Composition for forming a resist underlayer

Abstract

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

Description

Technology Field

[0001] The present invention relates to a composition for forming a resist underlayer, a resist underlayer, a laminate, a method for manufacturing a semiconductor device, and a method for forming a pattern. Background Technology

[0002] Conventionally, in the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has been performed. This microfabrication is a processing method in which a thin film of a photoresist composition is formed on a semiconductor substrate, such as a silicon wafer, and an active light, such as ultraviolet light, is irradiated over it using a mask pattern with a device pattern drawn thereon, and then developed. The substrate is then etched using the obtained photoresist pattern as a protective film to form fine irregularities corresponding to the photoresist pattern on the surface of the substrate. Recently, as the integration density of semiconductor devices has increased, the active light used is also being considered for advanced microfabrication. In addition to the conventionally used i-ray (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 explored. Consequently, defects in resist pattern formation caused by influence from the semiconductor substrate have become a major problem. To address this problem, methods of providing a resist underlayer between the resist and the semiconductor substrate are being widely considered.

[0003] As a resist underlayer forming composition, Formula (100) (wherein Ar represents a directional ventilation having 6 to 40 carbon atoms that may be substituted, L 0 represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms that may be substituted, or an alkenylene group having 2 to 10 carbon atoms that may be substituted, and T 0... represents a single bond, an ester bond, an ether bond, an alkylene group having 1 to 10 carbon atoms that may be substituted, or an alkenylene group having 2 to 10 carbon atoms that may be substituted, provided that L 0 and T 0 is different, and n R 0 A resist underlayer forming composition has been proposed comprising a polymer or compound having a structure represented by (where n independently represents a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amino group, or a monovalent organic group, n represents an integer from 0 to 5, and * represents a portion bonded with a polymer or compound residue) and a solvent (see Patent Document 1). Prior art literature

[0004] Pamphlet International Publication No. 2022 / 196662 The problem to be solved

[0005] Characteristics required for the resist underlayer include, for example, that intermixing with the resist film formed on the upper layer does not occur (it is insoluble in the resist solvent), and that the sensitivity and adhesion of the resist pattern are improved to form a good resist pattern.

[0006] The present invention is made in consideration of the above circumstances and aims to provide a composition for forming a resist underlayer capable of forming a good resist pattern by improving sensitivity and adhesion, a method for manufacturing a resist underlayer, a laminate, and a semiconductor device using the composition for forming a resist underlayer, and a method for forming a pattern. means of solving the problem

[0007] The inventors, in order to solve the above problem, conducted a thorough examination and discovered that the above problem could be solved, thereby completing the present invention having the following gist.

[0008] That is, the present invention includes the following aspects.

[0009] [1] A composition for forming a resist underlayer, comprising a polymer (A) containing phenolic hydroxyl groups and nitro groups, and a solvent (B).

[0010] [2] A composition for forming a resist underlayer as described in [1], wherein the polymer (A) is a vinyl polymer.

[0011] [3] A composition for forming a resist underlayer as described in [1] or [2], wherein the polymer (A) comprises a structural unit (A1) represented by the following formula (A1) and a structural unit (A2) represented by the following formula (A2).

[0012] [Chemical Formula 1]

[0013]

[0014] (In Equation (A1), R 1 Representing silver, a hydrogen atom, or a methyl group, X 1 Silver represents a single bond, ester bond, or amide bond, and Y 1 Silver represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R A1 Representing silver, a halogen atom, a carboxyl 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, where n is an integer from 1 to 7, m is an integer from 0 to 6, k is an integer from 0 to 2, and when m is 2 or greater, m R A1 It may be the same or different.)

[0015] [Chemical Formula 2]

[0016]

[0017] (In Equation (A2), R 2 represents a hydrogen atom or a methyl group, and X 2 represents a single bond, ester bond, or amide bond, and Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R A2represents a halogen atom, a carboxyl 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, where n represents an integer from 1 to 7, m represents an integer from 0 to 6, k represents an integer from 0 to 2, and when m is 2 or greater, m R A2 It may be the same or different.)

[0018] [4] A composition for forming a resist underlayer as described in any one of [1] to [3], wherein the solvent (B) comprises at least one selected from the group consisting of alkylene glycol monoalkyl ether and monocarboxylic acid ester of alkylene glycol monoalkyl ether.

[0019] [5] A composition for forming a resist underlayer, further comprising a crosslinking agent (C), as described in any one of [1] to [4].

[0020] [6] A composition for forming a resist underlayer as described in [5], wherein the crosslinking agent (C) is at least one selected from the group consisting of an aminoplast crosslinking agent and a fenoplast crosslinking agent.

[0021] [7] A composition for forming a resist underlayer film as described in any one of [1] to [6], further comprising a curing catalyst (D).

[0022] [8] A composition for forming a resist underlayer, as described in any one of [1] to [7], used in EUV lithography.

[0023] [9] A composition for forming a resist underlayer, as described in any one of [1] to [8], used for forming a resist underlayer of a metal-containing resist.

[0024]

[10] A resist underlayer, which is a cured product of a resist underlayer forming composition described in any one of [1] to [9].

[0025]

[11] Semiconductor substrate and,

[0026]

[10] The resist underlayer,

[0027] A laminate having

[0028]

[12] A process of forming a resist underlayer on a semiconductor substrate using a composition for forming a resist underlayer described in any one of [1] to [9], and

[0029] A process of forming a resist film on the above resist lower layer film,

[0030] A method for manufacturing a semiconductor device comprising

[0031]

[13] A process of forming a resist underlayer on a semiconductor substrate using a composition for forming a resist underlayer described in any one of [1] to [9], and

[0032] A process of forming a resist film on the above resist lower layer film, and

[0033] A process of irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern, and

[0034] A process of etching the resist underlayer film using the above resist pattern as a mask,

[0035] A pattern forming method including Effects of the invention

[0036] According to the present invention, a composition for forming a resist underlayer capable of forming a good resist pattern by improving sensitivity and adhesion, a method for manufacturing a resist underlayer, a laminate, and a semiconductor device using the composition for forming a resist underlayer, and a method for forming a pattern can be provided. Specific details for implementing the invention

[0037] (Composition for forming a resist underlayer)

[0038] The composition for forming a resist underlayer of the present invention comprises a polymer (A) and a solvent (B).

[0039] The composition for forming the resist underlayer film may include a crosslinking agent (C), a curing catalyst (D), etc.

[0040] The polymer (A) includes a phenolic hydroxyl group and a nitro group.

[0041] By including a polymer (A) comprising phenolic hydroxyl groups and nitro groups in a composition for forming a resist sublayer, a good resist pattern with improved sensitivity and adhesion can be formed on the resist sublayer formed from the composition for forming a resist sublayer. Meanwhile, as adhesion is improved, it becomes difficult for the pattern to collapse even if it is a fine resist pattern.

[0042] <Polymer(A)>

[0043] The polymer (A) is not particularly limited as long as it includes a phenolic hydroxyl group and a nitro group (-NO2).

[0044] A phenolic hydroxyl group refers to a hydroxyl group bonded to an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is not particularly limited, but a benzene ring, a naphthalene ring, and anthracene ring are preferred from the viewpoint of obtaining the effects of the present invention more effectively.

[0045] The nitro group is bonded to, for example, an aromatic hydrocarbon ring. The aromatic hydrocarbon ring is not particularly limited, but benzene rings, naphthalene rings, and anthracene rings are preferred from the viewpoint of obtaining the effects of the present invention more effectively.

[0046] The phenolic hydroxyl group and the nitro group may be bonded to the same aromatic hydrocarbon ring or to different aromatic hydrocarbon rings, but it is preferable that they be bonded to different aromatic hydrocarbon rings.

[0047] The polymer (A) is not particularly limited and, for example, addition polymers such as vinyl polymer, polyester, polyimide, phenol novolak, naphthol novolak, polyether, polyamide, and polycarbonate, as well as condensation polymers and ring-opening polymers, may be used. Among these, a vinyl polymer is preferred from the viewpoint of obtaining the effects of the present invention more effectively.

[0048] A vinyl polymer is a polymer formed by the polymerization of polymerizable unsaturated bonds of a compound having a group having polymerizable unsaturated bonds. Examples of groups having polymerizable unsaturated bonds include (meth)acryloyl groups, vinylaryl groups (e.g., styryl groups), vinyloxy groups, allyl groups, etc.

[0049] The vinyl polymer may be a homopolymer or a copolymer, but it is preferable that it be a copolymer to more effectively obtain the effects of the present invention.

[0050] As for the polymer (A), from the perspective of obtaining the effects of the present invention, it is preferable to include 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), and it is more preferable to include the structural unit (A1) represented by the following formula (A1) and the structural unit (A2) represented by the following formula (A2). Furthermore, as for the polymer comprising 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), a vinyl polymer is preferred.

[0051] [Chemical Formula 3]

[0052]

[0053] (In Equation (A1), R 1 Representing silver, a hydrogen atom, or a methyl group, X 1 Silver represents a single bond, ester bond, or amide bond, and Y 1Silver represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R A1 Representing silver, a halogen atom, a carboxyl 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, where n is an integer from 1 to 7, m is an integer from 0 to 6, k is an integer from 0 to 2, and when m is 2 or greater, m R A1 It may be the same or different.)

[0054] [Chemical Formula 4]

[0055]

[0056] (In Equation (A2), R 2 represents a hydrogen atom or a methyl group, and X 2 represents a single bond, ester bond, or amide bond, and Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R A2 represents a halogen atom, a carboxyl 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, where n represents an integer from 1 to 7, m represents an integer from 0 to 6, k represents an integer from 0 to 2, and when m is 2 or greater, m R A2 It may be the same or different.)

[0057] When k in equation (A1) is 0, n in equation (A1) represents an integer from 1 to 5, and m in equation (A1) represents an integer from 0 to 4.

[0058] When k in equation (A2) is 0, n in equation (A2) represents an integer from 1 to 5, and m in equation (A2) represents an integer from 0 to 4.

[0059] As for n in formula (A1), 1 to 5 is preferred, 1 to 3 is more preferred, 1 or 2 is even more preferred, and 1 is particularly preferred.

[0060] As for n in formula (A2), 1 to 5 is preferred, 1 to 3 is more preferred, 1 or 2 is even more preferred, and 1 is particularly preferred.

[0061] As for m in formula (A1), 0 to 4 is preferred, 0 to 2 is more preferred, 0 or 1 is even more preferred, and 0 is particularly preferred.

[0062] As for m in formula (A2), 0 to 4 is preferred, 0 to 2 is more preferred, 0 or 1 is even more preferred, and 0 is particularly preferred.

[0063] Specific examples of the structural unit (A1) represented by formula (A1) include, for example, the following structural units.

[0064] [Chemical Formula 5]

[0065]

[0066] [Chemical Formula 6]

[0067]

[0068] [Chemical Formula 7]

[0069]

[0070] [Chemical Formula 8]

[0071]

[0072] Specific examples of the structural unit (A2) represented by formula (A2) include, for example, the following structural units.

[0073] [Chemical Formula 9]

[0074]

[0075] [Chemical Formula 10]

[0076]

[0077] [Chemical Formula 11]

[0078]

[0079] [Chemical Formula 12]

[0080]

[0081] The polymer (A) may have structural units other than the structural unit (A1) represented by formula (A1) and the structural unit (A2) represented by formula (A2).

[0082] Such structural units include, for example, structural units derived from (meth)acrylic acid ester compounds, (meth)acrylamide compounds, or styrene compounds.

[0083] Meanwhile, in the present invention, the (meth)acrylic acid ester compound refers to an acrylic acid ester compound or a methacrylic acid ester compound. The same applies to (meth)acrylamide compounds.

[0084] Structural units derived from (meth)acrylic acid ester compounds include, for example, structural units (B1) represented by the following formula (B1).

[0085] Structural units derived from (meth)acrylamide compounds include, for example, structural units (B2) represented by the following formula (B2).

[0086] Structural units derived from styrene compounds include, for example, structural units (B3) represented by the following formula (B3).

[0087] [Chemical Formula 13]

[0088]

[0089] [Among Equations (B1) to (B3), R 11 Representing silver, hydrogen atoms, or an alkyl group having 1 to 3 carbon atoms, and R 12 R represents a monovalent group with 1 to 20 carbon atoms. 13 It represents a monovalent group consisting of 1 to 20 atoms of silver, hydrogen, or carbon. R 14Each represents, independently, a halogen atom, a carboxyl group, a cyano group, or a monovalent group having 1 to 10 carbon atoms. m represents an integer from 0 to 5.

[0090] R 12 and R 13 The number of carbon atoms in this case may be 1 to 20 or 1 to 10.

[0091] R 12 and R 13 A monovalent group having 1 to 20 carbon atoms may have heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, etc.

[0092] R 12 and R 13 The monovalent group having 1 to 20 carbon atoms in the above may have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocyclic rings. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings.

[0093] R 12 and R 13 The monovalent group having 1 to 20 carbon atoms in the above may have, for example, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an epoxy group, etc.

[0094] R 12 and R 13 Examples of monovalent carbon atoms with 1 to 20 carbon atoms include, for instance, alkyl groups that may be substituted, aromatic groups that may be substituted.

[0095] Examples of substituents for the alkyl group that may be substituted include, for instance, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an epoxy group, and an aromatic group that may be substituted.

[0096] Examples of substituents for the aromatic group that may be substituted include, for instance, a halogen atom, a carboxyl group, a cyano group, an epoxy group, an alkyl group having 1 to 6 carbon atoms that may be substituted with a halogen atom, and an alkoxy group having 1 to 6 carbon atoms that may be substituted with a halogen atom.

[0097] Examples of alkyl groups having 1 to 6 carbon atoms include methyl groups, ethyl groups, propyl groups, butyl groups, etc.

[0098] Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.

[0099] R 14 A monovalent group having 1 to 10 carbon atoms may have heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, etc.

[0100] R 14 The monovalent group having 1 to 10 carbon atoms in the above may have, for example, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an epoxy group, etc.

[0101] R 14 Examples of monovalent groups having 1 to 10 carbon atoms include, for instance, alkyl groups having 1 to 6 carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 1 to 6 carbon atoms that may be substituted with halogen atoms.

[0102] Examples of alkyl groups having 1 to 6 carbon atoms include methyl groups, ethyl groups, propyl groups, butyl groups, etc.

[0103] Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.

[0104] Specific examples of acrylic acid ester compounds include, but are not limited to, methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthylmethyl 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, glycidyl acrylate.

[0105] Specific examples of methacrylic acid ester compounds include, but are not limited to, 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, etc.

[0106] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, N-anthrylacrylamide, etc.

[0107] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, N-anthrylmethacrylamide, etc.

[0108] Specific examples of styrene compounds include, but are not limited to, styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc.

[0109] Additionally, the polymer may have other structural units. Monomers that derive such structural units include, but are not limited to, acrylic acid, methacrylic acid, vinyl compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0110] 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 acetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, vinyl anthracene, etc.

[0111] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-hydroxyethylmaleimide.

[0112] The lower limit of the molar ratio of the structural unit (A1) represented by the formula (A1) for the entire structural unit of the polymer (A) is not particularly limited, but from the perspective of obtaining 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.

[0113] The upper limit of the molar ratio of the structural unit (A1) represented by the formula (A1) for the entire structural unit of the polymer (A) is not particularly limited, but from the perspective of obtaining 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.

[0114] The lower limit of the molar ratio of the structural unit (A2) represented by the formula (A2) for the entire structural unit of the polymer (A) is not particularly limited, but from the perspective of obtaining 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.

[0115] The upper limit of the molar ratio of the structural unit (A2) represented by the formula (A2) for the entire structural unit of the polymer (A) is not particularly limited, but from the perspective of obtaining 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.

[0116] The molar ratio (A1:A2) of the structural unit (A1) and the structural unit (A2) in the polymer (A) is not particularly limited, but from the view of obtaining the effects of the present invention, 20:80 to 90:10 is preferred, 30:70 to 80:20 is more preferred, and 40:60 to 70:30 is particularly preferred.

[0117] The molar ratio of the sum of structural unit (A1) and structural unit (A2) to the total structural unit of polymer (A) is not particularly limited, but from the viewpoint of obtaining the effects of the present invention, 70 mol% to 100 mol% is preferred, 80 mol% to 100 mol% is more preferred, and 90 mol% to 100 mol% is particularly preferred.

[0118] The method of manufacturing polymer (A) is not particularly limited.

[0119] Polymer (A) can be prepared by polymerizing monomers by conventional methods, for example, bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferred, in which case, the monomers can be polymerized using, for example, a polymerization initiator.

[0120] Organic peroxides and diazo compounds can be used as polymerization initiators.

[0121] Examples of organic peroxides include diacyl peroxides, peroxydicarbonates, peroxyesters, and peroxysulfonates.

[0122] Examples of diacyl peroxides include diacetyl peroxide, diisobutyl peroxide, didecanoyl peroxide, benzoyl peroxide, succinic acid peroxide, etc.

[0123] Examples of peroxydicarbonates include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diallyl peroxydicarbonate, etc.

[0124] Examples of peroxyesters include tert-butylperoxyisobutyrate, tert-butylneodecanate, cumenperoxyneodecanate, etc.

[0125] Examples of sulfonate peroxides include acetylcyclohexylsulfonyl peroxide.

[0126] Examples of diazo compounds include, for instance, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(isobutyric acid)dimethyl, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(4-methoxy-2,4-dimethoxyvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile).

[0127] In order to terminate 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.

[0128] The amount of polymerization initiator used is, for example, 0.0001 to 0.2 equivalents with respect to the total monomer used, and preferably 0.0005 to 0.1 equivalents.

[0129] The solvent used for polymerization is not particularly limited as long as it is a solvent that does not participate in the polymerization reaction and is compatible with the polymer obtained, and examples include aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, esters, amides, sulfoxides, alcohols, polyhydric alcohol derivatives, etc.

[0130] Aromatic hydrocarbons include, for example, benzene, toluene, xylene, etc.

[0131] Examples of cyclohexane include cyclohydrocarbons.

[0132] Examples of aliphatic hydrocarbons include n-hexane and n-octane.

[0133] Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, etc.

[0134] Examples of ethers include tetrahydrofuran and dioxane.

[0135] Examples of esters include ethyl acetate and butyl acetate.

[0136] Examples of amides include N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0137] Examples of sulfoxides include dimethyl sulfoxide.

[0138] Examples of alcohols include methanol and ethanol.

[0139] 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.

[0140] These can be used as a single type or in combination of two or more types.

[0141] The polymerization temperature is not particularly limited as long as it is within a temperature range where side reactions such as migration or termination reactions do not occur and monomers are consumed to complete the polymerization; however, it is preferable to carry out the polymerization in a temperature range of -100°C or higher and below the boiling point of the solvent.

[0142] In addition, the concentration of the monomer in the solvent is not particularly limited, but is typically 1 to 40 mass%, and preferably 10 to 30 mass%.

[0143] The polymerization time can be appropriately selected, typically ranging from 2 to 50 hours.

[0144] In addition, to facilitate polymerization, the functional groups of the monomer may be protected, and after polymerization, deprotection may be performed.

[0145] Examples of protected functional groups include phenolic hydroxyl groups. Examples of protecting groups include acyl groups (e.g., acetyl groups). Deprotection can be carried out by a hydrolysis reaction using, for example, an amine (e.g., an organic amine).

[0146] The weight-average molecular weight of polymer (A) is not particularly limited, but 5,000 to 50,000 is preferred, and 7,500 to 30,000 is more preferred. Meanwhile, the weight-average molecular weight is a value obtained by using polystyrene as a standard sample by gel permeation chromatography (GPC).

[0147] The content of polymer (A) in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of obtaining the effects of the present invention, 40 mass% to 100 mass% is preferred with respect to the film constituent components, 50 mass% to 95 mass% is more preferred, and 60 mass% to 90 mass% is particularly preferred.

[0148] The term "film constituent" refers to a component other than the solvent in a composition for forming a resist underlayer.

[0149] <Solvent(B)>

[0150] The solvent (B) is not particularly limited and may be water or an organic solvent.

[0151] Examples of organic solvents include alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, etc.

[0152] Examples of alkylene groups of alkylene glycol monoalkyl ethers include, for instance, alkylene groups having 2 to 4 carbon atoms.

[0153] Examples of alkyl groups of alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms.

[0154] The number of carbon atoms in alkylene glycol monoalkyl ethers can be, for example, 3 to 8.

[0155] Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.

[0156] Examples of alkylene groups of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include, for instance, alkylene groups having 2 to 4 carbon atoms.

[0157] Examples of alkyl groups for monocarboxylic acid esters of alkylene glycol monoalkyl ethers include, for instance, alkyl groups having 1 to 4 carbon atoms.

[0158] Examples of monocarboxylic acids in monocarboxylic acid esters of alkylene glycol monoalkyl ethers include saturated monocarboxylic acids having 2 to 4 carbon atoms.

[0159] Saturated monocarboxylic acids with 2 to 4 carbon atoms include, for example, acetic acid, propionic acid, and butyric acid.

[0160] The number of carbon atoms in the monocarboxylic acid ester of an alkylene glycol monoalkyl ether can be, for example, 5 to 10.

[0161] Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.

[0162] 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, 2-methyl hydroxyisobutyrate, 2-ethyl hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-ethyl ethoxypropionate, 3-methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactic acid, butyl lactic acid, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, Examples include N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0163] Among these solvents (B), alkylene glycol monoalkyl ether and monocarboxylic acid ester of alkylene glycol monoalkyl ether are preferred.

[0164] These solvents (B) can be used as a single type or in combination of two or more types.

[0165] The mass ratio of the organic solvent in the solvent (B) is not particularly limited, but 50% to 100% is preferred.

[0166] The content of the solvent (B) in the composition for forming a resist underlayer film is not particularly limited, but 50 mass% to 99.99 mass% is preferred, 75 mass% to 99.95 mass% is more preferred, and 90 mass% to 99.9 mass% is particularly preferred.

[0167] <Crosslinking agent (C)>

[0168] The crosslinking agent (C) is not particularly limited.

[0169] The crosslinking agent (C) has a structure different from that of the polymer (A).

[0170] As for the crosslinking agent (C), an aminoplast crosslinking agent and a fenoplast crosslinking agent are preferred.

[0171] Aminoplast crosslinking agents are addition condensation products of formaldehyde and compounds having amino groups, such as melamine or guanamine.

[0172] A phenoplast crosslinking agent is an addition condensation product of a compound having a phenolic hydroxyl group and formaldehyde.

[0173] As a crosslinking agent (C), for example, a compound having two or more of the following structures can be used.

[0174] [Chemical Formula 14]

[0175]

[0176] (During rescue, R 101 It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * indicates a bond loss.)

[0177] Bonding hands are bonded, for example, to nitrogen atoms, carbon atoms constituting aromatic hydrocarbon rings, etc.

[0178] R 101 The group preferably consists of a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure.

[0179] [Chemical Formula 15]

[0180]

[0181] (During rescue, R 102 represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond hand.)

[0182] As for the crosslinking agent (C), melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, and compounds having phenolic hydroxyl groups are preferred. These may be used individually or in combination of two or more types.

[0183] Examples of melamine compounds include, for instance, hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated or a mixture thereof.

[0184] Examples of guanamin compounds include, for instance, tetramethylolguanamin, tetramethoxymethylguanamin, a compound in which 1 to 4 methylol groups of tetramethylolguanamin are methoxymethylated or a mixture thereof, tetramethoxyethylguanamin, tetraacyloxyguanamin, a compound in which 1 to 4 methylol groups of tetramethylolguanamin are acyloxymethylated or a mixture thereof.

[0185] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxyglycoluryl, tetramethoxymethylglycoluryl, a compound in which 1 to 4 methylol groups of tetramethylol glycoluryl are methoxymethylated or a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycoluryl are acyloxymethylated or a mixture thereof.

[0186] In addition, as a glycoluryl compound, it may be, for example, a glycoluryl derivative represented by the following formula (1E).

[0187] [Chemical Formula 16]

[0188]

[0189] (In formula (1E), the four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0190] As a glycoluryl derivative represented by the above formula (1E), for example, compounds represented by the following formulas (1E-1) to (1E-6) may be used.

[0191] [Chemical Formula 17]

[0192]

[0193] A glycoluryl derivative represented by formula (1E) is 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).

[0194] [Chemical Formula 18]

[0195]

[0196] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0197] [Chemical Formula 19]

[0198]

[0199] (In formula (3d), R1 represents a methyl or ethyl group.)

[0200] As a glycoluryl derivative represented by the above formula (2E), examples include compounds represented by the following formulas (2E-1) to (2E-4). Furthermore, as a compound represented by the above formula (3d), examples include compounds represented by the following formulas (3d-1) and (3d-2).

[0201] [Chemical Formula 20]

[0202]

[0203] [Chemical Formula 21]

[0204]

[0205] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 methylol groups of tetramethylolurea are methoxymethylated or a mixture thereof, tetramethoxyethylurea, etc.

[0206] Examples of compounds having a phenolic hydroxyl group include compounds represented by the following formula (G-1) or formula (G-2).

[0207] [Chemical Formula 22]

[0208]

[0209] (Among Equations (G-1) and (G-2), Q 1 It represents a single bond or an organic group of m1.

[0210] R 1 and R 4 Each 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.

[0211] R 2 and R 5 Each represents a hydrogen atom or a methyl group.

[0212] R 3 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms.

[0213] n1 represents an integer 1≤n1≤3, n2 represents an integer 2≤n2≤5, n3 represents an integer 0≤n3≤3, n4 represents an integer 0≤n4≤3, and 3≤(n1+n2+n3+n4)≤6.

[0214] n5 represents an integer 1≤n5≤3, n6 represents an integer 1≤n6≤4, n7 represents an integer 0≤n7≤3, n8 represents an integer 0≤n8≤3, and 2≤(n5+n6+n7+n8)≤5.

[0215] m1 represents an integer from 2 to 10.

[0216] In addition, compounds having a phenolic hydroxyl group may include, for example, compounds represented by the following formula (G-3) or formula (G-4).

[0217] A 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.

[0218] [Chemical Formula 23]

[0219]

[0220] (Among Equations (G-3) and (G-4), Q 2 represents a single bond or an organic group of m2.

[0221] R 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group.

[0222] R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms.

[0223] n9 is an integer such that 1 ≤ n9 ≤ 3, n 10 2≤n 10 integer, n ≤ 5 11 is 0≤n 11 integers ≤3, n 12 is 0≤n 12 Integers ≤3, 3≤(n⁹+n 10 +n 11 +n 12 Represents an integer of )≤6.

[0224] n 13 is 1≤n 13 integers ≤3, n 14 is 1≤n 14 integers ≤ 4, n 15 is 0≤n 15 integers ≤3, n 16 is 0≤n 16 Integers of ≤3, 2≤(n 13 +n 14 +n 15 +n 16 Represents an integer such that )≤5.

[0225] m2 represents an integer from 2 to 10.

[0226] Q 2 Examples of organic groups with m2 in this case include organic groups with 1 to 15 carbon atoms.

[0227] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0228] [Chemical Formula 24]

[0229]

[0230] [Chemical Formula 25]

[0231]

[0232] [Chemical Formula 26]

[0233]

[0234] [Chemical Formula 27]

[0235]

[0236] [Chemical Formula 28]

[0237]

[0238] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0239] [Chemical Formula 29]

[0240]

[0241] [Chemical Formula 30]

[0242]

[0243] [Chemical Formula 31]

[0244]

[0245] Me represents a methyl group.

[0246] The above compounds are available as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd. Examples of products include the trade names TMOM-BP and HMOM-TPPA of Asahi Organic Materials Industry Co., Ltd.

[0247] Among these, glycoluryl compounds are preferred, specifically tetramethylolglycoluryl, tetramethoxyglycoluryl, tetramethoxymethylglycoluryl, a compound in which 1 to 4 methylol groups of tetramethylolglycoluryl are methoxymethylated or a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylolglycoluryl are acyloxymethylated or a mixture thereof, and tetramethoxymethylglycoluryl is more preferred.

[0248] The molecular weight of the crosslinking agent (C) is not particularly limited, but is preferably 500 or less.

[0249] The content of the crosslinking agent (C) in the composition for forming the resist underlayer film is not particularly limited, but is, for example, 1% to 70% by mass with respect to the polymer (A), and preferably 5% to 60% by mass.

[0250] <Curing Catalyst (D)>

[0251] The curing catalyst (D) included as an optional component in the composition for forming the resist underlayer can be either a thermal acid generator or a photocatalytic generator, but it is preferable to use a thermal acid generator.

[0252] 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 p-phenolsulfonic acid 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, hydroxycyanoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid. It is possible.

[0253] Examples of photocatalytic agents include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0254] Examples of onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal 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 nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0255] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormal butanesulfonyloxy)succinimide, N-(campersulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0256] Examples of disulfonyl diazomethane compounds include, for instance, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0257] Only one type of curing catalyst (D) may be used, or two or more types may be used in combination.

[0258] When a curing catalyst (D) is used, the content ratio of the curing catalyst (D) is, for example, 0.1 mass% to 50 mass% with respect to the crosslinking agent (C), and preferably 1 mass% to 30 mass%.

[0259] Other ingredients

[0260] In the composition for forming a resist underlayer, a surfactant may be additionally added to further improve the coating ability against surface non-uniformity and prevent the occurrence of pinholes or streaks.

[0261] Surfactants include, for example, straight-chain or branched-chain alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid, etc.), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, fluorine-based surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), MegaPac F171, F173, R-30 (manufactured by DIC Co., Ltd., product name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd., product name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0262] The amount of these surfactants is typically 2.0 mass% or less, preferably 1.0 mass% or less, with respect to the total solid content of the composition for forming a resist underlayer.

[0263] These surfactants may be added individually or in combination of two or more types.

[0264] The solid content included in the composition for forming a resist underlayer of the present invention, that is, the component excluding the solvent, is, for example, 0.01 mass% to 10 mass%.

[0265] A composition for forming a resist underlayer is suitablely used in EUV lithography.

[0266] A composition for forming a resist underlayer is preferably used for forming a resist underlayer.

[0267] (Resist sublayer)

[0268] The resist underlayer of the present invention is a cured product of the composition for forming the resist underlayer described above.

[0269] A resist underlayer can be manufactured, for example, by applying the aforementioned composition for forming a resist underlayer onto a semiconductor substrate and firing it.

[0270] Examples of semiconductor substrates to which the composition for forming a resist underlayer is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0271] When using a semiconductor substrate having an inorganic film formed on its surface, 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 film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0272] On such a semiconductor substrate, the composition for forming a resist underlayer of the present invention is applied by a suitable application method such as a spinner or a coater. After that, a resist underlayer is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0273] As for the film thickness of the resist underlayer, for example, 0.001μm (1nm) to 10μm, 0.002μm (2nm) to 1μm, 0.005μm (5nm) to 0.5μm (500nm), 0.001μm (1nm) to 0.05μm (50nm), 0.002μm (2nm) to 0.05μm (50nm), 0.003μm (3nm) to 0.05μm (50nm), 0.004μm (4nm) to 0.05μm (50nm), 0.005μm (5nm) to 0.05μm (50nm), 0.003μm (3nm) to 0.03μm (30nm), 0.003μm (3nm) to 0.02μm (20nm), It is 0.005μm(5nm)~0.02μm(20nm), 0.003μm(3nm)~0.01μm(10nm), 0.005μm(5nm)~0.01μm(10nm), 0.003μm(3nm)~0.006μm(6nm), or 0.005μm(5nm).

[0274] The method for measuring the film thickness of the resist underlayer in this specification is as follows.

[0275] · Measuring Device Name: Elliptical Film Thickness Measuring Device RE-3100 (SCREEN Co., Ltd.)

[0276] · SWE (Short Wavelength Ellipsometer) Mode

[0277] · Arithmetic mean of 8 points (e.g., 8 measurements taken at 1cm intervals in the X direction of the wafer)

[0278] (Laminate)

[0279] The laminate of the present invention comprises a semiconductor substrate and a resist underlayer film of the present invention.

[0280] As for semiconductor substrates, for example, the aforementioned semiconductor substrate can be cited.

[0281] The resist underlayer is placed, for example, on a semiconductor substrate.

[0282] (Method for manufacturing semiconductor devices, method for forming patterns)

[0283] The method for manufacturing a semiconductor device according to the present invention comprises at least the following processes.

[0284] · A process of forming a resist lower layer on a semiconductor substrate using the composition for forming a resist lower layer of the present invention, and

[0285] · Process of forming a resist film on a resist lower layer

[0286] The pattern forming method of the present invention comprises at least the following processes.

[0287] · A process of forming a resist lower layer on a semiconductor substrate using the composition for forming a resist lower layer of the present invention,

[0288] · Process of forming a resist film on a resist lower layer

[0289] · A process of irradiating a resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern, and

[0290] · A process of etching the resist underlayer using a resist pattern as a mask

[0291] Typically, a resist film is formed on the resist underlayer.

[0292] 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, and 1,000 nm or less. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, and 10 nm.

[0293] The resist film formed on the resist sublayer by a known method (e.g., application of a resist composition and firing) is not particularly limited as long as it responds to light or electron beams (EB) used for irradiation. Both negative-type photoresists and positive-type photoresists may be used.

[0294] Meanwhile, in this specification, a resist that responds to EB is also referred to as a photoresist.

[0295] Examples of photoresists include positive-type photoresists composed of novolak resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists composed of a binder having a group that decomposes by acid to increase the alkali dissolution rate and a photogenerator, chemically amplified photoresists composed of a low-molecular-weight compound that decomposes by acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photogenerator, and chemically amplified photoresists composed of a binder having a group that decomposes by acid to increase the alkali dissolution rate of the photoresist, a low-molecular-weight compound that decomposes by acid to increase the alkali dissolution rate of the photoresist, and a photogenerator, and resists containing metal elements. Examples include JSR Corporation's product name V146G, Seaplay's product name APEX-E, Sumitomo Chemical Corporation's product name PAR710, and Shin-Etsu Chemical Co., Ltd.'s product names AR2772 and SEPR430. In addition, fluorine-containing atomic polymer-based photoresists can be cited, for example, as described in Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), or Proc.SPIE, Vol.3999, 365-374 (2000).

[0296] Additionally, 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, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Patent Publication 2018-180525, WO2018 / 190088, Japanese Patent Publication 2018-070596, Japanese Patent Publication 2018-028090, Japanese Patent Publication 2016-153409, Japanese Patent Publication 2016-130240, Japanese Patent Publication 2016-108325, Japanese Patent Publication 2016-047920, Japanese Patent Publication 2016-035570, Japanese Patent Publication 2016-035567, Japanese Patent Publication 2016-035565, Japanese Patent Publication 2019-101417, Japanese Patent Publication 2019-117373, Japanese Patent Publication 2019-052294, Japanese Patent Publication 2019-008280, Japanese Patent Publication 2019-008279, Japanese Patent Publication 2019-003176, Japanese Patent Publication 2019-003175, Japanese Patent Publication 2018-197853, Japanese Patent Publication 2019-191298, Japanese Patent Publication 2019-061217, Japanese Patent Publication 2018-045152, Japanese Patent Publication 2018-022039, Japanese Patent Publication 2016-090441, Japanese Patent Publication 2015-10878, Japanese Patent Publication 2012-168279, Japanese Patent Publication 2012-022261, Japanese Patent Publication 2012-022258, Japanese Patent Publication 2011-043749, Japanese Patent Publication 2010-181857, Japanese Patent Publication 2010-128369, WO2018 / 031896, Japanese Patent Publication 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Publication 2018-41099,So-called resist compositions and metal-containing resist compositions, such as resist compositions, radioactive resin compositions, and high-resolution patterning compositions based on organometallic solutions, as described in WO2016 / 065120, WO2015 / 026482, Japanese Patent Publication 2016-29498, Japanese Patent Publication 2011-253185, etc., may be used, but are not limited thereto.

[0297] Examples of resist compositions include the following compositions.

[0298] A resin A having repeating unit having a polar group protected by an acid-degradable group that detaches by the action of acid, and a compound represented by the following general formula (121), comprising a desensitizing light-sensitive or radiation-sensitive resin composition.

[0299] [Chemical Formula 32]

[0300]

[0301] In the general formula (121), m represents an integer from 1 to 6.

[0302] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0303] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0304] L2 represents an alkylene group or a single bond that may have a substituent.

[0305] W1 represents a cyclic organic group that may have a substituent.

[0306] M + represents a cation.

[0307] 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 through 7 of groups 3 through 15 of the periodic table.

[0308] A radiation-reducing 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) and including an acid-dissociable group, and an acid-generating agent.

[0309] [Chemical Formula 33]

[0310]

[0311] (In Equation (31), Ar is a group obtained by subtracting (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. R 1 It is silver, 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 is the same or different. R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 Silver 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 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0312] A resin (A1) comprising a structural unit having a cyclic carbonate ester structure, a structural unit represented by the following formula, and a structural unit having an acid instability group, and a resist composition containing an acid generating agent.

[0313] [Chemical Formula 34]

[0314]

[0315] [During the meal,

[0316] R 2 represents an alkyl group having 1 to 6 carbon atoms that may have a halogen atom, a hydrogen atom, or a halogen atom, and X 1 Silver, single bond, -CO-O-* or -CO-NR 4 -* represents, * represents the bond loss with -Ar, and R 4represents 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 that may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0317] Examples of resist films include the following.

[0318] A resist film comprising a base resin including 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 by exposure.

[0319] [Chemical Formula 35]

[0320]

[0321] (among Equations (a1) and (a2), R A is, independently, a hydrogen atom or a methyl group. R 1 and R 2 R is, each independently, a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each is independently a fluorine atom or a methyl group. m is an integer from 0 to 4. X 1 It is a linker having 1 to 12 carbon atoms comprising at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond, a lactone ring, a phenylene group, and a naphthylene group. X 2 is a single bond, ester bond, or amide bond.

[0322] Examples of resist materials include the following.

[0323] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0324] [Chemical Formula 36]

[0325]

[0326] (among Equations (b1) and (b2), RA is a hydrogen atom or a methyl group. X 1 It is a single bond or an ester group. X 2 is a straight-chain, 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 group constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and also, X 2 At least one hydrogen atom included in is replaced by a bromine atom. X 3 It is a single bond, an ether group, an ester group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting this alkylene group may be substituted with an ether group or an ester group. Rf 1 ~Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, at least one of which is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 They may combine to form a carbonyl group. R 1 ~R 5 Each is independently a straight-chain, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a straight-chain, 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 sulfonate group, 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. Additionally, R 1 and R 2 They may combine and form a ring together with the sulfur atom to which they combine.

[0327] A resist material comprising a base resin comprising a polymer comprising repeating units represented by the following formula (a).

[0328] [Chemical Formula 37]

[0329]

[0330] (in Equation (a), R A is a hydrogen atom or a methyl group. R 1 It is silver, a hydrogen atom, or an acid unstable group. R 2 is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 It is a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond, a phenylene group, an ester group, or a lactone ring. X 2 is -O-, -O-CH2-, or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. provided that m+u is an integer from 1 to 4.)

[0331] A resist composition that generates acid upon exposure and changes solubility in a developer solution through the action of the acid,

[0332] It contains a substrate component (A) whose solubility in the developer changes due to the action of an acid, and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, and

[0333] The above fluorine additive component (F) is a resist composition comprising a fluorine resin component (F1) having a constituent unit (f1) containing a basic dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1).

[0334] [Chemical Formula 38]

[0335]

[0336] [In Equation (f2-r-1), Rf 21Each 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. * is a bonding hand.]

[0337] The above-mentioned 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).

[0338] [Chemical Formula 39]

[0339]

[0340] [In formulas (f1-1) and (f1-2), R is, respectively, independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. X is a divalent linker that does not have an acid-dissociable site. A aryl It is a divalent aromatic cyclic group that may have substituents. X 01 It is a single bond or a divalent linker. R 2 is an organic group having a fluorine atom, each independently.

[0341] The resist composition may be a metal-containing resist.

[0342] Metal-containing resists are also called metal oxide resists (MOR), and representative examples include tin oxide-based resists.

[0343] As a metal oxide resist material, for example, a coating composition comprising a metal oxo-hydroxo network having organic ligands formed by metal-carbon bonds and / or metal-carboxylate bonds, as described in Japanese Patent Publication No. 2019-113855, may be cited.

[0344] An example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Peroxo-based metal oxo-hydroxo compounds are described in detail in the patent document, for example, paragraph

[0011] of Japanese Patent Publication No. 2019-532489. Such patent documents include, for example, 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.

[0345] Coating comprising a metal oxo-hydroxo network having organic ligands formed by metal-carbon bonds and / or metal-carboxylate bonds.

[0346] Inorganic oxo / hydroxo base composition.

[0347] As a coating solution, an organic solvent; as a first organometallic composition, formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (here, 0 <z≤2 및 0<(z+x)≤4이다), 식 R’ n SnX 4-n A first organometallic composition represented by (where n=1 or 2), or a mixture thereof, wherein R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolytic bond to Sn or a combination thereof; and as a hydrolytic metal compound, formula MX' v A coating solution comprising a hydrolyzable metal compound represented by (wherein 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 having a hydrolyzable MX bond or a combination thereof).

[0348] Organic solvent and formula RSnO (3 / 2-x / 2) (OH) x(While eating, 0 <x<3)로 표시되는 제1 유기 금속 화합물을 포함하는 코팅 용액으로서, 상기 용액 중에 약 0.0025M~약 1.5M의 주석이 포함되고, R이 3~31개의 탄소 원자를 갖는 알킬기 또는 시클로알킬기이고, 상기 알킬기 또는 시클로알킬기가 제2급 또는 제3급 탄소 원자에서 주석에 결합된, 코팅 용액.

[0349] 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-reducing ligand comprising a peroxide group.

[0350] Other examples of metal-containing resists include 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.

[0351] These contents are incorporated into this specification to the same extent as those specified.

[0352] A method for forming a metal-containing resist film from a metal-containing resist is not particularly limited and may include a method of applying and firing a coating-type resist material (a composition for forming a metal-containing resist film) which is a metal-containing resist.

[0353] In addition, a metal-containing resist film may be formed by deposition. As a method for forming a metal-containing resist film by deposition, for example, the method described in Japanese Patent Publication No. 2017-116923 may be cited. The contents of Japanese Patent Publication No. 2017-116923 are incorporated into this specification to the same extent as they are specified in their entirety. Meanwhile, in Japanese Patent Publication No. 2017-116923, the metal-containing resist film in the present invention is referred to as a metal oxide-containing film.

[0354] Irradiation with light or electron beams 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 composition for forming a resist underlayer of the present invention is preferably applied for EB (electron beams) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably applied for EUV (extreme ultraviolet) exposure.

[0355] There are no particular limitations on the irradiation energy of the electron beam and the amount of light exposure.

[0356] Post-exposure bake (PEB) may be performed after irradiation with light or electron beams and before development.

[0357] The baking temperature is not particularly limited, but 60°C to 150°C is preferred, 70°C to 120°C is more preferred, and 75°C to 110°C is particularly preferred.

[0358] The baking time is not particularly limited, but 1 second to 10 minutes is preferred, 10 seconds to 5 minutes is more preferred, and 30 seconds to 3 minutes is particularly preferred.

[0359] For the development, for example, alkaline developer and organic solvent are used.

[0360] For example, the development temperature can be 5℃ to 50℃.

[0361] For example, the phenomenon time can be 10 seconds to 300 seconds.

[0362] As an alkaline developer, for example, an aqueous solution of an alkali such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; a primary amine such as ethylamine and n-propylamine; a secondary amine such as diethylamine and di-n-butylamine; a tertiary amine such as triethylamine and methyldiethylamine; an alcohol amine such as dimethylethanolamine and triethanolamine; a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and a cyclic amine such as pyrrole and piperidine may be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the aqueous solution of the alkali. Among these, a preferred developer is an aqueous solution of a quaternary ammonium salt, more preferably an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. Furthermore, surfactants or the like may be added to these developers. Alternatively, instead of an alkaline developer, a method may be used to develop using an organic solvent such as butyl acetate to develop areas where the alkaline dissolution rate of the photoresist is not enhanced.

[0363] An organic solvent can be used as a developer for the metal-containing resist, and development is performed using the developer (solvent) after irradiation with light or electron beams. Accordingly, for example, when a negative-type metal-containing resist film is used, the metal-containing resist film in the unexposed portions is removed, and a pattern of the metal-containing resist film is formed.

[0364] As for the developer (organic solvent), for example, 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-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, Propylene Formate, Ethyl Lactate, Butyl Lactate, Propylene Lactate, Ethyl Carbonate, Examples include propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. Furthermore, surfactants, etc., may be added to these developing solutions.

[0365] Next, the resist underlayer is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred.

[0366] If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, the semiconductor substrate can be manufactured by undergoing a process of processing the semiconductor substrate by a known method (such as a dry etching method).

[0367] Examples

[0368] Next, the contents of the present invention will be specifically explained with reference to examples, but the present invention is not limited to these.

[0369] The weight-average molecular weight of the polymers shown in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 below is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosho Inc. was used for the measurement, and the measurement conditions, etc., are as follows.

[0370] ·GPC Column: TSKgel Super-MultiporeHZ-N (2 pieces)

[0371] · Column temperature: 40℃

[0372] · Solvent: Tetrahydrofuran (THF)

[0373] · Flow rate: 0.35 ml / min

[0374] · Standard sample: Polystyrene (manufactured by Toso Co., Ltd.)

[0375] <Synthesized Example 1>

[0376] 7.50 g of 4-vinylphenyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 6.91 g of 4-nitrostyrene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (molar ratio 50 / 50 (mol%)), and 0.61 g of azobisisobutyronitrile (manufactured by Tokyo Kasei Kogyo 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 heated to 80°C while stirring after nitrogen purging. Next, the monomer solution was added dropwise to the reaction vessel over a period of 1 hour. The start of the dropwise addition of the monomer solution was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for a total of 6 hours to obtain a polymerization solution. After the polymerization reaction was completed, the polymerization solution was cooled to room temperature. The cooled polymerization solution was added to isopropyl alcohol, and the precipitated yellow powder was separated. 6.80 g of the obtained 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 a hydrolysis reaction was carried out at 70°C for 6 hours while stirring. After the hydrolysis reaction was completed, the residual solvent was removed and dissolved in propylene glycol monomethyl ether to obtain a polymer solution. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 8500 and a dispersion of 2.1 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula (1).

[0377] [Chemical Formula 40]

[0378]

[0379] <Synthesized Example 2>

[0380] 7.50 g of 4-vinylphenyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 4.60 g of 4-nitrostyrene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (molar ratio 60 / 40 (mol%)), and 0.51 g of azobisisobutyronitrile (manufactured by Tokyo Kasei Kogyo 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 heated to 80°C while stirring after nitrogen purging. Next, the monomer solution was added dropwise to the reaction vessel over a period of 1 hour. The start of the dropwise addition of the monomer solution was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for a total of 6 hours to obtain a polymerization solution. After the polymerization reaction was completed, the polymerization solution was cooled to room temperature. The cooled polymerization solution was introduced into isopropyl alcohol, and the precipitated yellow powder was filtered. 6.80 g of the obtained 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 a hydrolysis reaction was carried out at 70°C for 6 hours while stirring. After the hydrolysis reaction was completed, the residual solvent was removed and dissolved in propylene glycol monomethyl ether to obtain a polymer solution. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 14,000 and a dispersion degree of 4.5 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the above formula (1).

[0381] <Synthesized Example 3>

[0382] 7.50 g of 4-vinylphenyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 3.71 g of 4-nitrostyrene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (molar ratio 65 / 35 (mol%)), and 0.47 g of azobisisobutyronitrile (manufactured by Tokyo Kasei Kogyo 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 heated to 80°C while stirring after nitrogen purging. Next, the monomer solution was added dropwise to the reaction vessel over a period of 1 hour. The start of the dropwise addition of the monomer solution was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for a total of 6 hours to obtain a polymerization solution. After the polymerization reaction was completed, the polymerization solution was cooled to room temperature. The cooled polymerization solution was introduced into isopropyl alcohol, and the precipitated yellow powder was filtered. 6.80 g of the obtained 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 a hydrolysis reaction was carried out at 70°C for 6 hours while stirring. After the hydrolysis reaction was completed, the residual solvent was removed and dissolved in propylene glycol monomethyl ether to obtain a polymer solution. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 9,700 and a dispersion of 4.0 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the above formula (1).

[0383] <Comparative Synthesis Example 1>

[0384] 100.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.), 66.4 g of 5,5-diethyl barbituric acid, and 4.1 g of benzyl triethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the reaction was carried out at 130°C for 24 hours to obtain a polymer solution. As a result of GPC analysis, the polymer in the obtained solution had a weight-average molecular weight of 6,800 and a dispersion degree of 4.8 in terms of standard polystyrene. The polymer obtained in this synthesis example has a structural unit represented by the following formula.

[0385] [Chemical Formula 41]

[0386]

[0387] <Preparation of a composition for forming a resist underlayer>

[0388] (Examples 1–5, Comparative Examples 1–2)

[0389] The polymers obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1, along with 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 fluoropolymer filter to prepare compositions for forming a resist underlayer film. The following were used as comparative polymers. Abbreviations in Tables 1 and 2 are also indicated.

[0390] · Comparative Polymer: Phenolic Resin (Product Name: VP-8000, manufactured by Nippon Soda Co., Ltd., polymer not containing nitro groups)

[0391] Other abbreviations in Tables 1 and 2 are as follows.

[0392] ·PL-LI: Tetramethoxymethylglycoluryl

[0393] ·PGME-PL: Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]-

[0394] ·TMOM-BP: 3,3',5,5'-tetrakis(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol

[0395] ·HMOM-TPPA: 4,4'-[1-[4-[1-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-1-methylethyl]phenyl]ethylidene]-bis[2,6-bis(methoxymethyl)phenol]

[0396] ·Py-PSA: Pyridinium-p-hydroxybenzenesulfonic acid

[0397] · R-30N: Surfactant (DIC agent)

[0398] ·PGMEA: Propylene glycol monomethyl ether acetate

[0399] ·PGME: Propylene glycol monomethyl ether

[0400] In Tables 1 and 2, each amount added is expressed in parts by mass, and the solvent is expressed in composition ratio.

[0401] [Table 1]

[0402]

[0403] [Table 2]

[0404]

[0405] <Elution Test of Photoresist into Solvent>

[0406] Each of the compositions for forming a resist sublayer of Examples 1 to 5 and Comparative Examples 1 to 2 was applied onto 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 sublayers 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 for photoresist. If the change in film thickness was 5 Å or less, it was classified as "good," and if it exceeded 5 Å, it was classified as "poor." The results are shown in Table 3.

[0407] [Table 3]

[0408]

[0409] <Formation of a resist pattern by an electron beam drawing device>

[0410] The compositions for forming a resist sublayer of Example 1 and Comparative Examples 1 and 2 were each applied onto a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist sublayer with a thickness of 5 nm. A positive type EUV resist solution was spin-coated onto the resist sublayer and heated at 110°C for 60 seconds to form an EUV resist film. The resist film was exposed under predetermined conditions using an electron beam lithography device (ELS-G130). After exposure, a bake (PEB) was performed at 90°C for 60 seconds, and the film was cooled to room temperature on a cooling plate. After development with an alkaline developer (2.38% TMAH), a resist pattern with a 22 nm line pattern and a 44 nm pitch was formed. A scanning electron microscope (CG4100, manufactured by Hitachi High Technologies Co., Ltd.) was used to measure the resist pattern. Regarding the formation of the resist pattern, in Table 4, a line and space (LS) pattern with a CD size of 22 nm was formed and labeled "Good," while a case where collapse or peeling of the line and space pattern was observed was labeled "Poor." Furthermore, the charge amount used to form the 22 nm line and space pattern was set as the optimal irradiation energy, and the irradiation energy (μC / cm²) when Comparative Example 1 was set to 1.00 for each case 2 ) is also shown in Table 4. Additionally, the resist pattern dimensions (pattern collapse limit dimensions) at the maximum exposure amount (limit exposure amount) 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.

[0411] [Table 4]

[0412]

[0413] From Table 4, it was confirmed that when a resist sublayer was formed using the composition for forming a resist sublayer of Example 1, the reduction in optimal irradiation energy and the expansion of the pattern collapse limit dimension were greater than when a resist sublayer was formed using the composition for forming a resist sublayer of Comparative Example 1.

Claims

Claim 1 A composition for forming a resist underlayer film comprising a polymer (A) containing phenolic hydroxyl groups and nitro groups, and a solvent (B). Claim 2 A composition for forming a resist underlayer, wherein, in claim 1, the polymer (A) is a vinyl polymer. Claim 3 A composition for forming a resist underlayer according to claim 1, wherein the polymer (A) comprises a structural unit (A1) represented by the following formula (A1) and a structural unit (A2) represented by the following formula (A2). [Chemical Formula 1] (In Equation (A1), R 1 Representing silver, a hydrogen atom, or a methyl group, X 1 Silver represents a single bond, ester bond, or amide bond, and Y 1 Silver represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R A1 Representing silver, a halogen atom, a carboxyl 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, where n is an integer from 1 to 7, m is an integer from 0 to 6, k is an integer from 0 to 2, and when m is 2 or greater, m R A1 It may be the same or different.)[Chemical Formula 2] (In Equation (A2), R 2 represents a hydrogen atom or a methyl group, and X 2 represents a single bond, ester bond, or amide bond, and Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R A2 represents a halogen atom, a carboxyl 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, where n represents an integer from 1 to 7, m represents an integer from 0 to 6, k represents an integer from 0 to 2, and when m is 2 or greater, m R A2 It may be the same or different.) Claim 4 A composition for forming a resist underlayer according to claim 1, 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. Claim 5 A composition for forming a resist underlayer, wherein, in claim 1, a crosslinking agent (C) is further included. Claim 6 A composition for forming a resist underlayer, wherein, in claim 5, the crosslinking agent (C) is at least one selected from the group consisting of an aminoplast crosslinking agent and a fenoplast crosslinking agent. Claim 7 A composition for forming a resist underlayer, wherein, in claim 1, a curing catalyst (D) is further included. Claim 8 A composition for forming a resist underlayer, used in EUV lithography, according to claim 1. Claim 9 A composition for forming a resist underlayer, used for forming a resist underlayer of a metal-containing resist, in claim 1. Claim 10 A resist underlayer, which is a cured product of a composition for forming a resist underlayer as described in any one of claims 1 to 9. Claim 11 A laminate comprising a semiconductor substrate and a resist underlayer film as described in claim 10. Claim 12 A method for manufacturing a semiconductor device, comprising: a process of forming a resist lower layer film on a semiconductor substrate using a composition for forming a resist lower layer film as described in any one of claims 1 to 9; and a process of forming a resist film on the resist lower layer film. Claim 13 A pattern forming method comprising: a process of forming a resist lower layer film on a semiconductor substrate using a composition for forming a resist lower layer film described in any one of claims 1 to 9; a process of forming a resist film on the resist lower layer film; a process of irradiating the resist film with light or an electron beam and subsequently developing the resist film to obtain a resist pattern; and a process of etching the resist lower layer film using the resist pattern as a mask.

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