Composition for forming resist underlayer film

Abstract

A composition for forming a resist underlayer film contains: a polymer (A) containing a phenolic hydroxy group and a nitro group; and a solvent (B).

Description

Composition for forming resist underlayer film

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a laminate, a method for producing a semiconductor element, and a method for forming a pattern.

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has traditionally been performed. This microfabrication process involves forming a thin film of a photoresist composition on a semiconductor substrate, such as a silicon wafer, irradiating the substrate with actinic rays such as ultraviolet light through a mask pattern bearing a device pattern, developing the thin film, and etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern. In recent years, the integration density of semiconductor devices has increased, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical use of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. As a result, poor resist pattern formation due to influences from the semiconductor substrate, etc., has become a major problem. To address this issue, methods of providing a resist underlayer film between the resist and the semiconductor substrate have been widely investigated.

[0003] As a resist underlayer film-forming composition, a compound represented by the formula (100) (in the formula (100), Ar represents an optionally substituted aromatic ring group having 6 to 40 carbon atoms, L ０ represents a single bond, an ester bond, an ether bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, or an optionally substituted alkenylene group having 2 to 10 carbon atoms; T ０ represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted, provided that L ０ and T ０ Unlike n R ０each independently represents a hydroxy group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group, n represents an integer of 0 to 5, and * represents a bonding portion to a polymer or compound residue. A resist underlayer film-forming composition has been proposed, which includes a polymer or compound having a structure represented by the following formula (see Patent Document 1), and a solvent.

[0004] International Publication No. 2022 / 196662

[0005] Properties required for a resist underlayer film include, for example, not intermixing with a resist film formed on top (being insoluble in a resist solvent), being able to form a good resist pattern by improving the sensitivity and adhesion of the resist pattern, etc. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a resist underlayer film that can improve the sensitivity and adhesion to form a good resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor device, and a pattern formation method that use the composition for forming a resist underlayer film.

[0006] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0007] That is, the present invention encompasses the following aspects. [1] A composition for forming a resist underlayer film, comprising a polymer (A) containing a phenolic hydroxy group and a nitro group, and a solvent (B). [2] The composition for forming a resist underlayer film according to [1], wherein the polymer (A) is a vinyl polymer. [3] The composition for forming a resist underlayer film according to [1] or [2], wherein the polymer (A) contains a structural unit (A1) represented by the following formula (A1) and a structural unit (A2) represented by the following formula (A2): (In formula (A1), R １ represents a hydrogen atom or a methyl group, and X １ represents a single bond, an ester bond or an amide bond, Y １ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R Ａ１represents a halogen atom, a carboxy group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 9 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms; n represents an integer of 1 to 7; m represents an integer of 0 to 6; k represents an integer of 0 to 2; and when m is 2 or more, m R Ａ１ may be the same or different.) (In formula (A2), R ２ represents a hydrogen atom or a methyl group, and X ２ represents a single bond, an ester bond or an amide bond, Y ２ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R Ａ２ represents a halogen atom, a carboxy group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 9 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms; n represents an integer of 1 to 7; m represents an integer of 0 to 6; k represents an integer of 0 to 2; and when m is 2 or more, m R Ａ２may be the same or different.) [4] The composition for forming a resist underlayer film according to any one of [1] to [3], wherein the solvent (B) comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers. [5] The composition for forming a resist underlayer film according to any one of [1] to [4], further comprising a crosslinking agent (C). [6] The composition for forming a resist underlayer film according to [5], wherein the crosslinking agent (C) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. [7] The composition for forming a resist underlayer film according to any one of [1] to [6], further comprising a curing catalyst (D). [8] The composition for forming a resist underlayer film according to any one of [1] to [7], which is used for EUV lithography. [9] The composition for forming a resist underlayer film according to any one of [1] to [8], which is used for forming an underlayer film of a metal-containing resist.

[10] A resist underlayer film that is a cured product of the composition for forming a resist underlayer film according to any one of [1] to [9].

[11] A laminate comprising: a semiconductor substrate; and the resist underlayer film according to

[10] .

[12] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [9], and forming a resist film on the resist underlayer film.

[13] A pattern formation method, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [9], forming a resist film on the resist underlayer film, irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern, and etching the resist underlayer film using the resist pattern as a mask.

[0008] According to the present invention, it is possible to provide a composition for forming a resist underlayer film that can improve sensitivity and adhesion to form a good resist pattern, as well as methods for producing a resist underlayer film, a laminate, and a semiconductor element, and a pattern forming method, all of which use the composition for forming a resist underlayer film.

[0009] (Composition for forming a resist underlayer film) The composition for forming a resist underlayer film of the present invention contains a polymer (A) and a solvent (B). The composition for forming a resist underlayer film may also contain a crosslinking agent (C), a curing catalyst (D), etc. The polymer (A) contains a phenolic hydroxy group and a nitro group.

[0010] By including the polymer (A) containing a phenolic hydroxy group and a nitro group in the composition for forming a resist underlayer film, a good resist pattern with improved sensitivity and adhesion can be formed on the resist underlayer film formed from the composition for forming a resist underlayer film. Furthermore, the improved adhesion makes it difficult for pattern collapse to occur even in a fine resist pattern.

[0011] <Polymer (A)> The polymer (A) is a polymer having a phenolic hydroxy group and a nitro group (—NO ２ The phenolic hydroxy group is not particularly limited as long as it contains the phenolic hydroxy group. The phenolic hydroxy group refers to a hydroxy group bonded to an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is not particularly limited, but is preferably a benzene ring, a naphthalene ring, or an anthracene ring from the viewpoint of more suitably achieving the effects of the present invention.

[0012] The nitro group is bonded to, for example, an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is not particularly limited, but from the viewpoint of more suitably achieving the effects of the present invention, a benzene ring, a naphthalene ring, or an anthracene ring is preferred. The phenolic hydroxy group and the nitro group may be bonded to the same aromatic hydrocarbon ring or to different aromatic hydrocarbon rings, but are preferably bonded to different aromatic hydrocarbon rings.

[0013] The polymer (A) is not particularly limited, and examples thereof include addition polymerization polymers, condensation polymerization polymers, and ring-opening polymerization polymers such as vinyl polymers, polyesters, polyimides, phenol novolac, naphthol novolac, polyethers, polyamides, polycarbonates, etc. Among these, vinyl polymers are preferred from the viewpoint of more suitably achieving the effects of the present invention.

[0014] A vinyl polymer is a polymer formed by polymerizing the polymerizable unsaturated bond of a compound having a group having a polymerizable unsaturated bond. Examples of the group having a polymerizable unsaturated bond include a (meth)acryloyl group, a vinylaryl group (e.g., a styryl group), a vinyloxy group, and an allyl group. The vinyl polymer may be a homopolymer or a copolymer, but is preferably a copolymer from the viewpoint of more suitably achieving the effects of the present invention.

[0015] From the viewpoint of suitably achieving the effects of the present invention, the polymer (A) preferably contains at least one of a structural unit (A1) represented by the following formula (A1) and a structural unit (A2) represented by the following formula (A2), and more preferably contains a structural unit (A1) represented by the following formula (A1) and a structural unit (A2) represented by the following formula (A2). Furthermore, the polymer containing at least one of the structural unit (A1) represented by the following formula (A1) and the structural unit (A2) represented by the following formula (A2) is preferably a vinyl polymer. (In formula (A1), R １ represents a hydrogen atom or a methyl group, and X １ represents a single bond, an ester bond or an amide bond, Y １ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R Ａ１ represents a halogen atom, a carboxy group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 9 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms; n represents an integer of 1 to 7; m represents an integer of 0 to 6; k represents an integer of 0 to 2; and when m is 2 or more, m R Ａ１ may be the same or different.) (In formula (A2), R ２ represents a hydrogen atom or a methyl group, and X ２ represents a single bond, an ester bond or an amide bond, Y ２ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R Ａ２represents a halogen atom, a carboxy group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 9 carbon atoms, or an alkoxy group having 1 to 9 carbon atoms; n represents an integer of 1 to 7; m represents an integer of 0 to 6; k represents an integer of 0 to 2; and when m is 2 or more, m R Ａ２ may be the same or different.)

[0016] When k in formula (A1) is 0, n in formula (A1) is an integer of 1 to 5, and m in formula (A1) is an integer of 0 to 4. When k in formula (A2) is 0, n in formula (A2) is an integer of 1 to 5, and m in formula (A2) is an integer of 0 to 4.

[0017] In formula (A1), n ​​is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. In formula (A2), n is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0018] In formula (A1), m is preferably 0 to 4, more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 0. In formula (A2), m is preferably 0 to 4, more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0019] Specific examples of the structural unit (A1) represented by formula (A1) include the following structural units.

[0020] Specific examples of the structural unit (A2) represented by formula (A2) include the following structural units.

[0021] The polymer (A) may have a structural unit other than the structural unit (A1) represented by formula (A1) and the structural unit (A2) represented by formula (A2). Examples of such structural units include structural units derived from (meth)acrylic acid ester compounds, (meth)acrylamide compounds, or styrene compounds. In the present invention, the term "(meth)acrylic acid ester compounds" refers to acrylic acid ester compounds or methacrylic acid ester compounds. The same applies to (meth)acrylamide compounds.

[0022] Examples of structural units derived from (meth)acrylic ester compounds include structural units (B1) represented by the following formula (B1): Examples of structural units derived from (meth)acrylamide compounds include structural units (B2) represented by the following formula (B2): Examples of structural units derived from styrene compounds include structural units (B3) represented by the following formula (B3): [In formulas (B1) to (B3), R １１ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R １２ represents a monovalent group having 1 to 20 carbon atoms. １３ represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. １４ each independently represents a halogen atom, a carboxy group, a cyano group, or a monovalent group having 1 to 10 carbon atoms, and m represents an integer of 0 to 5.

[0023] R １２ and R １３ The number of carbon atoms in may be 1 to 20, or may be 1 to 10. １２ and R １３ The monovalent group having 1 to 20 carbon atoms in R may have a heteroatom. Examples of the heteroatom include an oxygen atom and a nitrogen atom. １２ and R １３ The monovalent group having 1 to 20 carbon atoms in R may have an aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring.１２ and R １３ The monovalent group having 1 to 20 carbon atoms in R may have, for example, a halogen atom, a hydroxy group, a carboxy group, a cyano group, an epoxy group, or the like. １２ and R １３ In the above formula, examples of the monovalent group having 1 to 20 carbon atoms include an optionally substituted alkyl group and an optionally substituted aromatic group. Examples of the substituent in the optionally substituted alkyl group include a halogen atom, a hydroxy group, a carboxy group, a cyano group, an epoxy group, and an optionally substituted aromatic group. Examples of the substituent in the optionally substituted aromatic group include a halogen atom, a carboxy group, a cyano group, an epoxy group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0024] R １４ The monovalent group having 1 to 10 carbon atoms in R may have a heteroatom. Examples of the heteroatom include an oxygen atom and a nitrogen atom. １４ The monovalent group having 1 to 10 carbon atoms in R may have, for example, a halogen atom, a hydroxy group, a carboxy group, a cyano group, an epoxy group, or the like. １４ In the formula (I), examples of the monovalent group having 1 to 10 carbon atoms include an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0025] Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate, but are not limited to these.

[0026] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, bromophenyl methacrylate, and the like, but are not limited to these.

[0027] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0028] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0029] Specific examples of styrene compounds include, but are not limited to, styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0030] The polymer may further have other structural units, examples of which include, but are not limited to, acrylic acid, methacrylic acid, vinyl compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0031] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0032] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0033] The lower limit of the molar ratio of the structural unit (A1) represented by formula (A1) to all structural units of the polymer (A) is not particularly limited, but from the viewpoint of preferably achieving the effects of the present invention, the molar ratio of the structural unit (A1) is preferably 20 mol% or more, more preferably 30 mol% or more, and particularly preferably 40 mol% or more. The upper limit of the molar ratio of the structural unit (A1) represented by formula (A1) to all structural units of the polymer (A) is not particularly limited, but from the viewpoint of preferably achieving the effects of the present invention, the molar ratio of the structural unit (A1) is preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 70 mol% or less.

[0034] The lower limit of the molar ratio of the structural unit (A2) represented by formula (A2) to all structural units of the polymer (A) is not particularly limited, but from the viewpoint of preferably achieving the effects of the present invention, the molar ratio of the structural unit (A2) is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more. The upper limit of the molar ratio of the structural unit (A2) represented by formula (A2) to all structural units of the polymer (A) is not particularly limited, but from the viewpoint of preferably achieving the effects of the present invention, the molar ratio of the structural unit (A2) is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

[0035] The molar ratio (A1:A2) of the structural unit (A1) to the structural unit (A2) in the polymer (A) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 20:80 to 90:10, more preferably 30:70 to 80:20, and particularly preferably 40:60 to 70:30.

[0036] The total molar ratio of the structural unit (A1) and the structural unit (A2) to all structural units of the polymer (A) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and particularly preferably 90 mol% to 100 mol%.

[0037] The method for producing the polymer (A) is not particularly limited. The polymer (A) can be produced by polymerizing the monomers by a conventional method, such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferred, and in this case, for example, the monomers can be polymerized using a polymerization initiator. As the polymerization initiator, an organic peroxide or a diazo compound can be used.

[0038] Examples of organic peroxides include diacyl peroxides, peroxydicarbonates, peroxyesters, and peroxysulfonates. Examples of diacyl peroxides include diacetyl peroxide, diisobutyl peroxide, didecanoyl peroxide, benzoyl peroxide, and succinic acid peroxide. Examples of peroxydicarbonates include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diallyl peroxydicarbonate. Examples of peroxyesters include tert-butyl peroxyisobutyrate, tert-butyl neodecanoate, and cumene peroxyneodecanate. Examples of peroxysulfonates include acetylcyclohexylsulfonyl peroxide.

[0039] Examples of diazo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(dimethylisobutyrate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(4-methoxy-2,4-dimethoxyvaleronitrile), and 2,2'-azobis(2-cyclopropylpropionitrile).

[0040] When it is desired to complete the polymerization in a short time, it is preferable to use a polymerization initiator having a decomposition half-life of 10 hours or less at 80° C. As such a polymerization initiator, benzoyl peroxide and 2,2′-azobisisobutyronitrile are preferred, and 2,2′-azobisisobutyronitrile is more preferred.

[0041] The amount of the polymerization initiator used is, for example, 0.0001 to 0.2 equivalents, and preferably 0.0005 to 0.1 equivalents, based on the total amount of the monomers used.

[0042] The solvent used in the polymerization is not particularly limited as long as it is inert to the polymerization reaction and is compatible with the resulting polymer. Examples of the solvent include aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, esters, amides, sulfoxides, alcohols, and polyhydric alcohol derivatives. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aliphatic hydrocarbons include n-hexane and n-octane. Examples of ketones include acetone, methyl ethyl ketone, and cyclohexanone. Examples of ethers include tetrahydrofuran and dioxane. Examples of esters include ethyl acetate and butyl acetate. Examples of amides include N,N-dimethylformamide and N,N-dimethylacetamide. Examples of sulfoxides include dimethyl sulfoxide. Examples of alcohols include methanol and ethanol. Examples of polyhydric alcohol derivatives include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. These can be used alone or in combination of two or more.

[0043] The polymerization temperature is not particularly limited as long as it is within a temperature range in which side reactions such as transfer reactions and termination reactions do not occur and the monomer is consumed to complete the polymerization, but it is preferably carried out within a temperature range of -100°C or higher and the boiling point of the solvent or lower. The concentration of the monomer relative to the solvent is not particularly limited, but is usually 1 to 40% by mass, preferably 10 to 30% by mass. The polymerization reaction time can be appropriately selected, but is usually within a range of 2 to 50 hours.

[0044] To facilitate polymerization, the functional groups of the monomers may be protected and then deprotected after polymerization. Examples of the protected functional groups include phenolic hydroxy groups. Examples of the protecting groups include acyl groups (e.g., acetyl groups). Deprotection can be carried out, for example, by hydrolysis using an amine (e.g., an organic amine).

[0045] The weight-average molecular weight of the polymer (A) is not particularly limited, but is preferably 5,000 to 50,000, and more preferably 7,500 to 30,000. The weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0046] The content of polymer (A) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40% by mass to 100% by mass, more preferably 50% by mass to 95% by mass, and particularly preferably 60% by mass to 90% by mass, based on the film-constituting components. The film-constituting components refer to components other than the solvent in the composition for forming a resist underlayer film.

[0047] <Solvent (B)> The solvent (B) is not particularly limited and may be water or an organic solvent. Examples of the organic solvent include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0048] Examples of the alkylene group of the alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms of the alkylene glycol monoalkyl ether include 3 to 8. Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0049] Examples of the alkylene group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkylene groups having 2 to 4 carbon atoms. Examples of the alkyl group of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include alkyl groups having 1 to 4 carbon atoms. Examples of the monocarboxylic acid of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include saturated monocarboxylic acids having 2 to 4 carbon atoms. Examples of saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid. Examples of the number of carbon atoms of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include those having 5 to 10 carbon atoms. Examples of the monocarboxylic acid ester of alkylene glycol monoalkyl ether include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0050] Other organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0051] Among these solvents (B), alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0052] These solvents (B) may be used alone or in combination of two or more.

[0053] The mass proportion of the organic solvent in the solvent (B) is not particularly limited, but is preferably 50 mass % to 100 mass %.

[0054] The content of the solvent (B) in the composition for forming a resist underlayer film is not particularly limited, but is preferably 50% by mass to 99.99% by mass, more preferably 75% by mass to 99.95% by mass, and particularly preferably 90% by mass to 99.9% by mass.

[0055] <Crosslinking Agent (C)> The crosslinking agent (C) is not particularly limited. The crosslinking agent (C) has a structure different from that of the polymer (A).

[0056] The crosslinking agent (C) is preferably an aminoplast crosslinking agent or a phenoplast crosslinking agent. The aminoplast crosslinking agent is an addition condensation product of a compound having an amino group, such as melamine or guanamine, with formaldehyde. The phenoplast crosslinking agent is an addition condensation product of a compound having a phenolic hydroxy group with formaldehyde.

[0057] Examples of the crosslinking agent (C) include compounds having two or more of the following structures. (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.) The bond is bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0058] R １０１ is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.

[0059] The crosslinking agent (C) is preferably a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group, which may be used alone or in combination of two or more.

[0060] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0061] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0062] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.

[0063] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0064] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0065] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0066] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0067] (In formula (3d), R １ represents a methyl group or an ethyl group.)

[0068] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0069] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0070] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2). (In formula (G-1) and formula (G-2), Q １ represents a single bond or a monovalent organic group. １ and R ４ R represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ R represents a hydrogen atom or a methyl group. ３ and R ６n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. １ is 1≦n １ an integer ≦3, n ２ is 2≦n ２ n is an integer ≦5 ３ is 0≦n ３ an integer ≦3, n ４ is 0≦n ４ an integer ≦3, 3≦(n １ +n ２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n ５ an integer ≦3, n ６ is 1≦n ６ n is an integer ≦4 ７ is 0≦n ７ an integer ≦3, n ８ is 0≦n ８ an integer ≦3, 2≦(n ５ +n ６ +n ７ +n ８ ) represents an integer of ≦5. m1 represents an integer of 2 to 10.

[0071] Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or formula (G-4): The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In formula (G-3) and formula (G-4), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. ９ is 1≦n ９ an integer ≦3, n １０ is 2≦n １０ n is an integer ≦5１１ is 0≦n １１ an integer ≦3, n １２ is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n １４ is 1≦n １４ n is an integer ≦4 １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６ an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, examples of the m2-valent organic group include m2-valent organic groups having 1 to 15 carbon atoms.

[0072] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0073] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds: Me represents a methyl group.

[0074] The above compounds are available as products from Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. Examples of such products include those available from Asahi Organic Chemicals Co., Ltd. under the trade names TMOM-BP and HMOM-TPPA.

[0075] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups have been acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being more preferred.

[0076] The molecular weight of the crosslinking agent (C) is not particularly limited, but is preferably 500 or less.

[0077] The content of the crosslinking agent (C) in the composition for forming a resist underlayer film is not particularly limited, but is, for example, 1% by mass to 70% by mass, and preferably 5% by mass to 60% by mass, relative to the polymer (A).

[0078] <Curing Catalyst (D)> The curing catalyst (D) contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0079] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0080] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0081] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0082] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0083] The curing catalyst (D) may be used alone or in combination of two or more.

[0084] When the curing catalyst (D) is used, the content of the curing catalyst (D) relative to the crosslinking agent (C) is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.

[0085] <Other Components> A surfactant may be further added to the composition for forming a resist underlayer film in order to prevent pinholes, striations, and the like from occurring and to further improve the coatability against surface irregularities.

[0086] Examples of surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid, etc.), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by AGC Inc.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the composition for forming a resist underlayer film. These surfactants may be added alone or in combination of two or more.

[0087] The solid content of the composition for forming a resist underlayer film of the present invention, that is, the content of components excluding the solvent, is, for example, 0.01% by mass to 10% by mass.

[0088] The composition for forming a resist underlayer film is preferably used for EUV lithography.The composition for forming a resist underlayer film is preferably used for forming an underlayer film of a metal-containing resist.

[0089] (Resist Underlayer Film) The resist underlayer film of the present invention is a cured product of the composition for forming a resist underlayer film described above. The resist underlayer film can be produced, for example, by applying the composition for forming a resist underlayer film described above onto a semiconductor substrate and baking the applied composition.

[0090] Examples of semiconductor substrates onto which the resist underlayer film-forming composition can be applied include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0091] When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on glass: SOG). Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

[0092] The resist underlayer film-forming composition of the present invention is applied to such a semiconductor substrate by a suitable application method such as a spinner or coater. The composition is then baked using a heating means such as a hot plate to form a resist underlayer film. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 to 60 minutes. A baking temperature of 120°C to 350°C and a baking time of 0.5 to 30 minutes are preferred, and a baking temperature of 150°C to 300°C and a baking time of 0.8 to 10 minutes are more preferred.

[0093] The thickness of the resist underlayer film may be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm ( 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), or 0.005 μm (5 nm).

[0094] The method for measuring the film thickness of the resist underlayer film in this specification is as follows: Name of measuring device: Ellipso film thickness measuring device RE-3100 (SCREEN Corporation) SWE (single wavelength ellipsometer) mode Arithmetic mean of 8 points (for example, measuring 8 points at 1 cm intervals in the X direction of the wafer)

[0095] (Laminate) The laminate of the present invention includes a semiconductor substrate and the resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrates described above. The resist underlayer film is disposed on the semiconductor substrate, for example.

[0096] (Method for manufacturing a semiconductor element, method for forming a pattern) The method for manufacturing a semiconductor element of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, and forming a resist film on the resist underlayer film.

[0097] The pattern forming method of the present invention includes at least the following steps: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, forming a resist film on the resist underlayer film, irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern, and etching the resist underlayer film using the resist pattern as a mask.

[0098] Typically, a resist film is formed on the resist underlayer film. The film thickness of the resist film is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.

[0099] The resist film formed on the resist underlayer film by a known method (e.g., coating and baking a resist composition) is not particularly limited as long as it is responsive to light or electron beam (EB) irradiation. Both negative and positive photoresists can be used. In this specification, resists responsive to EB are also referred to as photoresists. Examples of photoresists include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate, a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and resists containing metal elements. Examples of such photoresists include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples include fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0100] Also, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., radiation-sensitive resin compositions, so-called resist compositions such as high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

[0101] Examples of the resist composition include the following compositions.

[0102] An actinic ray-sensitive or radiation-sensitive resin composition comprising: Resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid; and a compound represented by the following general formula (121):

[0103] In the general formula (121), m represents an integer of 1 to 6. １ and R ２ each independently represents a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ - or -SO ３ - represents. ２ represents an alkylene group which may have a substituent or a single bond. １ represents a cyclic organic group which may have a substituent. ＋ represents a cation.

[0104] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to Periods 3 to 7 of Groups 3 to 15 of the periodic table.

[0105] A radiation-sensitive resin composition comprising: a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) containing an acid-dissociable group; and an acid generator.

[0106] In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, multiple R １ are the same or different. ２ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. ３ is a monovalent group having 1 to 20 carbon atoms containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R ４is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0107] A resist composition comprising: a resin (A1) containing a structural unit having a cyclic carbonate structure, a structural unit represented by the following formula, and a structural unit having an acid labile group; and an acid generator.

[0108] [In the formula, R ２ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; X １ represents a single bond, —CO—O—*, or —CO—NR ４ -*, * represents a bond to -Ar, R ４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from the group consisting of a hydroxy group and a carboxy group.]

[0109] Examples of the resist film include the following.

[0110] A resist film comprising a base resin comprising a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to a polymer main chain upon exposure:

[0111] (In formula (a1) and formula (a2), R Ａ are each independently a hydrogen atom or a methyl group. １ and R ２ are each independently a tertiary alkyl group having 4 to 6 carbon atoms. ３ are each independently a fluorine atom or a methyl group, and m is an integer of 0 to 4. １ X is a single bond, a phenylene group, or a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ is a single bond, an ester bond, or an amide bond.

[0112] Examples of resist materials include the following:

[0113] A resist material comprising a polymer having a repeating unit represented by the following formula (b1) or (b2):

[0114] (In formula (b1) and formula (b2), R Ａ is a hydrogen atom or a methyl group. １ is a single bond or an ester group. ２ is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a lactone ring-containing group; and X ２ At least one hydrogen atom contained in X is substituted with a bromine atom. ３ Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. １ ~Rf ４ are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. １ and Rf ２ may combine to form a carbonyl group. １ ~R ５ are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, in which some or all of the hydrogen atoms may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and in which some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonate ester group. １ and R ２may be bonded to form a ring together with the sulfur atom to which they are attached.

[0115] A resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):

[0116] (In formula (a), R Ａ is a hydrogen atom or a methyl group. １ is a hydrogen atom or an acid labile group. ２ is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ X is a single bond, a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. ２ is -O-, -O-CH ２ - or -NH-. m is an integer of 1 to 4. u is an integer of 0 to 3. However, m+u is an integer of 1 to 4.

[0117] A resist composition that generates an acid upon exposure, and whose solubility in a developer changes due to the action of the acid, comprising: a base component (A) whose solubility in a developer changes due to the action of the acid; and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the fluorine additive component (F) comprises a fluororesin component (F1) that has a structural unit (f1) that includes a base dissociable group, and a structural unit (f2) that includes a group represented by the following general formula (f2-r-1):

[0118] [In formula (f2-r-1), Rf ２１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, or a cyano group. n" is an integer of 0 to 2. * is a bond.

[0119] The structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0120] [In formulas (f1-1) and (f1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group that does not have an acid-dissociable site. A ａｒｙｌ represents a divalent aromatic cyclic group which may have a substituent. ０１ is a single bond or a divalent linking group. ２ are each independently an organic group having a fluorine atom.

[0121] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP-A-2019-113855. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

[0011] of JP-A-2019-532489. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738.

[0122] A coating comprising a metal oxo-hydroxo network having organic ligands with metal carbon and / or metal carboxylate bonds.

[0123] Inorganic oxo / hydroxo-based compositions.

[0124] a coating solution comprising an organic solvent; a first organometallic composition having the formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (where 0<z≦2 and 0<(z+x)≦4), formula R′ｎ SnX ４－ｎ wherein n=1 or 2, or mixtures thereof, where R and R′ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn, or a combination thereof; and a hydrolyzable metal compound having the formula MX′ ｖ wherein M is a metal selected from groups 2 to 16 of the periodic table of the elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof.

[0125] an organic solvent and a solution of the formula RSnO （３／２－ｘ／２） (OH) ｘ and a first organometallic compound of the formula: wherein 0<x<3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having from 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.

[0126] An aqueous inorganic patterning precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.

[0127] Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0128] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0129] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0130] Irradiation with light or electron beams is carried out, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) can be used. The composition for forming a resist underlayer film of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, more preferably for EUV (extreme ultraviolet) exposure. The irradiation energy of the electron beam and the exposure dose of light are not particularly limited.

[0131] After irradiation with light or electron beams and before development, baking (PEB: Post Exposure Bake) may be performed. The baking temperature is not particularly limited, but is preferably 60° C. to 150° C., more preferably 70° C. to 120° C., and particularly preferably 75° C. to 110° C. The baking time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0132] For example, an alkaline developer or an organic solvent is used for development. The development temperature is, for example, 5°C to 50°C. The development time is, for example, 10 seconds to 300 seconds. Examples of alkaline developers that can be used include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-butylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole and piperidine). Furthermore, the aqueous solutions of the alkalis may be used by adding an appropriate amount of alcohols (e.g., isopropyl alcohol) or a nonionic surfactant. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like may also be added to these developers. Alternatively, development may be carried out with an organic solvent such as butyl acetate instead of an alkaline developer, and the portions of the photoresist where the alkaline dissolution rate is not improved may be developed.

[0133] An organic solvent can be used as a developer for the metal-containing resist, and development is carried out with the developer (solvent) after irradiation with light or electron beams. As a result, for example, when a negative metal-containing resist film is used, the metal-containing resist film in the unexposed areas is removed, and a pattern of the metal-containing resist film is formed. Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methyl ... -Methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3 -methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate,Examples of the developer include propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants and the like can also be added to these developers.

[0134] Next, the resist underlayer film is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed. If the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Thereafter, the semiconductor substrate is processed by a known method (e.g., dry etching), thereby manufacturing a semiconductor device.

[0135] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0136] The weight-average molecular weights of the polymers shown in the following Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: TSKgel Super-Multipore HZ-N (2 columns) Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0137] Synthesis Example 1 7.50 g of 4-vinylphenyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.91 g of 4-nitrostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio 50 / 50 (mol %)), and 0.61 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 35.03 g of propylene glycol monomethyl ether acetate and dissolved to prepare a monomer solution. 25.02 g of propylene glycol monomethyl ether acetate was placed in an empty reaction vessel, and the reaction vessel was purged with nitrogen and then heated to 80°C with stirring. Next, the monomer solution was added dropwise to the reaction vessel over 1 hour. The polymerization reaction was carried out for a total of 6 hours, with the start of the dropwise addition of the monomer solution being the initiation time of the polymerization reaction, to obtain a polymerized solution. After completion of the polymerization reaction, the polymerized solution was cooled to room temperature. The cooled polymerization solution was poured into isopropyl alcohol, and the precipitated yellow powder was filtered off. 6.80 g of the resulting powder was dissolved in 20.40 g of propylene glycol monomethyl ether acetate. Next, 42.5 g of methanol, 4.25 g of triethylamine, and 0.85 g of ultrapure water were added, and the mixture was stirred at 70 ° C. for 6 hours for hydrolysis. After completion of the hydrolysis reaction, the remaining solvent was distilled off and the resulting polymer was dissolved in propylene glycol monomethyl ether to obtain a polymer solution. GPC analysis revealed that the polymer in the resulting solution had a weight average molecular weight of 8,500 and a dispersity of 2.1, calculated in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1):

[0138] Synthesis Example 2 7.50 g of 4-vinylphenyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.60 g of 4-nitrostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio of 60 / 40 (mol %)), and 0.51 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 29.42 g of propylene glycol monomethyl ether acetate and dissolved to prepare a monomer solution. 21.02 g of propylene glycol monomethyl ether acetate was placed in an empty reaction vessel, and the reaction vessel was purged with nitrogen and then heated to 80°C with stirring. Next, the monomer solution was added dropwise to the reaction vessel over 1 hour. The polymerization reaction was carried out for a total of 6 hours, with the start of the dropwise addition of the monomer solution being the initiation time of the polymerization reaction, to obtain a polymerized solution. After completion of the polymerization reaction, the polymerized solution was cooled to room temperature. The cooled polymerization solution was poured into isopropyl alcohol, and the precipitated yellow powder was filtered off. 6.80 g of the resulting powder was dissolved in 20.40 g of propylene glycol monomethyl ether acetate. Next, 51.0 g of methanol, 5.10 g of triethylamine, and 1.02 g of ultrapure water were added, and the mixture was stirred at 70 ° C. for 6 hours for hydrolysis. After completion of the hydrolysis reaction, the remaining solvent was distilled off and the resulting polymer was dissolved in propylene glycol monomethyl ether to obtain a polymer solution. GPC analysis revealed that the polymer in the resulting solution had a weight average molecular weight of 14,000 and a dispersity of 4.5, calculated in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the above formula (1).

[0139] Synthesis Example 3 7.50 g of 4-vinylphenyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.71 g of 4-nitrostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) (molar ratio 65 / 35 (mol %)), and 0.47 g of azobisisobutyronitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 27.27 g of propylene glycol monomethyl ether acetate and dissolved to prepare a monomer solution. 19.48 g of propylene glycol monomethyl ether acetate was placed in an empty reaction vessel, and the reaction vessel was purged with nitrogen and then heated to 80°C with stirring. Next, the monomer solution was added dropwise to the reaction vessel over 1 hour. The polymerization reaction was carried out for a total of 6 hours, with the start of the dropwise addition of the monomer solution being the initiation time of the polymerization reaction, to obtain a polymerized solution. After completion of the polymerization reaction, the polymerized solution was cooled to room temperature. The cooled polymerization solution was poured into isopropyl alcohol, and the precipitated yellow powder was filtered off. 6.80 g of the resulting powder was dissolved in 20.40 g of propylene glycol monomethyl ether acetate. Next, 55.25 g of methanol, 5.53 g of triethylamine, and 1.11 g of ultrapure water were added, and the mixture was stirred at 70 ° C. for 6 hours for hydrolysis. After completion of the hydrolysis reaction, the remaining solvent was distilled off and the resulting polymer was dissolved in propylene glycol monomethyl ether to obtain a polymer solution. GPC analysis revealed that the polymer in the resulting solution had a weight average molecular weight of 9700 and a dispersity of 4.0, calculated in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the above formula (1).

[0140] Comparative Synthesis Example 1 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a polymer solution. GPC analysis showed that the polymer in the obtained solution had a weight average molecular weight of 6,800 and a dispersity of 4.8, calculated as standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula:

[0141] <Preparation of compositions for forming resist underlayer films> (Examples 1 to 5, Comparative Examples 1 and 2) The polymers obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 above, and the following comparative polymers, crosslinking agents, curing catalysts, and solvents were mixed in the proportions shown in Table 1 or Table 2, and filtered through a 0.1 μm fluororesin filter to prepare compositions for forming resist underlayer films. The comparative polymers used were as follows. The abbreviations in Tables 1 and 2 are also shown.

[0142] Comparative polymer: phenolic resin (product name: VP-8000, manufactured by Nippon Soda Co., Ltd., a polymer not containing a nitro group) Other abbreviations in Tables 1 and 2 are as follows: PL-LI: tetramethoxymethylglycoluril PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- TMOM-BP: 3,3',5,5'-tetrakis(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol HMOM-TPPA: 4,4'-[1-[4-[1-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-1-methylethyl]phenyl]ethylidene]-bis[2,6-bis(methoxymethyl)phenol] Py-PSA: pyridinium-p-hydroxybenzenesulfonic acid R-30N: surfactant (manufactured by DIC) PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether In Tables 1 and 2, the amount of each additive is shown in parts by mass, and the amount of the solvent is shown in composition ratio.

[0143]

[0144]

[0145] <Elution Test into Photoresist Solvent> Each of the resist underlayer film-forming compositions of Examples 1 to 5 and Comparative Examples 1 and 2 was applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (mass ratio), which is a solvent used in photoresists. A change in film thickness of 5 Å or less was rated as "good", and a change in film thickness of more than 5 Å was rated as "poor". The results are shown in Table 3.

[0146]

[0147] <Formation of Resist Pattern Using Electron Beam Lithography Apparatus> The resist underlayer film-forming compositions of Example 1 and Comparative Examples 1 and 2 were each applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a 5 nm-thick resist underlayer film. An EUV positive resist solution was spin-coated onto the resist underlayer film and heated at 110°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam lithography apparatus (ELS-G130). After exposure, the resist was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38% TMAH), forming a 22 nm line pattern / 44 nm pitch resist pattern. A scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation) was used to measure the resist pattern. In forming the resist pattern, in Table 4, when a line and space (LS) pattern with a CD size of 22 nm was formed, it was marked as "good," and when the line and space pattern collapsed or peeled off, it was marked as "poor." The charge amount at which the 22 nm line and space pattern was formed was taken as the optimal irradiation energy, and the irradiation energy (μC / cm) when Comparative Example 1 was taken as 1.00 was also measured. ２) are also shown in Table 4. In addition, the resist pattern dimensions (pattern collapse critical dimensions) at the maximum exposure dose (limiting exposure dose) at which the resist pattern does not collapse are also shown in Table 4. In Table 4, "-" indicates that the evaluation could not be performed.

[0148]

[0149] From Table 4, it was confirmed that when a resist underlayer film was formed using the composition for forming a resist underlayer film of Example 1, the optimum irradiation energy was reduced and the critical dimension for pattern collapse was increased compared to when a resist underlayer film was formed using the composition for forming a resist underlayer film of Comparative Example 1.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A) containing a phenolic hydroxy group and a nitro group, and a solvent (B).

2. The composition for forming a resist underlayer film according to claim 1, wherein the polymer (A) is a vinyl polymer.

3. The resist underlayer film-forming composition according to claim 1, wherein the polymer (A) contains a structural unit (A1) represented by the following formula (A1) and a structural unit (A2) represented by the following formula (A2). (In formula (A1), R １ represents a hydrogen atom or a methyl group, X １ represents a single bond, an ester bond or an amide bond, Y １ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R Ａ１ represents a halogen atom, a carboxy group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms, n represents an integer of 1 to 7, m represents an integer of 0 to 6, k represents an integer of 0 to 2, and when m is 2 or more, m R Ａ１ may be the same or different.) (In formula (A2), R ２ represents a hydrogen atom or a methyl group, X ２ represents a single bond, an ester bond or an amide bond, Y ２ represents a single bond or an alkylene group having 1 to 4 carbon atoms, R Ａ２ represents a halogen atom, a carboxy group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms, n represents an integer of 1 to 7, m represents an integer of 0 to 6, k represents an integer of 0 to 2, and when m is 2 or more, m R Ａ２ may be the same or different.) 4. The composition for forming a resist underlayer film according to claim 1, wherein the solvent (B) contains at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

5. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent (C).

6. The composition for forming a resist underlayer film according to claim 5, wherein the crosslinking agent (C) is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

7. The composition for forming a resist underlayer film according to claim 1, further comprising a curing catalyst (D).

8. The composition for forming a resist underlayer film according to claim 1, which is used in EUV lithography.

9. The composition for forming a resist underlayer film according to claim 1, which is used for forming an underlayer film of a metal-containing resist.

10. A resist underlayer film, which is a cured product of the composition for forming a resist underlayer film according to any one of claims 1 to 9.

11. A laminate comprising a semiconductor substrate and the resist underlayer film according to claim 10.

12. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of claims 1 to 9; and forming a resist film on the resist underlayer film.

13. A method for forming a pattern, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of claims 1 to 9; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

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