Resist underlayer film-forming composition in which modification of crosslinking agent is inhibited

Abstract

Provided are a resist underlayer film-forming composition which has high storage stability, a low film solidification start temperature, a small amount of sublimates, and can form a film which does not dissolve in a photoresist solvent, a resist pattern-forming method using the resist underlayer film-forming composition, and a method for manufacturing a semiconductor device. The resist underlayer film-forming composition contains a cross-linkable resin, a cross-linking agent, a cross-linking catalyst represented by the following formula (I), and a solvent. ‑ (BH) + [In the formula, A is a linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group which can be substituted, an aryl group which can be substituted except for a hydroxyl group, or a heteroaryl group which can be substituted, and B is a base having a pKa of 6.5 to 9.5.](A‑SO3)‑(BH) + (I).

Description

Technical Field

[0001] The present invention relates to a composition for forming a resist underlayer film by inhibiting the modification of the crosslinking agent, a resist patterning method using the composition for forming a resist underlayer film, and a method for manufacturing a semiconductor device. Background Technology

[0002] In recent years, the photolithography process in semiconductor device manufacturing has increasingly demanded higher quality semiconductor process materials, including the under-resist film (BARC). Recently, the modification of crosslinking catalysts used in the composition for forming the under-resist film, crosslinking agents using solvents, and polymer resins that are the main components of the under-resist film has become a new problem, requiring new crosslinking catalysts to suppress such modifications.

[0003] Patent document 1 discloses in formula (A) - (BH) + China A - (BH) is the anion of organic or inorganic acids with a pKa of 3 or less. + It is an ionic, thermally producing acid agent in the unprotonated form of a nitrogen-containing base B, having a pKa between 0 and 5.0 and a boiling point less than 170 °C. Specifically, perfluorobutane sulfonate with ammonium and pyridine is described. 3-Fluoropyridine or pyridazine The combination of .

[0004] Patent document 2 discloses that in formula X - YH + In this context, X represents the anionic component, and Y is a thermally generated acid-producing agent of substituted pyridine. Specifically, it describes the use of methylbenzenesulfonate and fluoropyridine. or trifluoromethylpyridine The combination of .

[0005] Patent document 3 discloses a sulfonic acid component without hydroxyl groups and a pyridine component with cyclic substituents. The ingredients are heat-generating acid-producing agents. Specifically, methylbenzenesulfonate and methylpyridine are described. methoxypyridine or trimethylpyridine The combination of .

[0006] Patent document 4 discloses a thermal acid-generating agent comprising triethylamine salt of p-toluenesulfonate, ammonium salt of p-toluenesulfonate, ammonium salt of mesitylenesulfonate, ammonium salt of dodecylbenzenesulfonate, or dimethylamine salt of p-toluenesulfonate.

[0007] Patent document 5 discloses a mixture containing various sulfonic acids and NH4. + Thermal acid-producing agents containing primary, secondary, tertiary, or quaternary ammonium ions.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent No. 6334900

[0011] Patent Document 2: Japanese Patent Application Publication No. 2019-56903

[0012] Patent Document 3: Japanese Patent No. 6453378

[0013] Patent Document 4: Japanese Patent No. 4945091

[0014] Patent Document 5: Japanese Patent No. 6256719 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] However, it was discovered that the thermally generated acid agents disclosed in the prior art promote the reaction of compounds with alcoholic hydroxyl groups, such as propylene glycol monomethyl ether and methyl 2-hydroxy-2-methylpropionate, which are frequently used as solvents in compositions for forming the lower layer of resist films, with amino plastic crosslinking agents, making them easier to modify. Furthermore, if high-boiling-point alkalis or strong alkalis are used as the thermally generated acid agents, the curability of the lower layer film decreases, thus increasing the amount of sublimation.

[0017] Therefore, the problem to be solved by the present invention is to provide a resist underlayer film forming composition with high storage stability, low curing start temperature of the film, low amount of sublimation, and the ability to form a film that is insoluble in photoresist solvent, a resist pattern forming method using the resist underlayer film forming composition, and a method for manufacturing a semiconductor device.

[0018] Methods for solving problems

[0019] The present invention includes the following solutions.

[0020] [1] A composition for forming a resist underlayer film, comprising a crosslinkable resin, a crosslinking agent, a crosslinking catalyst as shown in formula (I), and a solvent.

[0021] (A-SO3) - (BH) + (I)

[0022] In equation (I),

[0023] A can be a substituted straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group that can be substituted by a group other than a hydroxyl group, or a substituted heteroaryl group.

[0024] B is a base with a pKa of 6.5–9.5.

[0025] [2] A composition for forming a resist underlayer film comprising an epoxy compound and / or an epoxy resin, a crosslinking catalyst as shown in formula (I) below, and a solvent.

[0026] (A-SO3) - (BH) + (I)

[0027] In equation (I),

[0028] A can be a substituted straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group that can be substituted by a group other than a hydroxyl group, or a substituted heteroaryl group.

[0029] B is a base with a pKa of 6.5–9.5.

[0030] [3] In the composition for forming a resist underlayer film according to [1], the crosslinking agent is an amino plastic crosslinking agent or a phenolic plastic crosslinking agent.

[0031] [4] The composition for forming a resist underlayer film according to any one of [1] to [3], wherein B in the above formula (I) is R 1 R 2 R 3 N,

[0032] R 1 and R 2 Each can independently represent a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group.

[0033] R 1 With R 2 Rings can be formed with or without heteroatoms.

[0034] R 3 This indicates a replaceable aromatic group, or a replaceable straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group.

[0035] In R 1 With R 2 When no loop is formed, R 3 It is an aromatic group that can be replaced.

[0036] [5] The composition for forming a resist underlayer film according to any one of [1] to [4], wherein B in the above formula (I) is R of the following formula. 1 R 2 R 3 N or the base represented by formula (II) below.

[0037] R 1 R 2 R 3 N

[0038] [In the formula,

[0039] R 1 and R 2 Each can independently represent a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group.

[0040] R 3 This indicates an aromatic group that can be substituted.

[0041]

[0042] In equation (II),

[0043] R is a hydrogen atom, nitro group, cyano group, amino group, carboxyl group, halogen atom, alkoxy group with 1 to 10 carbon atoms, alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 40 carbon atoms, an organogroup containing an ether bond, an organogroup containing a ketone bond, an organogroup containing an ester bond, or a group obtained by combining them.

[0044] R' is:

[0045] -(R a ) n -X-(R b ) m -,

[0046] R a and R b Each can independently represent any substituted alkyl group.

[0047] X is O, S, or SO2.

[0048] n and m are each independently 2, 3, 4, 5, or 6.

[0049] [6] According to the composition for forming a resist underlayer film as described in [5], R in the above formula 3 This indicates that the phenyl, naphthyl, anthraceneyl, or phenanthrene groups can be substituted.

[0050] In formula (II) above, R is a hydrogen atom, methyl, ethyl, allyl, or cyanomethyl.

[0051] In the above formula (II), R' is the base shown in the following formula.

[0052] -(CH2) n -O-(CH2) m -

[0053] [7] The composition for forming a resist underlayer film according to any one of [1] to [6] further comprises a compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group.

[0054] [8] In the composition for forming the lower layer of the resist according to [7], the compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group is a propylene glycol solvent, an oxyisobutyrate solvent, or a butanediol solvent.

[0055] [9] The composition for forming a lower layer of resist according to [7] or [8] is a compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group, which is propylene glycol monomethyl ether or methyl 2-hydroxy-2-methylpropionate.

[0056]

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

[0057]

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

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

[0058]

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

[11] , wherein the amino plastic crosslinking agent is melamine, guanidine, glycourea, urea, or polymers thereof that are highly alkylated, alkoxylated, or alkoxyalkylated.

[0059]

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

[11] , wherein the phenolic plastic crosslinking agent is an aromatic or polymer thereof that has been highly alkylated, alkoxylated, or alkoxyalkylated.

[0060]

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

[13] , wherein the crosslinkable resin is at least one selected from phenolic varnish resin, polyester resin, polyimide resin and acrylic resin.

[0061]

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

[14] further comprises a surfactant.

[0062]

[16] A photoresist underlayer film, which is obtained by coating a photoresist underlayer film forming composition as described in any one of [1] to

[15] onto a semiconductor substrate and then firing it.

[0063]

[17] A method for forming a resist pattern for manufacturing a semiconductor includes the following steps: applying a resist underlayer film forming composition as described in any one of [1] to

[15] onto a semiconductor substrate and firing it to form a resist underlayer film.

[0064]

[18] A method for manufacturing a semiconductor device includes the following steps: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition as described in any one of [1] to

[15] ; forming a photoresist film on the photoresist underlayer film; forming a photoresist pattern by irradiation and development with light or electron beams; etching the photoresist underlayer film using the formed photoresist pattern; and processing the semiconductor substrate using the patterned photoresist underlayer film.

[0065]

[19] A method for manufacturing a semiconductor device includes the following steps: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition as described in any one of [1] to

[15] ; forming a hard mask on the photoresist underlayer film; further forming a photoresist film on the hard mask; forming a photoresist pattern by irradiation and development with light or electron beams; etching the hard mask using the formed photoresist pattern; etching the photoresist underlayer film using the patterned hard mask; and processing the semiconductor substrate using the patterned photoresist underlayer film.

[0066]

[20] According to the manufacturing method described in

[19] , the hard mask is formed by coating or vapor deposition of inorganic materials.

[0067] The effects of the invention

[0068] According to the present invention, a composition for forming a photoresist underlayer film is provided, which provides a photoresist underlayer film forming method, and a method for manufacturing a semiconductor device, wherein the crosslinking catalyst inhibits the side reactions (e.g., reactions with solvents) of amino plastic crosslinking agents or phenolic plastic crosslinking agents, thus resulting in high storage stability and allowing for a low curing start temperature of the photoresist underlayer film, thereby suppressing the amount of sublimation generated. Detailed Implementation

[0069] The composition for forming a resist underlayer film according to the present invention comprises a crosslinkable resin, a crosslinking agent, and a crosslinking catalyst as shown in formula (I).

[0070] (A-SO3) - (BH) + (I)

[0071] In equation (I),

[0072] A can be a substituted straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group that can be substituted by a group other than a hydroxyl group, or a substituted heteroaryl group.

[0073] B is a base with a pKa of 6.5–9.5.

[0074] [Resins capable of cross-linking]

[0075] In this invention, a crosslinkable resin refers to a resin that is not crosslinked or partially crosslinked, and that crosslinking occurs through the action of a crosslinking catalyst, enabling the formation of a film insoluble in photoresist solvents. Preferably, the crosslinkable resin is at least one selected from phenolic varnish resins, polyester resins, polyimide resins, and acrylic resins. Several specific examples (repeating unit structures) are given below.

[0076]

[0077]

[0078]

[0079]

[0080] (In the formula, m, n, l and the numbers represent the molar ratio or the number of repeating units (any number)).

[0081] [Compounds with epoxy groups and / or resins with epoxy groups]

[0082] In this invention, the term "epoxy-based compound" and "epoxy-based resin" refers to a compound and resin having one or more epoxy groups per molecule, meaning a compound and resin that can be cross-linked or polymerized by a cross-linking catalyst to form a film insoluble in photoresist solvents. Preferably, the epoxy-based compound and epoxy-based resin are at least one selected from glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine type epoxy resin. Several specific examples are given below.

[0083]

[0084] They preferably have a weight-average molecular weight of 600–1,000,000 or 600–200,000.

[0085] [Amino plastic crosslinking agent]

[0086] Examples of crosslinking agents for amino plastics include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanidine, glycourea, urea, and their polymers. Preferably, crosslinking agents having at least two crosslinking-forming substituents are compounds such as methoxymethylated glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanidine, butoxymethylated benzoguanidine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds may also be used.

[0087] Furthermore, as the aforementioned crosslinking agent, a crosslinking agent with high heat resistance can be used. Preferably, a compound containing a crosslinking-forming substituent with an aromatic ring (e.g., a benzene ring, naphthalene ring) is used as the crosslinking agent.

[0088] Preferably, it is selected from at least one of tetramethoxymethyl glycourea and hexamethoxymethyl melamine.

[0089] Amino plastic crosslinking agents can be used alone or in combination of two or more. Amino plastic crosslinking agents can be manufactured by methods known to them or in accordance with those methods; in addition, commercially available products can be used.

[0090] The amount of amino plastic crosslinking agent used varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but relative to the total solid content of the composition for forming the resist underlayer film involved in this invention, it is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, and is 80% by mass or less, 50% by mass or less, 40% by mass or less, 20% by mass or less, or 10% by mass or less.

[0091] If we give some specific examples, it would be as follows.

[0092]

[0093]

[0094] [Phenolic Plastic Crosslinking Agent]

[0095] Examples of crosslinking agents for phenolic plastics include highly alkylated, alkoxylated, or alkoxyalkylated aromatic compounds and their polymers. Preferably, crosslinking agents having at least two crosslinking-forming substituents per molecule are compounds 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.

[0096] Furthermore, as the aforementioned crosslinking agent, a crosslinking agent with high heat resistance can be used. Preferably, a compound containing a crosslinking-forming substituent with an aromatic ring (e.g., a benzene ring, naphthalene ring) is used as the crosslinking agent.

[0097] Preferably, it is selected from at least one of 3,3',5,5'-tetramethoxymethyl-4,4'-bisphenol and 4-(1,1-dimethylethyl)-2,6-bis(methoxymethyl)phenol.

[0098] Phenolic plastic crosslinking agents can be used alone or in combination of two or more. Phenolic plastic crosslinking agents can be manufactured by methods known to them or according to those methods; alternatively, commercially available products can be used.

[0099] The amount of phenolic plastic crosslinking agent used varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but relative to the total solid content of the composition for forming the resist underlayer film involved in this invention, it is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, and is 80% by mass or less, 50% by mass or less, 40% by mass or less, 20% by mass or less, or 10% by mass or less.

[0100] If we give some specific examples, it would be as follows.

[0101]

[0102] [Cross-linking catalyst]

[0103] The crosslinking catalyst in this invention is represented by the following formula (I).

[0104] (A-SO3) - (BH) + (I)

[0105] In formula (I),

[0106] A can be a substituted straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group that can be substituted by a group other than a hydroxyl group, or a substituted heteroaryl group.

[0107] B is a base with a pKa of 6.5–9.5.

[0108] B is preferred as R 1 R 2 R 3 N,

[0109] R 1 and R 2 Each can independently represent a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group.

[0110] R 1 With R 2 Rings can be formed with or without heteroatoms.

[0111] R 3 This indicates a replaceable aromatic group, or a replaceable straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group.

[0112] In R 1 With R 2 When no loop is formed, R 3 It is an aromatic group that can be replaced.

[0113] Preferred R 1 and R 2 Each independently represents a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group, R. 3 This indicates an aromatic group that can be replaced.

[0114] Preferred R 1 and R 2 Each independently represents a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group, R. 3 This indicates that the phenyl, naphthyl, anthracene, or phenanthrene groups can be substituted.

[0115] Preferred option B is represented by the following formula (II).

[0116]

[0117] In equation (II),

[0118] R is a hydrogen atom, nitro group, cyano group, amino group, carboxyl group, halogen atom, alkoxy group with 1 to 10 carbon atoms, alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 40 carbon atoms, an organogroup containing an ether bond, an organogroup containing a ketone bond, an organogroup containing an ester bond, or a group obtained by combining them.

[0119] R' is:

[0120] -(R a ) n -X-(R b ) m -,

[0121] R a and R b Each can independently represent any substituted alkyl group.

[0122] X is O, S, or SO2.

[0123] n and m are each independently 2, 3, 4, 5, or 6.

[0124] Preferably, R is a hydrogen atom, methyl, ethyl, allyl, or cyanomethyl.

[0125] R' is:

[0126] -(CH2) n -O-(CH2) m -,

[0127] n and m are each independently 2, 3, 4, 5, or 6.

[0128] Examples of saturated aliphatic hydrocarbon groups that are straight-chain, branched, or cyclic include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, etc. 2-Methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl 1-Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-Trimethyl-n-propyl, 1,2,2-Trimethyl-n-propyl, 1-Ethyl-1-methyl-n-propyl, 1-Ethyl-2-methyl-n-propyl, Cyclohexyl, 1-Methyl-cyclopentyl, 2-Methyl-cyclopentyl, 3-Methyl-cyclopentyl, 1-Ethyl-cyclobutyl, 2-Ethyl-cyclobutyl, 3-Ethyl-cyclobutyl, 1,2-Dimethyl-cyclobutyl, 1,3-Dimethyl-cyclobutyl, 2,2-Dimethyl-cyclobutyl, 2,3 -Dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0129] Examples of unsaturated aliphatic hydrocarbon groups that are straight-chain, branched, or cyclic include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2 -Methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl- 3-Pentenyl, 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-Methyl-1-pentenyl, 3-Methyl-2-pentenyl, 3-Methyl-3-pentenyl, 3-Methyl-4-pentenyl, 3-Ethyl-3-butenyl, 4-Methyl-1-pentenyl, 4-Methyl-2-pentenyl, 4-Methyl-3-pentenyl, 4-Methyl-4-pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-1-butenyl, 1,2-Dimethyl-2-butenyl, 1,2-Dimethyl-3-butenyl, 1-Methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1, 3-Dimethyl-1-butenyl, 1,3-Dimethyl-2-butenyl, 1,3-Dimethyl-3-butenyl, 1-Isobutylvinyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 2-Isopropyl-2-propenyl, 3,3-Dimethyl-1-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 1-n-Propyl-1-propenyl, 1-n-Propyl-2-propenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentene The list includes 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, among others.

[0130] Examples of aryl groups include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, and 9-phenanthyl.

[0131] Examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, imidazolyl, pyranyl, pyridyl, pyrimidinyl, pyrazinyl, pyrrolylalkyl, piperidinyl, piperazinyl, morpholinyl, quininecycloyl, indoleyl, purinyl, quinolinyl, isoquinolinyl, chromenyl, thiaanthryl, phenothiazinyl, and phenanthryl. azino, Tonyl, acridine, phenazinyl, carbazole, etc.

[0132] Aryl and heteroaryl groups are included in aromatic groups.

[0133] Examples of substituents include nitro, amino, cyano, sulfonyl, hydroxyl, carboxyl, halogen, alkoxy with 1 to 10 carbon atoms, alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, aryl with 6 to 40 carbon atoms, organogroups containing ether bonds, organogroups containing ketone bonds, organogroups containing ester bonds, or combinations thereof.

[0134] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0135] Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, and 3-methyl-n-pentyloxy. 4-Methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc.

[0136] Regarding alkyl, alkenyl, and aryl groups, as illustrated above.

[0137] Organic groups containing ether bonds can be derived from R 11 -OR 11 (R 11 Each can be independently represented as an alkyl, alkylene, phenyl, or phenylene group having 1 to 6 carbon atoms, such as methyl or ethyl. Examples of such groups include, for instance, organic groups containing ether bonds, such as methoxy, ethoxy, or phenoxy.

[0138] Organic groups containing ketone bonds can be derived from R 21 -C(=O)-R 21 (R 21 Each can be independently represented as an alkyl, alkylene, phenyl, or phenylene group having 1 to 6 carbon atoms, such as methyl or ethyl. Examples of such groups include organic groups containing ketone bonds, such as acetoxy or benzoyl groups.

[0139] Organic groups containing ester bonds can be derived from R 31 -C(=O)OR 31 (R 31 Each can be independently represented by an alkyl group, alkylene group, phenyl group, or phenylene group having 1 to 6 carbon atoms, such as methyl or ethyl. Examples of such organic groups containing ester bonds include methyl esters, ethyl esters, and phenyl esters.

[0140] Furthermore, A does not contain aryl groups substituted with hydroxyl groups. Therefore, anions derived from p-phenolsulfonic acid, o-cresol-4-sulfonic acid, p-cresol-2-sulfonic acid, etc., are not included in (A-SO3) of this invention. -Furthermore, it is preferable that A does not contain aryl groups substituted with carboxyl groups. Therefore, anions derived from 5-sulfosalicylic acid, etc., are not included in (A-SO3) of this invention. - .

[0141] Preferably, A is methyl, fluoromethyl, or tolyl.

[0142] In this invention, B is a base having a pKa of 6.5 to 9.5. Specific examples include N-methylmorpholine and N,N-diethylaniline.

[0143] As a crosslinking catalyst as shown in formula (I), several specific examples are given below.

[0144]

[0145]

[0146]

[0147] The amount of crosslinking catalyst is 0.0001 to 20% by mass relative to the total solid content in the composition for forming the lower layer of the resist film, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass.

[0148] In addition to the above, the composition for forming a resist underlayer film according to the present invention may also include solvents, surfactants, light absorbers, rheology modifiers, adhesives, etc. as needed.

[0149] [solvent]

[0150] The resist underlayer film forming compositions of the present invention may further comprise compounds having alcoholic hydroxyl groups, or compounds having groups capable of forming alcoholic hydroxyl groups, as solvents. They are typically used in an amount that uniformly dissolves the aforementioned crosslinkable resin, amino plastic crosslinking agent, or phenolic plastic crosslinking agent, and the crosslinking catalyst shown in formula (I).

[0151] As compounds having an alcoholic hydroxyl group, or compounds having a group capable of forming an alcoholic hydroxyl group, 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 acetate, propylene glycol propyl ether acetate, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc.

[0152] Among them, propylene glycol-based solvents, oxyisobutyrate-based solvents, or butanediol-based solvents are preferred.

[0153] Compounds having an alcoholic hydroxyl group, or compounds having a group capable of forming an alcoholic hydroxyl group, may be used alone or in combination of two or more.

[0154] Furthermore, high-boiling-point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be used in combination.

[0155] Preferred ingredients include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being more preferred.

[0156] [surfactant]

[0157] In the resist underlayer film forming composition of the present invention, in order to avoid the generation of pinholes, streaks, etc., and to further improve the coating performance on uneven surfaces, a surfactant can be mixed in.

[0158] Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol trioleate. Non-ionic surfactants such as sugar alcohol tristearate, polyoxyethylene sorbitan fatty acid esters, etc., Etotron EF301, EF303, EF352 (Todo Co., Ltd. Made by プロダクツ, trade name), メガファック F171, F173, R-30, R-40 (made by Dainippon Co., Ltd., trade name), フロラード FC430, Fluoropolymer surfactants such as FC431 (manufactured by Sumitomo Silem Co., Ltd., trade name), Asahigard AG710, Servolon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) are used. The amount of these surfactants mixed in relation to the total solids content of the resist underlayer film forming composition involved in this invention is typically 2.0% by mass or less, preferably 1.0% by mass or less. These surfactants can be added individually or in combination of two or more.

[0159] [Other Additives]

[0160] In the resist underlayer film forming composition of the present invention, in addition to the crosslinking catalyst of formula (I), acidic compounds such as citric acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin toluene sulfonate, 2-nitrobenzyl toluene sulfonate, other thermally generated acid agents such as alkyl esters of organic sulfonates, and bis(4-tert-butylphenyl)iodide can also be mixed in as a catalyst to promote the crosslinking reaction. Trifluoromethane sulfonate, triphenylsulfonium trifluoromethane sulfonate, etc. Salt-based photoacid generators, halogen-containing compound photoacid generators such as phenyl-bis(trichloromethyl)triazine, sulfonic acid-based photoacid generators such as benzoin toluene sulfonate and N-hydroxysuccinimide trifluoromethane sulfonate, etc.

[0161] As light absorbers, commercially available light absorbers listed in publications such as "Technology and Market of Industrial Pigments" (CMC Publishing) and "Dye Handbook" (Organic Synthetic Chemistry Society) are suitable, including 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; and CI Disperse Orange 1, 5, and 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; CI Fluorescent Whitening Agent 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The above-mentioned light absorbers are generally blended in a ratio of 10% by mass or less, preferably 5% by mass or less, relative to the total solid components of the resist underlayer film forming composition involved in this invention.

[0162] Rheology modifiers are mainly added to improve the flowability of the composition for forming the lower resist film, especially during the baking process, to improve the uniformity of the film thickness of the lower resist film and to improve the filling ability of the composition for forming the lower resist film into the pores. 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 octyl decyl 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; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in proportions of less than 30% by mass relative to the total solid components of the resist underlayer film forming composition involved in this invention.

[0163] Adhesive aids are mainly used to improve the adhesion between the substrate or photoresist and the composition used to form the underlying film of the photoresist, especially during development, for the purpose of preventing the photoresist from peeling off. 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 trimethylsilylimidazolium; silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-epoxypropoxypropyltrimethoxysilane; and silanes such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[]. Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesive aids are typically blended in proportions of less than 5% by mass, preferably less than 2% by mass, relative to the total solids content of the resist underlayer film forming composition involved in this invention.

[0164] The solid content of the resist underlayer film forming composition of the present invention is 0.1 to 70% by mass, or 0.1 to 60% by mass. The solid content refers to the proportion of all components remaining after removing the solvent from the resist underlayer film forming composition. A crosslinkable resin may be contained in the solid content at proportions of 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, or 50 to 90% by mass.

[0165] In this invention, a semiconductor device can be manufactured through the following steps: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition; forming a photoresist film on the aforementioned photoresist underlayer film; forming a photoresist pattern by irradiation and development with light or electron beams; etching the photoresist underlayer film using the formed photoresist pattern; and processing the semiconductor substrate using the patterned photoresist underlayer film.

[0166] Furthermore, in this invention, a semiconductor device can be manufactured through the following steps: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition; forming a hard mask on the photoresist underlayer film; further forming a photoresist film on the hard mask; forming a photoresist pattern by irradiation and development with light or electron beams; etching the hard mask using the formed photoresist pattern; etching the photoresist underlayer film using the patterned hard mask; and processing the semiconductor substrate using the patterned photoresist underlayer film. Preferably, the hard mask is formed by coating or vapor deposition of an inorganic material.

[0167] A photoresist underlayer film is obtained by coating the photoresist underlayer film forming composition of the present invention onto a semiconductor substrate and then firing it. By forming such a photoresist underlayer film, a photoresist pattern used in semiconductor manufacturing can be formed. In describing this photoresist pattern forming method, the photoresist underlayer film forming composition is coated onto a substrate used in the manufacture of precision integrated circuit components (e.g., a transparent substrate such as a silicon / silicon dioxide coated substrate, a glass substrate, or an ITO substrate) using a suitable coating method such as a spin coater or a coating machine, and then baked to cure, thus producing a coated underlayer film (photoresist underlayer film). Here, the thickness of the photoresist underlayer film is preferably 0.01 to 3.0 μm. Furthermore, the baking conditions after coating are typically 80 to 350°C for 0.5 to 120 minutes.

[0168] Then, the resist is directly coated on the lower resist film, or, as needed, one to several layers of coating material are formed on the lower resist film and then the resist is coated to form a resist film. The resist film is then irradiated with light or electron beams through a specified mask, and then developed, rinsed, and dried to obtain a good resist pattern.

[0169] If necessary, post-exposure baking (PEB) can also be performed. Then, the resist film, which has been removed by development in the above process, can be removed by dry etching to form the desired pattern on the substrate.

[0170] A hard mask can also be formed on the underlying resist film, or it can be formed by coating or vapor deposition of inorganic materials. The hard mask can be etched using the formed resist pattern to create a patterned hard mask. The underlying resist film can be etched through this patterned hard mask, and the semiconductor substrate can be processed using the patterned underlying resist film.

[0171] The so-called resist used in this invention is a photoresist or an electron beam resist.

[0172] As the photoresist applied to the upper part of the photoresist lower layer film in this invention, both negative and positive types can be used. Examples include positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazonyl sulfonate; chemically amplified photoresists composed of a binder having groups that increase the alkali dissolution rate through acid decomposition and a photoacid generator; chemically amplified photoresists composed of an alkali-soluble binder, a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition and a photoacid generator; chemically amplified photoresists composed of a binder having groups that increase the alkali dissolution rate through acid decomposition and a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition and a photoacid generator; and photoresists with Si atoms in the backbone. For example, the product manufactured by Robend Hearts, trade name APEX-E.

[0173] Furthermore, examples of electron beam resists that can be used as the upper layer of the photoresist lower layer film coated in this invention include compositions consisting of a resin whose main chain contains Si-Si bonds and whose ends contain aromatic rings, and an acid-generating agent that generates acid upon electron beam irradiation; or compositions consisting of poly(p-hydroxystyrene) in which hydroxyl groups are replaced by organic groups containing N-carboxyamines, and an acid-generating agent that generates acid upon electron beam irradiation. In the latter electron beam resist composition, the acid generated from the acid-generating agent upon electron beam irradiation reacts with the N-carboxyamine groups of the polymer side chains, causing the polymer side chains to decompose into hydroxyl groups, thus exhibiting alkali solubility and dissolving in an alkaline developer to form a resist pattern. Examples of acid-producing agents that generate acid through electron beam irradiation 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, as well as triphenylsulfonium salts and diphenyliodine. Salt, etc. Sulfonates such as salts, nitrobenzyl toluenesulfonate, and dinitrobenzyl toluenesulfonate.

[0174] The exposure light for photoresist is near-ultraviolet, far-ultraviolet, or ultra-ultraviolet (e.g., EUV, wavelength 13.5 nm) chemical rays, using wavelengths such as 248 nm (KrF laser), 193 nm (ArF laser), and 157 nm (F2 laser). During light irradiation, any method that can generate acid from the photoacid-producing agent can be used without particular restrictions, employing exposure doses of 1–2000 mJ / cm². 2 or 10~1500mJ / cm 2 or 50~1000mJ / cm 2 .

[0175] Furthermore, electron beam irradiation of electron beam resists can be performed, for example, using an electron beam irradiation device.

[0176] As the developer for the resist having a resist underlayer film formed using the resist underlayer film forming composition of the present invention, aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alkanolamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of an alcohol such as isopropanol or a nonionic surfactant can be added to the above-mentioned aqueous solutions of bases. Quaternary ammonium salts are preferred among these, and tetramethylammonium hydroxide and choline are more preferred.

[0177] Furthermore, in this invention, an organic solvent can be used as the developer. Development is performed using the developer (solvent) after exposure. Thus, for example, when a positive photoresist is used, the photoresist in the unexposed areas is removed, forming a photoresist pattern.

[0178] Examples of developing solutions include, for instance, 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. Acetic acid esters, 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 include 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, surfactants may be added to these developers. The developing conditions are appropriately selected from a temperature of 5–50°C and a time of 10–600 seconds.

[0179] The crosslinking catalyst used in the resist underlayer film forming composition of the present invention, which contains a crosslinkable resin and an amino plastic crosslinking agent or a phenolic plastic crosslinking agent, is characterized by selecting a compound with a moderate pKa as a base paired with sulfonic acid. This crosslinking catalyst exhibits high storage stability because it inhibits side reactions of the amino plastic crosslinking agent (e.g., reaction with the solvent), and because the curing start temperature of the resist underlayer film is relatively low, the amount of sublimation can be suppressed, enabling the highly productive formation of a film insoluble in the photoresist solvent from the crosslinkable resin.

[0180] Example

[0181] The present invention will now be illustrated by examples, but the invention is not limited thereto.

[0182] <Synthesis example 1>

[0183] 81.69 g of propylene glycol monomethyl ether was added to 0.20 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) to dissolve it. 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 the crosslinking catalyst propylene glycol monomethyl ether solution shown in formula (1-1).

[0184] Equation (1-1)

[0185]

[0186] <Synthesis example 2>

[0187] 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.) to dissolve it. 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 the crosslinking catalyst propylene glycol monomethyl ether solution shown in formula (1-2).

[0188] Equation (1-2)

[0189]

[0190] <Synthesis Example 3>

[0191] 0.20 g of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved by adding 73.94 g of propylene glycol monomethyl ether. 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 the crosslinking catalyst propylene glycol monomethyl ether solution shown in formula (1-3).

[0192] Equation (1-3)

[0193]

[0194] <Synthesis example 4>

[0195] 66.35 g of propylene glycol monomethyl ether was added to 0.20 g of trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) to dissolve it. 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 the crosslinking catalyst propylene glycol monomethyl ether solution shown in formula (1-4).

[0196] Equation (1-4)

[0197]

[0198] <Synthesis example 5>

[0199] 72.39 g of propylene glycol monomethyl ether was added to 0.20 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) to dissolve it. Then, 0.16 g of pyridine (manufactured by Kanto Chemical Co., Ltd.) was added at room temperature and stirred for 12 hours to obtain the crosslinking catalyst propylene glycol monomethyl ether solution shown in formula (1-5).

[0200] Equation (1-5)

[0201]

[0202] <Synthesis Example 6>

[0203] To dissolve 0.20 g of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), 63.19 g of propylene glycol monomethyl ether was added. Then, at room temperature, 0.12 g of N,N-dimethylbutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred for 12 hours to obtain the crosslinking catalyst propylene glycol monomethyl ether solution shown in formula (1-6).

[0204] Equation (1-6)

[0205]

[0206] <Example 1>

[0207] An acrylic resin of the photoresist underlayer film forming composition shown in Formula (2-1) below, 0.23 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd. of Japan) as a crosslinking agent, 1.32 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 1, and 0.0023 g of megafaq R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant were dissolved in 28.39 g of propylene glycol monomethyl ether to prepare a solution of the photoresist underlayer film forming composition.

[0208] Equation (2-1)

[0209]

[0210] <Example 2>

[0211] A solution of a photoresist underlayer film forming composition for photolithography was prepared by dissolving 0.23 g of acrylic resin, 0.058 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd. of Japan) as a crosslinking agent, 1.83 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 2, and 0.0023 g of megafaq R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 27.88 g of propylene glycol monomethyl ether.

[0212] <Example 3>

[0213] A solution of a photoresist underlayer film forming composition for photolithography was prepared by dissolving 0.23 g of acrylic resin, 0.058 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd. of Japan) as a crosslinking agent, 1.68 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 3, and 0.0023 g of megafaq R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 28.30 g of propylene glycol monomethyl ether.

[0214] <Example 4>

[0215] A solution of a photoresist underlayer film forming composition for photolithography was prepared by dissolving 0.23 g of acrylic resin, 0.058 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd. of Japan) as a crosslinking agent, 2.16 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 4, and 0.0023 g of megafaq R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 27.55 g of propylene glycol monomethyl ether.

[0216] <Example 5>

[0217] A solution of a photoresist underlayer film forming composition for photolithography was prepared by dissolving 0.23 g of acrylic resin, 0.058 g of hexamethoxymethyl melamine (trade name: MW-390 [registered trademark] Nikkalac, manufactured by Sanwa Kemikal Co., Ltd.) as a crosslinking agent, 1.83 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 2, and 0.002 g of melamine R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 27.88 g of propylene glycol monomethyl ether.

[0218] <Example 6>

[0219] An acrylic resin of the photoresist underlayer film forming composition shown in Formula (2-1) above, 0.23 g of hexamethoxymethyl melamine (trade name: MW-390 [registered trademark] Nikkalac, manufactured by Sanwa Kemikal Co., Ltd.) as a crosslinking agent, 1.68 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 4, and 0.0023 g of melamine R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant were dissolved in 28.30 g of propylene glycol monomethyl ether to prepare a solution of the photoresist underlayer film forming composition.

[0220] <Example 7>

[0221] A solution of a photoresist underlayer film forming composition was prepared by dissolving 0.40 g of phenolic varnish epoxy resin (trade name: EOCN-104S, manufactured by Nippon Kayaku Co., Ltd.) of the photoresist underlayer film forming composition shown in Formula (2-2) below and 0.49 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 4 in 5.27 g of propylene glycol monomethyl ether and 3.84 g of propylene glycol monomethyl ether acetate.

[0222] Equation (2-2)

[0223]

[0224] <Comparative Example 1>

[0225] A solution of a photoresist underlayer film forming composition for photolithography was prepared by dissolving 0.23 g of acrylic resin, 0.058 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd. of Japan) as a crosslinking agent, 1.18 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 5, and 0.002 g of megafaq R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 28.53 g of propylene glycol monomethyl ether.

[0226] <Comparative Example 2>

[0227] The composition for forming the lower layer film of the resist shown in formula (2-1) consists of 0.23 g of an acrylic resin, 0.058 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd., Japan) as a crosslinking agent, and pyridine as a crosslinking catalyst as shown in formula (1-7). - A solution of a composition for forming a photoresist lower layer film was prepared by dissolving 0.008 g of p-toluenesulfonate (Midori Chemical Co., Ltd.) and 0.002 g of megafaq R-40 (DIC Co., Ltd., trade name) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0228] Equation (1-7)

[0229]

[0230] <Comparative Example 3>

[0231] The composition for forming the lower layer film of the resist shown in formula (2-1) consists of 0.23 g of an acrylic resin, 0.058 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd., Japan) as a crosslinking agent, and pyridine as a crosslinking catalyst as shown in formula (1-8). A solution of a composition for forming a photoresist lower layer film was prepared by dissolving 0.008 g of trifluoromethane sulfonate (manufactured by ADEKA Co., Ltd.) and 0.002 g of megafac R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0232] Equation (1-8)

[0233]

[0234] <Comparative Example 4>

[0235] The composition for forming the lower layer film of the resist shown in formula (2-1) consists of 0.23 g of an acrylic resin, 0.058 g of hexamethoxymethyl melamine (trade name: MW-390 [registered trademark] Nikkalac, manufactured by Sanwa Kemikal Co., Ltd.) as a crosslinking agent, and pyridine as a crosslinking catalyst as shown in formula (1-7). - A solution of a composition for forming a photoresist lower layer film was prepared by dissolving 0.008 g of p-toluenesulfonate (Midori Chemical Co., Ltd.) and 0.002 g of megafaq R-40 (DIC Co., Ltd., trade name) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0236] <Comparative Example 5>

[0237] The composition for forming the lower layer film of the resist shown in formula (2-1) consists of 0.23 g of an acrylic resin, 0.058 g of hexamethoxymethyl melamine (trade name: MW-390 [registered trademark] Nikkalac, manufactured by Sanwa Kemikal Co., Ltd.) as a crosslinking agent, and pyridine as a crosslinking catalyst as shown in formula (1-8). A solution of a composition for forming a photoresist lower layer film was prepared by dissolving 0.008 g of trifluoromethane sulfonate (manufactured by ADEKA Co., Ltd.) and 0.002 g of megafac R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 29.70 g of propylene glycol monomethyl ether.

[0238] <Comparative Example 6>

[0239] A solution of a photoresist underlayer film forming composition for photolithography was prepared by dissolving 0.23 g of acrylic resin, 0.058 g of tetramethoxymethyl urea (trade name: POWDER LINK [registered trademark] 1174, manufactured by Cynic Industries Co., Ltd. of Japan) as a crosslinking agent, 1.83 g of propylene glycol monomethyl ether solution of the crosslinking catalyst obtained in Synthesis Example 6, and 0.002 g of megafaq R-40 (manufactured by DIC Co., Ltd., trade name) as a surfactant in 27.88 g of propylene glycol monomethyl ether.

[0240] <Comparative Example 7>

[0241] The composition for forming the lower layer film of the resist shown in formula (2-2) consists of 0.40 g of phenolic varnish epoxy resin and pyridine of formula (1-8) as a crosslinking catalyst. 0.002 g of trifluoromethane sulfonate (manufactured by ADEKA Co., Ltd.) was 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 composition for forming the lower layer film of photoresist.

[0242] (Dissolution test in photoresist solvent)

[0243] The photoresist underlayer film forming compositions prepared in Examples 1-4 and Comparative Examples 1-3 were respectively coated onto silicon wafers serving as semiconductor substrates using a spin coater. The silicon wafers were placed on a hot plate and baked at 230°C for 1 minute to form photoresist underlayer films with a thickness of 20 nm to 30 nm. These photoresist underlayer films were then immersed in a solvent consisting of 70% by mass of propylene glycol monomethyl ether and 30% by mass of propylene glycol monomethyl ether acetate for 1 minute, confirming that the change in film thickness before and after immersion was less than 5%. This result demonstrates that the coatings prepared using the photoresist underlayer film forming compositions prepared in Examples 1-4 and Comparative Examples 1-3 can have photoresist or photoresist underlayer films laminated on them.

[0244] (Storage stability test of the composition for forming the lower layer film of the resist)

[0245] Specifically, the storage stability test of the crosslinking agent was conducted using the following method. Samples from Examples 1-6 and Comparative Examples 1-5 were stored at 35°C for 3 weeks. Using gel permeation chromatography (GPC), the peak area % (A / [A+B]×100) of the crosslinking agent and the peak area % (B / [A+B]×100) of the modified body were calculated from the peak area (A) of the crosslinking agent in the resist lower layer film forming composition and the peak area (B) of the modified body. That is, a higher modification rate indicates a faster modification rate of the crosslinking agent in the resist lower layer film forming composition, and a lower modification rate is desirable in the storage stability test. Furthermore, the peak area % (A / [A+B]×100) of the crosslinking agent and the peak area % (B / [A+B]×100) of the modified body are shown in Tables 1 and 2. Table 1 shows the results using tetramethoxymethylglyoxal as the crosslinking agent, and Table 2 shows the results using hexamethoxymethylmelamine as the crosslinking agent. In addition, the pKa of the bases in the crosslinking catalysts in Tables 1, 2, 3, and 4 are referenced in the following literature.

[0246] Reference 1 J.Org.Chem. 1960, 25, 2, 290-290

[0247] Reference 2: Kotake Muneo (ed.), "Organic Chemistry, Vol. 2, Organic Chemistry Constants Handbook", p. 584 (1963), (Asakura Shoten).

[0248] Reference 3 CAN. J. CHEM. VOL. 1993, 71

[0249] Reference 4: Tetrahedron Letters 2012, 53, 1830-1832

[0250] Table 1: Comparison of the modification rates of crosslinking agents in compositions for forming the lower layer of resist film

[0251]

[0252] Table 2: Comparison of the modification rates of crosslinking agents in compositions for forming the lower layer of resist film

[0253]

[0254] According to Table 1, the modification rate of the crosslinking agent in the resist underlayer film forming composition of Example 1 is lower than that of the crosslinking agent in the resist underlayer film forming composition of Comparative Example 1. Furthermore, the modification rate of the crosslinking agent in the resist underlayer film forming compositions of Examples 2-3 is lower than that of the crosslinking agent in the resist underlayer film forming composition of Comparative Example 2. Further, the modification rate of the crosslinking agent in the resist underlayer film forming composition of Example 4 is lower than that of the crosslinking agent in the resist underlayer film forming composition of Comparative Example 3. That is, the crosslinking catalyst used in Examples 1-4 can effectively suppress the modification of the crosslinking agent. Furthermore, according to Table 2, the modification rate of the crosslinking agent in the resist underlayer film forming composition of Example 5 is lower than that of the crosslinking agent 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 was lower than that of the crosslinking agent in the resist underlayer film forming composition of Comparative Example 5. That is, the crosslinking catalyst used in Examples 4 and 5 effectively suppressed the modification of the crosslinking agent regardless of the type of crosslinking agent in the resist underlayer film forming composition. Therefore, the nitrogen-containing base sulfonate salt with a pKa between 6.5 and 9.5 according to the present invention can effectively suppress the modification of the crosslinking agent in the resist underlayer film forming composition compared to nitrogen-containing base sulfonates with a pKa below 6.5.

[0255] (Storage stability test of the composition for forming the lower layer film of the resist)

[0256] Specifically, the storage stability test of the epoxy resin was conducted as follows. Samples from Example 7 and Comparative Example 7 were stored at 35°C for 3 weeks. By gel permeation chromatography (GPC), changes in the weight-average molecular weight (Mw) of the composition for forming the lower layer of the resist before and after the storage stability test were defined as follows: less than 5% was marked as "0", 6–19% as "△", and more than 20% as "×". The results are shown in Table 3 below. That is, a larger change in weight-average molecular weight (Mw) indicates a faster rate of epoxy group modification in the composition for forming the lower layer of the resist, and a smaller change in weight-average molecular weight (Mw) is desirable in the storage stability test.

[0257] Table 3

[0258]

[0259] According to Table 3, the change in weight-average molecular weight of the composition for forming the resist underlayer film in Example 7 before and after the storage stability test was lower than that of the composition for forming the resist underlayer film in Comparative Example 7. That is, the crosslinking catalyst used in Example 7 can effectively suppress the modification of the epoxy resin. Therefore, the nitrogen-containing base sulfonate salt with a pKa between 6.5 and 9.5 involved in this invention can effectively suppress the modification of the epoxy resin in the composition for forming the resist underlayer film compared to nitrogen-containing base sulfonates with a pKa below 6.5.

[0260] (Comparison of the curing start temperature of the underlayer film of the photoresist using various crosslinking catalysts)

[0261] The photoresist underlayer film forming compositions prepared in Example 2 and Comparative Example 6 were respectively coated onto silicon wafers serving as semiconductor substrates using a spin coater. The silicon wafers were placed on a hot plate and baked at 80°C, 90°C, and 100°C for 1 minute, respectively, to form photoresist underlayer films with a thickness of 25 nm to 35 nm. These photoresist underlayer films were immersed in a solvent consisting of 70% by mass of propylene glycol monomethyl ether and 30% by mass of propylene glycol monomethyl ether acetate for 1 minute. Changes in film thickness before and after immersion of less than 10% were marked as "0", 11% to 89% as "△", and more than 90% as "×". The results are shown in Table 4 below.

[0262] Table 4: Residual film yield at various temperatures

[0263]

[0264] The photoresist underlayer film formed using the photoresist underlayer film forming composition prepared in Example 2, compared with the photoresist underlayer film formed using the photoresist underlayer film forming composition prepared in Comparative Example 6, showed that curing began at a lower temperature.

[0265] (Determination of sublimation content)

[0266] The determination of sublimation content was performed using the sublimation content measuring apparatus described in International Publication No. 2007 / 111147. First, the resist underlayer film forming composition prepared in Example 2 and Comparative Example 6 was coated onto 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 aforementioned sublimation content measuring apparatus, which integrates a hot plate, and baked for 120 seconds to capture the sublimation onto a QCM (Quartz Crystal Microbalance) sensor, i.e., a crystal oscillator with electrodes. The QCM sensor can measure minute changes in mass by utilizing the property that if sublimation adheres to the surface (electrodes) of the crystal oscillator, the frequency of the crystal oscillator changes (decreases) according to its mass.

[0267] The detailed measurement procedure is as follows. Heat the heating plate of the sublimation content measuring device to the firing temperature recorded in Table 5, and set the pump flow rate to 1 m³ / min. 3 The initial 60 seconds were for device stabilization. Then, the wafer coated with a resist underlayer was immediately and rapidly placed onto the hot plate from the sliding port, and sublimation was collected from 60 seconds to 180 seconds (120 seconds). Furthermore, the flow accessory (detection section) connecting the QCM sensor and the collection funnel in the aforementioned sublimation measurement device is used without a nozzle; therefore, the flow flows in from the chamber unit (orifice diameter: 32 mm) at a distance of 30 mm from the sensor (crystal oscillator) without compressing the airflow. Additionally, the QCM sensor uses a material with silicon and aluminum as the main components (AlSi) as electrodes, a crystal oscillator diameter (sensor diameter) of 14 mm, an electrode diameter of 5 mm on the crystal oscillator surface, and a resonant frequency of 9 MHz.

[0268] The obtained frequency change was converted to grams from the intrinsic value of the crystal oscillator used in the measurement, thus clarifying the relationship between the amount of sublimation of a wafer coated with the resist underlayer and the passage of time. Furthermore, the initial 60 seconds were a time band for device stabilization (without the wafer placed), and the measurements from 60 seconds after the wafer was placed on the hot plate to 180 seconds later were measured values ​​related to the amount of sublimation of the wafer. The amount of sublimation of the resist underlayer quantified by this device is shown as the sublimation amount ratio in Table 5. The sublimation amount ratio is expressed as a value normalized to 1, with the amount of sublimation generated from the resist underlayer of Comparative Example 1 as 1.

[0269] Table 5: Amount of sublimation generated from the resist underlayer film

[0270]

[0271] According to Table 5, the amount of sublimation produced by the resist underlayer film forming composition of Example 2 is less than that produced by 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 sublimation produced. Therefore, the nitrogen-containing base sulfonate salt with a pKa of 6.5 to 9.5 according to the present invention can rapidly form a resist underlayer film compared to nitrogen-containing base sulfonates with a pKa of 9.5 or higher, thus suppressing the generation of sublimation and the like.

[0272] Industry availability

[0273] Therefore, the resist underlayer film forming composition of the present invention can suppress the modification of the crosslinking agent in the resist underlayer film forming composition, thus providing a resist underlayer film forming composition with high storage stability and high quality.

Claims

1. A composition for forming a resist underlayer film, comprising a crosslinkable resin, a crosslinking agent, a crosslinking catalyst as shown in formula (I), and a solvent. In equation (I), A can be a substituted straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group that can be substituted with a group other than a hydroxyl group, or a substituted heteroaryl group. B is a base with a pKa of 6.5–9.

5. In the formula (I), B is R. 1 R 2 R 3 N, R 1 and R 2 Each can independently represent a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group. R 1 With R 2 Rings can be formed with or without heteroatoms. R 3 This indicates a replaceable aromatic group, or a replaceable straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group. In R 1 With R 2 When no loop is formed, R 3 It is an aromatic group that can be replaced.

2. The composition for forming a resist underlayer film according to claim 1, wherein the crosslinking agent is an amino plastic crosslinking agent or a phenolic plastic crosslinking agent.

3. A composition for forming a resist underlayer film, comprising an epoxy-based compound and / or an epoxy-based resin, a crosslinking catalyst as shown in formula (I), and a solvent. In equation (I), A can be a substituted straight-chain, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an aryl group that can be substituted with a group other than a hydroxyl group, or a substituted heteroaryl group. B is a base with a pKa of 6.5–9.

5. In the formula (I), B is R. 1 R 2 R 3 N, R 1 and R 2 Each can independently represent a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group. R 1 With R 2 Rings can be formed with or without heteroatoms. R 3 This indicates a replaceable aromatic group, or a replaceable straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group. In R 1 With R 2 When no loop is formed, R 3 It is an aromatic group that can be replaced.

4. The composition for forming a resist underlayer film according to any one of claims 1 to 3, wherein B in formula (I) is R of the following formula: 1 R 2 R 3 N or the base represented by the following formula (II), Formula R 1 R 2 R 3 In N, R 1 and R 2 Each can independently represent a substituted straight-chain or branched saturated or unsaturated aliphatic hydrocarbon group. R 3 Indicates an aromatic group that can be replaced; In equation (II), R is a hydrogen atom, nitro group, cyano group, amino group, carboxyl group, halogen atom, alkoxy group with 1 to 10 carbon atoms, alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, aryl group with 6 to 40 carbon atoms, an organogroup containing an ether bond, an organogroup containing a ketone bond, an organogroup containing an ester bond, or a group obtained by combining them. R' is: ， R a and R b Each can independently represent any substituted alkyl group. X is O, S, or SO2. n and m are each independently 2, 3, 4, 5, or 6.

5. The composition for forming a resist underlayer film according to claim 4, wherein R in the formula 3 This indicates that the phenyl, naphthyl, anthraceneyl, or phenanthrene groups can be substituted. In formula (II), R is a hydrogen atom, methyl, ethyl, allyl, or cyanomethyl. In formula (II), R' is the base shown in the following formula. 。 6. The composition for forming a resist underlayer film according to any one of claims 1 to 3, further comprising a compound having an alcoholic hydroxyl group, or a compound having a group capable of forming an alcoholic hydroxyl group.

7. The composition for forming a lower layer of resist according to claim 6, wherein the compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group is a propylene glycol solvent, an oxyisobutyrate solvent, or a butanediol solvent.

8. The composition for forming a lower layer of resist according to claim 6, wherein the compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group is propylene glycol monomethyl ether or methyl 2-hydroxy-2-methylpropionate.

9. The composition for forming a resist underlayer film according to any one of claims 1 to 3, wherein A in formula (I) is methyl, fluoromethyl, or tolyl.

10. The composition for forming a resist underlayer film according to any one of claims 1 to 3, wherein B in formula (I) is N-methylmorpholine or N,N-diethylaniline.

11. The composition for forming a resist underlayer film according to claim 2, wherein the amino plastic crosslinking agent is a highly alkylated, alkoxylated, or alkoxyalkylated melamine, guanidine, glycourea, urea, or a polymer thereof.

12. The composition for forming a resist underlayer film according to claim 2, wherein the phenolic plastic crosslinking agent is an aromatic compound or a polymer thereof that has been highly alkylated, alkoxylated, or alkoxyalkylated.

13. The composition for forming a resist underlayer film according to claim 1 or 2, wherein the crosslinkable resin is selected from at least one of phenolic varnish resin, polyester resin, polyimide resin, and acrylic resin.

14. The composition for forming a resist underlayer film according to any one of claims 1 to 3, further comprising a surfactant.

15. A photoresist underlayer film, obtained by coating a photoresist underlayer film forming composition according to any one of claims 1 to 14 onto a semiconductor substrate and then firing it.

16. A method for forming a resist pattern for manufacturing a semiconductor, comprising the steps of: coating a resist underlayer film forming composition according to any one of claims 1 to 14 onto a semiconductor substrate and firing it to form a resist underlayer film.

17. A method for manufacturing a semiconductor device, comprising the steps of: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition according to any one of claims 1 to 14; forming a photoresist film on the photoresist underlayer film; forming a photoresist pattern by irradiation and development with light or electron beams; etching the photoresist underlayer film using the formed photoresist pattern; and processing the semiconductor substrate using the patterned photoresist underlayer film.

18. A method for manufacturing a semiconductor device, comprising the steps of: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition according to any one of claims 1 to 14; forming a hard mask on the photoresist underlayer film; further forming a photoresist film on the hard mask; forming a photoresist pattern by irradiation and development with light or electron beams; etching the hard mask using the formed photoresist pattern; etching the photoresist underlayer film using the patterned hard mask; and processing the semiconductor substrate using the patterned photoresist underlayer film.

19. The manufacturing method according to claim 18, wherein the hard mask is formed by coating or vapor deposition of an inorganic material.

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