Resist underlayer film-forming composition containing a reaction product of a hydantoin compound

Abstract

The present invention provides a resist underlayer film-forming composition capable of forming a desired resist pattern, and a resist pattern manufacturing method and a semiconductor device manufacturing method using the resist underlayer film-forming composition. The resist underlayer film-forming composition comprises a reaction product, and an organic solvent, wherein the reaction product is a reaction product of (A) a hydantoin-containing compound having two epoxy groups and (B) a hydantoin-containing compound different from (A). Preferably, the reaction product is a reaction product of a secondary amino group possessed by the hydantoin-containing compound (B) and an epoxy group possessed by the hydantoin-containing compound (A).

Description

Technical Field

[0001] The present invention relates to a composition used in a photolithography process in semiconductor manufacturing, particularly in the most advanced photolithography processes (ArF, EUV, EB, etc.), and also relates to a method for manufacturing a substrate with a resist pattern to which the resist underlayer film is applied, and a method for manufacturing a semiconductor device. Background Art

[0002] All along, in the manufacture of semiconductor devices, micro-machining is performed by using photolithography of a resist composition. The above-mentioned micro-machining is to form a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiate active light such as ultraviolet rays through a mask pattern depicting a device pattern, develop, and use the obtained photoresist pattern as a protective film to etch the substrate, thereby forming a processing method of fine concave-convex corresponding to the above-mentioned pattern on the substrate surface. In recent years, semiconductor devices tend to be highly integrated, and the active light used is in addition to the i-rays (wavelength 365nm), KrF excimer lasers (wavelength 248nm), and ArF excimer lasers (wavelength 193nm) used in the past. In the most advanced micro-machining, the practical application of EUV light (extreme ultraviolet light, wavelength 13.5nm) or EB (electron beam) is also being studied. Accompanied by this, the influence of semiconductor substrates on resists has become a big problem.

[0003] Therefore, in order to solve this problem, a method of providing a resist underlayer film between the resist and the semiconductor substrate has been widely studied.

[0004] Patent Document 1 discloses a resist underlayer film-forming composition containing a compound having a hydantoin ring. Patent Document 2 discloses a resist underlayer film-forming composition for EUV lithography, which contains a polymer obtained by condensing an isocyanuric acid-containing compound with barbital. Patent Document 3 discloses a resist underlayer film-forming composition for lithography, which has a structure containing a sulfonyl group at the end of a polymer chain.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2018 / 012253

[0008] Patent Document 2: International Publication No. 2013 / 018802

[0009] Patent Document 3: International Publication No. 2015 / 163195 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Examples of the properties required of the resist underlayer film include no mixing with the resist film formed on the upper layer (insolubility in the resist solvent) and a higher dry etching rate than the resist film.

[0012] In the case of photolithography with EUV exposure, the line width of the formed resist pattern reaches less than 32nm, and the resist underlayer film for EUV exposure is used to form a thinner film thickness than in the past. When forming such a thin film, pinholes and condensation are easily generated due to the influence of the substrate surface and the polymer used, making it difficult to form a uniform film without defects.

[0013] On the other hand, when the resist pattern is formed, a method is sometimes adopted in which a solvent capable of dissolving the resist film, usually an organic solvent, is used in the development process to remove the unexposed portion of the resist film, leaving the exposed portion of the resist film as the resist pattern. In such a negative-tone development process, improving the adhesion of the resist pattern becomes a major problem.

[0014] In addition, it is necessary to suppress deterioration of LWR (Line Width Roughness) during resist pattern formation, form a resist pattern having a good rectangular shape, and improve resist sensitivity.

[0015] An object of the present invention is to provide a resist underlayer film-forming composition that solves the above-mentioned problems and can form a desired resist pattern, and a resist pattern forming method using the resist underlayer film-forming composition.

[0016] Means of solving the problem

[0017] The present invention includes the following contents.

[0018] [1] A resist underlayer film-forming composition comprising a reaction product of (A) a hydantoin-containing compound having two epoxy groups and (B) a hydantoin-containing compound different from (A), and an organic solvent.

[0019] [2] The resist underlayer film-forming composition according to [1], wherein the reaction product is a reaction product of a secondary amino group contained in the (B) hydantoin-containing compound and an epoxy group contained in the (A) hydantoin-containing compound.

[0020] [3] The resist underlayer film-forming composition according to [1], wherein the compound (A) is represented by the formula (A-1), and the compound (B) is represented by the formula (B-1):

[0021]

[0022] In formula (A-1) and formula (B-1), T 1 , T 2 , T 3 and T 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom and which may be substituted by a hydroxyl group, an aryl group having 6 to 40 carbon atoms which may be substituted by a hydroxyl group, or an alkenyl group having 3 to 6 carbon atoms.

[0023] [4] The resist underlayer film forming composition according to any one of [1] to [3], wherein the terminal of the reaction product is capped with a compound having a functional group.

[0024] [5] The resist underlayer film forming composition according to [4], wherein the functional group is selected from a carboxyl group, a hydroxyl group, an amino group, an imino group and a thiol group.

[0025] [6] The resist underlayer film-forming composition according to [4], wherein the compound having a functional group includes an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which may be substituted by a substituent.

[0026] [7] The resist underlayer film-forming composition according to [4] or [5], wherein the structure blocked with the compound having a functional group is represented by the following formula (1) and formula (2):

[0027]

[0028] In formula (1) and formula (2), R 1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogen group or a hydroxyl group, R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen group, or an ester group represented by -C(=O)OX, X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R 3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a halogen group, and R 4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms, R 5 represents a divalent organic group having 1 to 8 carbon atoms, A represents an aromatic ring or an aromatic heterocyclic ring, t represents 0 or 1, and u represents 1 or 2.

[0029] [8] The resist underlayer film forming composition according to any one of [1] to [7], further comprising an acid generator.

[0030] [9] The resist underlayer film forming composition according to any one of [1] to [8], further comprising a crosslinking agent.

[0031]

[10] The composition for forming an underlayer film according to any one of [1] to [9], which is a composition for forming an electron beam or EUV resist underlayer film.

[0032]

[11] A resist underlayer film characterized by being a fired product of a coating film formed from the resist underlayer film forming composition according to any one of [1] to

[10] .

[0033]

[12] A method for manufacturing a patterned substrate, comprising the steps of coating a resist underlayer film forming composition as described in any one of [1] to

[10] on a semiconductor substrate and baking the composition to form a resist underlayer film, coating a resist on the resist underlayer film and baking the composition to form a resist film, exposing the semiconductor substrate coated with the resist underlayer film and the resist, and developing and patterning the resist film after exposure.

[0034]

[13] A method for manufacturing a semiconductor device, comprising:

[0035] A step of forming a resist underlayer film formed from the resist underlayer film-forming composition according to any one of [1] to

[10] on a semiconductor substrate,

[0036] a step of forming a resist film on the resist underlayer film,

[0037] A process of forming a resist pattern by irradiating a resist film with light or electron beams and then developing the resist film.

[0038] a step of etching the resist underlayer film through the formed resist pattern to form a patterned resist underlayer film, and

[0039] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0040] Effects of the Invention

[0041] When a resist pattern is formed using a resist underlayer film-forming composition comprising a reaction product of (A) a hydantoin-containing compound having two epoxy groups and (B) a hydantoin-containing compound different from (A), the limiting resolution size at which the collapse of the resist pattern after development is not observed becomes smaller than that of a conventional resist underlayer film, and a finer resist pattern can be formed. In addition, the range of the resist pattern size showing a good pattern is increased compared with the prior art. DETAILED DESCRIPTION

[0042] The resist underlayer film-forming composition of the present application comprises a reaction product, and an organic solvent, wherein the reaction product is a reaction product of (A) a hydantoin-containing compound having two epoxy groups and (B) a hydantoin-containing compound different from (A). The reaction product is preferably a reaction product of a secondary amino group possessed by the hydantoin-containing compound (B) and an epoxy group possessed by the hydantoin-containing compound (A). The reaction can be carried out by a known method.

[0043] The above-mentioned (A) compound is represented by formula (A-1), and the above-mentioned (B) compound is represented by formula (B-1):

[0044]

[0045] In formula (A-1) and formula (B-1), T 1 , T 2 , T 3 and T 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom and which may be substituted by a hydroxyl group, an aryl group having 6 to 40 carbon atoms which may be substituted by a hydroxyl group, or an alkenyl group having 3 to 6 carbon atoms. 1 , T 2 , T 3 and T 4 They may be all the same, all different, or partially the same.

[0046] Among them, T 1 , T 2 , T 3 and T 4 An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms is preferred.

[0047] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 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-methylcyclobutyl, 2-methylcyclopropyl, 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-methylcyclobutyl, 2 -methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 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-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethyl cyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl and decyl.

[0048] Examples of the aryl group having 6 to 40 carbon atoms 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-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl.

[0049] Examples of the alkenyl group having 3 to 6 carbon atoms include 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-dimethylvinyl, methyl-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-cyclopentenyl cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, etc.

[0050] Preferred specific examples of the compound (A) include the following compounds.

[0051]

[0052] Preferred specific examples of the compound (B) include the following compounds.

[0053]

[0054] Examples of the organic solvent contained in the resist underlayer film-forming composition of the present invention 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 monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, 2- Methyl hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

[0055] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, etc. are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0056] The weight average molecular weight of the reaction product is preferably 500 to 50,000, and more preferably 1000 to 30,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography as described in Examples.

[0057] The terminal of the above reaction product is preferably capped with a compound having a functional group.

[0058] It is preferred that the functional group is selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an imino group and a thiol group.

[0059] The compound having a functional group preferably includes an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which may be substituted by a substituent.

[0060] The aliphatic ring is preferably a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.

[0061] The polycyclic aliphatic ring is preferably a bicyclic or tricyclic ring.

[0062] The aliphatic ring preferably has at least one unsaturated bond.

[0063] The description of the carboxyl-containing compound comprising an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which may be substituted by a substituent is based on the contents described in PCT / JP2020 / 018436.

[0064] The structure in which the terminal of the reaction product of the above-mentioned (A) compound and (B) compound is terminated by an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and may be substituted by a substituent can be produced by reacting the reaction product of the above-mentioned (A) compound and (B) compound with a carboxyl-containing compound containing an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and may be substituted by a substituent as described below.

[0065] Specific examples of carboxyl-containing compounds containing an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which may be substituted by a substituent include the following compounds. Compounds in which the carboxyl groups of the following specific examples are substituted by hydroxyl groups, amino groups, and thiol groups may also be listed as specific examples.

[0066]

[0067]

[0068] The structure terminated with the compound having a functional group is preferably represented by the following formula (1) or formula (2):

[0069]

[0070] In formula (1) and formula (2), R 1represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogen group or a hydroxyl group, R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen group, or an ester group represented by -C(=O)OX, X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R 3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a halogen group, and R 4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms, R 5 represents a divalent organic group having 1 to 8 carbon atoms, A represents an aromatic ring or an aromatic heterocyclic ring, t represents 0 or 1, and u represents 1 or 2.

[0071] The description of the terms described in the above formula (1) and formula (2) is in accordance with the contents described in WO2015 / 163195.

[0072] The terminal structure of the reaction product of the above-mentioned compound (A) and compound (B) represented by the above-mentioned formula (1) and formula (2) can be produced by reacting the reaction product of the above-mentioned compound (A) and compound (B) with a compound represented by the following formula (1a) and / or a compound represented by the following formula (2a).

[0073]

[0074] The symbols in the above formula (1a) and formula (2a) have the same meanings as described in the above formula (1) and formula (2).

[0075] Examples of the compound represented by the formula (1a) include compounds represented by the following formula: Compounds in which the carboxyl group or the hydroxyl group exemplified below is substituted with an amino group or a thiol group can also be given as specific examples.

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] Examples of the compound represented by the formula (2a) include compounds represented by the following formula: Compounds in which the carboxyl group of the following specific examples is substituted with a hydroxyl group, an amino group or a thiol group can also be given as specific examples.

[0082]

[0083] In addition, examples of the imino group-containing compound include the following compounds.

[0084]

[0085] <Acid Generator>

[0086] As the acid generator included as an optional component in the resist underlayer film-forming composition of the present invention, either a thermal acid generator or a photoacid generator can be used, and preferably a thermal acid generator is used. Examples of the thermal acid generator include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0087] Examples of the photoacid generator include onium salt compounds, sulfonyl imide compounds, and disulfonyldiazomethane compounds.

[0088] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0089] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0090] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0091] The above-mentioned acid generators may be used alone or in combination of two or more.

[0092] When the acid generator is used, the content ratio of the acid generator is, for example, 0.1 mass % to 50 mass %, or preferably 1 mass % to 30 mass % based on the cross-linking agent described below.

[0093] <Crosslinking agent>

[0094] Examples of the crosslinking agent contained as an optional component in the resist underlayer film-forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK (registered trademark) 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, and 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine ((trade names) Cymel (registered trademark)-303, Nicalack (registered trademark) MW-390).

[0095] In addition, the cross-linking agent of the present application may be a nitrogen-containing compound described in WO2017 / 187969, which has 2 to 6 substituents represented by the following formula (1X) bonded to a nitrogen atom in one molecule.

[0096]

[0097] In formula (1X), R 1 It represents a methyl or ethyl group.

[0098] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1X) in one molecule may be a glycoluril derivative represented by the following formula (1A).

[0099]

[0100] In formula (1A), the four R 1 Each independently represents a methyl group or an ethyl group, R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0101] Examples of the glycoluril derivatives represented by the above formula (1A) include compounds represented by the following formulae (1A-1) to (1A-6).

[0102]

[0103] The compound represented by the above formula (1A) can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2X) bonded to a nitrogen atom in each molecule with at least one compound represented by the following formula (3) to produce a nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1X) in each molecule.

[0104]

[0105] In formula (2X) and formula (3), R 1 Represents methyl or ethyl, R 4 It represents an alkyl group having 1 to 4 carbon atoms.

[0106] The glycoluril derivative represented by the above formula (1A) can be obtained by reacting a glycoluril derivative represented by the following formula (2A) with at least one compound represented by the above formula (3).

[0107] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2X) in one molecule is, for example, a glycoluril derivative represented by the following formula (2A).

[0108]

[0109] In formula (2A), R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 Each independently represents an alkyl group having 1 to 4 carbon atoms.

[0110] Examples of glycoluril derivatives represented by formula (2A) include compounds represented by the following formulas (2A-1) to (2A-4). Furthermore, examples of compounds represented by the above formula (3) include compounds represented by the following formulas (3-1) and (3-2).

[0111]

[0112] The contents of the nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1X) bonded to a nitrogen atom in one molecule are in accordance with the contents described in WO2017 / 187969.

[0113] When the cross-linking agent is used, the content ratio of the cross-linking agent is, for example, 1 mass % to 50 mass %, or preferably 5 mass % to 30 mass % based on the reaction product.

[0114] <Other ingredients>

[0115] In the resist underlayer film-forming composition of the present invention, a surfactant may be further added in order to prevent pinholes, streaks, etc. from being generated and to further improve the coating property with respect to surface unevenness. Examples of the surfactant 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 octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Non-ionic surfactants such as stearate and other polyoxyethylene sorbitan fatty acid esters, Efthot EF301, EF303, EF352 (Tofu Co., Ltd. Made by ダクツ, trade name), Milk F171, F173, R-30 (made by Dainippon Co., Ltd., trade name), フロラード FC430, FC431 (Sumitomo Slide (co., trade name), Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (co., trade name)) and other fluorine-based surfactants, organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), etc. The amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less relative to the total solids of the resist underlayer film forming composition of the present invention. These surfactants can be added alone or in combination of two or more.

[0116] The resist underlayer film-forming composition of the present application is preferably an electron beam resist underlayer film-forming composition or an EUV resist underlayer film-forming composition used in an electron beam (EB) drawing step and an EUV exposure step, and is preferably an EUV resist underlayer film-forming composition.

[0117] <Resist Underlayer Film>

[0118] The resist underlayer film according to the present invention can be produced by applying the above-mentioned resist underlayer film-forming composition on a semiconductor substrate and firing the coating.

[0119] The resist underlayer film according to the present invention is preferably an electron beam resist underlayer film or an EUV resist underlayer film.

[0120] Examples of the semiconductor substrate to which the resist underlayer film-forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0121] When a semiconductor substrate having an inorganic film formed on the surface is used, the inorganic film is formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum evaporation method, spin coating method (spin-on glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium oxynitride film, tungsten film, gallium nitride film, and gallium arsenide film.

[0122] On such a semiconductor substrate, the resist underlayer film forming composition of the present invention is applied by an appropriate coating method such as a spin coater or a coater. Then, a heating means such as a hot plate is used to bake, thereby forming a resist underlayer film. As baking conditions, it is appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C, and the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C, and the baking time is 0.8 minutes to 10 minutes. When the temperature during baking is lower than the above range, crosslinking becomes insufficient. On the other hand, when the temperature during baking is higher than the above range, the resist underlayer film sometimes thermally decomposes.

[0123] The thickness of the resist underlayer film to be formed is, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (1 nm) ~0.05μm (50nm), 0.004μm (4nm) ~ 0.05μm (50nm), 0.005μm (5nm) ~ 0.05μm (50nm), 0.003μ m (3nm) ~ 0.03μm (30nm), 0.003μm (3nm) ~ 0.02μm (20nm), 0.005μm (5nm) ~ 0.02μm (20nm).

[0124] <Method for Manufacturing Patterned Substrate, Method for Manufacturing Semiconductor Device>

[0125] The method for manufacturing a patterned substrate is carried out through the following steps. Generally, it can be manufactured by forming a photoresist layer on a resist underlayer film. As a photoresist formed by coating and firing on the resist underlayer film by a method known per se, there is no particular limitation as long as it is a photoresist that is sensitive to the light used for exposure. Both negative photoresists and positive photoresists can be used. There are positive photoresists containing novolac resin and 1,2-naphthoquinone diazosulfonic acid ester, chemically amplified photoresists containing a binder having a group whose alkali dissolution rate increases by acid decomposition and a photoacid generator, chemically amplified photoresists containing a low molecular weight compound whose alkali dissolution rate of the photoresist increases by acid decomposition, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists containing a binder having a group whose alkali dissolution rate increases by acid decomposition, a low molecular weight compound whose alkali dissolution rate of the photoresist increases by acid decomposition, and a photoacid generator, resists containing metal elements, etc. For example, JSR Corp.'s product name V146G, Shipley Co., Ltd.'s product name APEX-E, Sumitomo Chemical Co., Ltd.'s product name PAR710, Shin-Etsu Chemical Co., Ltd.'s product names AR2772 and SEPR430, etc. can be cited. In addition, fluorine atom-containing polymer photoresists such as those described in, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be cited.

[0126] Exposure is performed through a mask (intermediate mask) for forming a prescribed pattern, using, for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam), but the resist underlayer film forming composition of the present application is preferably used for EUV (extreme ultraviolet) or EB (electron beam) exposure, and is particularly preferably used for EUV (extreme ultraviolet) exposure. An alkali developer is used in development, and is appropriately selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. As an alkali developer, for example, an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, a primary amine such as ethylamine, n-propylamine, a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, an alcohol amine such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, a quaternary ammonium salt such as choline, a cyclic amine such as pyrrole and piperidine can be used. Furthermore, it is also possible to add an appropriate amount of alcohols such as isopropyl alcohol, nonionic surfactants and the like to the aqueous solution of the above-mentioned alkalis for use. Among them, the preferred developer is a quaternary ammonium salt, and more preferably tetramethylammonium hydroxide and choline. Furthermore, it is also possible to add a surfactant and the like to these developers. It is also possible to adopt the following method, that is, to replace the alkaline developer with an organic solvent such as butyl acetate for development, and to develop the portion of the photoresist whose alkali dissolution rate is not improved. Through the above-mentioned process, the substrate on which the above-mentioned resist is patterned can be manufactured.

[0127] Next, the resist underlayer film is dry-etched using the formed resist pattern as a mask. At this time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, the substrate is processed by a method known per se (dry etching method, etc.), and a semiconductor device can be manufactured through this process.

[0128] Example

[0129] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0130] The weight average molecular weight (Mw) of the polymer (A) shown in the following synthesis example is the measurement result based on the gel permeation chromatography (GPC) method. The measurement was performed using a GPC apparatus manufactured by Tosoh Corporation, and the measurement conditions were as follows.

[0131] Measuring device: HLC-8020GPC (trade name) (manufactured by Tosoh Corporation)

[0132] GPC column: TSKgel G2000HXL: 2 pieces, G3000HXL: 1 piece, G4000HXL: 1 piece (trade name) (all manufactured by Tosei Co., Ltd.)

[0133] Column temperature: 40°C

[0134] Solvent: Tetrahydrofuran (THF)

[0135] Flow rate: 1.0ml / min

[0136] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0137] [Synthesis Example 1] Synthesis of Reaction Product 1

[0138] 4.91 g of N,N-diglycidyl-5,5-dimethylhydantoin, 2.83 g of 5,5-dimethylhydantoin, and 0.27 g of tetrabutylphosphonium bromide were added to 12.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 24 hours under reflux heating to obtain a solution of reaction product 1. GPC analysis was performed, and the reaction product 1 in the obtained solution had a weight average molecular weight of 1400 in terms of standard polystyrene.

[0139] Reaction product 1 contains the following structure as a repeating unit structure.

[0140]

[0141] [Synthesis Example 2] Synthesis of Reaction Product 2

[0142] 4.00 g of N,N-diglycidyl-5,5-dimethylhydantoin, 3.71 g of 5-phenylhydantoin, and 0.30 g of tetrabutylphosphonium bromide were added to 12.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 24 hours under reflux heating to obtain a solution of reaction product 2. GPC analysis was performed, and the reaction product 2 in the obtained solution had a weight average molecular weight of 3500 in terms of standard polystyrene.

[0143] Reaction product 2 contains the following structure as a repeating unit structure.

[0144]

[0145] [Synthesis Example 3] Synthesis of Reaction Product 3

[0146] 3.66 g of N,N-diglycidyl-5,5-dimethylhydantoin, 4.15 g of 5,5-diphenylhydantoin, and 0.20 g of tetrabutylphosphonium bromide were added to 12.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 24 hours under reflux heating to obtain a solution of reaction product 3. GPC analysis was performed, and the reaction product 3 in the obtained solution had a weight average molecular weight of 3100 in terms of standard polystyrene.

[0147] The reaction product 3 contains the following structure as a repeating unit structure.

[0148]

[0149] [Synthesis Example 4] Synthesis of Reaction Product 4

[0150] 4.52 g of N,N-diglycidyl-5,5-dimethylhydantoin, 2.97 g of 5-phenylhydantoin, 1.17 g of 3-hydroxy-1-adamantanecarboxylic acid, and 0.34 g of tetrabutylphosphonium bromide were added to 11.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 24 hours under reflux heating to obtain a solution of reaction product 4. GPC analysis was performed, and the reaction product 4 in the obtained solution had a weight average molecular weight of 2400 in terms of standard polystyrene.

[0151] Reaction product 4 contains the following structure as a repeating unit structure.

[0152]

[0153] [Synthesis Example 5] Synthesis of Reaction Product 5

[0154] 4.01 g of N,N-diglycidyl-5,5-dimethylhydantoin, 2.64 g of 5-phenylhydantoin, 1.06 g of 4-(methylsulfonyl)benzoic acid, and 0.30 g of tetrabutylphosphonium bromide were added to 12.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 24 hours under reflux heating to obtain a solution of reaction product 5. GPC analysis was performed, and the reaction product 5 in the obtained solution had a weight average molecular weight of 1900 in terms of standard polystyrene.

[0155] The reaction product 5 contains the following structure as a repeating unit structure.

[0156]

[0157] [Synthesis Example 6] Synthesis of Reaction Product 6

[0158] 4.62 g of N,N-diglycidyl-5,5-dimethylhydantoin, 3.04 g of 5-phenylhydantoin, 1.06 g of 5-norbornene-2,3-dicarboxylic anhydride, and 0.34 g of tetrabutylphosphonium bromide were added to 11.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 24 hours under reflux heating to obtain a solution of reaction product 6. GPC analysis was performed, and the reaction product 6 in the obtained solution had a weight average molecular weight of 2100 in terms of standard polystyrene.

[0159] The reaction product 6 contains the following structure as a repeating unit structure.

[0160]

[0161] <Comparative Synthesis Example 1>

[0162] 8.00 g of monoallyl diglycidyl isocyanuric acid, 5.45 g of barbital, and 0.48 g of tetrabutylphosphonium bromide were added to 56.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 10 hours under reflux heating to obtain a solution of reaction product 7. GPC analysis was performed, and the reaction product 7 in the obtained solution had a weight average molecular weight of 10,000 in terms of standard polystyrene.

[0163] The reaction product 7 contains the following structure as a repeating unit structure.

[0164]

[0165] <Comparative Synthesis Example 2>

[0166] 3.66 g of N,N-diglycidyl-5,5-dimethylhydantoin, 5.45 g of barbital, and 0.48 g of tetrabutylphosphonium bromide were added to 56.00 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction container, the reaction was allowed to react for 10 hours under reflux heating to obtain a solution of reaction product 8. GPC analysis was performed, and the reaction product 8 in the obtained solution had a weight average molecular weight of 4000 in terms of standard polystyrene.

[0167] The reaction product 8 contains the following structure as a repeating unit structure.

[0168]

[0169] [Example 1]

[0170] 0.11 g of tetramethoxymethyl glycoluril and 0.012 g of pyridinium p-phenolsulfonate were mixed with 3.12 g of a solution containing 0.047 g of the reaction product 1 obtained in Synthesis Example 1, and 263.41 g of propylene glycol monomethyl ether and 29.89 g of propylene glycol monomethyl ether acetate were added and dissolved. The mixture was then filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a resist underlayer film-forming composition.

[0171] [Examples 2 to 6]

[0172] Resist underlayer film-forming compositions were prepared by the same method as in Example 1, except that reaction products 2 to 6 were used instead of reaction product 1.

[0173] [Comparative Examples 1-2]

[0174] Resist underlayer film-forming compositions were prepared in the same manner as in Example 1 except that reaction products 7 to 8 were used instead of reaction product 1.

[0175] (Resist Patterning Evaluation)

[0176] Resist patterning test using electron beam lithography equipment

[0177] Use a spin coater to apply the resist underlayer film-forming composition on a silicon wafer. Bake the silicon wafer at 205°C for 60 seconds on a hot plate to obtain a resist underlayer film with a thickness of 5 nm. Spin-coat an EUV negative resist solution (containing a methacrylic polymer) on the resist underlayer film and heat it at 100°C for 60 seconds to form an EUV resist film. For the resist film, an electron beam drawing device (ELS-G130) is used to expose it under specified conditions. After exposure, bake (PEB) at 100°C for 60 seconds, cool to room temperature on a cooling plate, and develop with butyl acetate to form a resist pattern with a column size of 17nm to 28nm. The resist pattern is measured using a scanning electron microscope (manufactured by Hitachi High-Tech Nologis, CG4100).

[0178] The photoresist pattern thus obtained was observed from the top of the pattern, and the minimum CD size at which the resist pattern did not collapse (collapse) and the maximum CD size at which the adjacent pattern did not connect (bridge) were not observed were confirmed, and the range in which the pattern was well resolved was confirmed. The larger the range, the wider the pattern range in which a good pattern can be formed. The results of Examples 1 to 6 showed that the size range in which a good pattern can be formed was wider than that of Comparative Examples 1 and 2.

[0179] Table 1 shows the observation results of the resist patterns confirmed in Examples 1 to 6 and Comparative Examples 1 and 2.

[0180] Table 1

[0181] Industrial Applicability

[0182] The resist underlayer film forming composition of the present invention can provide a composition for forming a resist underlayer film that can form a desired resist pattern, as well as a method for manufacturing a substrate with a resist pattern formed using the resist underlayer film forming composition and a method for manufacturing a semiconductor device.

Claims

1. A resist underlayer film-forming composition comprising a reaction product of (A) a hydantoin-containing compound having two epoxy groups and (B) a hydantoin-containing compound different from (A), and an organic solvent. The reaction product is a reaction product of a secondary amino group contained in the (B) hydantoin-containing compound and an epoxy group contained in the (A) hydantoin-containing compound, The (A) compound is represented by formula (A-1), and the (B) compound is represented by formula (B-1): In formula (A-1) and formula (B-1), T 1 , T 2 , T 3 and T 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom and which may be substituted by a hydroxyl group, an aryl group having 6 to 40 carbon atoms which may be substituted by a hydroxyl group, or an alkenyl group having 3 to 6 carbon atoms. 2 . The resist underlayer film-forming composition according to claim 1 , wherein the terminal of the reaction product is capped with a compound having a functional group. 3 . The resist underlayer film-forming composition according to claim 2 , wherein the functional group is selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, an imino group, and a thiol group. 4 . The resist underlayer film-forming composition according to claim 2 , wherein the compound having a functional group comprises an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which may be substituted by a substituent.

5. The resist underlayer film-forming composition according to claim 2, wherein the structure blocked with the compound having a functional group is represented by the following formula (1) and formula (2): In formula (1) and formula (2), R 1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogen group or a hydroxyl group, R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen group, or an ester group represented by -C(=O)OX, X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R 3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a halogen group, and R 4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms, R 5 represents a divalent organic group having 1 to 8 carbon atoms, A represents an aromatic ring or an aromatic heterocyclic ring, t represents 0 or 1, and u represents 1 or 2. 6 . The resist underlayer film forming composition according to claim 1 , further comprising an acid generator. 7 . The resist underlayer film forming composition according to claim 1 , further comprising a crosslinking agent. 8 . The resist underlayer film forming composition according to claim 1 , which is an electron beam or EUV resist underlayer film forming composition.

9. A resist underlayer film, It is characterized in that A fired product of a coating film formed from the resist underlayer film forming composition according to any one of claims 1 to 8.

10. A method for manufacturing a patterned substrate, comprising the steps of coating a resist underlayer film-forming composition according to any one of claims 1 to 8 on a semiconductor substrate and baking the coating to form a resist underlayer film, coating a resist on the resist underlayer film and baking the coating to form a resist film, exposing the semiconductor substrate coated with the resist underlayer film and the resist, and developing and patterning the exposed resist film.

11. A method for manufacturing a semiconductor device, It is characterized in that Include: A step of forming a resist underlayer film formed from the resist underlayer film-forming composition according to any one of claims 1 to 8 on a semiconductor substrate, a step of forming a resist film on the resist underlayer film, A process of forming a resist pattern by irradiating a resist film with light or electron beams and then developing the resist film. a step of etching the resist underlayer film through the formed resist pattern to form a patterned resist underlayer film, and A step of processing a semiconductor substrate using the patterned resist underlayer film.

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