Composition for forming resist underlayer film

Abstract

The present invention provides a composition for forming a resist underlayer film that is capable of forming a satisfactory resist pattern while improving sensitivity.　This composition for forming a resist underlayer film includes: a polymer (A) in which a urethane bond is formed by the reaction of a hydroxyl group in a polymer (C), which has the hydroxyl group and also has one or more polymerizable multiple bonds selected from the group consisting of a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-nitrogen double bond, and a carbon-nitrogen triple bond in a side chain, with an isocyanate group in a compound (B), which has the isocyanate group and a monovalent organic group (B1), and in which the monovalent organic group (B1) is bonded to the polymer (C) via the urethane bond; and a solvent.

Description

Composition for forming a 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 manufacturing a semiconductor device, and a method for forming a pattern.

[0002] Conventionally, microfabrication using lithography with resist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then 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, semiconductor devices have become more highly integrated, 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 application of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, poor resist pattern formation has become a major problem. Therefore, in order to solve this problem, methods of providing a resist underlayer film between the resist and the semiconductor substrate are being widely investigated.

[0003] A composition for forming a resist underlayer has been proposed, comprising a polymer (A) having one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds in its side chain, and a solvent (see Patent Document 1).

[0004] International Publication No. 2024 / 029548 brochure

[0005] The properties required of a resist underlayer include, for example, that it does not intermix with the resist film formed on top (i.e., it is insoluble in the resist solvent), and that it can form a good resist pattern by improving the sensitivity and adhesion of the resist pattern. The present invention has been made in view of the above circumstances, and aims to provide a resist underlayer film formation composition that can form a good resist pattern while improving sensitivity, as well as a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film formation composition.

[0006] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, found that they could solve the above problems, and completed the present invention having the following gist.

[0007] In other words, the present invention encompasses the following embodiments: [1] A resist underlayer film forming composition comprising a polymer (A) having one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds in its side chains and having a hydroxyl group, wherein the hydroxyl group in a polymer (C) is bonded to the polymer (C) via a urethane bond obtained by reacting the hydroxyl group in a polymer (C) having an isocyanate group and a monovalent organic group (B1), and a solvent; and a solvent. [2] The resist underlayer film forming composition according to [1], wherein the polymer (A) has a structural unit represented by the following formula (1). (In formula (1), R １ L represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １１ L represents the linking group having the urethane bond. ２ X represents a monovalent group having the polymerizable multiple bond. １ (wherein represents a monovalent organic group.) [3] The resist underlayer film forming composition according to [1] or [2], wherein the polymer (C) has a structural unit represented by the following formula (2). (In formula (2), R １ L represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １represents a linking group having the hydroxyl group. L ２ represents a monovalent group having the polymerizable multiple bond.) [4] In the polymer (C), the polymerizable multiple bond has a structure obtained by the reaction of an epoxy group and a nucleophilic functional group, and is bonded to the main chain of the polymer (C) via the linking group having the hydroxyl group. The composition for forming a resist underlayer film according to any one of [1] to [3]. [5] The composition for forming a resist underlayer film according to [4], wherein the nucleophilic functional group is one or more selected from the group consisting of a carboxy group, a hydroxy group, an amino group, and a thiol group. [6] The composition for forming a resist underlayer film according to any one of [1] to [5], wherein the monovalent organic group (B1) in the compound (B) is a monovalent organic group having a polymerizable multiple bond. [7] The composition for forming a resist underlayer film according to [6], wherein the compound (B) is represented by the following formula (10). (In the formula (10), R １１ represents a linear or branched saturated aliphatic group having 1 to 10 carbon atoms. R １２ represents a hydrogen atom or a methyl group, and R １３ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, and R １４ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group.) [8] The composition for forming a resist underlayer film according to [7], wherein the compound (B) is represented by the following formula (11). (In the formula (11), R １２ represents a hydrogen atom or a methyl group, and R ２０(wherein represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) [9] A resist underlayer film forming composition according to any one of [1] to [8], wherein the solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[10] A resist underlayer film forming composition according to any one of [1] to [9], further comprising a crosslinking agent.

[11] A resist underlayer film forming composition according to

[10] , wherein the crosslinking agent comprises at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

[12] A resist underlayer film forming composition according to any one of [1] to

[10] , further comprising a curing catalyst.

[13] A resist underlayer film forming composition according to any one of [1] to

[12] , used in EUV lithography.

[14] A resist underlayer film forming composition according to any one of [1] to

[13] , used for forming an underlayer film of a metal-containing resist.

[15] A resist underlayer film which is a cured product of a resist underlayer film forming composition according to any one of [1] to

[14] .

[16] A laminate comprising a semiconductor substrate and the resist underlayer film according to

[15] .

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

[14] ; and forming a resist film on the resist underlayer film.

[18] A pattern forming method, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of [1] to

[14] ; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, 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 resist underlayer film formation composition that can form a good resist pattern while improving sensitivity, as well as a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film formation composition.

[0009] (Composition for forming a resist underlayer film) The resist underlayer film formation composition of the present invention comprises a polymer (A) and a solvent. Here, polymer (A) can be obtained by reacting a hydroxyl group in polymer (C) with an isocyanate group in compound (B). More specifically, polymer (A) is a polymer in which the monovalent organic group (B1) is bonded to polymer (C) via a urethane bond obtained by reacting a hydroxyl group in polymer (C), which has one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds in its side chains and has a hydroxyl group, with an isocyanate group in compound (B), which has an isocyanate group and a monovalent organic group (B1). The resist underlayer film formation composition may also contain a crosslinking agent, a curing catalyst, etc. By using polymer (A) as the polymer contained in the resist underlayer film forming composition, a good resist pattern can be formed on the resist underlayer film formed from the resist underlayer film forming composition, while improving sensitivity and suppressing pattern collapse and bridging. The inventors believe that the polymerizable multiple bonds and the urethane bonds that bond the monovalent organic group (B1) to polymer (C) in polymer (A) according to the present invention contribute to the improvement of sensitivity and resist pattern.

[0010] <Polymer (A) according to the present invention> Polymer (A) according to the present invention is a polymer having one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds in its side chains, and having a hydroxyl group, wherein the hydroxyl group in polymer (C) is bonded to polymer (C) via a urethane bond obtained by reacting the hydroxyl group in polymer (C) with the isocyanate group in compound (B) having an isocyanate group and a monovalent organic group (B1).

[0011] The polymer (A) according to the present invention has, for example, a structural unit represented by the following formula (1).

[0012] In formula (1), R １ L represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １１ L represents a linking group having a urethane bond. ２ X represents a monovalent group having polymerizable multiple bonds. １ This represents a monovalent organic group.

[0013] The structural unit represented by formula (1) is preferably the structural unit represented by the following formula (4).

[0014] In formula (4), R １ L represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ２１ L represents a linking group. ２ X represents a monovalent group having polymerizable multiple bonds. １ This represents a monovalent organic group.

[0015] R in equations (1) and (4) １ This is R in equation (2) described later. １ This is equivalent to L in equations (1) and (4). ２ This is L in equation (2) described later. ２ This is equivalent to X in equations (1) and (4). １ This is X in equation (3) described later. １ It is synonymous with [the above].

[0016] A polymer (A) having a structural unit represented by the following formula (1) is obtained by reacting a hydroxyl group in a polymer (C) having a structural unit represented by the following formula (2) with an isocyanate group in a compound (B) represented by the following formula (3).

[0017] In the above equation (2), R １ and L ２ R in the above formula (1) is １ and L ２ This shows something similar to L. １ X represents a linking group having a hydroxyl group. In formula (3) above, X １ This is X in the above equation (1). １ This shows something similar.

[0018] The polymer (A) according to the present invention may contain structural units other than the structural unit represented by formula (1), as long as it has a structural unit represented by formula (1). For example, structural units other than the structural unit represented by formula (1) include the structural unit represented by formula (2).

[0019] Before describing more detailed embodiments of polymer (A) according to the present invention, polymer (C) and compound (B) will be described first.

[0020] <<Polymer (C)>> Polymer (C) has polymerizable multiple bonds in its side chains. These polymerizable multiple bonds are one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds.

[0021] Polymer (C) is an organic polymer. Polymer (C) may be a homopolymer or a copolymer.

[0022] As described above, polymer (C) has a monovalent group having polymerizable multiple bonds in its side chain. Preferred monovalent groups having polymerizable multiple bonds include, for example, (meth)acryloyl groups, vinylaryl groups (e.g., styryl groups), vinyloxy groups, and allyl groups.

[0023] For example, in polymer (C), the polymerizable multiple bond is bonded to the main chain of polymer (C) via a linking group having a hydroxyl group, which has a structure obtained by the reaction of an epoxy group and a nucleophilic functional group. Here, the nucleophilic functional group can be one or more selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and a thiol group. The hydroxyl group may be a phenolic hydroxyl group or not. Polymer (C) according to the present invention has a linking group having a hydroxyl group. For example, when an epoxy group and a carboxyl group react, they react as follows to form the following structure (S1). (In the formula, * represents a bond.)

[0024] The polymer (C) preferably has a structural unit represented by the following formula (2). (In formula (2), R １ L represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １ L represents the linking group having the hydroxyl group. ２ (This represents a monovalent group having the polymerizable multiple bond.)

[0025] Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. 1,1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, n-heptyl group, cycloheptyl group, norbornyl group, n-octyl group, cyclooctyl group, n-nonyl group, isobornyl group, tricyclononyl group, n-decyl group, adamantyl group, and tricyclodecyl group. Among these, the methyl group is preferred.

[0026] L １ When it is a linking group, there are no particular restrictions on the number of carbon atoms in the linking group, but for example, 1 to 10 can be cited. １ In the case of a linking group, examples of linking groups include those having a structure obtained by the reaction of an epoxy group and a nucleophilic functional group.

[0027] L １ Examples include the following linking groups (L1-1) to (L1-7). (In the formula, *1 is R in formula (2) １ This represents the bond between carbon atoms that are bonded to each other. *2 is L in formula (2). ２ (Represents a coupling or connection.)

[0028] L ２ This is a monovalent group having a polymerizable multiple bond. This monovalent group may be the polymerizable multiple bond itself. The number of carbon atoms in this monovalent group is not particularly limited, but may be, for example, 1 to 20 or 1 to 10.

[0029] L ２ Examples include the following monovalent groups (L2-1) to (L2-82). (In the formula, * represents a bond.)

[0030] Examples of combinations between linking groups (L1-1) to (L1-6) and monovalent groups (L2-1) to (L2-7) include the following: • Combination of (L1-1) and (L2-1) • Combination of (L1-1) and (L2-2) • Combination of (L1-1) and (L2-7) • Combination of (L1-2) and (L2-3) • Combination of (L1-2) and (L2-4) • Combination of (L1-2) and (L2-7) • Combination of (L1-3) and (L2-3) • Combination of (L1-3) and (L2-4) Combinations: Combinations of (L1-4) and (L2-7), Combinations of (L1-5) and (L2-1), Combinations of (L1-5) and (L2-2), Combinations of (L1-6) and (L2-1), Combinations of (L1-6) and (L2-2). Note that the combination of (L1-1) and (L2-1) and the combination of (L1-2) and (L2-3) are synonymous. The combination of (L1-1) and (L2-2) and the combination of (L1-2) and (L2-4) are synonymous.

[0031] Examples of structural units represented by equation (2) include the following:

[0032] An example of a polymer (C) containing the structural unit represented by formula (2) can be obtained, for example, by reacting a glycidyl (meth)acrylate polymer with a compound (C1) having polymerizable multiple bonds and a carboxyl group, as shown below. The glycidyl (meth)acrylate polymer may be a homopolymer or a copolymer. Examples of copolymers include copolymers of glycidyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, and copolymers of glycidyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0033] (In the formula, R １ , and L ２ These are R in equation (2), respectively. １ , and L ２ (This is synonymous with...)

[0034] The reaction can be carried out in the presence of a catalyst, such as tetrabutylphosphonium bromide.

[0035] During the above reaction, polymerization inhibitors may be used to suppress the polymerization of polymerizable multiple bonds. Examples of polymerization inhibitors include hydroquinone, methoquinone, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical.

[0036] Examples of compounds (C1) having polymerizable multiple bonds and carboxyl groups include acrylic acid, methacrylic acid, 4-vinylbenzoic acid, sorbic acid, tetrolic acid, tigric acid, 1-cyclohexene-1-carboxylic acid, 2-benzylacrylic acid, trans-cinnamic acid, trans-4-methoxycinnamic acid, α-phenylcinnamic acid, monomethyl fumarate, α-cyanocinnamic acid, 4-nitrocinnamic acid, and 3-nitrocinnamic acid.

[0037] <<Compound (B)>> Compound (B) is a compound having an isocyanate group and a monovalent organic group (B1). For example, it is represented by the following formula (3).

[0038] In formula (3), X １ This represents a monovalent organic group.

[0039] In the above compound (B), the monovalent organic group (B1) is preferably a monovalent organic group having a polymerizable multiple bond. The polymerizable multiple bond is one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds. １ The polymerizable group () preferably has polymerizable multiple bonds such as a (meth)acryloyl group, a vinylaryl group (e.g., a styryl group), a vinyloxy group, or an allyl group.

[0040] Examples of the above compound (B) include those represented by the following formula (10).

[0041] In formula (10), R １１ R represents a linear or branched saturated aliphatic group having 1 to 10 carbon atoms. １２ R represents a hydrogen atom or a methyl group. １３ R represents a single bond, or a linear or branched alkylene group having 1 to 5 carbon atoms. １４ This represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group.

[0042] A more preferred embodiment of the above compound (B) is one represented by the following formula (11).

[0043] In formula (11), R １２ R in equation (10) １２ This shows something similar to R. ２０ This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0044] <<Preferred Embodiment of Polymer (A)>> As described above, polymer (A) having a structural unit represented by the following formula (1) is obtained by reacting a hydroxyl group in polymer (C) having a structural unit represented by the following formula (2) with an isocyanate group in compound (B) represented by the following formula (3).

[0045] An example of a polymer (A) containing the structural unit represented by formula (1) can be obtained, for example, by reacting a vinyl polymer having epoxy groups (e.g., polyglycidyl methacrylate) with methacrylic acid (see step (I-i) below), as shown in step (I) below, and then reacting the resulting hydroxyl groups with a compound (B) having isocyanate groups (see step (I-ii) below).

[0046] (In the formula, X １ X in equation (3) １ It is similar to this.

[0047] The reaction in step (I-iii) above may be carried out, for example, in the presence of a catalyst. The catalyst is, for example, an amine such as triethylamine. The reaction temperature and time in step (I-iii) can be selected from the range of, for example, 50 to 120°C and 2 to 50 hours to find the optimal conditions.

[0048] The proportion of structural units represented by formula (1) in polymer (A) is not particularly limited, but the molar ratio of structural units represented by formula (1) to the total structural units of polymer (A) may be, for example, 5 mol% to 100 mol%.

[0049] Polymer (A) may contain structural units other than those represented by formula (1). For example, polymer (A) may contain structural units represented by formula (2). In that case, the molar ratio of structural units represented by formula (1) to structural units represented by formula (2) in polymer (A) should be, for example, 5 mol% to 100 mol% : 0 mol% to 95 mol%. Furthermore, the combined proportion of structural units represented by formula (1) and formula (2) in polymer (A) should be 70 to 100 mol%.

[0050] The molecular weight of polymer (A) is not particularly limited. The lower limit of the weight-average molecular weight of polymer (A) is, for example, 1000 to 3000. The upper limit of the weight-average molecular weight of polymer (A) is, for example, 10000 to 40000.

[0051] The content of polymer (A) of the present invention in the resist underlayer film forming composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, for example, 50 to 100% by mass and more preferably 70 to 95% by mass relative to the film forming component is preferred. In this invention, the film component refers to components other than the solvent contained in the resist underlayer film forming composition.

[0052] <Solvent> The solvent is not particularly limited and may be water or an organic solvent. Examples of organic solvents include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0053] Examples of alkylene groups in alkylene glycol monoalkyl ethers include alkylene groups having 2 to 4 carbon atoms. Examples of alkyl groups in alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms in alkylene glycol monoalkyl ethers include 3 to 8. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0054] Examples of alkylene groups in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene groups having 2 to 4 carbon atoms. Examples of alkyl groups in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms. Examples of monocarboxylic acids in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers 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 in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include 5 to 10. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0055] 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.

[0056] Among these solvents, alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0057] These solvents can be used individually or in combination of two or more.

[0058] The mass percentage of the organic solvent in the solvent is not particularly limited, but 50% to 100% by mass is preferred.

[0059] The solvent content in the resist underlayer film forming composition is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0060] <Crosslinking agent> The crosslinking agent is not particularly limited. The crosslinking agent has a different structure from polymer (A) of the present invention.

[0061] As crosslinking agents, aminoplast crosslinking agents and phenoplast crosslinking agents are preferred. Aminoplast crosslinking agents are addition condensates of compounds having amino groups, such as melamine and guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensates of compounds having phenolic hydroxyl groups with formaldehyde.

[0062] Examples of crosslinking agents 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, for example, attached to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0063] R １０１ Preferably, the group is 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 bonding bond.

[0064] Preferred crosslinking agents include melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, and compounds having a phenolic hydroxyl group. These can be used individually or in combination of two or more.

[0065] Examples of melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0066] Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are methoxymethylated or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated or mixtures thereof.

[0067] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof.

[0068] Furthermore, the glycoluryl compound may also be, for example, a glycoluryl derivative represented by the following formula (1E). (In equation (1E), four R １ Each of these independently represents either a methyl group or an ethyl group, R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group.

[0069] Examples of glycoluryl derivatives represented by formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0070] A glycoluryl derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0071] (In formula (2E), R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R ４ Each of these independently represents an alkyl group having 1 to 4 carbon atoms.

[0072] (In formula (3d), R １ (This represents a methyl group or an ethyl group.)

[0073] Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0074] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which one to four methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0075] Examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-1) or (G-2). (In equations (G-1) and (G-2), Q １ R indicates a single bond or an m1-valent organic group. １ and R ４ Each of these represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ Each represents either a hydrogen atom or a methyl group. ３ and R ６ Each of these 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 n is an integer ≤ 3. ２ is 2 ≤ n ２ An integer n ≤ 5 ３ is 0 ≤ n ３ n is an integer ≤ 3. ４ is 0 ≤ n ４ integers ≤ 3, 3 ≤ (n １ +n ２ +n ３ +n ４ This shows integers n ≤ 6. ５ is 1 ≤ n５ An integer of ≦ 3, n ６ where 1 ≦ n ６ An integer of ≦ 4, n ７ where 0 ≦ n ７ An integer of ≦ 3, n ８ where 0 ≦ n ８ An integer of ≦ 3, 2 ≦ (n ５ + n ６ + n ７ + n ８ ), which is an integer of ≦ 5. m1 represents an integer of 2 to 10.)

[0076] Further, examples of the compound 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 the 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 an m2-valent organic group. R ８ , R ９ , R １１ and R １２ each represent a hydrogen atom or a methyl group. R ７ and R １０ each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n ９ where 1 ≦ n ９ An integer of ≦ 3, n １０ where 2 ≦ n １０ An integer of ≦ 5, n １１ where 0 ≦ n １１ An integer of ≦ 3, n １２ where 0 ≦ n １２ An integer of ≦ 3, 3 ≦ (n ９ + n １０ + n １１ + n １２ ), which is an integer of ≦ 6. n １３ where 1 ≦ n １３ An integer of ≦ 3, n １４ where 1 ≦ n １４ An integer of ≦ 4, n １５ where 0 ≦ n １５ An integer of ≦ 3, n １６ where 0 ≦ n １６integers ≤ 3, 2 ≤ (n １３ +n １４ +n １５ +n １６ ) indicates an integer ≤ 5. m² indicates an integer between 2 and 10. ) Q ２ Examples of m2 valent organic groups in this context include m2 valent organic groups having 1 to 4 carbon atoms.

[0077] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0078] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds. The above compound can be obtained as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of such a product is TMOM-BP, a trade name of Asahi Organic Chemicals Co., Ltd.

[0079] Among these, glycoluryl compounds are preferred, specifically tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof, and tetramethoxymethyl glycoluryl is more preferred.

[0080] The molecular weight of the crosslinking agent is not particularly limited, but it is preferably 500 or less.

[0081] The content of the crosslinking agent in the resist underlayer film forming composition is not particularly limited, but is, for example, 1% to 70% by mass, preferably 5% to 60% by mass, relative to the polymer (A) of the present invention.

[0082] <Curing Catalyst> The curing catalyst included as an optional component in the resist underlayer film formation composition can be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of thermal acid generating agents 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 salt of p-phenolsulfonic acid), 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.

[0083] Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0084] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-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 nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0085] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0086] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0087] Only one type of curing catalyst may be used, or two or more types may be used in combination.

[0088] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% to 50% by mass relative to the crosslinking agent, preferably 1% to 30% by mass.

[0089] <Other components> The resist underlayer film forming composition does not produce pinholes or striations, and surfactants can be added to further improve the coatability against surface unevenness.

[0090] Examples of surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid), 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. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the resist underlayer film forming composition. These surfactants may be added individually or in combination of two or more types.

[0091] The resist underlayer film forming composition may optionally contain a polymerization inhibitor (radical trapping agent). Examples of polymerization inhibitors include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and 4-methoxy-1-naphthol. The content of the polymerization inhibitor in the resist underlayer film forming composition is not particularly limited, but is preferably 1% by mass or less relative to the solid content.

[0092] The solid content of the resist underlayer film forming composition of the present invention, i.e., the components excluding the solvent, is, for example, 0.01% to 10% by mass.

[0093] The resist underlayer formation composition is preferably used in EUV lithography. The resist underlayer formation composition is preferably used to form an underlayer of a metal-containing resist.

[0094] (Resist Underlayer Film) The resist underlayer film of the present invention is a cured product of the resist underlayer film forming composition described above. The resist underlayer film can be manufactured, for example, by coating the resist underlayer film forming composition described above onto a semiconductor substrate and firing it.

[0095] Examples of semiconductor substrates to which the resist underlayer film formation composition is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0096] When a semiconductor substrate with an inorganic film formed on its surface is used, the inorganic film is 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 polysilicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phosphoric Acid Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0097] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Subsequently, the resist underlayer film is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a bake temperature of 100°C to 400°C and a bake time of 0.3 minutes to 60 minutes. Preferably, the bake temperature is 120°C to 350°C and the bake time is 0.5 minutes to 30 minutes, and more preferably, the bake temperature is 150°C to 300°C and the bake time is 0.8 minutes to 10 minutes.

[0098] The thickness of the resist underlayer film can 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 ( The wavelengths are 5 nm to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 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).

[0099] The method for measuring the film thickness of the resist underlayer in this specification is as follows: • Measurement device name: Ellipsometer-type film thickness measuring device RE-3100 (SCREEN Corporation) • SWE (single-wavelength ellipsometer) mode • Arithmetic mean of 8 points (for example, 8 points measured at 1 cm intervals in the wafer X direction)

[0100] (Laminate) The laminate of the present invention comprises a semiconductor substrate and a resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrate described above. The resist underlayer film is disposed on top of the semiconductor substrate, for example.

[0101] (Method for manufacturing semiconductor devices, method for forming patterns) The method for manufacturing semiconductor devices of the present invention includes at least the following steps: - A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition of the present invention; and - A step of forming a resist film on the resist underlayer film.

[0102] The pattern formation method of the present invention includes at least the following steps: • A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition of the present invention; • A step of forming a resist film on the resist underlayer film; • A step of irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and • A step of etching the resist underlayer film using the resist pattern as a mask.

[0103] Typically, a resist film is formed on top of a resist underlayer. The thickness of the resist film can be, 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 limits are 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, and 10 nm.

[0104] The resist film formed on the resist underlayer by a known method (e.g., coating and firing of a resist composition) is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation. Both negative-type and positive-type photoresists can be used. In this specification, resists that respond to EB are also referred to as photoresists. Examples of photoresists include positive-type photoresists consisting of a novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, and resists containing metal elements. Examples include V146G (manufactured by JSR Corporation), APEX-E (manufactured by Cyprey Corporation), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), and AR2772 and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, 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).

[0105] 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 While so-called resist compositions and metal-containing resist compositions such as resist compositions, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions described in JP 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., can be used, they are not limited to these.

[0106] Examples of resist compositions include the following compositions.

[0107] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by the following general formula (121).

[0108] In general formula (121), m represents an integer from 1 to 6. １ and R ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ -, or -SO ３ Represents -. L ２ W represents an alkylene group or single bond which may have substituents. １ This represents a cyclic organic group which may have substituents. ＋ This represents a cation.

[0109] 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 the third to seventh periods of groups 3 to 15 of the periodic table.

[0110] 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) that includes an acid-dissociable group, and an acid generator.

[0111] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ R is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R １ They are the same or different. R ２ R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), ３ R is a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. ４(These are a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0112] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by the following formula, and structural units having an acid-unstable group, and an acid generator.

[0113] [In the formula, R ２ X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. １ These are single bonds, -CO-O-* or -CO-NR ４ - represents *, where * represents a bond with -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 hydroxyl groups and carboxyl groups.

[0114] Examples of resist films include the following:

[0115] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0116] (In equations (a1) and (a2), R Ａ Each of these is independently either a hydrogen atom or a methyl group. １ and R ２ These are each independently tertiary alkyl groups having 4 to 6 carbon atoms. ３ Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. １ X is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ (These are single bonds, ester bonds, or amide bonds.)

[0117] Examples of resist materials include the following:

[0118] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0119] (In equations (b1) and (b2), R Ａ X is a hydrogen atom or a methyl group. １ X is a single bond or an ester group. ２ X 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 a portion 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 in is replaced by 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 Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf １ and Rf ２ These may combine to form a carbonyl group. １ ~R ５ Each of these is 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, and some or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl 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 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 sulfonic acid ester group. １ and R ２These may combine to form a ring with the sulfur atom to which they are bonded.

[0120] A resist material comprising a base resin containing a polymer having repeating units represented by the following formula (a).

[0121] (In formula (a), R Ａ R is a hydrogen atom or a methyl group. １ R is a hydrogen atom or an acid-unstable group. ２ This is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ This is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond or a phenylene group, or an ester group or a lactone ring. ２ is -O-, -O-CH ２ It is - or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. However, m + u is an integer from 1 to 4.

[0122] A resist composition that generates 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) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1), the resist composition.

[0123] [In formula (f2-r-1), Rf ２１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n'' is an integer from 0 to 2. * represents a bond.

[0124] The aforementioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0125] [In formulas (f1-1) and (f1-2), 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 X is a divalent aromatic cyclic group which may have substituents. ０１ R is a single bond or a divalent linking group. ２ These are, independently, organic groups that contain a fluorine atom.

[0126] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MORs), and a typical example is a tin oxide-based resist. Examples of metal oxide resist materials include a coating composition containing a metal oxo-hydroxo network having an organic ligand via a metal-carbon bond and / or metal-carboxylate bond, as described in Japanese Patent Application Publication No. 2019-113855. An example of a metal-containing resist uses a peroxo ligand as a radiosensitizing stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described in the patent document described in paragraph

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

[0127] A coating comprising a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal-carboxylate bonds.

[0128] Inorganic oxo / hydroxo-based compositions.

[0129] A coating solution comprising an organic solvent; a first organometallic composition comprising formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (Here, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), equation R'ｎ SnX ４－ｎ A first organometallic composition represented by (where n = 1 or 2), or a mixture thereof, where R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand or a combination thereof having a hydrolyzable bond to Sn; and a hydrolyzable metal compound of the formula MX' ｖ A coating solution comprising a hydrolyzable metal compound represented by (where M is a metal selected from groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X' is a ligand or combination thereof having a hydrolyzable M-X bond).

[0130] Organic solvent and formula RSnO （３／２－ｘ／２） (OH) ｘ A coating solution comprising a first organometallic compound represented by the formula (wherein 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, wherein the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0131] An aqueous solution of an inorganic pattern-forming precursor comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0132] Other examples of metal-containing resists include the compositions described in Japanese Patent Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Publication No. 2020-122959, Japanese Patent Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229. These contents are incorporated into this specification to the same extent as if they were all explicitly stated.

[0133] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and includes a method of applying a coating-type resist material (a composition for forming a metal-containing resist film), which is a metal-containing resist, and firing it.

[0134] Furthermore, the metal-containing resist film may be formed by vapor deposition. An example of a method for forming a metal-containing resist film by vapor deposition is the method described in Japanese Patent Application Publication No. 2017-116923. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein to the same extent as if they were fully disclosed. In Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film in the present invention is referred to as a metal oxide-containing film.

[0135] Irradiation with light or an electron beam is performed, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet) or EB (electron beams) are used. The resist underlayer film forming composition of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably for EUV (extreme ultraviolet) exposure. The electron beam irradiation energy and the amount of light exposure are not particularly limited.

[0136] A bake (PEB: Post Exposure Bake) may be performed after irradiation with light or electron beam and before development. The bake 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 bake 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.

[0137] For development, for example, alkaline developers and organic solvents are used. The development temperature can be, for example, 5°C to 50°C. The development time can be, for example, 10 seconds to 300 seconds. As alkaline developers, aqueous solutions of the following alkalis can be used: inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, and more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Alternatively, instead of using an alkaline developer, development can be performed with an organic solvent such as butyl acetate, and the areas of the photoresist where the alkaline dissolution rate has not improved can be developed.

[0138] Organic solvents can be used as the developer for metal-containing resists, and development is performed with the developer (solvent) after irradiation with light or electron beam. As a result, for example, when a negative-type metal-containing resist film is used, the unexposed areas of the metal-containing resist film are removed, and a pattern of the metal-containing resist film is formed. Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethoxyethyl acetate, 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 - 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 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 can be added to these developers.

[0139] 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. After that, the semiconductor substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device.

[0140] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0141] The weight-average molecular weights of the polymers shown in Synthesis Examples 1 to 4 below were measured by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: Shodex KF803L, Shodex KF802, Shodex KF801 [registered trademark] (Showa Denko K.K.) Column temperature: 40°C Solvent: N,N-dimethylformamide (DMF) Flow rate: 0.6 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0142] <Synthesis Example 1> 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.45 g of diethyl barbituric acid (manufactured by Tokyo Chemical Industries, Inc.), and 0.48 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Co., Ltd.) were added to 56.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out under reflux heating for 10 hours to obtain a solution containing polymer 1. The polymer solution did not become cloudy or otherwise discolored when cooled to room temperature, and its solubility in propylene glycol monomethyl ether was good. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 10,000 on a standard polystyrene basis. The polymer obtained in this synthesis example has structural units represented by the following formulas (1a) and (1b).

[0143]

[0144] <Synthesis Example 2> 20.00 g of polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.), 4.88 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 16.77 g of propylene glycol monomethyl ether and 2.58 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 85°C for 24 hours to obtain a solution containing polymer 2. The polymer solution did not become cloudy or otherwise discolored when cooled to room temperature, and its solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent was good. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 21,000 on a standard polystyrene basis. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1c).

[0145]

[0146] <Synthesis Example 3> 20.00 g of polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.), 3.75 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.02 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 15.07 g of propylene glycol monomethyl ether and 0.88 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 3. The polymer solution did not become cloudy or otherwise discolored when cooled to room temperature, and its solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent was good. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 21,000 on a standard polystyrene basis. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1d).

[0147]

[0148] <Synthesis Example 4> 15.00 g of polyglycidyl methacrylate (manufactured by Maruzen Petrochemical Co., Ltd.), 2.65 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.46 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.05 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 15.07 g of propylene glycol monomethyl ether and 8.25 g of propylene glycol monomethyl ether acetate in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours. After the reaction solution was returned to room temperature, 5.53 g of Karenz® BEI (manufactured by Resonac Co., Ltd.), 0.31 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 13.64 g of propylene glycol monomethyl ether acetate were added to the polymer solution in the reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a solution containing polymer 4. The polymer solution did not become cloudy or otherwise discolored when cooled to room temperature, and its solubility in the propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate mixed solvent was good. GPC analysis revealed that the obtained polymer 4 had a weight-average molecular weight of 21,000 on a standard polystyrene basis. The polymer obtained in this synthesis example has structural units represented by the following formulas (1d) and (1e).

[0149]

[0150] [Preparation of compositions for forming resist underlayer films] (Examples, Comparative Examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1 to 4 above were mixed in the proportions shown in Table 1, and the mixture was filtered through a fluororesin filter with a pore size of 0.1 μm to prepare the EUV lithography resist underlayer film forming compositions for Example 1 and Comparative Examples 1 to 3.

[0151] The abbreviations in Table 1 are as follows: PL-LI: Tetramethoxymethylglycoluryl PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methyl-1-methylethylethoxy)methyl]-(see structural formula below)

[0152] Py-PSA: Pyridinium-p-hydroxybenzenesulfonic acid PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[0153]

[0154] [Elution Test in Photoresist Solvent] The resist underlayer film formation compositions of Example 1 and Comparative Examples 1-3 were each applied onto a silicon wafer, which is a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 205°C for 1 minute to form a resist underlayer film (thickness 10 nm). These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 70 / 30 (volume ratio), which is the solvent used for photoresists. A change in film thickness of less than 10 Å was judged as "good," and a change of 10 Å or more was judged as "poor." The results are shown in Table 2.

[0155]

[0156] [Formation of Negative Resist Patterns by EUV Exposure] The resist underlayer formation compositions of Example 1 and Comparative Examples 1-3 were applied to silicon wafers using a spinner. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer with a thickness of 10 nm. An EUV resist solution (tin oxide-based resist) was spin-coated onto the resist underlayer and heated at 130°C for 1 minute to form an EUV resist layer. Subsequently, exposure was performed using an ASML EUV exposure apparatus (NXE3400) under the conditions of NA = 0.33, σ = 0.60 / 0.82 (outer / inner), and 50017. During exposure, exposure was performed through a mask set so that the line and space pattern (hereinafter referred to as L / S) of the EUV resist after development was 14 nm line / 28 nm pitch (L / S = 1 / 1). After exposure, post-exposure heating (PEB, 180°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate. Development was then carried out for 60 seconds using an organic solvent (acetic acid-containing propylene glycol monomethyl ether acetate solution), followed by rinsing to form a resist pattern with a CD size of 14 nm. A scanning electron microscope (Hitachi High-Technologies Corporation, CG6100) was used to measure the length of the resist pattern. The photoresist patterns obtained in this manner were evaluated by observation from the top of the pattern. A pattern was judged as "good" if a CD size of 17.0 nm L / S was formed, and as "poor" if pattern collapse or bridge margins were observed. The exposure amount that formed a CD size of 14 nm L / S was defined as the optimal exposure amount, and the exposure amount at that time (mJ / cm²) was determined. ２ Table 3 shows the results.

[0157]

[0158] Compared to Comparative Examples 1-3, Example 1 showed improved sensitivity and bridge margin in L / S with a CD size of 14 nm. These results demonstrate that the resist underlayer film obtained from the resist underlayer film formation composition of the present invention, which includes multiple bonds and urethane bonds, is capable of improving sensitivity and bridge margin and has good pattern formation ability.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A) having one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds in its side chains and having a hydroxyl group, wherein the hydroxyl group in a polymer (C) is bonded to the polymer (C) via a urethane bond obtained by reacting the hydroxyl group in a polymer (C) having an isocyanate group and a monovalent organic group (B1), and a solvent.

2. The resist underlayer film forming composition according to claim 1, wherein the polymer (A) has a structural unit represented by the following formula (1). (In formula (1), R １ L represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １１ L represents the linking group having the urethane bond. ２ X represents a monovalent group having the polymerizable multiple bond. １ (This represents a monovalent organic group.) 3. The resist underlayer film forming composition according to claim 1, wherein the polymer (C) has a structural unit represented by the following formula (2). (In formula (2), R １ L represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １ L represents the linking group having the hydroxyl group. ２ (This represents a monovalent group having the polymerizable multiple bond.) 4. The resist underlayer film forming composition according to claim 1, wherein in the polymer (C), the polymerizable multiple bond is bonded to the main chain of the polymer (C) via a hydroxyl group having a linking group having a structure obtained by the reaction of an epoxy group and a nucleophilic functional group.

5. The resist underlayer film forming composition according to claim 4, wherein the nucleophilic functional group is one or more selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and a thiol group.

6. The resist underlayer film forming composition according to claim 1, wherein the monovalent organic group (B1) in compound (B) is a monovalent organic group having polymerizable multiple bonds.

7. The resist underlayer film-forming composition according to claim 6, wherein the compound (B) is represented by the following formula (10). (In formula (10), R １１ represents a linear or branched saturated aliphatic group having 1 to 10 carbon atoms. R １２ represents a hydrogen atom or a methyl group, and R １３ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. R １４ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group.) 8. The resist underlayer film forming composition according to claim 7, wherein the compound (B) is represented by the following formula (11). (In formula (11), R １２ R represents a hydrogen atom or a methyl group. ２０ (This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) 9. The resist underlayer film forming composition according to claim 1, wherein the solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

10. The resist underlayer film forming composition according to claim 1, further comprising a crosslinking agent.

11. The resist underlayer film forming composition according to claim 10, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

12. The resist underlayer film forming composition according to claim 1, further comprising a curing catalyst.

13. A composition for forming a resist underlayer film according to claim 1, used in EUV lithography.

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

15. A resist underlayer film, which is a cured product of a resist underlayer film forming composition according to any one of claims 1 to 14.

16. A laminate comprising a semiconductor substrate and a resist underlayer film according to claim 15.

17. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 14; and forming a resist film on the resist underlayer film.

18. A pattern formation method comprising: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 14; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, 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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