Resist underlayer film-forming composition containing a heterocyclic compound

Abstract

The present invention provides a resist underlayer film having a particularly high dry etching rate, a composition for forming the resist underlayer film, a resist pattern forming method, and a method for manufacturing a semiconductor device. A composition for forming a resist underlayer film, comprising: a compound containing an epoxy group, a reaction product with a heterocyclic compound containing 1 site having reactivity with the epoxy group; and a solvent. It is preferable that the heterocyclic ring contained in the above-mentioned heterocyclic compound be selected from the group consisting of furan, pyrrole, pyran, imidazole, pyrazole, oxazole, thiophene, thiazole, thiadiazole, imidazolidine, thiazolidine, imidazoline, dioxane, morpholine, diazine, thiazine, triazole, tetrazole, dioxolane, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thioxanthene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole.

Description

Technical Field

[0001] The present invention relates to a composition for forming a resist underlayer film with particularly high dry etching speed, a resist underlayer film using the composition for forming a resist underlayer film, a method for manufacturing the same, a method for forming a resist pattern, and a method for manufacturing a semiconductor device. Background Technology

[0002] When a photoresist film is exposed to light, reflected waves can sometimes have adverse effects on it. The underlying photoresist film formed to suppress this effect is also known as an anti-reflective film.

[0003] The resist underlayer film requires easy film formation by coating a solution-like resist underlayer film composition and allowing it to cure. Therefore, the composition needs to contain a compound (polymer) that can be easily cured by heating or the like and has high solubility in a specified solvent.

[0004] The resist pattern formed on the resist underlayer is expected to have a rectangular cross-sectional shape perpendicular to the substrate (without a straight bottom shape such as an undercut or a wide bottom). For example, if the resist pattern becomes an undercut or wide bottom shape, problems such as resist pattern collapse and inability to process the workpiece (substrate, insulating film, etc.) into the desired shape or size during the photolithography process will occur.

[0005] In addition, the lower resist film is required to have a higher dry etching rate than the upper resist film, that is, a greater selectivity for dry etching rate.

[0006] Patent Document 1 discloses a composition for forming a photoresist lower layer film using a polymer with disulfide bonds in its main chain. Patent Document 2 discloses an epoxy compound having glycidyl ester groups. Patent Document 3 discloses a composition for forming an antireflective film, characterized in that it comprises a triazine trione compound, an oligomer compound, or a polymer compound having a hydroxyalkyl structure as a substituent on the nitrogen atom.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Re-evaluation No. 2009-096340

[0010] Patent Document 2: Japanese Patent Application Publication No. 8-81461

[0011] Patent Document 3: Japanese Re-evaluation No. 2004-034148 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] In the manufacture of semiconductor devices, a high dry etch rate resist underlayer is still required. To produce a resist underlayer with a high dry etch rate, it is known that the polymer of the composition contains a substance containing heteroatoms.

[0014] The inventors of this application conducted in-depth research and found that if a reaction product of a compound containing an epoxy group, preferably a compound containing a glycidyl ester group, preferably a nitrogen-containing heterocyclic compound (such as isocyanuric acid) having a glycidyl ester group, and a heterocyclic compound containing a site that is reactive with an epoxy group is applied to a composition for forming a resist underlayer film, a higher etching rate can be achieved compared with the prior art.

[0015] The present invention addresses this problem by providing a composition for forming a resist underlayer film with a particularly high dry etching rate. Furthermore, the present invention also aims to provide a resist underlayer film using this composition, a method for manufacturing the same, a method for forming a resist pattern, and a method for manufacturing a semiconductor device.

[0016] Methods for solving problems

[0017] The present invention includes the following solutions. [1]

[0019] A composition for forming a resist underlayer film comprises: a compound containing an epoxy group, a reaction product with a heterocyclic compound containing a site reactive with the epoxy group, and a solvent. [2]

[0021] According to the composition for forming a resist underlayer film as described in [1], the heterocyclic compound contains heterocycles selected from furan, pyrrole, pyran, imidazole, pyrazole, etc. azole, thiophene, thiazole, thiadiazole, imidazoline, thiazoline, imidazoline Alkane, Morpholine, Diazine, Thiazide, Triazole, Tetrazol, Dioxolane, Pyrimidine, Pyrazine, Piperidine, Piperazine, Indole, Purine, Quinoline, Isoquinoline, Quinine Ring, Chromene, Thianthracene, Phenothiazine, Phenylene Azine, thiamethoxam, acridine, phenazine, and carbazole. [3]

[0023] According to the composition for forming a lower layer film of the resist as described in [1] or [2], the site that is reactive with the epoxy group is selected from hydroxyl, thiol, amino, imide and carboxyl groups. [4]

[0025] The composition for forming a resist underlayer film according to any one of [1] to [3], wherein the epoxy-containing compound is a compound represented by the following formula (1).

[0026]

[0027] (In equation (1), X is a divalent organic group as shown in equation (2), equation (3) or equation (4) below, and n1 and n2 each independently represent integers from 1 to 10.)

[0028]

[0029] (In equations (2), (3) and (4),)

[0030] R 1 and R 2 Each of the following can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group can be substituted with at least one monovalent functional group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, and alkylthio groups having 1 to 6 carbon atoms.

[0031] R3 represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group with 3 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group with 3 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent functional group selected from alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 10 carbon atoms, nitro groups, cyano groups, alkylthio groups with 1 to 6 carbon atoms, and the organogroup shown in formula (5) below.

[0032]

[0033] (In equation (5), n3 represents an integer from 1 to 10.) [5]

[0035] The composition for forming a resist underlayer film according to any one of [1] to [4] further comprises at least one selected from crosslinking agents, crosslinking catalysts and surfactants. [6]

[0037] A resist underlayer film, characterized in that it is a sintered product of a coating film formed by any one of the resist underlayer film forming compositions described in any one of [1] to [5]. [7]

[0039] A method for manufacturing a substrate with patterned substrate includes the following steps: coating a resist underlayer film forming composition as described in any one of [1] to [5] onto a semiconductor substrate and baking it to form a resist underlayer film; coating a resist onto the resist underlayer film and baking it to form a resist film; exposing the semiconductor substrate covered with the resist underlayer film and the resist; and developing the exposed resist film to form a pattern. [8]

[0041] A method for manufacturing a semiconductor device, characterized by comprising the following steps:

[0042] A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film as described in any one of [1] to [5];

[0043] The process of forming a resist film on the aforementioned lower resist film;

[0044] The process of irradiating a resist film with light or electron beams and then developing it to form a resist pattern;

[0045] The process of etching the resist underlayer film through the formed resist pattern to form a patterned resist underlayer film; and

[0046] The process of processing a semiconductor substrate using the patterned resist underlayer film described above. [9]

[0048] The product of the reaction of the compound shown in formula (1) with a heterocyclic compound containing a site that is reactive with an epoxy group.

[0049]

[0050] (In equation (1), X is a divalent organic group as shown in equation (2), equation (3) or equation (4) below, and n1 and n2 each independently represent integers from 1 to 10.)

[0051]

[0052] (In equations (2), (3) and (4),)

[0053] R 1 and R 2Each of the following can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group can be substituted with at least one monovalent functional group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, and alkylthio groups having 1 to 6 carbon atoms.

[0054] R 3 The term "phenyl" refers to a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group having 3 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group having 3 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent functional group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, alkylthio groups having 1 to 6 carbon atoms, and an organogroup represented by formula (5) below.

[0055]

[0056] (In equation (5), n3 represents an integer from 1 to 10.)

[0057] The effects of the invention

[0058] The resist underlayer film formation composition of the present invention has a high dry etching rate, which can solve various problems caused by the thinning of resist film thickness and realize the micro-processing of finer semiconductor substrates. Detailed Implementation

[0059] <A composition for forming a resist underlayer film, a compound containing an epoxy group, and a reaction product of a heterocyclic compound containing a site reactive with the epoxy group>

[0060] The composition for forming a resist underlayer in this application comprises: a compound containing an epoxy group, a reaction product of a heterocyclic compound containing a site reactive with the epoxy group, and a solvent.

[0061] The above-mentioned epoxy-containing compounds are not limited as long as they can achieve the above-mentioned purpose, but compounds containing glycidyl ester groups are preferred, and nitrogen-containing heterocyclic compounds (such as isocyanuric acid) having glycidyl ester groups are even more preferred.

[0062] The aforementioned epoxy-containing compounds may be, for example, compounds containing an aromatic ring structure with 6 to 40 carbon atoms, compounds containing triazine ketones, compounds containing triazine diketones, or compounds containing triazine triketones, but are preferably compounds containing triazine triketones.

[0063] The above-mentioned compounds containing epoxy groups are preferably compounds represented by the following formula (1).

[0064]

[0065] (In equation (1), X is a divalent organic group as shown in equation (2), equation (3) or equation (4) below, and n1 and n2 each independently represent integers from 1 to 10.)

[0066]

[0067] (In equations (2), (3) and (4),)

[0068] R 1 and R 2 Each of the following can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group can be substituted with at least one monovalent functional group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, and alkylthio groups having 1 to 6 carbon atoms.

[0069] R 3 The term "phenyl" refers to a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group having 3 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group having 3 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent functional group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, alkylthio groups having 1 to 6 carbon atoms, and an organogroup represented by formula (5) below.

[0070]

[0071] (In equation (5), n3 represents an integer from 1 to 10.)

[0072] Examples of alkyl groups having 1 to 10 carbon atoms 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, 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-Di-Cyclobutyl Methyl-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.

[0073] Examples of alkenyl groups with 2 to 10 carbon atoms 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, and 2-methyl-3-butenyl. 1,1-dimethyl-2-butenyl, 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.

[0074] Examples of alkynyl groups with 2 to 10 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-methyl-1-pentynyl, and 3-methyl-1-pentynyl.

[0075] The phrase "can be interrupted by oxygen or sulfur atoms" means that, for example, the carbon atoms contained in the alkyl, alkenyl, and alkynyl groups mentioned above are replaced by oxygen or sulfur atoms. For example, if a carbon atom in an alkyl, alkenyl, or alkynyl group is replaced by an oxygen atom, it becomes an ether bond; if a carbon atom in an alkyl, alkenyl, or alkynyl group is replaced by a sulfur atom, it becomes a thioether bond.

[0076] As an alkyl group having 1 to 6 carbon atoms, it is an alkyl group having 1 to 6 carbon atoms among the aforementioned alkyl groups having 1 to 10 carbon atoms.

[0077] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0078] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 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, 3-methyl-n-pentyloxy, etc. The compounds include 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.

[0079] Examples of alkylthio groups with 1 to 6 carbon atoms include ethylthio, butylthio, and hexylthio.

[0080] In the above formula (1), X is preferably represented by formula (4).

[0081] In the above equation (1), X is preferably represented by equation (4), where n1 and n2 are 1, and R 3 It is an alkyl group with 1 to 5 carbon atoms that can be interrupted by an oxygen atom. In this case, a specific example of an alkyl group with 1 to 5 carbon atoms is an alkyl group with 1 to 5 carbon atoms among the aforementioned alkyl groups with 1 to 10 carbon atoms.

[0082] In the above equation (1), X is preferably represented by equation (4), where n1 and n2 are 1, and R 3 It is a methyl, methoxymethyl, or compound represented by formula (5) with n3 being 1, as shown in formula (A-1), formula (A-7), or formula (A-19).

[0083]

[0084] The compounds represented by formula (1) of this application may be exemplified as shown in formulas (A-1) to (A-21) below, but are not limited thereto.

[0085]

[0086]

[0087] The above-mentioned compounds containing epoxy groups can also be selected from compounds (a) to (s) below. In formula (o), R 0 Indicates alkylene groups having 1 to 10 carbon atoms.

[0088]

[0089] Alternatively, the epoxy-containing compound may be a compound containing three or more epoxy groups, as shown below. Specific examples include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, and isocyanurates containing glycidyl groups. Epoxy-containing compounds used in this invention may be exemplified by the following formulas (A0-1) to (A0-13).

[0090]

[0091] Formula (A0-1) can be obtained by Nissan Chemical Co., Ltd. under the trade names TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, and TEPIC-L (all of which are 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid).

[0092] Formula (A0-2) can be obtained as manufactured by Nissan Chemical Co., Ltd., under the trade name TEPIC-VL.

[0093] Formula (A0-3) can be obtained as manufactured by Nissan Chemical Co., Ltd., under the trade name TEPIC-FL.

[0094] Formula (A0-4) can be obtained as manufactured by Nissan Chemical Co., Ltd., under the trade name TEPIC-UC.

[0095] The formula (A0-5) is available as the brand name of Nastron EX-411 manufactured by Nostalgic Co., Ltd.

[0096] Formula (A0-6) is available as the product name of Nacotron EX-521 manufactured by Nacotech Co., Ltd.

[0097] Formula (A0-7) is available as manufactured by Mitsubishi Gas Chemical Co., Ltd., under the trade name TETRAD-X.

[0098] Formula (A0-8) can be obtained as a product of Showa Denko Co., Ltd., under the trade name BATG.

[0099] Formula (A0-9) can be obtained as a product of Nippon Steel & Sumitomo Metal Chemicals Co., Ltd., under the trade name YH-434L.

[0100] Formula (A0-10) can be obtained as manufactured by Asahi Organic Materials Co., Ltd., under the trade name TEP-G.

[0101] Formula (A0-11) can be obtained as DIC Corporation, under the trade name EPICLON HP-4700.

[0102] The formula (A0-12) can be obtained as Cellulase GT401, a product of Daicel Corporation. It should be noted that a, b, c, and d are each 0 or 1, and a + b + c + d = 1.

[0103] The following epoxy compounds can also be used.

[0104]

[0105] The reaction between the above epoxy group-containing compound and the heterocyclic compound containing one site reactive with the epoxy group can be carried out by a method known per se.

[0106] The above heterocyclic compound is a compound containing the heterocycle described below.

[0107] The above heterocycle is preferably selected from furan, pyrrole, pyran, imidazole, pyrazole, azole, thiophene, thiazole, thiadiazole, imidazolidine, thiazolidine, imidazoline, di ane, morpholine, diazine, thiazine, triazole, tetrazole, dioxolane, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phen azine, xanthene, acridine, phenazine, and carbazole.

[0108] Some of the elements of the above heterocycle can be substituted with substituents such as an alkyl group having 1 to 5 carbon atoms, methylthio group, etc.

[0109] Among them, thiophene, tetrazole, thiazole, and thiadiazole, which have a high dry etching rate of the resist underlayer film, are particularly preferred.

[0110] Preferably, the site reactive with the epoxy group is selected from a hydroxyl group, a thiol group, an amino group, an imide group, and a carboxyl group.

[0111] Among them, the carboxyl group and the thiol group, which have a high dry etching rate of the resist underlayer film, are particularly preferred.

[0112] Specific examples of the heterocyclic compound containing one site reactive with the epoxy group include the compounds described below.

[0113]

[0114]

[0115] The molar ratio (i.e., the former: the latter) of the epoxy group of the compound represented by the above formula (1) to the heterocyclic compound containing one site reactive with the epoxy group during the reaction is, for example, (0.1 to 1): 1. Preferably, it is (0.5 to 1): 1.

[0116] The remaining epoxy group, excluding the reaction saturation, can react with compounds other than those containing one heterocyclic compound that is reactive with the epoxy group (e.g., aromatic and / or aliphatic compounds containing one reactive site with the epoxy group (aromatic carboxylic acids, aromatic thiols, aliphatic carboxylic acids, aromatic thiols, heterocyclic compounds containing two or more reactive sites with the epoxy group, etc.)).

[0117] The compounds containing a site that is reactive with an epoxy group can be exemplified by the following formulas (B-1) to (B-62), but are not limited to them.

[0118]

[0119]

[0120]

[0121] The weight-average molecular weight (Mw) of the reaction products of this application is, for example, 300 to 4,000, 400 to 3,000, or 500 to 2,000.

[0122] [solvent]

[0123] The resist underlayer film forming composition of the present invention can be manufactured by dissolving the above-mentioned components in an organic solvent and used in a homogeneous solution state.

[0124] As a solvent for the resist underlayer film forming composition of the present invention, any solvent capable of dissolving the above-mentioned compound or its reaction products may be used without particular limitation. In particular, since the resist underlayer film forming composition of the present invention is used in a uniform solution state, it is recommended to use it in solvents generally used in photolithography processes, taking into account its coating performance.

[0125] Examples of organic solvents mentioned above include, for instance, 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, and 2-hydroxyisobutyric acid. Methyl acetate, 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 can be used alone or in combination of two or more.

[0126] Preferred solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0127] [Cross-linking catalyst]

[0128] To promote the crosslinking reaction, the resist underlayer film forming composition of the present invention may contain a crosslinking catalyst as an optional component. As this crosslinking catalyst, in addition to acidic compounds and basic compounds, compounds that generate acid or base through heat may also be used. As acidic compounds, sulfonic acid compounds or carboxylic acid compounds may be used; as compounds that generate acid through heat, thermally generated acid agents may be used.

[0129] Examples of sulfonic acid or carboxylic acid compounds include phenol sulfonic acid, p-toluene sulfonic acid, trifluoromethanesulfonic acid, and pyridine. Trifluoromethanesulfonate, pyridine - p-Toluenesulfonate (pyridine) -Phenolsulfonic acid), salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, pyridine -4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, 4-nitrobenzenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid.

[0130] Examples of heat-generating acid agents include, for example, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689 (all manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0131] These crosslinking catalysts can be used in one or in combination of two or more. Furthermore, amine compounds or ammonium hydroxide compounds can be used as basic compounds, and urea can be used as a compound that produces a base through heat.

[0132] Examples of amine compounds include, for example, tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane, as well as aromatic amines such as pyridine and 4-dimethylaminopyridine. Furthermore, primary amines such as benzylamine and n-butylamine, and secondary amines such as diethylamine and di-n-butylamine can also be cited as amine compounds. These amine compounds can be used alone or in combination of two or more.

[0133] Examples of ammonium hydroxide compounds include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide.

[0134] Furthermore, as compounds that produce a base by heat, compounds having thermally unstable groups such as amide, carbamate, or aziridinium groups, which generate amines upon heating, can be used. In addition, urea, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyldimethylphenylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltributylammonium chloride, and choline chloride can also be mentioned as compounds that produce a base by heat.

[0135] When the above-mentioned composition for forming the lower layer of the resist film contains a crosslinking catalyst, its content is 0.0001 to 20% by mass relative to the total solid content of the composition for forming the lower layer of the resist film, preferably 0.01 to 15% by mass, and more preferably 0.1 to 10% by mass.

[0136] Of the above, acidic compounds and / or compounds that generate acid by heat (crosslinked acid catalysts) are preferred.

[0137] [Cross-linking agent]

[0138] The resist underlayer film forming composition of the present invention may include a crosslinking agent component. Examples of such crosslinking agents include melamine-based, substituted urea-based, or polymeric forms thereof. Preferably, the crosslinking agent has at least two crosslinking-forming substituents, and is a compound such as methoxymethylated glycourea (e.g., tetramethoxymethylated glycourea), butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Furthermore, condensates of these compounds may also be used.

[0139] Among them, methoxymethylated glycourea (e.g., tetramethoxymethylglycourea) is preferred.

[0140] Furthermore, as the aforementioned crosslinking agent, a crosslinking agent with high heat resistance can be used. A compound containing crosslinking-forming substituents with aromatic rings (e.g., benzene rings, naphthalene rings) within its molecule can be used as a crosslinking agent with high heat resistance.

[0141] Examples of such compounds include compounds having a partial structure of the following formula (5-1), polymers or oligomers having repeating units of the following formula (5-2).

[0142]

[0143] The above R 11 R 12 R 13 and R 14It is an alkyl group having 1 to 10 carbon atoms or hydrogen atoms. m1, m2, m3, and m4 represent integers from 0 to 3. Examples of alkyl groups having 1 to 10 carbon atoms 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, 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-Di-Cyclobutyl Methyl-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.

[0144] m1 satisfies 1≤m1≤6-m2, m2 satisfies 1≤m2≤5, m3 satisfies 1≤m3≤4-m2, and m4 satisfies 1≤m4≤3.

[0145] The following examples illustrate compounds, polymers, and oligomers of formulas (5-1) and (5-2).

[0146]

[0147] The above-mentioned compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, the compound of formula (6-22) in the above-mentioned crosslinking agent can be obtained as a product of Asahi Organic Materials Co., Ltd., under the trade name TMOM-BP.

[0148] The amount of crosslinking agent added varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80% by mass relative to the total solid content of the composition for forming the resist underlayer film, preferably 0.01 to 50% by mass, and more preferably 0.1 to 40% by mass. These crosslinking agents may sometimes undergo crosslinking reactions caused by self-condensation, but in the case where crosslinking substituents are present in the polymer of the present invention, crosslinking reactions can occur with these crosslinking substituents.

[0149] [surfactant]

[0150] To improve the coating properties of semiconductor substrates, the resist underlayer film forming composition of the present invention may contain a surfactant as an optional component. Examples of such surfactants include, for instance, 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 octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, and sorbitol monooleate. Sorbitol trioleate, sorbitol tristearate, and other sorbitol fatty acid esters; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate, and other polyoxyethylene sorbitol fatty acid esters, as well as nonionic surfactants; EF30 (registered trademark). 1. EFT EF303, EFT EF352 (Mitsubishi Mitsubishi Electronics Co., Ltd. Co., Ltd.), メガファック [registered trademark] F171, メガファック F173, メガファックR -30、メガファックR-30N、メガファックR-40、メガファックR-40-L M (manufactured by DIC Co., Ltd.), Fluoro FC430, Fluoro FC431 (Sumitomo Solar Fluoropolymer surfactants such as Asahi Glass Co., Ltd., Asahi Guard (registered trademark) AG710, Servolon (registered trademark) S-382, Servolon SC101, Servolon SC102, Servolon SC103, Servolon SC104, Servolon SC105, and Servolon SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) are used. Two or more of these surfactants may be used alone or in combination. When the above-mentioned composition for forming the lower layer of the resist contains surfactants, their content is 0.0001 to 10% by mass relative to the total solid content of the composition for forming the lower layer of the resist, preferably 0.01 to 5% by mass.

[0151] The solid content of the resist underlayer film forming composition of the present invention is typically 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content refers to the percentage of all components remaining after removing the solvent from the resist underlayer film forming composition. The proportion of the compound or reaction product of this application in the solid content is preferably in the following order: 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

[0152] [Other ingredients]

[0153] In the resist underlayer film forming composition of the present invention, light absorbers, rheology modifiers, adhesive additives, etc., may be added. Rheology modifiers are effective in improving the flowability of the resist underlayer film forming composition. Adhesive additives are effective in improving the adhesion between the semiconductor substrate or the resist and the underlayer film.

[0154] 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 mixed in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solid components of the composition for forming the resist underlayer film.

[0155] Rheology modifiers are mainly added to improve the flowability of the composition for forming the lower layer of the resist film, especially in the baking process, to improve the uniformity of the film thickness of the lower layer of the resist film and to improve the filling ability of the composition for forming the lower layer of the resist film into the cavities. 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 composition for forming the resist underlayer film.

[0156] Adhesion aids are mainly added to improve the adhesion between the substrate or resist and the composition used to form the underlying film of the resist, especially during development to prevent the resist from peeling off. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylhydroxymethylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylhydroxymethylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium; silanes such as hydroxymethyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-epoxypropoxypropyltrimethoxysilane; and 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 formulated in proportions of less than 5% by mass, preferably less than 2% by mass, relative to the total solids content of the composition for forming the resist underlayer.

[0157] [Methods for manufacturing a resist underlayer, a patterned substrate, and a semiconductor device]

[0158] Hereinafter, a method for manufacturing a photoresist underlayer film using the photoresist underlayer film forming composition of the present invention, a method for manufacturing a patterned substrate, and a method for manufacturing a semiconductor device will be described.

[0159] (Resist underlayer film)

[0160] The resist underlayer film of the present invention can be manufactured by coating the above-mentioned resist underlayer film forming composition onto a semiconductor substrate and then firing it.

[0161] Examples of semiconductor substrates for coating the resist underlayer film formation composition of the present invention include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0162] When using a semiconductor substrate on which an inorganic film is formed on its surface, this inorganic film is formed, for example, by ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (spin-coated glass: SOG). Examples of such inorganic films include, for instance, polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho Silicate Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0163] On such a semiconductor substrate, the resist underlayer film formation composition of the present invention is coated using a suitable coating method such as a spin coater or a coating machine. Then, the resist underlayer film is formed by baking using a heating means such as a hot plate. Baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes; more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0164] The thickness of the formed photoresist underlayer is, for example, 0.001 μm (1 nm) to 10 μm, preferably 0.002 μm (2 nm) to 1 μm, and more preferably 0.005 μm (5 nm) to 0.5 μm (500 nm). Crosslinking becomes insufficient when the baking temperature is below the above range. On the other hand, when the baking temperature is above the above range, the photoresist underlayer may sometimes decompose due to heat.

[0165] (A method for manufacturing a substrate with patterned substrates)

[0166] The method for manufacturing a patterned substrate involves the following steps. Typically, a photoresist layer is formed on a photoresist underlayer. As for the photoresist formed by coating and firing on the photoresist underlayer using methods known to the public, there are no particular limitations as long as it is a photosensitive substance used for exposure. Both negative and positive photoresists can be used. Examples include: positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazonyl sulfonate; chemically amplified photoresists composed of binders and photoacid-generating agents that increase the rate of alkali dissolution through acid decomposition; chemically amplified photoresists composed of low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition, alkali-soluble binders, and photoacid-generating agents; and chemically amplified photoresists composed of binders that increase the rate of alkali dissolution through acid decomposition, low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition, and photoacid-generating agents. Examples include JSR Corporation's product V146G, Shiplay Corporation's product APEX-E, Sumitomo Chemical Industries Co., Ltd.'s product PAR710, and Shin-Etsu Chemical Industries Co., Ltd.'s products AR2772 and SEPR430. In addition, examples of fluorinated atom polymer photoresists can be cited, for instance, as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0167] Exposure is performed using a mask (photomask) to form a prescribed pattern, employing, for example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (ultraviolet light), or EB (electron ray). Development is performed using an alkaline developer, with a development temperature appropriately selected from 5°C to 50°C and a development time from 10 seconds to 300 seconds. As an alkaline developer, aqueous solutions of bases such as inorganic bases (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia), primary amines (e.g., ethylamine, n-propylamine), secondary amines (e.g., diethylamine, di-n-butylamine), tertiary amines (e.g., triethylamine, methyldiethylamine), alkanolamines (e.g., dimethylethanolamine, triethanolamine), quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide), cyclic amines (e.g., choline), and cyclic amines (e.g., pyrrole, piperidine) can also be used. Furthermore, appropriate amounts of alcohols such as isopropanol or nonionic surfactants can be added to the aforementioned aqueous solutions of alkaline bases. Preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants may be added to these developers. Alternatively, organic solvents such as butyl acetate may be used instead of alkaline developers to develop the portions of the photoresist whose alkaline dissolution rate has not been increased. Through the above processes, a substrate patterned with the aforementioned photoresist can be manufactured.

[0168] Next, using the formed resist pattern as a mask, the underlying resist film is dry-etched. At this time, if the inorganic film is formed on the surface of the semiconductor substrate, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate, the surface of the semiconductor substrate is exposed. Then, by processing the substrate using a method known in itself (such as dry etching), a semiconductor device can be manufactured.

[0169] Example

[0170] The weight-average molecular weight (Mw) of the polymers shown in the following synthesis examples in this specification is the result obtained by gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus manufactured by Higasoo Co., Ltd., and the determination conditions are as follows.

[0171] GPC pillars: Shodex (registered trademark) · Asahipak (registered trademark) (Showa Denko Co., Ltd.)

[0172] Column temperature: 40℃

[0173] Solvent: Tetrahydrofuran (THF)

[0174] Flow rate: 0.35 ml / min

[0175] Standard sample: Polystyrene (Tosoo Corporation)

[0176] (Synthesis of raw material monomers)

[0177] <Synthesis example 1>

[0178] Add 38.70 g of tricarboxymethyl isocyanuric acid (TAICA), synthesized according to the method described in US Patent No. 3230220; 300.00 g of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.); 70.91 g of allyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.); and 79.38 g of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.). Heat to 80-90°C. Then, allow the reaction to proceed for 2 hours until the reaction reaches a constant volume. After the reaction is complete, add 580.50 g of toluene (manufactured by Kanto Chemical Co., Ltd.). Filter and wash three times with 580.50 g of water. After concentrating and drying the organic layer, add 387.00 g of ethanol (manufactured by Kanto Chemical Co., Ltd.), and stir at 20-30°C for 30 minutes. After stirring, the mixture was filtered and the resulting crystals were dried, yielding 44.32 g of the target product (tartary propyl acetate isocyanuric acid: TAAICA) as shown in formula (A1-1) in a yield of 85.2%.

[0179]

[0180] <Synthesis example 2>

[0181] 44.32 g of TAAICA synthesized in Synthesis Example 1 and 443.20 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added, followed by 125.06 g of m-chloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). The reaction was carried out for 47 hours. After the reaction was completed, 88.64 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) was added. The mixture was then washed with 886.40 g of 5% sodium bicarbonate (manufactured by Kanto Chemical Co., Ltd.). Next, it was washed with 443.20 g of 10% sodium sulfite (manufactured by Kanto Chemical Co., Ltd.) and 886.40 g of 5% sodium bicarbonate (manufactured by Kanto Chemical Co., Ltd.), and further washed twice with 443.20 g of water. After concentration, column purification was performed. After column purification, 41.31 g of the target product (triglycidyl acetate isocyanuric acid: TAGICA) shown in formula (A1-2) was obtained in a yield of 83.7%.

[0182]

[0183] <Synthesis Example 3>

[0184] The TAGICA 5.00 g, 2-mercapto-5-methylthio-1,3,4-thiadiazole 5.22 g, and ethyltriphenyl bromide obtained in Synthesis Example 2 were compared. 0.41 g of propylene glycol monomethyl ether was added to a reaction flask containing 42.05 g of propylene glycol monomethyl ether. The mixture was heated and stirred at 105 °C for 23 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (A1-3). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 1000.

[0185]

[0186] <Synthesis example 4>

[0187] The TAGICA 5.00 g, 2-mercapto-1,3,4-thiadiazole 3.82 g, and ethyltriphenyl bromide obtained in Synthesis Example 2 were compared. 0.41 g of propylene glycol monomethyl ether was added to a reaction flask containing 36.91 g of propylene glycol monomethyl ether. The mixture was heated and stirred at 105 °C for 4 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (A1-4). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 850.

[0188]

[0189] <Synthesis Example 5>

[0190] The TAGICA 5.00 g, 2-mercapto-5-methyl-1,3,4-thiadiazole 4.20 g, and ethyltriphenyl bromide obtained in Synthesis Example 2 were compared. In a reaction flask containing 0.41 g of propylene glycol monomethyl ether and 38.42 g of propylene glycol monomethyl ether, the mixture was heated and stirred at 105 °C for 22 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (A1-5). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 800.

[0191]

[0192] <Synthesis example 6>

[0193] The TAGICA 5.00 g, 5-mercapto-1-methyltetrazole 3.69 g, and ethyltriphenyl bromide obtained in Synthesis Example 2 were compared. 0.41 g of propylene glycol monomethyl ether was added to a reaction flask containing 36.37 g of propylene glycol monomethyl ether. The mixture was heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (A1-6). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 800.

[0194]

[0195] <Synthesis Example 7>

[0196] The TAGICA 5.00 g, 1H-tetrazole-1-acetic acid 4.07 g, and ethyltriphenyl bromide obtained in Synthesis Example 2 were compared. In a reaction flask containing 37.89 g of propylene glycol monomethyl ether, 0.41 g of the product was added and heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (A1-7). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 850.

[0197]

[0198] <Synthesis example 8>

[0199] 10.00 g of methyl isocyanuric acid (Me-ICA) synthesized according to the method described in Patent Publication (WO2017 / 208910), 14.49 g of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), 20.48 g of allyl chloroacetate (manufactured by Artrich), and 40.00 g of N,N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) were added, and the mixture was stirred at 60°C for 25 hours. 100.00 g of toluene (manufactured by Kanto Chemical Co., Ltd.) was added, and the mixture was filtered. 100.00 g of water was added, and the mixture was separated at 50°C. Another 100.00 g of water was added to the resulting organic layer, and the mixture was separated at 50°C. By concentrating the resulting organic layer, 20.51 g of the target product (methyl diallyl acetate isocyanuric acid: Me-DAAICA) shown in formula (B1-1) was obtained in a yield of 86.5%.

[0200]

[0201] <Synthesis Example 9>

[0202] 20.51 g of Me-DAAICA obtained in Synthesis Example 8 and 153.83 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added, followed by 38.52 g of m-chloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). The reaction was carried out for 71 hours until the reaction reached a constant volume. After the reaction was completed, 205.10 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) and 410.20 g of 5% sodium bicarbonate (manufactured by Kanto Chemical Co., Ltd.) were added. The mixture was separated, and 205.10 g of 10% sodium sulfite (manufactured by Kanto Chemical Co., Ltd.) was added to the resulting organic layer. The mixture was separated again, and 410.20 g of 5% sodium bicarbonate (manufactured by Kanto Chemical Co., Ltd.) was added to the resulting organic layer. Then, the mixture was separated, and 205.10 g of water was added to the resulting organic layer for two washes. After the organic layer was concentrated and dried, column purification was performed to obtain 10.46 g of the target product (methyl diglycidyl acetate isocyanuric acid: Me-DAGICA) shown in formula (B1-2) in a yield of 46.6%.

[0203]

[0204] <Synthesis Example 10>

[0205] The ingredients obtained in Synthesis Example 9 were Me-DAGICA 5.00 g, 2-mercapto-5-methylthio-1,3,4-thiadiazole 4.60 g, and ethyltriphenyl bromide. In a reaction flask containing 0.13 g of propylene glycol monomethyl ether and 38.91 g of propylene glycol monomethyl ether, the mixture was heated and stirred at 105 °C for 23 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (B1-3). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 600.

[0206]

[0207] <Synthesis Example 11>

[0208] The TAGICA 5.00 g, thiazol-4-carboxylic acid 4.10 g, and ethyltriphenyl bromide obtained in Synthesis Example 2 In a reaction flask containing 38.02 g of propylene glycol monomethyl ether, 0.41 g of the product was added and heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (A1-8). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 1200.

[0209]

[0210] <Synthesis Example 12>

[0211] The TAGICA 5.00 g, 2-mercaptothiazole 3.72 g, and ethyltriphenyl bromide obtained in Synthesis Example 2 were compared. 0.41 g of propylene glycol monomethyl ether was added to a reaction flask containing 36.50 g of propylene glycol monomethyl ether. The mixture was heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere to obtain a reaction product equivalent to formula (A1-9). The weight-average molecular weight (Mw) obtained by GPC and converted to polystyrene was 760.

[0212]

[0213] (Composition Modulation)

[0214] [Example 1]

[0215] In Synthesis Example 3, 1.23 g of a solution containing 0.23 g of the reaction product was mixed with 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40) to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0216] [Example 2]

[0217] In Synthesis Example 4, 1.23 g of a solution containing 0.23 g of the reaction product was added to 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40) to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0218] [Example 3]

[0219] In Synthesis Example 5, 1.23 g of a solution containing 0.23 g of the reaction product was prepared by adding 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40). The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0220] [Example 4]

[0221] In Synthesis Example 6, 1.23 g of a solution containing 0.23 g of the reaction product was prepared by adding 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40). The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0222] [Example 5]

[0223] In Synthesis Example 7, 1.23 g of a solution containing 0.23 g of the reaction product was added to 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40) to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0224] [Example 6]

[0225] In Synthesis Example 10, a solution containing 0.23 g of the reaction product was prepared by adding 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40). The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0226] [Example 7]

[0227] In Synthesis Example 11, 1.23 g of a solution containing 0.23 g of the reaction product was prepared by adding 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40). The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0228] [Example 8]

[0229] In Synthesis Example 12, 1.23 g of a solution containing 0.23 g of the reaction product was added to 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.001 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40) to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0230] [Comparative Example 1]

[0231] A solution containing 0.72 g of the reaction product was obtained by the method described in Synthesis Example 1 of WO2009 / 096340. 88.43 g of propylene glycol monomethyl ether, 9.90 g of propylene glycol monomethyl ether acetate, 0.18 g of tetramethoxymethyl urea (Nippon Saitek Indistries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174), 0.01 g of phenol sulfonic acid (Tokyo Kasei Corporation), and 0.01 g of surfactant (Dai Nippon Inki Chemical Co., Ltd., trade name: R-40) were added to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist lower film.

[0232] (Determination of dry etching rate)

[0233] The resist underlayer film forming compositions prepared in Examples 1-8 and Comparative Example 1 were respectively coated onto silicon wafers using a spin coater and baked on a hot plate at 205°C for 1 minute to form resist underlayer films with a thickness of 100 nm. The dry etching rate (the amount of film thickness reduction per unit time) was measured using a Samco (RIE-10NR) dry etching apparatus with CF4 as the dry etching gas. Table 1 shows the etch selectivity of each underlayer film with an etch selectivity of 1.00 for the resist underlayer film obtained from Comparative Example 1.

[0234] [Table 1]

[0235] Table 1

[0236]

[0237] The results above show that Examples 1-8 have sufficiently high etch selectivity compared to Comparative Example 1. Consequently, the composition for forming the resist underlayer film obtained by the present invention can shorten the etching time during dry etching of the resist underlayer film, and can suppress the undesirable phenomenon of resist film thickness reduction when the resist underlayer film is removed by dry etching. Furthermore, since the dry etching time can be shortened and undesirable etching damage to the substrate of the resist underlayer film can be suppressed, it is particularly useful as a resist underlayer film.

[0238] (Evaluation of optical parameters)

[0239] The resist underlayer film forming compositions prepared in Examples 1-8 and Comparative Example 1 described in this specification were respectively coated onto silicon wafers using a spin coater. The coated silicon wafers were then heated on a hot plate at 205°C for 1 minute to form a resist underlayer film forming composition (film thickness 30 nm). Furthermore, the n-value (refractive index) and k-value (attenuation coefficient or absorption coefficient) of these resist underlayer film forming compositions were measured at a wavelength of 193 nm using a spectroscopic ellipsometry (product name: VUV-VASE VU-302, manufactured by JAWoollam). The results of the optical parameter measurements are shown in Table 2.

[0240] [Table 2]

[0241] Table 2

[0242]

[0243] Industry availability

[0244] The composition for forming a resist underlayer film according to the present invention provides a resist underlayer film with a particularly high dry etching rate.

Claims

1. A composition for forming a resist underlayer film, comprising: Compounds containing an epoxy group, and reaction products of heterocyclic compounds containing a site reactive with the epoxy group; and solvent, The epoxy-containing compound is a compound represented by formula (A-1), formula (A-7), or formula (A-19). The heterocyclic compound containing one site reactive with an epoxy group is selected from Chemical 20 and Chemical 21 below, or the heterocycle contained in the heterocyclic compound containing one site reactive with an epoxy group is selected from furan, pyrrole, pyran, imidazole, pyrazole, etc. azole, thiophene, thiazole, thiadiazole, imidazoline, thiazoline, imidazoline Alkane, Morpholine, Diazine, Thiazide, Triazole, Tetrazol, Dioxolane, Pyrimidine, Pyrazine, Piperidine, Piperazine, Indole, Purine, Quinoline, Isoquinoline, Quinine Ring, Chromene, Thianthracene, Phenothiazine, Phenylene Azine, xanthan, acridine, phenazine, and carbazole, 20 2. The composition for forming a lower layer of resist film according to claim 1, wherein the molar ratio of the epoxy group of the epoxy-containing compound to the molar ratio of the heterocyclic compound containing a site reactive with the epoxy group is (0.1 to 1):

1.

3. The composition for forming a lower layer of resist film according to claim 2, wherein the molar ratio during the reaction is (0.5 to 1):

1.

4. The composition for forming a lower layer of resist film according to claim 1, wherein the site reactive with the epoxy group is selected from hydroxyl, thiol, amino, imide and carboxyl groups.

5. The composition for forming a resist underlayer film according to claim 1, comprising at least one selected from crosslinking agents, crosslinking catalysts, and surfactants.

6. A resist underlayer film, characterized in that, It is a sintered product of a coating film formed from the composition for forming a resist underlayer film according to any one of claims 1 to 5.

7. 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 5 onto a semiconductor substrate and baking it to form a resist underlayer film; coating a resist onto the resist underlayer film and baking it to form a resist film; exposing the semiconductor substrate covered with the resist underlayer film and the resist; and developing the exposed resist film to form a pattern.

8. A method for manufacturing a semiconductor device, characterized in that, Includes the following processes: A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film according to any one of claims 1 to 5; The process of forming a resist film on the lower resist film; The process of irradiating a resist film with light or electron beams and then developing it to form a resist pattern; The process of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; and The process of processing a semiconductor substrate using the patterned resist underlayer film.

9. The reaction product of a compound represented by formula (A-1), formula (A-7), or formula (A-19) with a heterocyclic compound containing a site reactive with an epoxy group, The heterocyclic compound containing one site reactive with an epoxy group is selected from Chemical 20 and Chemical 21 below, or the heterocycle contained in the heterocyclic compound containing one site reactive with an epoxy group is selected from furan, pyrrole, pyran, imidazole, pyrazole, etc. azole, thiophene, thiazole, thiadiazole, imidazoline, thiazoline, imidazoline Alkane, Morpholine, Diazine, Thiazide, Triazole, Tetrazol, Dioxolane, Pyrimidine, Pyrazine, Piperidine, Piperazine, Indole, Purine, Quinoline, Isoquinoline, Quinine Ring, Chromene, Thianthracene, Phenothiazine, Phenylene Azine, xanthan, acridine, phenazine, and carbazole, 20 Chemical 21

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