 2-(chloromethyl)-1,2-epoxypropane d-10: 4-Chloromethyl-1,3-dioxiran-2-one d-11: (2-chloroethoxy)ethene d-12: 4-Chloromethylbenzocyclobutene
• C-1 A compound represented by the following formula (C-1)
• C-2 A compound represented by the following formula (C-2)
• C-3 A compound represented by the following formula (C-3)
• Example 1-1 25 parts by mass of (A-1) as the polymer [A] was dissolved in 7,900 parts by mass of (B-1) and 2,000 parts by mass of (B-2) as the solvent [B]. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter having a pore size of 0.45 ⁇ m to prepare a composition (J-1).
• PTFE polytetrafluoroethylene
• Example 1-2 to 1-65 and Comparative Examples 1-1 to 1-2 Compositions (J-2) to (J-58) and (CJ-1) to (CJ-2) were prepared in the same manner as in Example 1, except that the components were used in the types and amounts shown in Table 1 below. In Table 3, "-" indicates that the corresponding component was not used.
• the composition prepared above was applied onto a 12-inch silicon wafer by a spin coating method using a spin coater (Tokyo Electron Limited's "CLEAN TRACK ACT12"). Next, in an air atmosphere, the wafer was heated at 250°C for 60 seconds, and then cooled at 23°C for 60 seconds to form a resist underlayer film having an average thickness of 5 nm, thereby obtaining a substrate with a resist underlayer film formed on the substrate.
• the substrate with the resist underlayer film obtained above was immersed in cyclohexanone (23°C) for 1 minute. The average film thicknesses before and after immersion were measured.
• the average thickness of the resist underlayer film before immersion was X0
• the average thickness of the resist underlayer film after immersion was X
• the absolute value of the value obtained by ⁇ (X-X0)/X0 ⁇ x100 was calculated to obtain the film thickness change rate (%).
• the solvent resistance was evaluated as "A” (good) when the film thickness change rate was less than 1%, as “B” (fairly good) when it was 1% or more but less than 10%, and as "C” (poor) when it was 10% or more.
• an organic underlayer film forming material (“HM8006” by JSR Corporation) was applied by a spin coating method using a spin coater ("CLEAN TRACK ACT12" by Tokyo Electron Co., Ltd.), and then heated at 250° C. for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• a silicon-containing film forming composition (“NFC SOG080” by JSR Corporation) was applied, heated at 220° C. for 60 seconds, and then cooled at 23° C. for 30 seconds to form a silicon-containing film having an average thickness of 20 nm.
• the composition prepared above was applied to form a resist underlayer film.
• the resist underlayer film formed above was heated at 250° C. for 90 seconds, and then cooled at 23° C. for 30 seconds to obtain a resist underlayer film having an average thickness of 5 nm.
• a 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 having an average thickness of 50 nm.
• the resist film was irradiated with extreme ultraviolet rays using an EUV scanner (ASML's "TWINSCAN NXE:3300B" (NA 0.3, sigma 0.9, quadrupole illumination, 1:1 line and space mask with a line width of 16 nm on the wafer).
• EUV scanner ASML's "TWINSCAN NXE:3300B” (NA 0.3, sigma 0.9, quadrupole illumination, 1:1 line and space mask with a line width of 16 nm on the wafer).
• the substrate was heated at 110°C for 60 seconds, and then cooled at 23°C for 60 seconds. Thereafter, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (20°C to 25°C) was used for development by the paddle method, followed by washing with water and drying to obtain an evaluation substrate on which a resist pattern was formed.
• a scanning electron microscope (Hitachi High-Technologies Corporation's "SU8220" was used to measure and observe the resist pattern of the evaluation substrate.
• the pattern rectangularity was evaluated as "A” (good) when the cross-sectional shape of the pattern was rectangular, and as “B” (bad) when the cross-section of the pattern had a skirt.
• resist composition (R-2) 2 parts by weight of the compound (S-1) synthesized above was mixed with 98 parts by weight of propylene glycol monoethyl ether, and the resulting mixture was passed through an activated 4 ⁇ molecular sieve to remove residual water, and then filtered through a filter with a pore size of 0.2 ⁇ m to prepare resist composition (R-2).
• an organic underlayer film forming material (“HM8006” by JSR Corporation) was applied by a spin coating method using a spin coater ("CLEAN TRACK ACT12" by Tokyo Electron Limited), and then heated at 250°C for 60 seconds to form an organic underlayer film having an average thickness of 100 nm.
• the resist underlayer film forming composition 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.
• a resist composition (R-2) was applied by a spin coating method using the spin coater, and after a predetermined time had elapsed, the resist film was heated at 90°C for 60 seconds, and then cooled at 23°C for 30 seconds to form a resist film having an average thickness of 35 nm.
• the resist film was exposed to light using an EUV scanner (ASML's "TWINSCAN NXE:3300B" (NA 0.3, sigma 0.9, quadrupole illumination, 1:1 line and space mask with a line width of 16 nm on the wafer). After exposure, the substrate was heated at 110°C for 60 seconds and then cooled at 23°C for 60 seconds.
• the substrate was developed by the paddle method using 2-heptanone (20 to 25°C) and then dried to obtain an evaluation substrate on which a resist pattern was formed.
• a scanning electron microscope (Hitachi High-Tech's "CG-6300") was used to measure and observe the resist pattern of the evaluation substrate.
• the pattern rectangularity was evaluated as "A” (good) when the cross-sectional shape of the pattern was rectangular, and as "B” (bad) when the cross-section of the pattern had a footing.
• the resist underlayer films formed from the compositions of the examples had superior solvent resistance and pattern rectangularity compared to the resist underlayer films formed from the compositions of the comparative examples.
• composition for forming a resist underlayer film of the present invention a film having excellent solvent resistance and pattern rectangularity can be formed.
• a composition for forming a resist underlayer film capable of forming a resist underlayer film having excellent solvent resistance and pattern rectangularity is used, so that a semiconductor substrate can be efficiently produced. Therefore, these can be suitably used for the production of semiconductor devices, etc.

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