Resist underlayer film-forming composition in which denaturation of crosslinking agent is suppressed

Abstract

Provided are: a resist underlayer film forming composition which has high storage stability, has a low film curing start temperature, can cause the generation of a sublimated product in a reduced amount, and enables the formation of a film that is rarely eluted into a photoresist solvent; a method for forming a resist pattern using the resist underlayer film forming composition; and a method for manufacturing a semiconductor device. The resist underlayer film forming composition comprises a crosslinkable resin, a crosslinking agent, a crosslinking catalyst represented by formula (I) and a solvent. (A-SO3)-(BH)+ [wherein A represents a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group which may be substituted, an aryl group which may be substituted by a group other than a hydroxy group, or a heteroaryl group which may be substituted; and B represents a base having a pKa value of 6.5 to 9.5.]

Description

[Technical Field]

[0001] The present invention relates to a resist underlayer film-forming composition in which modification of a crosslinking agent is suppressed, a method for forming a resist pattern using the resist underlayer film-forming composition, and a method for manufacturing a semiconductor device. [Background technology]

[0002] In recent years, in the lithography process of semiconductor device manufacturing, semiconductor process materials, including resist underlayer coatings (BARC), are required to have increasingly higher quality. Recently, a new problem has arisen: degeneration of the crosslinking agent and polymer resin, which is a main component of the resist underlayer coating, due to crosslinking catalysts and solvents used in the resist underlayer coating-forming composition. Therefore, a new crosslinking catalyst that can suppress such degeneration is required.

[0003] Patent Document 1 describes a compound of the formula (A - )(BH) + In A - is the anion of an organic or inorganic acid having a pKa of 3 or less, (BH) + Disclosed is an ionic thermal acid generator that is the monoprotonated form of a nitrogen-containing base B having a pKa between 0 and 5.0 and a boiling point below 170° C. Specifically, a combination of perfluorobutanesulfonate with ammonium, pyridinium, 3-fluoropyridinium, or pyridazinium is described.

[0004] Patent Document 2 describes a compound of formula X - YH + discloses a thermal acid generator in which X is an anionic component and Y is a substituted pyridine. Specifically, the combination of methylbenzenesulfonate with fluoropyridinium or trifluoromethylpyridinium is described.

[0005] Patent Document 3 discloses a thermal acid generator containing a sulfonic acid component without a hydroxyl group and a pyridinium component with a ring substituent. Specifically, it describes a combination of methylbenzenesulfonate with methylpyridinium, methoxypyridinium, or trimethylpyridinium.

[0006] Patent Document 4 discloses a thermal acid generator containing triethylamine paratoluenesulfonate, ammonium paratoluenesulfonate, ammonium mesitylenesulfonate, ammonium dodecylbenzenesulfonate, or dimethylamine paratoluenesulfonate.

[0007] Patent Document 5 describes a method for producing a hydroxybenzoate containing various sulfonic acids and NH4 + or a primary, secondary, tertiary, or quaternary ammonium ion are disclosed. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 6334900 [Patent Document 2] Japanese Patent Application Publication No. 2019-56903 [Patent Document 3] Patent No. 6453378 [Patent Document 4] Patent No. 4945091 [Patent Document 5] Patent No. 6256719 Summary of the Invention [Problem to be solved by the invention]

[0009] However, it has been found that the thermal acid generators disclosed in the prior art have the problem of accelerating the reaction between the aminoplast crosslinking agent and a compound having an alcoholic hydroxyl group, such as propylene glycol monomethyl ether or methyl 2-hydroxy-2-methylpropionate, which are frequently used as solvents in resist underlayer film-forming compositions, and easily denaturing the crosslinking agent. Furthermore, it has also been found that the use of a high-boiling point base or a strong base as the thermal acid generator reduces the curability of the underlayer film, resulting in an increased amount of sublimate generation.

[0010] Therefore, an object of the present invention is to provide a resist underlayer film-forming composition that has high storage stability, a low film curing initiation temperature, generates a small amount of sublimate, and is capable of forming a film that does not dissolve in a photoresist solvent; a method for forming a resist pattern using the resist underlayer film-forming composition; and a method for manufacturing a semiconductor device. [Means for solving the problem]

[0011] The present invention encompasses the following. [1] A resist underlayer film-forming composition comprising a crosslinkable resin, a crosslinking agent, a crosslinking catalyst represented by the following formula (I), and a solvent: [ka] [In formula (I), A is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted aryl group with a group other than a hydroxy group, or an optionally substituted heteroaryl group, B is a base with a pKa between 6.5 and 9.5. [2] A resist underlayer film-forming composition comprising a compound having an epoxy group and / or a resin having an epoxy group, a crosslinking catalyst represented by the following formula (I), and a solvent: [ka] [In formula (I), A is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted aryl group with a group other than a hydroxy group, or an optionally substituted heteroaryl group, B is a base with a pKa between 6.5 and 9.5. [3] The resist underlayer film-forming composition according to [1], wherein the crosslinking agent is an aminoplast crosslinking agent or a phenoplast crosslinking agent. [4] In the above formula (I), B is R 1 R 2 R 3 N, R 1 , and R 2 each independently represents an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon group, R 1 and R 2 may form a ring with or without a heteroatom, R 3 represents an optionally substituted aromatic group, or an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R 1 and R 2 When does not form a ring, R 3 is an optionally substituted aromatic group, [1] The resist underlayer film-forming composition according to any one of [1] to [3]. [5] B in the above formula (I) is [ka] [In the formula, R 1 , and R 2 each independently represents an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon group, R 3 represents an optionally substituted aromatic group; or The following formula (II) [ka] [In formula (II), R is a hydrogen atom, a nitro group, a cyano group, an amino group, a carboxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, an organic group containing an ether bond, an organic group containing a ketone bond, an organic group containing an ester bond, or a group consisting of any combination thereof; R' is [ka] and R a and R b each independently represents an optionally substituted alkyl; X is O, S, or SO2; n and m are each independently 2, 3, 4, 5, or 6. [4] The resist underlayer film-forming composition according to any one of [1] to [4], wherein the base is represented by the following formula: [6] R in the above formula 3 represents an optionally substituted phenyl, naphthyl, anthracenyl, or phenanthrenyl group; R in the above formula (II) is a hydrogen atom, a methyl group, an ethyl group, an allyl group, or a cyanomethyl group, In the above formula (II), R' is [ka] The resist underlayer film-forming composition according to [5], wherein the base is represented by the formula: [7] The resist underlayer film forming composition according to any one of [1] to [6], further comprising a compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group. [8] The resist underlayer film forming composition according to [7], wherein the compound having an alcoholic hydroxyl group or the compound having a group capable of forming an alcoholic hydroxyl group is a propylene glycol-based solvent, an oxyisobutyric acid ester-based solvent, or a butylene glycol-based solvent. [9] The resist underlayer film forming composition according to [7] or [8], wherein the compound having an alcoholic hydroxyl group or the compound having a group capable of forming an alcoholic hydroxyl group is propylene glycol monomethyl ether or methyl 2-hydroxy-2-methylpropionate.

[10] The resist underlayer film forming composition according to any one of [1] to [9], wherein A in the above formula (I) is a methyl group, a fluoromethyl group, or a tolyl group.

[11] The resist underlayer film forming composition according to any one of [1] to

[10] , wherein B in the above formula (I) is N-methylmorpholine or N,N-diethylaniline.

[12]

[12] The resist underlayer film-forming composition according to any one of [3] to

[11] , wherein the aminoplast crosslinking agent is a highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, or a polymer thereof.

[13] The resist underlayer film-forming composition according to any one of [3] to

[11] , wherein the phenoplast crosslinker is a highly alkylated, alkoxylated, or alkoxyalkylated aromatic, or a polymer thereof.

[14] The resist underlayer film-forming composition according to any one of [1] and [3] to

[13] , wherein the crosslinkable resin is at least one selected from the group consisting of a novolac resin, a polyester resin, a polyimide resin, and an acrylic resin.

[15] The resist underlayer film forming composition according to any one of [1] to

[14] , further comprising a surfactant.

[16] A resist underlayer film obtained by applying the resist underlayer film-forming composition according to any one of [1] to

[15] onto a semiconductor substrate and baking the applied composition.

[17] A method for forming a resist pattern used in the manufacture of semiconductors, comprising the steps of applying the resist underlayer film-forming composition according to any one of [1] to

[15] onto a semiconductor substrate and baking the composition to form a resist underlayer film.

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

[15] ; forming a resist film thereon; forming a resist pattern by irradiating with light or an electron beam and developing; etching the resist underlayer film using the formed resist pattern; and processing the semiconductor substrate using the patterned resist underlayer film.

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

[15] ; forming a hard mask thereon; further forming a resist film thereon; forming a resist pattern by irradiating with light or an electron beam and developing; etching the hard mask using the formed resist pattern; etching the resist underlayer film using the patterned hard mask; and processing a semiconductor substrate using the patterned resist underlayer film.

[20] The manufacturing method according to

[19] , wherein the hard mask is formed by coating or vapor deposition of an inorganic material. [Effects of the Invention]

[0012] According to the present invention, there are provided a resist underlayer film-forming composition that has high storage stability because the crosslinking catalyst prevents side reactions (e.g., reaction with a solvent) of the aminoplast crosslinking agent or the phenoplast crosslinking agent, that can suppress the amount of sublimate generated because the curing initiation temperature of the resist underlayer film is relatively low, and that can form a film that does not dissolve in a photoresist solvent, a method for forming a resist pattern using the resist underlayer film-forming composition, and a method for manufacturing a semiconductor device. DETAILED DESCRIPTION OF THE INVENTION

[0013] The resist underlayer film-forming composition according to the present invention contains a crosslinkable resin, a crosslinking agent, and a crosslinking catalyst represented by the following formula (I). [ka] [In formula (I), A is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted aryl group with a group other than a hydroxy group, or an optionally substituted heteroaryl group, B is a base with a pKa between 6.5 and 9.5.

[0014] [Crosslinkable resin] In the present invention, the crosslinkable resin refers to a resin that is uncrosslinked or partially crosslinked, and that undergoes crosslinking under the action of a crosslinking catalyst to form a film that does not dissolve in a photoresist solvent. Preferably, the crosslinkable resin is at least one selected from the group consisting of novolac resin, polyester resin, polyimide resin, and acrylic resin. Some specific examples (repeating unit structures) are as follows:

[0015] [ka]

[0016] [ka]

[0017] [ka]

[0018] [ka]

[0019] (wherein m, n, l and the numbers represent the molar ratio or the number of repeating units (any number)).

[0020] [Compound having an epoxy group and / or resin having an epoxy group] In the present invention, the term "compound having an epoxy group" and "resin having an epoxy group" refer to compounds and resins having one or more epoxy groups per molecule, which undergo crosslinking or polymerization under the action of a crosslinking catalyst and can form a film that does not dissolve in a photoresist solvent. Preferably, the compound having an epoxy group and the resin having an epoxy group are at least one selected from the group consisting of glycidyl ether epoxy resins, glycidyl ester epoxy resins, and glycidyl amine epoxy resins. Some specific examples are as follows:

[0021] [ka]

[0022] These preferably have a weight average molecular weight of 600 to 1,000,000, or 600 to 200,000.

[0023] [Aminoplast crosslinking agent] Aminoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, and polymers thereof. Preferred are crosslinking agents having at least two crosslink-forming substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and methoxymethylated thiourea. Condensates of these compounds can also be used.

[0024] In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As a crosslinking agent having high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0025] Preferably, it is at least one selected from the group consisting of tetramethoxymethyl glycoluril and hexamethoxymethyl melamine.

[0026] The aminoplast crosslinking agent may be used alone or in combination of two or more thereof. The aminoplast crosslinking agent may be produced by a method known per se or a method equivalent thereto, or a commercially available product may be used.

[0027] The amount of aminoplast crosslinking agent used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, and the like, but is 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.5 mass % or more, or 1.0 mass % or more, and is 80 mass % or less, 50 mass % or less, 40 mass % or less, 20 mass % or less, or 10 mass % or less, relative to the total solids content of the resist underlayer film-forming composition of the present invention.

[0028] Some specific examples are as follows:

[0029] [ka]

[0030] [ka]

[0031] [Phenoplast Crosslinker] Phenoplast crosslinkers include highly alkylated, alkoxylated, or alkoxyalkylated aromatics and their polymers. Preferred crosslinkers have at least two crosslink-forming substituents per molecule, such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Condensates of these compounds can also be used.

[0032] In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As a crosslinking agent having high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0033] Preferably, it is at least one selected from the group consisting of 3,3',5,5'-tetramethoxymethyl-4,4'-bisphenol and 4-(1,1-dimethylethyl)-2,6-bis(methoxymethyl)phenol.

[0034] The phenoplast crosslinking agent may be used alone or in combination of two or more. The phenoplast crosslinking agent may be produced by a method known per se or a method equivalent thereto, or a commercially available product may be used.

[0035] The amount of the phenoplast crosslinking agent used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, and the like, but is 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.5 mass % or more, or 1.0 mass % or more, and is 80 mass % or less, 50 mass % or less, 40 mass % or less, 20 mass % or less, or 10 mass % or less, relative to the total solids content of the resist underlayer film-forming composition of the present invention.

[0036] Some specific examples are as follows:

[0037] [ka]

[0038] [ka]

[0039] [Crosslinking catalyst] The crosslinking catalyst in the present invention is represented by the following formula (I). [ka] [In formula (I), A is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted aryl group with a group other than a hydroxy group, or an optionally substituted heteroaryl group, B is a base with a pKa between 6.5 and 9.5.

[0040] Preferably B is R 1 R 2 R 3 N, R1 , and R 2 each independently represents an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon group, R 1 and R 2 may form a ring with or without a heteroatom, R 3 represents an optionally substituted aromatic group, or an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R 1 and R 2 When does not form a ring, R 3 is an optionally substituted aromatic group.

[0041] Preferably, R 1 , and R 2 each independently represents an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R 3 represents an aromatic group which may be substituted.

[0042] Preferably, R 1 , and R 2 each independently represents an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R 3 represents an optionally substituted phenyl, naphthyl, anthracenyl, or phenanthrenyl group.

[0043] Preferably, B is a group represented by the following formula (II): [ka] [In formula (II), R is a hydrogen atom, a nitro group, a cyano group, an amino group, a carboxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, an organic group containing an ether bond, an organic group containing a ketone bond, an organic group containing an ester bond, or a group consisting of any combination thereof; R' is [ka] and R a and R b each independently represents an optionally substituted alkyl; X is O, S, or SO2; n and m are each independently 2, 3, 4, 5, or 6. It is expressed as:

[0044] Preferably, R is a hydrogen atom, a methyl group, an ethyl group, an allyl group, or a cyanomethyl group; R' is [ka] and n and m are each independently 2, 3, 4, 5, or 6.

[0045] Examples of the linear, branched, or cyclic saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl -n-Propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl 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 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, 2,2,Examples include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, and a 2-ethyl-3-methyl-cyclopropyl group.

[0046] Examples of the linear, branched, or cyclic unsaturated aliphatic hydrocarbon group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl- 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group , 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group Examples of the alkyl group include phenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0047] Examples of the aryl group include a phenyl group, an o-methylphenyl group, a m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, a m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0048] Examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, imidazolyl, pyranyl, pyridinyl, pyrimidinyl, pyrazinyl, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, quinuclidinyl, indolyl, purinyl, quinolinyl, isoquinolinyl, chromenyl, thianthrenyl, phenothiazinyl, phenoxazinyl, xanthenyl, acridinyl, phenazinyl, and carbazolyl groups.

[0049] Aryl and heteroaryl groups are included in the aromatic groups.

[0050] Examples of the substituent include a nitro group, an amino group, a cyano group, a sulfo group, a hydroxy group, a carboxyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, an organic group containing an ether bond, an organic group containing a ketone bond, an organic group containing an ester bond, or a combination thereof.

[0051] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0052] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n -pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.

[0053] The alkyl group, alkenyl group, and aryl group are as exemplified above.

[0054] Organic groups containing ether bonds are R 11 -OR 11 (R 11 each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, an alkylene group, a phenyl group, or a phenylene group.) Examples of the organic groups include organic groups having an ether bond, such as a methoxy group, an ethoxy group, and a phenoxy group.

[0055] The organic group containing the ketone bond is R 21 -C(=O)-R 21 (R 21 each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, an alkylene group, a phenyl group, or a phenylene group.) Examples of the organic groups include organic groups having a ketone bond, such as an acetoxy group or a benzoyl group.

[0056] The organic group containing the ester bond is R 31 -C(=O)OR 31 (R 31 each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, an alkylene group, a phenyl group, or a phenylene group.) Examples of the organic groups include organic groups containing an ester bond, such as methyl ester, ethyl ester, and phenyl ester.

[0057] Note that A does not include aryl groups substituted with hydroxy groups. Therefore, anions derived from p-phenolsulfonic acid, o-cresol-4-sulfonic acid, p-cresol-2-sulfonic acid, etc. are not included in the (A-SO3) of the present invention. - Preferably, A does not include an aryl group substituted with a carboxyl group. Therefore, anions derived from 5-sulfosalicylic acid, etc., are not included in the (A-SO3) of the present invention. - is not included in

[0058] Preferably, A is a methyl group, a fluoromethyl group, or a tolyl group.

[0059] In the present invention, B is a base having a pKa of 6.5 to 9.5, specific examples of which include N-methylmorpholine and N,N-diethylaniline.

[0060] Some specific examples of the crosslinking catalyst represented by formula (I) are as follows:

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] The amount of the crosslinking catalyst is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total solid content in the resist underlayer film-forming composition.

[0065] The resist underlayer film forming composition according to the present invention may contain, in addition to the above, a solvent, a surfactant, a light absorbing agent, a rheology adjuster, an adhesive aid, and the like, as needed.

[0066] [solvent] The resist underlayer film-forming composition according to the present invention may further contain, as a solvent, a compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group, which is usually used in an amount that uniformly dissolves the above-mentioned crosslinkable resin, aminoplast crosslinking agent or phenoplast crosslinking agent, and crosslinking catalyst represented by Formula (I). Examples of compounds having an alcoholic hydroxyl group or compounds having a group capable of forming an alcoholic hydroxyl group include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol propyl ether acetate, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and the like can be used. Of these, propylene glycol-based solvents, oxyisobutyric acid ester-based solvents, and butylene glycol-based solvents are preferred. The compound having an alcoholic hydroxyl group or the compound having a group capable of forming an alcoholic hydroxyl group can be used alone or in combination of two or more kinds. Furthermore, a high boiling point solvent such as propylene glycol monobutyl ether or propylene glycol monobutyl ether acetate may be mixed and used. Preferred are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, and the like, and more preferred are propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

[0067] [Surfactants] The resist underlayer film forming composition according to the present invention can contain a surfactant in order to prevent pinholes, striations, and the like from occurring and to further improve the coatability against surface irregularities. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate; Examples of suitable surfactants include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, and R-40 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

[0068] [Other additives] In addition to the crosslinking catalyst of formula (I), the resist underlayer film-forming composition according to the present invention may also contain, as a catalyst for promoting the crosslinking reaction, acidic compounds such as citric acid, thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, onium salt-based photoacid generators such as bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate and triphenylsulfonium trifluoromethanesulfonate, halogen-containing compound-based photoacid generators such as phenyl-bis(trichloromethyl)-s-triazine, and sulfonic acid-based photoacid generators such as benzoin tosylate and N-hydroxysuccinimide trifluoromethanesulfonate.

[0069] Examples of the light-absorbing agent include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI Disperse Violet 43; CI Disperse Blue 96; and CI Fluorescent Brightening Agent. Suitable examples of the light-absorbing agent that can be used include CI Solvent Orange 2 and 45, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pigment Green 10, and CI Pigment Brown 2. The light-absorbing agent is typically blended in an amount of 10% by mass or less, and preferably 5% by mass or less, based on the total solid content of the resist underlayer film-forming composition of the present invention.

[0070] The rheology modifier is added mainly to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition of the present invention.

[0071] The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film-forming composition, and particularly to prevent peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; Examples of the adhesion promoter include silanes such as silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion promoters are typically blended in an amount of less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the resist underlayer film-forming composition of the present invention.

[0072] The resist underlayer film-forming composition according to the present invention has a solids content of 0.1 to 70% by mass, or 0.1 to 60% by mass. The solids content is the content of all components of the resist underlayer film-forming composition excluding the solvent. The solids content may contain a crosslinkable resin in an amount of 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass.

[0073] In the present invention, a semiconductor device can be manufactured through the steps of forming a resist underlayer film on a semiconductor substrate from a resist underlayer film-forming composition, forming a resist film thereon, forming a resist pattern by irradiating with light or an electron beam and developing, etching the resist underlayer film using the formed resist pattern, and processing a semiconductor substrate using the patterned resist underlayer film. Furthermore, in the present invention, a semiconductor device can be manufactured through the steps of forming a resist underlayer film on a semiconductor substrate from a resist underlayer film-forming composition, forming a hard mask thereon, further forming a resist film thereon, forming a resist pattern by irradiating with light or an electron beam and developing, etching the hard mask using the formed resist pattern, etching the resist underlayer film using the patterned hard mask, and processing a semiconductor substrate using the patterned resist underlayer film. Preferably, the hard mask is formed by coating or vapor-depositing an inorganic material.

[0074] A resist underlayer film can be obtained by applying the resist underlayer film-forming composition of the present invention to a semiconductor substrate and baking it. By forming such a resist underlayer film, a resist pattern for use in semiconductor manufacturing can be formed. This resist pattern formation method involves applying the resist underlayer film-forming composition to a substrate (e.g., a transparent substrate such as a silicon / silicon dioxide-coated substrate, a glass substrate, or an ITO substrate) used in the manufacture of precision integrated circuit devices using a suitable application method such as a spinner or coater, followed by baking and curing to form a coated underlayer film (resist underlayer film). The resist underlayer film preferably has a thickness of 0.01 to 3.0 μm. The post-application baking conditions are typically 80 to 350° C. for 0.5 to 120 minutes.

[0075] Thereafter, a resist is applied directly onto the resist underlayer film, or one to several layers of a coating material are formed on the resist underlayer film as needed, followed by coating to form a resist film, which is then irradiated with light or an electron beam through a predetermined mask, and developed, rinsed, and dried to obtain a good resist pattern. If necessary, post-exposure baking (PEB) may be performed after irradiation with light or electron beams. The resist underlayer film in the area where the resist has been developed and removed in the above step is then removed by dry etching, thereby forming a desired pattern on the substrate. A hard mask can be formed on the resist underlayer film, and the hard mask can be formed by coating or vapor deposition of an inorganic material. The hard mask can be etched using the formed resist pattern to form a patterned hard mask. The resist underlayer film can be etched through this patterned hard mask, and the semiconductor substrate can be processed using the patterned resist underlayer film.

[0076] The resist used in the present invention is a photoresist or an electron beam resist.

[0077] The photoresist to be applied on top of the resist underlayer film for lithography in the present invention may be either a negative or positive type, and examples thereof include a positive photoresist composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; a chemically amplified photoresist composed of a binder having a group that is decomposed by acid to increase the alkaline dissolution rate and a photoacid generator; a chemically amplified photoresist composed of an alkali-soluble binder, a low molecular weight compound that is decomposed by acid to increase the alkaline dissolution rate of the photoresist and a photoacid generator; a chemically amplified photoresist composed of a binder having a group that is decomposed by acid to increase the alkaline dissolution rate and a low molecular weight compound that is decomposed by acid to increase the alkaline dissolution rate of the photoresist and a photoacid generator; and a photoresist having Si atoms in its skeleton, such as APEX-E, a product of Rohm and Haas.

[0078] Examples of the electron beam resist to be applied on top of the resist underlayer film for lithography in the present invention include a composition comprising a resin containing a Si-Si bond in the main chain and an aromatic ring at the terminal, and an acid generator that generates acid upon irradiation with an electron beam, or a composition comprising poly(p-hydroxystyrene) in which the hydroxyl group is substituted with an organic group containing N-carboxyamine, and an acid generator that generates acid upon irradiation with an electron beam. In the latter electron beam resist composition, the acid generated from the acid generator upon irradiation with an electron beam reacts with the N-carboxyaminooxy group in the polymer side chain, decomposing the polymer side chain into a hydroxyl group, making it alkali-soluble and dissolving in an alkaline developer, thereby forming a resist pattern. Acid generators that generate acid upon irradiation with an electron beam include halogenated organic compounds such as 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, and 2-chloro-6-(trichloromethyl)pyridine; onium salts such as triphenylsulfonium salts and diphenyliodonium salts; and sulfonic acid esters such as nitrobenzyl tosylate and dinitrobenzyl tosylate.

[0079] The exposure light for the photoresist is actinic radiation such as near ultraviolet, far ultraviolet, or extreme ultraviolet (e.g., EUV, wavelength 13.5 nm), and light with wavelengths of, for example, 248 nm (KrF laser light), 193 nm (ArF laser light), or 157 nm (F2 laser light) is used. For light irradiation, any method can be used without particular limitation as long as it can generate acid from a photoacid generator, and the exposure dose is 1 to 2000 mJ / cm. 2 , or 10 to 1500 mJ / cm 2 , or 50 to 1000 mJ / cm 2 by.

[0080] The electron beam resist can be irradiated with electron beams using, for example, an electron beam irradiation device.

[0081] Examples of developers for resists having resist underlayer films formed using the resist underlayer film-forming composition of the present invention include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia), primary amines (e.g., ethylamine and n-propylamine), secondary amines (e.g., diethylamine and di-n-butylamine), tertiary amines (e.g., triethylamine and methyldiethylamine), alcohol amines (e.g., dimethylethanolamine and triethanolamine), quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline), and cyclic amines (e.g., pyrrole and piperidine). Furthermore, aqueous solutions of the alkalis described above can be used by adding an appropriate amount of alcohols (e.g., isopropyl alcohol) or a nonionic surfactant. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.

[0082] In the present invention, an organic solvent can be used as a developer. After exposure, development is carried out with the developer (solvent). As a result, when a positive photoresist is used, for example, the photoresist in the unexposed areas is removed, and a photoresist pattern is formed.

[0083] Examples of the developer include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ... Propyl 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 Examples of the alkyl esters include methyl esters, propyl lactate, ethyl carbonate, 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, and propyl-3-methoxypropionate.Furthermore, a surfactant may be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

[0084] The crosslinking catalyst used in the resist underlayer film-forming composition of the present invention, which contains a crosslinkable resin and an aminoplast crosslinking agent or a phenoplast crosslinking agent, is characterized by the fact that a compound having a moderate pKa is selected as the base paired with the sulfonic acid. This crosslinking catalyst has high storage stability because it prevents side reactions of the aminoplast crosslinking agent (e.g., reaction with the solvent), and can suppress the amount of sublimate generated because the curing initiation temperature of the resist underlayer film can be relatively low, allowing for the formation of a film from the crosslinkable resin that does not dissolve in the photoresist solvent with high productivity. [Example]

[0085] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0086] <Synthesis Example 1> 81.69 g of propylene glycol monomethyl ether was added to 0.20 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and then 0.21 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and stirred for 12 hours to obtain a crosslinking catalyst propylene glycol monomethyl ether solution represented by formula (1-1).

[0087] [ka]

[0088] <Synthesis Example 2> 62.94 g of propylene glycol monomethyl ether was added to 0.20 g of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and then 0.12 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and stirred for 12 hours to obtain a crosslinking catalyst propylene glycol monomethyl ether solution represented by formula (1-2).

[0089] [ka]

[0090] <Synthesis Example 3> 73.94 g of propylene glycol monomethyl ether was added to 0.20 g of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and then 0.17 g of N,N-diethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and stirred for 12 hours to obtain a crosslinking catalyst propylene glycol monomethyl ether solution represented by formula (1-3).

[0091] [ka]

[0092] <Synthesis Example 4> 66.35 g of propylene glycol monomethyl ether was added to 0.20 g of trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and then 0.13 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and stirred for 12 hours to obtain a crosslinking catalyst propylene glycol monomethyl ether solution represented by formula (1-4).

[0093] [ka]

[0094] <Synthesis Example 5> 72.39 g of propylene glycol monomethyl ether was added to 0.20 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and then 0.16 g of pyridine (manufactured by Kanto Chemical Co., Ltd.) was added at room temperature and stirred for 12 hours to obtain a crosslinking catalyst propylene glycol monomethyl ether solution represented by formula (1-5).

[0095] [ka]

[0096] <Synthesis Example 6> 63.19 g of propylene glycol monomethyl ether was added to 0.20 g of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and then 0.12 g of N,N-dimethylbutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added at room temperature and stirred for 12 hours to obtain a crosslinking catalyst propylene glycol monomethyl ether solution represented by formula (1-6).

[0097] [ka]

[0098] Example 1 A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of an acrylic resin of a resist underlayer film-forming composition represented by the following formula (2-1), 0.058 g of tetramethoxymethylglycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 1.32 g of the propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 1, and 0.0023 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 28.39 g of propylene glycol monomethyl ether.

[0099] [ka]

[0100] <Example 2> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of tetramethoxymethyl glycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 1.83 g of the propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 2, and 0.0023 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 27.88 g of propylene glycol monomethyl ether.

[0101] Example 3 A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of tetramethoxymethyl glycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 1.68 g of the propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 3, and 0.0023 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 28.30 g of propylene glycol monomethyl ether.

[0102] Example 4 A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of tetramethoxymethylglycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 2.16 g of the propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 4, and 0.0023 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 27.55 g of propylene glycol monomethyl ether.

[0103] <Example 5> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of hexamethoxymethylmelamine (trade name: MW-390 [registered trademark] Nikalac, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent, 1.83 g of the crosslinking catalyst propylene glycol monomethyl ether solution obtained in Synthesis Example 2, and 0.002 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 27.88 g of propylene glycol monomethyl ether.

[0104] Example 6 A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of hexamethoxymethylmelamine (trade name: MW-390 [registered trademark] Nikalac, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent, 1.68 g of the propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 4, and 0.0023 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 28.30 g of propylene glycol monomethyl ether.

[0105] Example 7 0.40 g of a novolak epoxy resin of a resist underlayer film-forming composition represented by the following formula (2-2) (trade name: EOCN-104S, manufactured by Nippon Kayaku Co., Ltd.) and 0.49 g of the crosslinking catalyst propylene glycol monomethyl ether solution obtained in Synthesis Example 4 were dissolved in 5.27 g of propylene glycol monomethyl ether and 3.84 g of propylene glycol monomethyl ether acetate to prepare a solution of a resist underlayer film-forming composition for lithography.

[0106] [ka]

[0107] <Comparative Example 1> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of tetramethoxymethylglycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 1.18 g of the propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 5, and 0.002 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 28.53 g of propylene glycol monomethyl ether.

[0108] <Comparative Example 2> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of tetramethoxymethylglycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 0.008 g of pyridinium-p-toluenesulfonate (manufactured by Midori Chemical Co., Ltd.) represented by the formula (1-7) as a crosslinking catalyst, and 0.002 g of Megafac R-40 (manufactured by DIC Corporation, trade name) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0109] [ka]

[0110] <Comparative Example 3> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of tetramethoxymethyl glycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 0.008 g of pyridinium trifluoromethanesulfonate (manufactured by ADEKA Corporation) represented by the formula (1-8) as a crosslinking catalyst, and 0.002 g of Megafac R-40 (manufactured by DIC Corporation, trade name) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0111] [ka]

[0112] <Comparative Example 4> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of hexamethoxymethylmelamine (trade name: MW-390 [registered trademark] Nikalac, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent, 0.008 g of pyridinium-p-toluenesulfonate (manufactured by Midori Chemical Co., Ltd.) represented by the formula (1-7) as a crosslinking catalyst, and 0.002 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0113] <Comparative Example 5> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of hexamethoxymethylmelamine (trade name: MW-390 [registered trademark] Nikalac, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent, 0.008 g of pyridinium trifluoromethanesulfonate (manufactured by ADEKA Corporation) represented by the formula (1-8) as a crosslinking catalyst, and 0.002 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0114] <Comparative Example 6> A solution of a resist underlayer film-forming composition for lithography was prepared by dissolving 0.23 g of the acrylic resin of the resist underlayer film-forming composition represented by the above formula (2-1), 0.058 g of tetramethoxymethylglycoluril (trade name: POWDER LINK [registered trademark] 1174, manufactured by Japan Scientific Industries Co., Ltd.) as a crosslinking agent, 1.83 g of the propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 6, and 0.002 g of Megafac R-40 (trade name, manufactured by DIC Corporation) as a surfactant in 27.88 g of propylene glycol monomethyl ether.

[0115] <Comparative Example 7> 0.40 g of the novolac epoxy resin of the resist underlayer film-forming composition represented by the above formula (2-2) and 0.002 g of pyridinium trifluoromethanesulfonate (manufactured by ADEKA CORPORATION) represented by the formula (1-8) as a crosslinking catalyst were dissolved in 5.76 g of propylene glycol monomethyl ether and 3.84 g of propylene glycol monomethyl ether acetate to prepare a solution of a resist underlayer film-forming composition for lithography.

[0116] (Photoresist solvent elution test) The resist underlayer film-forming compositions for lithography prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were each applied to a silicon wafer, which is a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 230°C for 1 minute to form a resist underlayer film with a thickness of 20 to 30 nm. These resist underlayer films were then immersed for 1 minute in a solvent consisting of 70% by mass of propylene glycol monomethyl ether and 30% by mass of propylene glycol monomethyl ether acetate, and it was confirmed that the change in film thickness of the coating film before and after immersion was 5% or less. This result demonstrates that the coating films prepared using the resist underlayer film-forming compositions for lithography prepared in Examples 1 to 4 and Comparative Examples 1 to 3 can be overlaid with a resist or resist underlayer film.

[0117] (Storage Stability Test of Resist Underlayer Film-Forming Composition) Specifically, the storage stability test of the crosslinking agent was performed by the following method. The samples of Examples 1 to 6 and Comparative Examples 1 to 5 were stored at 35°C for 3 weeks, and the peak area % of the crosslinking agent (A / [A+B]×100) and the peak area % of the modified product (B / [A+B]×100) were calculated from the peak area (A) of the crosslinking agent in the resist underlayer film-forming composition and the peak area (B) of the modified product by gel permeation chromatography (GPC). That is, a higher modification rate indicates a faster modification rate of the crosslinking agent in the resist underlayer film-forming composition, and a lower modification rate is more desirable in the storage stability test. The peak area % of the crosslinking agent (A / [A+B]×100) and the peak area % of the modified product (B / [A+B]×100) are shown in Tables 1 and 2. Table 1 shows the results when tetramethoxymethylglycoluril was used as the crosslinking agent, and Table 2 shows the results when hexamethoxymethylmelamine was used as the crosslinking agent. The pKa values ​​of the bases in the crosslinking catalysts in Tables 1, 2, 3, and 4 were determined based on the following literature: Reference 1 J.Org.Chem.1960,25,2,290-290 Reference 2: Edited by Mujio Kodake: "Organic Chemistry Supplementary Volume 2, Handbook of Organic Chemistry Constants", p. 584 (1963), (Asakura Shoten) Reference 3 CAN.J.CHEM.VOL.1993,71 Reference 4 Tetrahedron Letters 2012,53,1830-1832

[0118] [Table 1]

[0119] [Table 2]

[0120] As can be seen from Table 1, the modification rate of the crosslinking agent in the resist underlayer film-forming composition of Example 1 is lower than that in the resist underlayer film-forming composition of Comparative Example 1. Furthermore, the modification rates of the crosslinking agent in the resist underlayer film-forming compositions of Examples 2 and 3 are lower than that in the resist underlayer film-forming composition of Comparative Example 2. Furthermore, the modification rate of the crosslinking agent in the resist underlayer film-forming composition of Example 4 is lower than that in the resist underlayer film-forming composition of Comparative Example 3. In other words, the crosslinking catalysts used in Examples 1 to 4 can effectively suppress the modification of the crosslinking agent. Furthermore, as can be seen from Table 2, the modification rate of the crosslinking agent in the resist underlayer film-forming composition of Example 5 is lower than that in the resist underlayer film-forming composition of Comparative Example 4. Furthermore, the modification rate of the crosslinking agent in the resist underlayer film-forming composition of Example 6 is lower than that in the resist underlayer film-forming composition of Comparative Example 5. That is, the crosslinking catalysts used in Examples 4 and 5 can effectively suppress the degeneration of the crosslinking agent in the resist underlayer film-forming composition, regardless of the type of crosslinking agent in the resist underlayer film-forming composition. Therefore, the sulfonate having a nitrogen-containing base showing a pKa of 6.5 to 9.5 according to the present invention can more effectively suppress the degeneration of the crosslinking agent in the resist underlayer film-forming composition than the sulfonate having a nitrogen-containing base showing a pKa of 6.5 or less.

[0121] (Storage Stability Test of Resist Underlayer Film-Forming Composition) Specifically, the storage stability test for the epoxy resin was performed by the following method. The samples of Example 7 and Comparative Example 7 were stored at 35°C for 3 weeks, and the change in weight-average molecular weight Mw of the resist underlayer film-forming composition before and after the storage stability test was measured by gel permeation chromatography (GPC). A change of 5% or less in weight-average molecular weight Mw was evaluated as "Good," 6 to 19% as "Average," and 20% or more as "Poor." The results are shown in Table 3 below. That is, the greater the change in weight-average molecular weight Mw, the faster the rate of modification of the epoxy groups in the resist underlayer film-forming composition. Therefore, in the storage stability test, a smaller change in weight-average molecular weight Mw is desirable.

[0122] [Table 3]

[0123] As can be seen from Table 3, the change in weight-average molecular weight before and after the storage stability test of the resist underlayer film-forming composition of Example 7 is lower than the change in weight-average molecular weight before and after the storage stability test of the resist underlayer film-forming composition of Comparative Example 7. That is, the crosslinking catalyst used in Example 7 can effectively suppress the modification of the epoxy resin. Therefore, the sulfonate having a nitrogen-containing base showing a pKa of 6.5 to 9.5 according to the present invention can more effectively suppress the modification of the epoxy resin in the resist underlayer film-forming composition than a sulfonate having a nitrogen-containing base showing a pKa of 6.5 or less.

[0124] (Comparison of the curing initiation temperature of resist underlayer films using each crosslinking catalyst) The resist underlayer film-forming compositions for lithography prepared in Example 2 and Comparative Example 6 were each applied to a silicon wafer, which is a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked for 1 minute at 80°C, 90°C, and 100°C, respectively, to form resist underlayer films with thicknesses of 25 to 35 nm. These resist underlayer films were immersed for 1 minute in a solvent consisting of 70% by mass of propylene glycol monomethyl ether and 30% by mass of propylene glycol monomethyl ether acetate. A change in the thickness of the coating film before and after immersion was evaluated as "Good" if it was 10% or less, "Average" if it was 11 to 89%, and "Poor" if it was 90% or more. The results are shown in Table 4 below.

[0125] [Table 4]

[0126] It was confirmed that the resist underlayer film formed using the resist underlayer film-forming composition prepared in Example 2 began to cure at a lower temperature than the resist underlayer film formed using the resist underlayer film-forming composition prepared in Comparative Example 6.

[0127] (Measurement of the amount of sublimation) The amount of sublimated material was measured using the sublimation amount measurement device described in International Publication No. 2007 / 111147. First, the resist underlayer film-forming compositions prepared in Example 2 and Comparative Example 6 were applied to a 4-inch diameter silicon wafer substrate using a spin coater to a film thickness of 30 nm. The wafer coated with the resist underlayer film was placed in the sublimation amount measurement device with an integrated hot plate and baked for 120 seconds, and the sublimated material was collected in a QCM (Quartz Crystal Microbalance) sensor, i.e., a quartz crystal oscillator with electrodes. The QCM sensor can measure minute changes in mass by utilizing the property that when sublimated material adheres to the surface (electrode) of the quartz crystal oscillator, the frequency of the quartz crystal oscillator changes (decreases) depending on the mass of the sublimated material.

[0128] The detailed measurement procedure is as follows: The hot plate of the sublimation amount measurement device was heated to the baking temperature shown in Table 5, and the pump flow rate was set to 1 m 3 The flow rate was set to / s and the device was left to stabilize for the first 60 seconds. Immediately afterwards, the wafer coated with the resist underlayer film was quickly placed on the hot plate through the slide port, and sublimate collection was performed from 60 seconds to 180 seconds (120 seconds). The flow attachment (detection part) connecting the QCM sensor and collection funnel of the sublimate amount measurement device was used without a nozzle. Therefore, the airflow was unrestricted from the flow path (diameter: 32 mm) of the chamber unit, which was 30 mm away from the sensor (quartz crystal oscillator). The QCM sensor used electrodes made of a material primarily composed of silicon and aluminum (AlSi), with a quartz crystal oscillator diameter (sensor diameter) of 14 mm, an electrode diameter on the quartz crystal oscillator surface of 5 mm, and a resonant frequency of 9 MHz.

[0129] The obtained frequency change was converted into grams from the characteristic value of the quartz crystal oscillator used in the measurement, and the relationship between the amount of sublimation per wafer coated with the resist underlayer film and the passage of time was clarified. Note that the first 60 seconds was a time period during which the device was left to stabilize (no wafer was set), and the measurements taken from 60 seconds after the wafer was placed on the hot plate to 180 seconds were the measurements of the amount of sublimation per wafer. The amount of sublimation per resist underlayer film quantified by the device is shown in Table 5 as a sublimation amount ratio. Note that the sublimation amount ratio is expressed as a value normalized by setting the amount of sublimation generated from the resist underlayer film in Comparative Example 1 as 1.

[0130] [Table 5]

[0131] As can be seen from Table 5, the ratio of the amount of sublimate generated from the resist underlayer film-forming composition of Example 2 is smaller than the ratio of the amount of sublimate generated from the resist underlayer film-forming composition of Comparative Example 6. That is, the crosslinking catalyst used in Example 2 can effectively suppress the amount of sublimate generated. Therefore, the sulfonate having a nitrogen-containing base showing a pKa between 6.5 and 9.5 according to the present invention can form a resist underlayer film more quickly than the sulfonate having a nitrogen-containing base showing a pKa of 9.5 or more, and therefore can suppress the generation of sublimate, etc. [Industrial Applicability]

[0132] As a result, the resist underlayer film-forming composition of the present invention can suppress denaturation of the crosslinking agent in the resist underlayer film-forming composition, and therefore a high-quality resist underlayer film-forming composition with high storage stability can be provided.

Claims

1. A resist underlayer film-forming composition comprising a crosslinkable resin, a crosslinking agent, a crosslinking catalyst represented by the following formula (I), and a solvent: 【Chemistry 1】 [In formula (I), A is an unsubstituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group which may be substituted by a group other than a hydroxy group, or an optionally substituted heteroaryl group; or (A-SO ３ ) － but, 【Chemistry 2】 and B is a base having a pKa of 6.5 to 9.5 and R １ R ２ R ３ N, R １ , and R ２ each independently represents an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon group, R １ and R ２ may form a ring with or without a heteroatom, R ３ represents an optionally substituted aromatic group, or an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R １ and R ２ does not form a ring, R ３ is an aromatic group which may be substituted.

2. A resist underlayer film-forming composition comprising a compound having an epoxy group and / or a resin having an epoxy group, a crosslinking catalyst represented by the following formula (I), and a solvent: 【Transformation 3】 [In formula (I), A is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted aryl group with a group other than a hydroxy group, or an optionally substituted heteroaryl group, B is a base having a pKa of 6.5 to 9.5 and R １ R ２ R ３ N, R １ , and R ２ each independently represents an optionally substituted linear or branched, saturated or unsaturated aliphatic hydrocarbon group, R １ and R ２ may form a ring with or without a heteroatom, R ３ represents an optionally substituted aromatic group, or an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R １ and R ２ does not form a ring, R ３ is an aromatic group which may be substituted.

3. 2. The resist underlayer film forming composition according to claim 1, wherein the crosslinking agent is an aminoplast crosslinking agent or a phenoplast crosslinking agent.

4. A resist underlayer film-forming composition comprising a crosslinkable resin, a crosslinking agent, a crosslinking catalyst represented by the following formula (I), and a solvent: 【Chemistry 4】 [In formula (I), A is an unsubstituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group which may be substituted by a group other than a hydroxy group, or an optionally substituted heteroaryl group; or (A-SO ３ ) － but, 【Transformation 5】 and B is a base having a pKa of 6.5 to 9.5; The following formula (II) 【Transformation 6】 [In formula (II), R is a hydrogen atom, a methyl group, an ethyl group, an allyl group, or a cyanomethyl group; R' is 【Transformation 7】 and n and m are each independently 2, 3, 4, 5, or 6. The resist underlayer film-forming composition, wherein the base is represented by the formula:

5. A resist underlayer film-forming composition comprising a compound having an epoxy group and / or a resin having an epoxy group, a crosslinking catalyst represented by the following formula (I), and a solvent: 【Transformation 8】 [In formula (I), A is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted aryl group with a group other than a hydroxy group, or an optionally substituted heteroaryl group, B is a base having a pKa of 6.5 to 9.5; The following formula (II) 【Chemistry 9】 [In formula (II), R is a hydrogen atom, a methyl group, an ethyl group, an allyl group, or a cyanomethyl group; R' is 【Chemistry 10】 and n and m are each independently 2, 3, 4, 5, or 6. The resist underlayer film-forming composition, wherein the base is represented by the formula:

6. R ３ The resist underlayer film forming composition according to claim 1 or 3, wherein is a base represented by an optionally substituted phenyl, naphthyl, anthracenyl, or phenanthrenyl group.

7. The resist underlayer film forming composition according to claim 2, wherein R 3 is a base represented by an optionally substituted phenyl, naphthyl, anthracenyl, or phenanthrenyl group.

8. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, cyclopentanone, cyclohexanone, 2-hydroxypropyl 7. The resist underlayer film forming composition according to claim 1, further comprising a compound selected from the group consisting of ethyl pionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, and butyl lactate.

9. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, cyclopentanone, cyclohexanone, 2-hydroxybenzoates 6. The resist underlayer film forming composition according to claim 2, further comprising a compound selected from the group consisting of ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, and butyl lactate.

10. The resist underlayer film forming composition according to claim 1, wherein A in the formula (I) is a methyl group, a fluoromethyl group, or a tolyl group.

11. The resist underlayer film forming composition according to claim 2, wherein A in the formula (I) is a methyl group, a fluoromethyl group, or a tolyl group.

12. The resist underlayer film forming composition according to claim 1, wherein B in formula (I) is N-methylmorpholine or N,N-diethylaniline.

13. The resist underlayer film forming composition according to any one of claims 2, 5, 7, 9, and 11, wherein B in formula (I) is N-methylmorpholine or N,N-diethylaniline.

14. The resist underlayer film forming composition according to claim 3, wherein the aminoplast crosslinking agent is methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea, or a condensate thereof.

15. The resist underlayer film forming composition according to claim 3, wherein the phenoplast crosslinker is methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea, or a condensate thereof.

16. A resist underlayer film forming composition described in any one of claims 1, 3, 4, 6, 8, 10, 12, 14, and 15, wherein the crosslinkable resin is at least one selected from the group consisting of novolac resin, polyester resin, polyimide resin, and acrylic resin.

17. A resist underlayer film forming composition according to any one of claims 1 to 16, further comprising a surfactant.

18. A resist underlayer film obtained by applying the resist underlayer film-forming composition according to any one of claims 1 to 17 onto a semiconductor substrate and baking the composition.

19. A method for forming a resist pattern used in semiconductor manufacturing, comprising the step of applying a resist underlayer film forming composition described in any one of claims 1 to 17 onto a semiconductor substrate and baking it to form a resist underlayer film.

20. A method for manufacturing a semiconductor device, comprising the steps of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition described in any one of claims 1 to 17, forming a resist film thereon, forming a resist pattern by irradiating with light or an electron beam and developing, etching the resist underlayer film using the formed resist pattern, and processing a semiconductor substrate using the patterned resist underlayer film.

21. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of claims 1 to 17; forming a hard mask thereon; further forming a resist film thereon; forming a resist pattern by irradiating with light or an electron beam and developing; etching the hard mask using the formed resist pattern; etching the resist underlayer film using the patterned hard mask; and processing a semiconductor substrate using the patterned resist underlayer film.

22. A manufacturing method described in claim 21, wherein the hard mask is formed by applying an inorganic material or by vapor deposition of an inorganic material.

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