Resist underlayer film forming composition containing heterocyclic compounds

Abstract

Provided are: a resist underlayer film having an especially high dry etching rate; a composition for forming the resist underlayer film; a method for forming a resist pattern; and a method for producing a semiconductor device. The composition for forming the resist underlayer film comprises a solvent and a product of reaction between an epoxidized compound and a heterocyclic compound containing at least one moiety having reactivity with an epoxy group. It is preferable that the heteroring contained in the heterocyclic compound be selected from among 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, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole.

Description

[Technical Field]

[0001] The present invention relates in particular to a resist underlayer film forming composition having a high dry etching rate, a resist underlayer film using the resist underlayer film forming composition, 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 resist film is exposed to light, reflected waves can sometimes adversely affect the resist film. The underlayer film formed to suppress this effect is also called an anti-reflective coating.

[0003] The resist underlayer film must be easily formed by applying a solution-type resist underlayer film-forming composition and curing it. Therefore, the composition must contain a compound (polymer) that cures easily by heating or other means and has high solubility in a predetermined solvent.

[0004] The resist pattern formed on the resist underlayer film should preferably have a rectangular cross-sectional shape in the direction perpendicular to the substrate (a straight bottom shape without so-called undercuts or drooping). For example, if the resist pattern has an undercut or drooping shape, problems may arise such as the collapse of the resist pattern or the inability to process the workpiece (substrate, insulating film, etc.) into the desired shape or size during the lithography process.

[0005] Furthermore, the underlying resist film is required to have a higher dry etching rate than the upper resist film, i.e., a higher selectivity ratio for dry etching rates.

[0006] Patent Document 1 discloses a resist underlayer film forming composition using a polymer having a disulfide bond in its main chain. Patent Document 2 discloses an epoxy compound having a glycidyl ester group. Patent Document 3 discloses an anti-reflective film forming composition characterized by containing a triazinetrione compound, oligomer compound, or polymer compound having a hydroxyalkyl structure as a substituent on the nitrogen atom. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Re-tabled publication No. 2009-096340 [Patent Document 2] Japanese Patent Application Publication No. 8-81461 [Patent Document 3] Retable No. 2004-034148 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] In semiconductor device manufacturing, there is still a demand for resist underlayer films with high dry etching rates. It is known that using polymers containing heteroatoms in the composition of a resist underlayer film with a high dry etching rate is effective.

[0009] As a result of diligent research by the inventors of this application, it has been found that when a reaction product of an epoxy group-containing compound, preferably a glycidyl ester group-containing compound, preferably a nitrogen-containing heterocyclic compound having a glycidyl ester group (such as isocyanuric acid), and a heterocyclic compound containing one moiety that is reactive with an epoxy group is applied to a resist underlayer film-forming composition, a higher etch rate can be achieved compared to the prior art.

[0010] In view of solving the above problems, the present invention aims to provide a resist underlayer film forming composition having a particularly high dry etching rate. The present invention also aims to provide a resist underlayer film using the resist underlayer film forming composition, a method for manufacturing the same, a method for forming a resist pattern, and a method for manufacturing a semiconductor device. [Means for solving the problem]

[0011] This invention encompasses the following:

[0012] [1] A resist underlayer film forming composition comprising a reaction product of an epoxy group-containing compound and a heterocyclic compound containing one moiety reactive with an epoxy group, and a solvent.

[0013] [2] The resist underlayer film forming composition according to [1], wherein the heterocycle contained in the above heterocyclic compound is selected from 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, thiantrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole.

[0014] [3] A resist underlayer film forming composition according to [1] or [2], wherein the site that reacts with the epoxy group is selected from a hydroxyl group, a thiol group, an amino group, an imide group, and a carboxyl group.

[0015] [4] The resist underlayer film forming composition according to any one of claims 1 to 3, wherein the epoxy group-containing compound is a compound represented by the following formula (1).

[0016] [Chemical formula] (In formula (1), X is a divalent organic group represented by the following formula (2), formula (3) or formula (4), and n1 and n2 each independently represent an integer from 1 to 10.) [Chemical formula] (In formula (2), formula (3) and formula (4), R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms which may be interrupted by a hydrogen atom, an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group or a phenyl group, and the phenyl group may be substituted with at least one monovalent functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group and an alkylthio group having 1 to 6 carbon atoms.)

[0017] R 3 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, an alkenyl group having 3 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 3 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group or a phenyl group, and the phenyl group may be substituted with at least one monovalent functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms and an organic group represented by the following formula (5).) [Chemical formula] (In formula (5), n3 represents an integer from 1 to 10.)

[0018] [5] Furthermore, the resist underlayer film forming composition according to any one of [1] to [4], comprising at least one selected from the group consisting of a crosslinking agent, a crosslinking catalyst, and a surfactant.

[0019] [6] A resist underlayer film characterized by being a fired product of a coated film made from any one of the resist underlayer film forming compositions described in [1] to [5].

[0020] [7] A method for manufacturing a patterned substrate, comprising the steps of: applying a resist underlayer forming composition described in any one of [1] to [5] onto a semiconductor substrate and baking it to form a resist underlayer; applying a resist onto the resist underlayer and baking it to form a resist film; exposing the semiconductor substrate covered with the resist underlayer and the resist; and developing and patterning the resist film after exposure.

[0021] [8] A step of forming a resist underlayer on a semiconductor substrate, comprising a resist underlayer forming composition according to any one of items [1] to [5], 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 an electron beam and then developing it, A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, A process of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the following:

[0022] [9] A reaction product of a compound represented by the following formula (1) and a heterocyclic compound containing one site that is reactive with an epoxy group.

[0023] [ka] (In formula (1), X is a divalent organic group represented by formula (2), formula (3), or formula (4) below, and n1 and n2 each independently represent an integer from 1 to 10.) [ka] (In equations (2), (3), and (4), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 10 carbon atoms that may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms that may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms that may be interrupted by an oxygen atom or a 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 the group consisting of 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.

[0024] R 3 This represents an alkyl group having 1 to 10 carbon atoms that may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom; an alkenyl group having 3 to 10 carbon atoms that may be interrupted by an oxygen atom or a sulfur atom; an alkynyl group having 3 to 10 carbon atoms that may be interrupted by an oxygen atom or a sulfur atom; a benzyl group; or a phenyl group. The phenyl group may be substituted with at least one monovalent functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms, and an organic group represented by the following formula (5). [ka] (In equation (5), n3 represents an integer between 1 and 10.) [Effects of the Invention]

[0025] The resist underlayer film forming composition of the present invention has a high dry etching rate, can solve various problems caused by thinning of the resist film thickness, and enables finer microfabrication of semiconductor substrates. [Modes for carrying out the invention]

[0026] <Reaction product of a resist underlayer film-forming composition, an epoxy group-containing compound, and a heterocyclic compound containing one moiety that is reactive with an epoxy group> The resist underlayer film forming composition of the present invention comprises a reaction product of an epoxy group-containing compound and a heterocyclic compound containing one moiety that is reactive with an epoxy group, and a solvent.

[0027] The epoxy group-containing compound is not limited as long as it can achieve the above objective, but is preferably a glycidyl ester group-containing compound, and more preferably a nitrogen-containing heterocyclic compound having a glycidyl ester group (such as isocyanuric acid).

[0028] The epoxy group-containing compound may be, for example, a compound containing an aromatic ring structure with 6 to 40 carbon atoms, a compound containing a triazineone, a compound containing a triazinedione, or a compound containing a triazinetrione, but a compound containing a triazinetrione is preferred.

[0029] The epoxy group-containing compound described above is preferably a compound represented by the following formula (1).

[0030] [ka] (In formula (1), X is a divalent organic group represented by formula (2), formula (3), or formula (4) below, and n1 and n2 each independently represent an integer from 1 to 10.) [ka] (In equations (2), (3), and (4), R 1 and R 2represents, independently of each other, an alkyl group having 1 to 10 carbon atoms which may be interrupted by a hydrogen atom, an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group or a phenyl group, and the phenyl group may be substituted with at least one monovalent functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group and an alkylthio group having 1 to 6 carbon atoms.

[0031] R 3 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, an alkenyl group having 3 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 3 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group or a phenyl group, and the phenyl group may be substituted with at least one monovalent functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, an alkylthio group having 1 to 6 carbon atoms and an organic group represented by the following formula (5).)

Chemical formula

[0032] Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. ,cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2 -dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group.

[0033] Alkenyl groups having 2 to 10 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2- Ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group , 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i- Examples include propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0034] Examples of alkynyl groups having 2 to 10 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 4-methyl-1-pentynyl group, and 3-methyl-1-pentynyl group.

[0035] The phrase "may be interrupted by an oxygen atom or a sulfur atom" means, for example, that the carbon atoms in the alkyl group, alkenyl group, and alkynyl group are replaced by an oxygen atom or a sulfur atom. For example, if a carbon atom in an alkyl group, alkenyl group, or alkynyl group is replaced by an oxygen atom, it will contain an ether bond. For example, if a carbon atom in an alkyl group, alkenyl group, or alkynyl group is replaced by a sulfur atom, it will contain a thioether bond.

[0036] The alkyl group having 1 to 6 carbon atoms is one of the alkyl groups having 1 to 10 carbon atoms as described above, specifically the alkyl group having 1 to 6 carbon atoms.

[0037] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0038] Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-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, and 3-methyl Examples include ru-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.

[0039] Examples of alkylthio groups having 1 to 6 carbon atoms include ethylthio groups, butylthio groups, and hexylthio groups.

[0040] In formula (1) above, it is preferable that X is represented by formula (4).

[0041] In equation (1) above, X is expressed by equation (4), n1 and n2 are 1, and R 3 It is preferable that the alkyl group has 1 to 5 carbon atoms, which may be interrupted by oxygen atoms. In this case, a specific example of an alkyl group having 1 to 5 carbon atoms is an alkyl group having 1 to 5 carbon atoms from the above-mentioned alkyl groups having 1 to 10 carbon atoms.

[0042] In equation (1) above, X is expressed by equation (4), n1 and n2 are 1, and R 3 It is preferable that the compound is represented by formula (A-1), formula (A-7), or formula (A-19), where n3 is 1, and is represented by a methyl group, a methoxymethyl group, or formula (5).

[0043] [ka] [ka] [ka]

[0044] The compounds represented by formula (1) of this application include, but are not limited to, the following formulas (A-1) to (A-21).

[0045] [ka] [ka] [ka]

[0046] The epoxy group-containing compound mentioned above may be selected from the following compounds (a) to (s). In formula (o), R 0 This represents an alkylene group with 1 to 10 carbon atoms.

[0047] [ka]

[0048] Furthermore, the epoxy group-containing compound may be a compound containing three or more epoxy groups as shown below. Specific examples include glycidyl ether compounds, glycidyl ester compounds, glycidylamine compounds, and glycidyl group-containing isocyanurates. Examples of epoxy group-containing compounds used in the present invention include the following formulas (A0-1) to (A0-13).

[0049] [ka] [ka]

[0050] Formula (A0-1) is available from Nissan Chemical Corporation under the trade names TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, and TEPIC-L (all containing 1,3,5-tris(2,3-epoxypropyl)isocyanuric acid).

[0051] Formula (A0-2) is manufactured by Nissan Chemical Corporation and is available under the trade name TEPIC-VL.

[0052] Formula (A0-3) is manufactured by Nissan Chemical Corporation and is available under the trade name TEPIC-FL.

[0053] Formula (A0-4) is manufactured by Nissan Chemical Corporation and is available under the trade name TEPIC-UC.

[0054] Formula (A0-5) is manufactured by Nagase Chemtec Co., Ltd. and is available under the product name Denacol EX-411.

[0055] Formula (A0-6) is manufactured by Nagase Chemtec Co., Ltd. and is available under the product name Denacol EX-521.

[0056] Formula (A0-7) is manufactured by Mitsubishi Gas Chemical Company, Inc. and is available under the trade name TETRAD-X.

[0057] Formula (A0-8) is manufactured by Showa Denko Corporation and is available under the product name BATG.

[0058] Formula (A0-9) is manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. and is available under the trade name YH-434L.

[0059] Formula (A0-10) is manufactured by Asahi Organic Chemicals Co., Ltd. and is available under the product name TEP-G.

[0060] Formula (A0-11) is available from DIC Corporation under the product name EPICLON HP-4700.

[0061] Formula (A0-12) can be obtained from Daicel Corporation under the product name Epollead GT401. Note that a, b, c, and d are each either 0 or 1, and a+b+c+d=1.

[0062] The following epoxy compounds may also be used.

[0063] [ka]

[0064] The reaction between the epoxy group-containing compound and the heterocyclic compound containing one site reactive with the epoxy group can be carried out by methods that are already known.

[0065] The above heterocyclic compound is a compound containing the heterocyclic ring described below.

[0066] The above heterocycle is preferably selected from 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, thiantrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, and carbazole.

[0067] Some of the elements in the above heterocycle may be substituted with substituents such as C1-C5 alkyl groups or methylthio groups.

[0068] Among these, it is preferable to select from thiophene, tetrazole, thiazole, and thiadiazole, which have a particularly fast dry etching rate of the resist underlayer film.

[0069] It is preferable that the site that reacts with the epoxy group is selected from a hydroxyl group, a thiol group, an amino group, an imide group, and a carboxyl group.

[0070] Among these, carboxyl groups and thiol groups are particularly preferred because they increase the dry etching rate of the resist underlayer film.

[0071] Specific examples of heterocyclic compounds containing one site that is reactive with an epoxy group include the compounds listed below.

[0072] [ka] [ka]

[0073] The ratio of moles (i.e., former:latter) of the epoxy group of the compound represented by formula (1) to the heterocyclic compound containing one site reactive with the epoxy group in the reaction is, for example, (0.1 to 1):1. Preferably, it is (0.5 to 1):1.

[0074] The remaining epoxy groups, other than the reaction equivalent, may have reacted with compounds other than heterocyclic compounds containing one moiety that reacts with the epoxy group (for example, aromatic and / or aliphatic compounds containing moieties that react with the epoxy group, such as aromatic carboxylic acids, aromatic thiols, aliphatic carboxylic acids, aromatic thiols, and heterocyclic compounds containing two or more moieties that react with the epoxy group).

[0075] Compounds containing a moiety reactive with the epoxy group described above can be exemplified by the following formulas (B-1) to (B-62), but are not limited to these.

[0076] [ka] [ka] [ka] [ka]

[0077] The weight-average molecular weight (Mw) of the reaction product of this application is, for example, 300 to 4,000, 400 to 3,000, or 500 to 2,000.

[0078] [solvent] The resist underlayer film forming composition of the present invention can be manufactured by dissolving each of the above components in an organic solvent and is used in a homogeneous solution state.

[0079] The solvent used in the resist underlayer film forming composition according to the present invention is not particularly limited, as long as it is a solvent capable of dissolving the above compound or its reaction product. In particular, since the resist underlayer film forming composition according to the present invention is used in a uniform solution state, it is recommended to use a solvent commonly used in lithography processes in combination, considering its coating performance.

[0080] Examples of the aforementioned organic solvents 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, and cyclohexanoyl ether. Examples of solvents include cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 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 individually or in combination of two or more.

[0081] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0082] [Crosslinking catalyst] The resist underlayer film forming composition of the present invention may optionally contain a crosslinking catalyst to promote the crosslinking reaction. As the crosslinking catalyst, in addition to acidic compounds and basic compounds, compounds that generate an acid or base upon heating can be used. As the acidic compound, a sulfonic acid compound or a carboxylic acid compound can be used, and as the compound that generates an acid upon heating, a thermal acid generator can be used.

[0083] Examples of sulfonic acid compounds or carboxylic acid compounds include phenolsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium trifluoromethanesulfonate, pyridinium-p-toluenesulfonate (pyridinium-p-phenolsulfonic acid), salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, pyridinium-4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, 4-nitrobenzenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0084] Examples of thermal acid generating agents include K-PURE® CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG2689 (all manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0085] These crosslinking catalysts can be used individually or in combination of two or more. Furthermore, amine compounds or ammonium hydroxide compounds can be used as the basic compound, and urea can be used as the compound that generates a base upon heating.

[0086] Examples of amine compounds include tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, trin-normal propylamine, triisopropylamine, trin-normal butylamine, tri-tert-butylamine, trin-normal octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane, as well as aromatic amines such as pyridine and 4-dimethylaminopyridine. Primary amines such as benzylamine and n-butylamine, and secondary amines such as diethylamine and din-normal butylamine are also examples of amine compounds. These amine compounds can be used individually or in combination of two or more.

[0087] Examples of ammonium hydroxide compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide.

[0088] Furthermore, as compounds that generate bases upon heating, for example, compounds having thermally unstable groups such as amide groups, urethane groups, or aziridine groups that produce amines upon heating can be used. Other examples of compounds that generate bases upon heating include urea, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyldimethylphenylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltributylammonium chloride, and collinchloride.

[0089] If the resist underlayer film forming composition contains a crosslinking catalyst, its content is 0.0001 to 20% by mass, preferably 0.01 to 15% by mass, and more preferably 0.1 to 10% by mass, relative to the total solid content of the resist underlayer film forming composition.

[0090] Among the above, acidic compounds and / or compounds that generate acid upon heating (crosslinked acid catalysts) are preferred.

[0091] [Crosslinking agent] The resist underlayer film forming composition of the present invention may contain a crosslinking agent component. Examples of such crosslinking agents include melamine-based, substituted urea-based, or polymer-based versions thereof. Preferably, the crosslinking agent has at least two crosslinking substituents and is a compound such as methoxymethylated glycoluryl (e.g., tetramethoxymethyl glycoluryl), butoxymethylated glycoluryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds can also be used.

[0092] Among these, methoxymethylated glycoluryl (e.g., tetramethoxymethyl glycoluryl) is preferred.

[0093] Furthermore, a highly heat-resistant crosslinking agent can be used as the crosslinking agent. As a highly heat-resistant crosslinking agent, a compound containing a crosslinking substituent having an aromatic ring (e.g., a benzene ring, a naphthalene ring) in its molecule can be used.

[0094] Examples of this compound include compounds having the substructure of formula (5-1) below, or polymers or oligomers having the repeating unit of formula (5-2) below.

[0095] [ka]

[0096] The above R 11 , R 12 , R 13 , and R 14m1, m2, m3, and m4 are hydrogen atoms or alkyl groups with 1 to 10 carbon atoms. m1, m2, m3, and m4 each represent integers from 0 to 3. Examples of alkyl groups with 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. Cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2- Dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3 -Ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group.

[0097] m1 satisfies 1 ≤ m1 ≤ 6 - m2, m2 satisfies 1 ≤ m2 ≤ 5, m3 satisfies 1 ≤ m3 ≤ 4 - m2, and m4 satisfies 1 ≤ m4 ≤ 3.

[0098] Examples of compounds, polymers, and oligomers of formulas (5-1) and (5-2) are given below.

[0099] [ka] [ka]

[0100] The above compounds can be obtained as products of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (6-22) can be obtained from Asahi Organic Chemicals Co., Ltd. under the trade name TMOM-BP.

[0101] 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, preferably 0.01 to 50% by mass, and more preferably 0.1 to 40% by mass, relative to the total solid content of the resist underlayer film forming composition. These crosslinking agents may undergo crosslinking reactions by self-condensation, but if crosslinkable substituents are present in the polymer of the present invention, they can undergo crosslinking reactions with those crosslinkable substituents.

[0102] [Surfactants] The resist underlayer film forming composition of the present invention may optionally contain a surfactant to improve its coatability on a semiconductor substrate. Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, fluorine-based surfactants such as F-Top® EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac® F171, F173, R-30, R-30N, R-40, R-40-LM (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard® AG710, Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants can be used individually or in combination of two or more. If the resist underlayer film-forming composition contains a surfactant, its content is 0.0001 to 10% by mass, preferably 0.01 to 5% by mass, relative to the total solid content of the resist underlayer film-forming composition.

[0103] The solid content of the resist underlayer film forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the percentage of all components in the resist underlayer film forming composition excluding the solvent. The percentage of the compound or reaction product of the present 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.

[0104] [Other ingredients] The resist underlayer film forming composition of the present invention may contain absorbents, rheology modifiers, adhesion aids, and the like. Rheology modifiers are effective in improving the fluidity of the resist underlayer film forming composition. Adhesion aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

[0105] Examples of light absorbers include commercially available light absorbers listed in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry), such as CIDisperse 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; CID isperse Orange 1,5,13,25,29,30,31,44,57,72 and 73; CIDisperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199 and 210; CIDisperse Violet 43; CIDisperse Blue 96; and CIFluorescent Brightening Agent. 112, 135 and 163; CISolvent Orange 2 and 45; CISolvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CIPigment Green 10; CIPigment Brown 2, etc., can be suitably used. The above light absorbers are usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solid content of the resist underlayer film forming composition.

[0106] Rheology modifiers are primarily added to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the uniformity of the resist underlayer film thickness and enhance the filling of holes by the resist underlayer film-forming composition. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as din-normal butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as din-normal butyl malate, diethyl malate, and dinonyl malate; 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 a proportion of less than 30% by mass relative to the total solid content of the resist underlayer film-forming composition.

[0107] Adhesion aids are added primarily to improve the adhesion between the substrate or resist and the resist underlayer film-forming composition, and especially to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; and methyloltric Examples of adhesive aids include silanes such as lorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesive aids are usually blended in a proportion of less than 5% by mass, preferably less than 2% by mass, relative to the total solid content of the resist underlayer film forming composition.

[0108] [Method for manufacturing a resist underlayer film, a patterned substrate, and a semiconductor device] The following describes a resist underlayer film manufactured using the resist underlayer film forming composition according to the present invention, a method for manufacturing a patterned substrate, and a method for manufacturing a semiconductor device.

[0109] (Underlying resist film) The resist underlayer film according to the present invention can be manufactured by applying the above-described resist underlayer film forming composition onto a semiconductor substrate and firing it.

[0110] Examples of semiconductor substrates to which the resist underlayer film forming composition of the present invention is coated include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0111] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon 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.

[0112] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Subsequently, the resist underlayer film is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a bake temperature of 100°C to 400°C and a bake time of 0.3 minutes to 60 minutes. Preferably, the bake temperature is 120°C to 350°C and the bake time is 0.5 minutes to 30 minutes, and more preferably, the bake temperature is 150°C to 300°C and the bake time is 0.8 minutes to 10 minutes.

[0113] The thickness of the resist underlayer film formed 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). If the baking temperature is lower than the above range, crosslinking will be insufficient. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may decompose due to heat.

[0114] (Manufacturing method for patterned substrates) The manufacturing process for patterned substrates involves the following steps. Typically, a photoresist layer is formed on top of a resist underlayer film. The photoresist formed by coating and firing on top of the resist underlayer film using a known method is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. Examples include positive photoresists consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator. Examples include V146G (manufactured by JSR Corporation), APEX-E (manufactured by Cyprey Corporation), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), and AR2772 and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, examples include fluorine-containing polymer photoresists, such as those described in Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), and Proc.SPIE, Vol.3999, 365-374 (2000).

[0115] Exposure is performed through a mask (reticle) to form a predetermined pattern, and examples of such lasers used include i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet), or EB (electron beam). For development, an alkaline developer is used, with a development temperature of 5°C to 50°C and a development time of 10 to 300 seconds, which are appropriately selected. As the alkaline developer, aqueous solutions of the following alkalis can be used: inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can also be added to the aqueous solutions of the above alkalis. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants and the like can be added to these developers. Alternatively, instead of an alkaline developer, development can be performed using an organic solvent such as butyl acetate, and the parts of the photoresist whose alkaline dissolution rate has not improved can be developed. Through the above process, a substrate with the resist patterned can be manufactured.

[0116] 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; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. After that, the substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device. [Examples]

[0117] The weight-average molecular weight (Mw) of the polymers shown in the synthesis examples below in this specification is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows.

[0118] GPC columns: Shodex® and Asahipak® (Showa Denko K.K.) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 0.35ml / min Standard sample: Polystyrene (Tosoh Corporation)

[0119] (Synthesis of raw material monomers) <Synthesis Example 1> 38.70 g of tricarboxymethylisocyanuric acid (TAICA), synthesized according to the method described in U.S. 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.) were charged and the temperature was raised to 80-90°C. The reaction was then carried out for 2 hours to confirm that the reaction reached a constant weight. After the reaction was complete, 580.50 g of toluene (manufactured by Kanto Chemical Co., Ltd.) was added. The mixture was filtered and washed three times with 580.50 g of water. After the organic layer was concentrated and dried, 387.00 g of ethanol (manufactured by Kanto Chemical Co., Ltd.) was charged and the mixture was stirred at 20-30°C for 30 minutes. After stirring, the mixture was filtered, and the resulting crystals were dried to obtain 44.32 g of the target product (trialyl acetate isocyanuric acid: TAAICA) represented by formula (A1-1) in a yield of 85.2%.

[0120] [ka]

[0121] <Synthesis Example 2> 44.32 g of TAAICA synthesized in Synthesis Example 1 and 443.20 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were charged, and 125.06 g of m-chloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The reaction was carried out for 47 hours. After the reaction was complete, 88.64 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) was added. Furthermore, the mixture was washed with 886.40 g of 5% sodium bicarbonate (manufactured by Kanto Chemical Co., Ltd.). Subsequently, the mixture 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 then washed twice more 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), represented by formula (A1-2), was obtained in a yield of 83.7%.

[0122] [ka]

[0123] <Synthesis Example 3> In Synthesis Example 2, 5.00 g of TAGICA, 5.22 g of 2-mercapto-5-methylthio-1,3,4-thiadiazole, and 0.41 g of ethyltriphenylphosphonium bromide were 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 corresponding to formula (A1-3). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 1000.

[0124] [ka]

[0125] <Synthesis Example 4> In Synthesis Example 2, 5.00 g of TAGICA, 3.82 g of 2-mercapto-1,3,4-thiadiazole, and 0.41 g of ethyltriphenylphosphonium bromide were 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 corresponding to formula (A1-4). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 850.

[0126] [ka]

[0127] <Synthesis Example 5> In Synthesis Example 2, 5.00 g of TAGICA, 4.20 g of 2-mercapto-5-methyl-1,3,4-thiadiazole, and 0.41 g of ethyltriphenylphosphonium bromide were added to a reaction flask containing 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 corresponding to formula (A1-5). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 800.

[0128] [ka]

[0129] <Synthesis Example 6> In Synthesis Example 2, 5.00 g of TAGICA, 3.69 g of 5-mercapto-1-methyltetrazole, and 0.41 g of ethyltriphenylphosphonium bromide were 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 corresponding to formula (A1-6). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 800.

[0130] [ka]

[0131] <Synthesis Example 7> In Synthesis Example 2, 5.00 g of TAGICA, 4.07 g of 1H-tetrazole-1-acetic acid, and 0.41 g of ethyltriphenylphosphonium bromide were added to a reaction flask containing 37.89 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 corresponding to formula (A1-7). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 850.

[0132] [ka]

[0133] <Synthesis Example 8> 10.00 g of methyl isocyanuric acid (Me-ICA), synthesized according to the method described in the patent publication (WO2017 / 208910), 14.49 g of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), 20.48 g of allyl chloroacetate (manufactured by Aldrich), and 40.00 g of N,N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) were charged and stirred at 60°C for 25 hours. 100.00 g of toluene (manufactured by Kanto Chemical Co., Ltd.) was charged and 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. The resulting organic layer was concentrated to obtain 20.51 g of the target product (methyl diallyl acetate isocyanuric acid: Me-DAAICA) represented by formula (B1-1) in a yield of 86.5%.

[0134] [ka]

[0135] <Synthesis Example 9> 20.51 g of Me-DAAICA obtained in Synthesis Example 8 and 153.83 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were charged, and 38.52 g of m-chloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The reaction was carried out for 71 hours, and it was confirmed that the reaction reached a constant weight. After the reaction was complete, 205.10 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) and 410.20 g of 5 wt% sodium bicarbonate (manufactured by Kanto Chemical Co., Ltd.) were added. Liquid-liquid separation was performed, and 205.10 g of 10 wt% sodium sulfite (manufactured by Kanto Chemical Co., Ltd.) was charged into the resulting organic layer. Liquid-liquid separation was performed again, and 410.20 g of 5 wt% sodium bicarbonate (manufactured by Kanto Chemical Co., Ltd.) was charged into the resulting organic layer. Then, liquid-liquid separation was performed, and 205.10 g of water was added to the resulting organic layer and washed twice. The organic layer was concentrated and dried, then purified by column chromatography to obtain 10.46 g of the target product (methyl diglycidyl acetate isocyanuric acid: Me-DAGICA), represented by formula (B1-2), in a yield of 46.6%.

[0136] [ka]

[0137] <Synthesis Example 10> In Synthesis Example 9, 5.00 g of Me-DAGICA, 4.60 g of 2-mercapto-5-methylthio-1,3,4-thiadiazole, and 0.13 g of ethyltriphenylphosphonium bromide were added to a reaction flask containing 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 corresponding to formula (B1-3). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 600.

[0138] [ka]

[0139] <Synthesis Example 11> In Synthesis Example 2, 5.00 g of TAGICA, 4.10 g of thiazole-4-carboxylic acid, and 0.41 g of ethyltriphenylphosphonium bromide were added to a reaction flask containing 38.02 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 corresponding to formula (A1-8). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 1200.

[0140] [ka]

[0141] <Synthesis Example 12> In Synthesis Example 2, 5.00 g of TAGICA, 3.72 g of 2-mercaptothiazole, and 0.41 g of ethyltriphenylphosphonium bromide were 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 corresponding to formula (A1-9). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was 760.

[0142] [ka]

[0143] (Composition preparation) [Example 1] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 3, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0144] [Example 2] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 4, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0145] [Example 3] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 5, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0146] [Example 4] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 6, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0147] [Example 5] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 7, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0148] [Example 6] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 10, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0149] [Example 7] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 11, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0150] [Example 8] To 1.23 g of a solution containing 0.23 g of the reaction product obtained in Synthesis Example 12, 29.70 g of propylene glycol monomethyl ether, 0.06 g of tetramethoxymethyl glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.001 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0151] [Comparative Example 1] To 3.58 g of a solution containing 0.72 g of the reaction product 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 glycol uryl (Nippon Scitec Industries, Ltd., trade name: POWDERLINK® 1174), 0.01 g of phenol sulfonic acid (Tokyo Chemical Industries, Ltd.), and 0.01 g of surfactant (Dainippon Ink and Chemicals, Inc., trade name: R-40) were added to prepare a solution. Subsequently, the solution was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[0152] (Measurement of dry etching rate) The resist underlayer compositions prepared in Examples 1-8 and Comparative Example 1 were each coated onto a silicon wafer using a spinner and baked on a hot plate at 205°C for 1 minute to form a resist underlayer with a thickness of 100 nm. The dry etching rate (decrease in film thickness per unit time) was measured using a Samco RIE-10NR dry etching apparatus under conditions where CF4 was used as the dry etching gas. Table 1 shows the etching selectivity of each underlayer, with the etching selectivity of the resist underlayer obtained from Comparative Example 1 set to 1.00.

[0153] [Table 1]

[0154] From the above results, it can be seen that Examples 1 to 8 have significantly higher etching selectivity than Comparative Example 1. As a result, the resist underlayer film formation composition 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 reduced resist film thickness when the resist underlayer film is removed by dry etching. Furthermore, shortening the dry etching time can suppress undesirable etching damage to the substrate beneath the resist underlayer film, making it particularly useful as a resist underlayer film.

[0155] (Evaluation of optical parameters) The resist underlayer-forming compositions prepared in Examples 1-8 and Comparative Example 1 described herein were each coated (spin-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-forming composition (film thickness 30 nm). The n-value (refractive index) and k-value (attenuation coefficient or absorption coefficient) of these resist underlayer-forming compositions were measured at a wavelength of 193 nm using a spectroscopic ellipsometer (product name: VUV-VASE VU-302, JAWoollam). The measurement results of the optical parameters are shown in the table. 2 This will be shown.

[0156] [Table 2] [Industrial applicability]

[0157] The resist underlayer film forming composition according to the present invention provides a resist underlayer film having a particularly high dry etching rate.

Claims

1. The reaction product of an epoxy group-containing compound and a heterocyclic compound containing one moiety that is reactive to the epoxy group, and a solvent, The epoxy group-containing compound is a compound represented by the following formula (1), The heterocyclic compound is selected from the group consisting of thiazole, thiadiazole, and tetrazole. Resist underlayer film forming composition. 【Chemistry 1】 (In formula (1), X is a divalent organic group represented by formula (2), formula (3), or formula (4) below, and n1 and n2 each independently represent an integer from 1 to 10.) 【Chemistry 2】 (In equations (2), (3), and (4), R1 and R2 each independently represent a C1 to C10 alkyl group which may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom, a C2 to C10 alkenyl group which may be interrupted by an oxygen atom or a sulfur atom, a C2 to C10 alkynyl group which may be interrupted by an oxygen atom or a 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 the group consisting of a C1 to C6 alkyl group, a halogen atom, a C1 to C10 alkoxy group, a nitro group, a cyano group, and a C1 to C6 alkylthio group. R3 represents an alkyl group having 1 to 10 carbon atoms that may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom; an alkenyl group having 3 to 10 carbon atoms that may be interrupted by an oxygen atom or a sulfur atom; an alkynyl group having 3 to 10 carbon atoms that may be interrupted by an oxygen atom or a sulfur atom; a benzyl group; or a phenyl group. The phenyl group may be substituted with at least one monovalent functional group selected from the group consisting of 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 organic groups represented by the following formula (5). 【Transformation 3】 (In equation (5), n3 represents an integer from 1 to 10.)

2. The resist underlayer film forming composition according to claim 1, wherein the site that is reactive with the epoxy group is selected from a hydroxyl group, a thiol group, an amino group, an imide group, and a carboxyl group.

3. The resist underlayer film forming composition according to claim 1 or claim 2, further comprising at least one selected from the group consisting of a crosslinking agent, a crosslinking catalyst, and a surfactant.

4. A resist underlayer film characterized by being a fired product of a coated film made from the resist underlayer film forming composition according to any one of Claims 1 to 3.

5. A method for manufacturing a patterned substrate, comprising the steps of: applying a resist underlayer forming composition according to any one of Claims 1 to 3 onto a semiconductor substrate and baking to form a resist underlayer; applying a resist onto the resist underlayer and baking to form a resist film; exposing the semiconductor substrate covered with the resist underlayer and the resist; and developing and patterning the resist film after exposure.

6. A step of forming a resist underlayer on a semiconductor substrate, comprising the resist underlayer forming composition according to any one of Claims 1 to 3, 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 an electron beam and then developing it, A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, A process of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the following:

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