Resist underlayer film forming composition containing a radical trapping agent

Abstract

Provided is a resist underlayer film-forming composition with excellent storage stability for use in the lithography process of semiconductor manufacturing. The resist underlayer film-forming composition comprises a polymer containing a disulfide bond in its main chain, a radical trapping agent, and a solvent. The radical trapping agent is preferably a compound having a ring structure or a thioether structure. The ring structure is preferably an aromatic ring structure having 6 to 40 carbon atoms or a 2,2,6,6-tetramethylpiperidine structure.

Description

[Technical Field]

[0001] This invention relates to a resist underlayer film forming composition used in lithography processes in semiconductor manufacturing. It also relates to a method for manufacturing a resist-patterned substrate and a semiconductor device using the resist underlayer film forming composition. [Background technology]

[0002] In semiconductor manufacturing, the lithography process, which involves forming a resist underlayer film between a substrate and a resist film formed thereon to create a resist pattern of a desired shape, is widely known. Patent Document 1 discloses a resist underlayer film forming composition for lithography, comprising a polymer having disulfide bonds in its main chain and a solvent. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2009 / 096340 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In the lithography process used in semiconductor device manufacturing, resist underlayer forming compositions require that their composition remains unchanged (storage stability) even after a certain period of time, in order to ensure a smooth supply of materials during the lithography process in semiconductor device manufacturing when the manufacturing process is carried out continuously. In particular, the polymer, which is the main component of the composition, is required to maintain its molecular weight (e.g., weight-average molecular weight) without change. However, polymers with disulfide bonds in their main chain have the problem of lacking storage stability because their molecular weight decreases during storage. The object of the present invention is to solve the above problem. [Means for solving the problem]

[0005] This invention encompasses the following: [1] A resist underlayer film forming composition comprising a polymer containing disulfide bonds, a radical trapping agent, and a solvent. [2] The aforementioned polymer A compound (A) having at least one disulfide bond and two or more functional compounds, The above compound (A) and a different compound (B) with two or more functional properties The reaction product is the resist underlayer film forming composition described in [1]. [3] The resist underlayer film forming composition according to [1], wherein the radical trapping agent is a compound (T) having a ring structure or a thioether structure. [4] The resist underlayer film forming composition according to [3], wherein the ring structure is an aromatic ring structure having 6 to 40 carbon atoms or a 2,2,6,6-tetramethylpiperidine structure. [5] The resist underlayer film forming composition according to [3], wherein the compound (T) comprises a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. [6] The resist underlayer forming composition according to [2], wherein the compound (B) having two or more functionalities comprises an aromatic ring structure or a heterocyclic structure having 6 to 40 carbon atoms. [7] A resist underlayer film forming composition according to any one of [1] to [6], further comprising a crosslinking catalyst. [8] A resist underlayer film forming composition according to any one of [1] to [7], further comprising a crosslinking agent. [9] 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 [8].

[10] A method for manufacturing a resist-patterned substrate for use in the manufacture of a semiconductor device, comprising the steps of: applying a resist underlayer film forming composition according to any one of [1] to [8] onto a semiconductor substrate and baking to form a resist underlayer film; applying a resist onto the resist underlayer film and baking to form a resist film; exposing the semiconductor substrate covered with the resist underlayer film and the resist; and developing the resist film after exposure.

[11] 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 [8], A step of forming a resist film on the resist underlayer film, The steps include: exposing the resist film, A step of developing the resist film after exposure to form a resist pattern, 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: [Effects of the Invention]

[0006] The resist underlayer film forming composition of the present invention exhibits minimal change in the weight-average molecular weight of the polymer even after a certain period of time has elapsed, and has excellent storage stability. Therefore, it enables a stable supply of materials and can contribute to the smooth manufacturing of semiconductor devices. [Modes for carrying out the invention]

[0007] ≪Explanation of Terms≫ Unless otherwise specified, the terms used in this invention have the following definitions.

[0008] 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. 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-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, etc.

[0009] Examples of the "alkoxy group having 1 to 20 carbon atoms" include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group, cyclopentyloxy group, cyclohexyloxy group, norbornyloxy group, adamantyloxy group, adamantylmethyloxy group, adamantylethyloxy group, tetracyclodecanyloxy group, tricyclodecanyloxy group, etc.

[0010] Examples of "alkenyl groups with 3 to 6 carbon atoms" include 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, and 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 -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.

[0011] Examples of "alkylene groups with 1 to 10 carbon atoms" include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, cyclobutylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, and 1-ethyl-n-propylene. Polyethylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group , 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene n group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples thereof include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, or an n-decylene group.,

[0012] Examples of the "alkylthio group having 1 to 6 carbon atoms" include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, and a hexylthio group.,

[0013] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.,

[0014] Examples of the "aromatic ring structure having 6 to 40 carbon atoms" include an aromatic ring structure derived from benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, dibenzo[a,j]anthracene, etc.,

[0015] The "aromatic ring structure having 6 to 40 carbon atoms" may be derived from, for example, an "aryl group having 6 to 4 organizations". Specific examples of the "aryl group having 6 to 40 carbon atoms" include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.,

[0016] Examples of "heterocyclic structures" include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthlene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazineone, triazinedione, and triazinetrione.

[0017] "Functionality" is a concept that focuses on the chemical attributes and chemical reactivity of a substance. When we refer to a functional group, we assume that each has its own unique physical properties and chemical reactivity. However, in this application, it refers to a reactive substituent that can bond with other compounds. For example, a trifunctional compound has three reactive substituents. In this application, the number of functionalities is expressed as an integer. Specific examples of reactive substituents include hydroxyl groups, epoxy groups, acyl groups, acetyl groups, formyl groups, benzoyl groups, carboxyl groups, carbonyl groups, amino groups, imino groups, cyano groups, azo groups, azi groups, thiol groups, sulfo groups, and allyl groups.

[0018] <Resist Underlayer Film Forming Composition> The resist underlayer forming composition of the present invention comprises a polymer containing disulfide bonds, preferably a polymer containing disulfide bonds in its main chain, a radical trapping agent, and a solvent. The details will be explained below in order.

[0019] <Polymers containing disulfide bonds> Polymers containing disulfide bonds as described in this application include, but are not limited to, the polymers described in International Publication No. 2009 / 096340, and the reaction products of a bifunctional or higher compound having at least one disulfide bond and a trifunctional or higher compound, as described in International Publication No. 2019 / 151471.

[0020] When the polymer is a reaction product of a bifunctional compound (A) having at least one disulfide bond and a bifunctional compound (B) different from the compound (A), a disulfide bond is present in the main chain of the polymer. The polymer may have a repeating unit structure represented by the following formula (1).

[0021]

Chemical formula

[0022] (In the above formula (1), R1 represents a direct bond or a methyl group, n is the number of repeating unit structures and represents an integer of 0 to 1, m represents an integer of 0 or 1. Z1 represents a group represented by the following formula (2), formula (3) or formula (2-1),

[0023]

Chemical formula

[0024] In the above formula (3), X represents a group represented by the following formula (4), formula (51) or formula (6),

[0025]

Chemical formula

[0026] In the above formula (4), formula (51) and formula (6), R2, R3, R4, R 51 and R 61 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, the phenyl group may be substituted with at least one 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 6 carbon atoms, a nitro group, a cyano group and an alkylthio group having 1 to 6 carbon atoms, Furthermore, R2 and R3, and R4 and R5 may bond to each other to form rings with 3 to 6 carbon atoms. A1 to A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group. Q1 represents an alkylene group with 1 to 10 carbon atoms interrupted by a disulfide bond. l represents the number of repeating unit structures, and is an integer between 5 and 100.

[0027] Q1 is preferably an alkylene group having 2 to 6 carbon atoms, interrupted by a disulfide bond.

[0028] Examples of the "rings with 3 to 6 carbon atoms" mentioned above include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene, and cyclohexane.

[0029] The above equation (1) may also be expressed as the following equation (5).

[0030] [ka]

[0031] [In formula (5) above, X represents the base represented by formula (4), formula (51), or formula (6), R 6 and R 7 Each of these independently represents an alkylene group with 1 to 3 carbon atoms or a direct bond. p is the number of repeating unit structures, representing an integer between 5 and 100.

[0032] The polymer of this application is preferably represented by the following formulas (P-6) to (P-8).

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] Preferably, the polymer is a reaction product synthesized by reacting a bifunctional compound (A) having at least one disulfide bond with a bifunctional compound (B) different from compound (A) using a method known to the extent of the reaction. When compound (A), which has at least one disulfide bond, and compound (B), which is different from compound (A), are both bifunctional, the molar ratio during the reaction is preferably 0.7:1.0 to 1.0:0.7. The weight-average molecular weight of the above polymer is, for example, 1,000 to 100,000, or 1,100 to 50,000, or 1,200 to 30,000, or 1,300 to 20,000, or 1,500 to 10,000.

[0037] <A compound with at least one disulfide bond and two or more functional properties (A)> A compound (A) having at least one disulfide bond and being bifunctional or more functional may have two or more of the above-mentioned functional groups, but is preferably bifunctional or trifunctional, and most preferably bifunctional. The functional group is preferably a carboxylic acid group. The above compound (A) is preferably a dicarboxylic acid containing a disulfide bond. The above compound (A) is more preferably a dicarboxylic acid having an alkylene group having 2 or more carbon atoms interrupted by a disulfide bond. The above compound (A) is more preferably a dicarboxylic acid having an alkylene group having 2 to 6 carbon atoms interrupted by a disulfide bond. The dicarboxylic acid containing the disulfide bond is preferably represented by the following formula (1-1).

[0038] [ka]

[0039] (In formula (1-1), X1 and X2 each represent an alkylene group having 1 to 10 carbon atoms that may be substituted, an arylene group having 6 to 40 carbon atoms that may be substituted, or a combination thereof.)

[0040] The phrase "may be substituted" above means that some or all of the hydrogen atoms present in the alkylene group having 1 to 10 carbon atoms or the arylene group having 6 to 40 carbon atoms may be substituted with, for example, a hydroxyl group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, or an alkoxy group having 1 to 9 carbon atoms. Examples of difunctional or multifunctional compounds (A) having at least one disulfide bond include the following formulas (A-1) to (A-4).

[0041] [ka]

[0042] <Compounds with two or more functions (B)> (Compounds with two or more functions) Compound (B) of the present application, which has two or more functional groups, is a different compound from compound (A) described above. Compound (B) of the present application, which has two or more functional groups, only needs to have two or more of the above functional groups, but is preferably bifunctional or trifunctional, and most preferably bifunctional. It is preferable that the functional group has a glycidyl group. Compounds with three or more functional groups will be described later. The above-mentioned compound (B) with two or more functions preferably does not contain a disulfide bond. The above-mentioned compound (B) with two or more functions preferably contains an aromatic ring structure or a heterocyclic structure with 6 to 40 carbon atoms.

[0043] The heterocyclic structure is preferably such that the heteroatom is a nitrogen atom and / or an oxygen atom, has 4 to 24 carbon atoms, and is preferably a triazineone, triazinedione, or triazinetrione, with triazinetrione being the most preferred. The bifunctional compound (B) is preferably selected from the following compounds (a) to (z) and (aa), but is not limited to these. In formula (n), R 0 This represents an alkylene group with 1 to 10 carbon atoms.

[0044] [ka]

[0045] [ka]

[0046] <Compounds with two or more functions (B)> (Compounds with three or more functions) The compound (B) of the present application may include a compound with three or more functions, but may also include a compound with three to ten functions, a compound with three to eight functions, or a compound with three to six functions, and preferably includes a compound with three or four functions.

[0047] The aforementioned trifunctional or more compound is preferably a compound containing three or more epoxy groups.

[0048] Needless to say, "containing three or more epoxy groups" means "containing three or more epoxy groups in a single molecule." The aforementioned trifunctional or more compound is preferably a compound containing 3 to 10 epoxy groups. It is preferably a compound containing 3 to 8 epoxy groups. It is preferably a compound containing 3 to 6 epoxy groups. It is even more preferably a compound containing 3 or 4 epoxy groups. It is most preferably a compound containing 3 epoxy groups.

[0049] Examples of compounds (B) containing three or more epoxy groups include glycidyl ether compounds, glycidyl ester compounds, glycidylamine compounds, and glycidyl group-containing isocyanurates. Examples of epoxy group-containing compounds (B) used in the present invention include the following formulas (A-1) to (A-15).

[0050] [ka]

[0051] [ka]

[0052] Formula (A-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). Formula (A-2) is manufactured by Nissan Chemical Corporation and is available under the trade name TEPIC-VL. Formula (A-3) is manufactured by Nissan Chemical Corporation and is available under the product name TEPIC-FL. Formula (A-4) is manufactured by Nissan Chemical Corporation and is available under the product name TEPIC-UC. Formula (A-5) is manufactured by Nagase Chemtec Co., Ltd. and is available under the product name Denacol EX-411. Formula (A-6) is manufactured by Nagase Chemtec Co., Ltd. and is available under the product name Denacol EX-521. Formula (A-7) is manufactured by Mitsubishi Gas Chemical Company, Inc. and is available under the trade name TETRAD-X. Formula (A-8) is manufactured by Showa Denko Corporation and is available under the product name BATG. Formula (A-9) is manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. and is available under the product name YH-434L. Formula (A-10) is manufactured by Asahi Organic Chemicals Co., Ltd. and is available under the product name TEP-G. Model (A-11) is manufactured by DIC Corporation and is available under the product name EPICLON HP-4700. Formula (A-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.

[0053] The molar ratio of compound (A) having at least one sulfide bond and trifunctional or more functions, and compound (B) having trifunctional or more functions different from compound (A), is, for example, 1:0.1 to 10. Preferably, it is 1:1 to 5, and more preferably 1:3.

[0054] The polymer of this application may be, but is not limited to, a reaction product having the structures of the following formulas (P-1) to (P-5).

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] <Solvent> The resist underlayer film forming composition of the present invention can be manufactured by dissolving each of the above components in a solvent, preferably an organic solvent, and is used in a homogeneous solution state. 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. 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. 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.

[0060] The solid content of the resist underlayer film-forming composition according to this application 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 protective film-forming composition excluding the solvent. The percentage of ring-opened polymers 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.

[0061] <Radical trapping agent> The resist underlayer film-forming composition of the present invention contains a radical trapping agent. The radical trapping agent may be used alone or in combination of two or more agents. It is believed that the inclusion of a radical trapping agent can suppress the radical cleavage of the disulfide bonds of the polymer contained in the resist underlayer film-forming composition of the present invention, thereby contributing to the stabilization of the polymer molecular weight.

[0062] The radical trapping agent is preferably a compound (T) having a cyclic structure or a thioether structure. The compound (T) is preferably a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0063] The radical trapping agent preferably has at least one ring structure. The ring structure is preferably an aromatic ring structure having 6 to 40 carbon atoms or a 2,2,6,6-tetramethylpiperidine structure.

[0064] The resist underlayer forming composition of the present invention may contain at least one radical trapping agent selected from naphthalene derivatives, thioether compounds, hindered amine compounds, ultraviolet absorbers, antioxidants, and thermal polymerization inhibitors. Examples of the above naphthalene derivatives include naphthohydroquinone compounds such as naphthohydroquinone sulfonate onium salt, and include 1,4-dihydroxynaphthalene, 6-amino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-methylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-ethylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, Examples include 6-propylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-butylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 2-(α,α-dimethyl)naphthalene, 2-(α,α-dimethylbenzyl)naphthalene, 2-t-amylnaphthalene, and 2-trimethylsilyl-1,4,5,8,-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0065] The thioether compound is not particularly limited as long as it has at least one thioether group in its molecule. For example, dimethyl 3,3'-thiodipropionate, dihexyl thiodipropionate, dinonyl thiodipropionate, didecyl thiodipropionate, diundecyl thiodipropionate, didodecyl thiodipropionate, ditridecyl thiodipropionate, ditetradecyl thiodipropionate, dipentadecyl thiodipropionate, hexadecyl thiodipropionate, diheptadecyl thiodipropionate, dioctadecyl thiodipropionate, dihexyl Examples include ruthiodibutyrate, dinonylthiodibutyrate, didecylthiodibutyrate, diundecylthiodibutyrate, didodecylthiodibutyrate, ditridecylthiodibutyrate, ditetradecylthiodibutyrate, dipentadecylthiodibutyrate, hexadecylthiodibutyrate, 3-methoxy-2-[2-[cyclopropyl(3-fluorophenylimino)methylthiomethyl]phenyl]acrylate methyl ester, and diheptadecylthiodibutyrate.

[0066] As a commercially available product, ADEKA Stab® AO503, a thioether-based antioxidant manufactured by ADEKA Corporation, is preferred.

[0067] Examples of hindered amine compounds include compounds having a substructure represented by the following formula (RT1).

[0068] [ka]

[0069] (In equation (RT1), R 11 ~R 41 Each of these independently represents a hydrogen atom or an alkyl group, and R 51 (This represents an alkyl group, alkoxy group, or aryloxy group.)

[0070] The alkyl group mentioned above is preferably a linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group included in the alkoxy group is preferably a linear alkyl group having 1 to 4 carbon atoms. The aryl group included in the aryloxy group is preferably a phenyl group, a naphthyl group, etc.

[0071] Furthermore, the molecular weight of the hindered amine compound is preferably 2000 or less, and more preferably 1000 or less. Considering ease of availability in the market, the molecular weight of the hindered amine compound is preferably 400 to 700. As hindered amine compounds as described above, commercially available products such as TINUVIN® 123, TINUVIN® 144, and TINUVIN® 152 manufactured by BASF, and ADEKA Stub® LA-52, LA-81, and LA-82 manufactured by ADEKA Corporation can be preferably used. Among these, Adeka Stubs® LA-81 and LA-82 manufactured by Adeka Corporation are preferred.

[0072] Examples of UV absorbers include salicylates, benzophenones, benzotriazoles, cyanoacrylates, and nickel chelates. Examples of benzotriazole compounds include 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2'-hydroxy-5'-melphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole. Commercially available benzotriazole compounds that can be used include TINUVIN® 900, TINUVIN® 928, TINUVIN® P, TINUVIN® 234, TINUVIN® 326, and TINUVIN® 329, all manufactured by BASF. Other ultraviolet absorbers that can be used in this application include phenyl salicylate, 4-t-butylphenyl salicylate, and 2,4-di-t-butylphenyl-3 Examples include ',5'-di-t-butyl-4'-hydroxybenzoate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, ethyl-2-cyano-3,3-diphenylacrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyldithiocarbamate, bis(2,2,6,6-tetramethyl-4-piperidine)-sebacate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinate-bis(2,2,6,6-tetramethyl-4-piperidine) ester, and 7-{[4-chloro-6-(diethylamino)-1,3,5-triazine-2-yl]amino}-3-phenylcoumarin. Examples of commercially available UV absorbers include the ADEKA® LA series (LA-24, LA-29, LA-31RG, LA-31G, LA-32, LA-36, LA-36RG, LA-46, LA-F70, 1413, etc.) manufactured by ADEKA Corporation.

[0073] Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, phlorogricinol, t-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine, and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Among these, hydroquinone, dibutylhydroxytoluene, pyrogallol, and phlorogricinol are preferred. Commercially available products include, for example, the ADEKA® AO series of phenolic antioxidants manufactured by ADEKA Corporation (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, etc.) and the Irganox® series of hindered phenolic antioxidants manufactured by BASF (1010 / FF, 1035 / FF, 1076 / FD, 1098, 1135, 1141, 1330, 1520 L, 245 / FF, 259, 3114, etc.). Other commercially available products include, for example, the ADEKA Stab® PEP series (PEP-8, PEP-36, HP-10, 2112, 2112RG, 1178, 1500, C, 135A, 3010, TPP, etc.), which are phosphite-based antioxidants manufactured by ADEKA Corporation. Among these, Adekastab® PEP1500 is preferred.

[0074] In addition to the radical trapping agent described above, the resist underlayer film forming composition of this application may also use oxidizing agents described in paragraphs 0183 to 0210 of Japanese Patent Application Publication No. 2011-141534, polymerizable compounds having radical scavenging ability described in paragraphs 0103 to 0153 of Japanese Patent Application Publication No. 2011-253174 (e.g., hindered amine type, hindered phenol type polymerizable compounds), and the contents of these are incorporated into the present specification. Among the above, it is preferable that the radical trapping agent is represented by the following formulas (R-1) to (R-8), preferably by the following formulas (R-1) to (R-4), preferably by the following formulas (R-1) to (R-3), and especially preferably by the following formulas (R-2) and (R-3).

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] The amount of radical trapping agent in the resist underlayer film forming composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and particularly preferably 0.4 to 5.0% by mass, based on the total solid content.

[0081] <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 an acidic compound, a compound that generates 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.

[0082] Examples of sulfonic acid compounds or carboxylic acid compounds include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium trifluoromethanesulfonate, pyridinium-p-toluenesulfonate, pyridinium-4-hydroxybenzenesulfonate, 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.

[0083] 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.).

[0084] These crosslinking acid catalysts can be used individually or in combination of two or more. If the resist underlayer film-forming composition contains a crosslinking acid catalyst, its content is 0.0001 to 20% by weight, preferably 0.01 to 15% by weight, and more preferably 0.1 to 10% by weight, relative to the total solid content of the protective film-forming composition.

[0085] <Crosslinking agent> The resist underlayer film forming composition of the present invention can contain a crosslinking agent component. Examples of the crosslinking agent include melamine-based, substituted urea-based, or their polymer-based ones, etc. Preferably, it is a crosslinking agent having at least two crosslinking-forming substituents, and compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Also, condensates of these compounds can be used.

[0086] Also, as the above crosslinking agent, a crosslinking agent with high heat resistance can be used. As the crosslinking agent with high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (for example, benzene ring, naphthalene ring) in the molecule can be used. Examples of this compound include a compound having a partial structure of the following formula (5-1), or a polymer or oligomer having a repeating unit of the following formula (5-2).

[0087]

Chemical formula

[0088] The above R 11 , R 12 , R 13 , and R 14 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples of these alkyl groups are as described above. m1 is 1 ≦ m1 ≦ 6−m2, m2 is 1 ≦ m2 ≦ 5, m3 is 1 ≦ m3 ≦ 4−m2, and m4 is 1 ≦ m4 ≦ 3. The compounds, polymers, and oligomers of formula (5-1) and formula (5-2) are exemplified below.

[0089]

Chemical formula

[0090] [ka]

[0091] 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. These crosslinking agents can be used individually or in combination of two or more. The amount of crosslinking agent added varies depending on the coating solvent used, the substrate used, the required solution viscosity, and the required film shape, but is 0.001 to 80% by weight, preferably 0.01 to 50% by weight, and more preferably 0.1 to 40% by weight, relative to the total solid content of the protective 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.

[0092] <Surfactants> The protective film-forming composition of the present invention may optionally contain a surfactant to improve its coatability on semiconductor substrates. 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 sorb Examples of nonionic surfactants include polyoxyethylene sorbitan fatty acid esters such as tan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as F-Top® EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac® F171, F173, R-30, and R-40 (manufactured by DIC Corporation), Florard FC430 and FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard® AG710, Surflon® S-382, SC101, SC102, SC103, SC104, SC105, and 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 protective film-forming composition contains a surfactant, its content is 0.0001 to 10% by weight, preferably 0.01 to 5% by weight, relative to the total solid content of the protective film-forming composition.

[0093] <Other ingredients> The protective 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 protective film-forming composition. Adhesion aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlying film.

[0094] 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-mentioned light-absorbing agent is 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 protective film-forming composition.

[0095] Rheology modifiers are primarily added to improve the fluidity of protective film-forming compositions, particularly in the baking process, to enhance the uniformity of the film thickness of the resist underlayer and improve the filling of the protective film-forming composition into holes. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as dinormal 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 normal 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 protective film-forming composition.

[0096] Adhesion aids are added primarily to improve the adhesion between the substrate or resist and the protective 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 protective film-forming composition.

[0097] <Manufacturing method for resist underlayer film, resist patterned substrate, and semiconductor device manufacturing method> The following describes a protective film manufactured using the protective film forming composition according to the present invention, a method for manufacturing a substrate with a resist pattern, and a method for manufacturing a semiconductor device.

[0098] A resist patterned substrate according to the present invention can be manufactured by applying the above-described protective film forming composition onto a semiconductor substrate and firing it.

[0099] Examples of semiconductor substrates to which the protective film-forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0100] 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 oxynitride films, tungsten nitride films, gallium nitride films, and gallium arsenide films.

[0101] The protective 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. Then, a protective film is formed by baking using a heating means such as a hot plate. The 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. The thickness of the formed protective film is, for example, 0.001 μm to 10 μm, preferably 0.002 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm. If the baking temperature is lower than the above range, crosslinking may be insufficient, and the formed protective film may not be able to obtain sufficient resistance to resist solvents or basic hydrogen peroxide aqueous solutions. On the other hand, if the baking temperature is higher than the above range, the protective film may decompose due to heat.

[0102] 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, an appropriate amount of alcohol such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solution of the above alkalis. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants and other additives can be added to these developers. Alternatively, instead of an alkaline developer, development can be performed using an organic solvent such as butyl acetate, developing the portions of the photoresist where the alkaline dissolution rate has not improved.

[0103] Next, the protective 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.

[0104] Furthermore, the desired pattern is formed by wet etching using a semiconductor wet etching solution, with the protective film after dry etching (and the resist pattern remaining on the protective film, if any) as a mask. [Examples]

[0105] The present invention will be specifically described with reference to synthesis examples and embodiments, but the present invention is not limited to these. The weight-average molecular weights shown herein are the results of measurements performed by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurements, and the measurement conditions were as follows. GPC columns: Shodex® and Asahipak® (Showa Denko K.K.) Column temperature: 40℃ Solvent: N,N-dimethylformamide (DMF) Flow rate: 0.6ml / min Standard sample: Polystyrene (Tosoh Corporation)

[0106] <Synthesis Example 1> A reaction flask containing 43.86 g of diglycidyl terephthalate (product name: Denacol EX-711, manufactured by Nagase ChemteX Corporation), 33.34 g of 3,3'-dithiopropionic acid, 2.80 g of ethyltriphenylphosphonium bromide, and 320.00 g of propylene glycol monomethyl ether was heated and stirred at 100°C for 24 hours under a nitrogen atmosphere. The resulting reaction product corresponds to (formula P-6), and its weight-average molecular weight, measured in polystyrene equivalent by GPC, was 5100.

[0107] [ka]

[0108] <Synthesis Example 2> 131.59 g of 5,5-dimethylhydantoin diglycidyl (product name: DG-DMH, manufactured by Shikoku Chemicals, Inc., 30% propylene glycol monoethyl ether solution), 37.26 g of 3,3'-dithiopropionic acid, 3.13 g of ethyltriphenylphosphonium bromide, and 28.07 g of propylene glycol monomethyl ether were added to a reaction flask, which was heated and stirred at 100°C for 24 hours under a nitrogen atmosphere. The resulting reaction product corresponds to (formula P-7), and its weight-average molecular weight, measured in polystyrene equivalent by GPC, was 3530.

[0109] [ka]

[0110] <Example 1> To 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product obtained in Synthesis Example 1, 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of dibutylhydroxytoluene (compound of formula (R-1)) were added to prepare a solution. <Example 2> To 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product obtained in Synthesis Example 1, 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of hydroquinone (compound of formula (R-2)) were added to prepare a solution. <Example 3> To 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product obtained in Synthesis Example 1, 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of pyrogallol (1,2,3-trihydroxybenzene) (compound of formula (R-3)) were added to prepare a solution. <Example 4> To 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product obtained in Synthesis Example 2, 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of dibutylhydroxytoluene (compound of formula (R-1)) were added to prepare a solution. <Example 5> To 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product obtained in Synthesis Example 2, 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of hydroquinone (compound of formula (R-2)) were added to prepare a solution. <Example 6> To 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product obtained in Synthesis Example 2, 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of pyrogallol (1,2,3-trihydroxybenzene) (compound of formula (R-3)) were added to prepare a solution. <Example 7> A solution was prepared by adding 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of dibutylhydroxytoluene (compound of formula (R-1)) to 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product (corresponding to formula P-8, with a weight-average molecular weight of 8900 measured in polystyrene equivalent by GPC) obtained by the method described in Synthesis Example 1 of Table 2009 / 096340.

[0111] [ka]

[0112] <Example 8> A solution was prepared by adding 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of hydroquinone (compound of formula (R-2)) to 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product (corresponding to formula P-8, with a weight-average molecular weight of 8900 measured in polystyrene equivalent by GPC) obtained by the method described in Synthesis Example 1 of Table 2009 / 096340. <Example 9> A solution was prepared by adding 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of pyrogallol (1,2,3-trihydroxybenzene) (compound of formula (R-3)) to 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product (corresponding to formula P-8, with a weight-average molecular weight of 8900 measured in polystyrene equivalent by GPC) obtained by the method described in Synthesis Example 1 of Table 2009 / 096340. <Example 10> A solution was prepared by adding 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of ADEKA® 1500 (compound of formula (R-5)) to 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product (corresponding to formula P-8, with a weight-average molecular weight of 8900 measured in polystyrene equivalent by GPC) obtained by the method described in Synthesis Example 1 of Table 2009 / 096340. <Example 11> A solution was prepared by adding 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of ADEKA® AO503 (compound of formula (R-6)) to 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product (corresponding to formula P-8, with a weight-average molecular weight of 8900 measured in polystyrene equivalent by GPC) obtained by the method described in Synthesis Example 1 of Table 2009 / 096340. <Example 12> A solution was prepared by adding 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of ADEKA® LA-81 (compound of formula (R-7)) to 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product (corresponding to formula P-8, with a weight-average molecular weight of 8900 measured in polystyrene equivalent by GPC) obtained by the method described in Synthesis Example 1 of Table 2009 / 096340. <Example 13> A solution was prepared by adding 83.526 g of propylene glycol monomethyl ether, 9.900 g of propylene glycol monomethyl ether acetate, and 0.009 g of ADEKA® LA-82 (compound of formula (R-8)) to 5.584 g of a propylene glycol monomethyl ether solution containing 0.990 g of the reaction product (corresponding to formula P-8, with a weight-average molecular weight of 8900 measured in polystyrene equivalent by GPC) obtained by the method described in Synthesis Example 1 of Table 2009 / 096340.

[0113] <Comparative Example 1> To 5.640 g of a propylene glycol monomethyl ether solution containing 1.000 g of the reaction product obtained by the method of Synthesis Example 1, 85.460 g of propylene glycol monomethyl ether and 9.900 g of propylene glycol monomethyl ether acetate were added to prepare a solution. <Comparative Example 2> To 5.640 g of a propylene glycol monomethyl ether solution containing 1.000 g of the reaction product obtained by the method of Synthesis Example 2, 85.460 g of propylene glycol monomethyl ether and 9.900 g of propylene glycol monomethyl ether acetate were added to prepare a solution. <Comparative Example 3> To 5.640 g of a propylene glycol monomethyl ether solution containing 1.000 g of the reaction product obtained by the method described in Synthesis Example 1 of Re-Patent 2009 / 096340 (corresponding to Formula P-8, and the weight average molecular weight measured in terms of polystyrene by GPC is 8900), 85.460 g of propylene glycol monomethyl ether and 9.900 g of propylene glycol monomethyl ether acetate were added to prepare a solution.

[0114] <Molecular weight measurement by GPC> The solutions prepared in Examples 1 to 13 and Comparative Examples 1 to 3 were reacted in a eggplant flask at 100 °C under nitrogen for 6 hours and then measured by GPC. The initial molecular weight and the molecular weight after the reaction are shown in Table 1 below. As a result, it can be seen that the resist underlayer film forming composition containing the radical trap agent of the present invention has improved stability compared to the resist underlayer film forming composition not containing the radical trap agent.

[0115]

Table 1

[0116]

Table 2

[0117]

Table 3

Industrial Applicability

[0118] The resist underlayer film forming composition according to the present invention can provide a composition with excellent storage stability without change in polymer molecular weight even after a certain period of time.

Claims

1. A resist underlayer film forming composition comprising a polymer containing disulfide bonds, a radical trapping agent, and a solvent, The radical trapping agent is selected from the group consisting of naphthalene derivatives, thioether compounds, hindered amine compounds, and phosphite-based antioxidants represented by the following formula (R-5). 【Chemistry 1】 The naphthalene derivatives include naphthohydroquinone sulfonate onium salt, 1,4-dihydroxynaphthalene, 6-amino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-methylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-ethylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, and 6-propylamino-2,3 Selected from -dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-butylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 2-(α,α-dimethyl)naphthalene, 2-(α,α-dimethylbenzyl)naphthalene, 2-t-amylnaphthalene and 2-trimethylsilyl-1,4,5,8,-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene, The aforementioned polymer A compound (A) having at least one disulfide bond and two or more functional compounds, Compound (B) having two or more epoxy groups, different from the above compound (A) The reaction product is a resist underlayer film forming composition.

2. A resist underlayer film forming composition comprising a polymer containing disulfide bonds, a radical trapping agent, and a solvent, The radical trapping agent is selected from naphthalene derivatives, thioether compounds, hindered amine compounds, and thermal polymerization inhibitors. The naphthalene derivatives include naphthohydroquinone sulfonate onium salt, 1,4-dihydroxynaphthalene, 6-amino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-methylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-ethylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, and 6-propylamino-2,3 Selected from -dihydro-5,8-dihydroxynaphthalene-1,4-dione, 6-butylamino-2,3-dihydro-5,8-dihydroxynaphthalene-1,4-dione, 2-(α,α-dimethyl)naphthalene, 2-(α,α-dimethylbenzyl)naphthalene, 2-t-amylnaphthalene and 2-trimethylsilyl-1,4,5,8,-dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene, The thermal polymerization inhibitor is selected from dibutylhydroxytoluene, di-t-butyl-p-cresol, phlorogricinol, 2-mercaptobenzimidazole, phenothiazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and a phosphite-based antioxidant represented by the following formula (R-5). 【Chemistry 2】 The aforementioned polymer A compound (A) having at least one disulfide bond and two or more functional compounds, Compound (B) having two or more epoxy groups, different from the above compound (A) The reaction product is a resist underlayer film forming composition.

3. The resist underlayer forming composition according to claim 1 or 2, wherein the compound (B) having two or more epoxy groups includes an aromatic ring structure or a heterocyclic structure having 6 to 40 carbon atoms.

4. The resist underlayer film forming composition according to any one of claims 1 to 3, further comprising a crosslinking catalyst.

5. The resist underlayer film forming composition according to any one of claims 1 to 4, further comprising a crosslinking agent.

6. 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 5.

7. A method for manufacturing a resist-patterned substrate for use in the manufacture of a semiconductor device, comprising the steps of: applying a resist underlayer forming composition according to any one of Claims 1 to 5 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 the resist film after exposure.

8. 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 5, A step of forming a resist film on the resist underlayer film, The steps include: exposing the resist film, A step of developing the resist film after exposure to form a resist pattern, 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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