Composition for forming a chemical-resistant protective film containing a hydroxyaryl-terminated polymer

Abstract

The present invention provides the following protective film-forming composition and a protective film manufactured using the composition, a substrate with a resist pattern, and a method for manufacturing a semiconductor device. The above-mentioned protective film-forming composition has a good masking (protection) function for wet etching liquid during semiconductor substrate processing, a high dry etching rate, and further has good coverage for high-height substrates, a small film thickness difference after embedding, and can form a flat film. A protective film-forming composition for semiconductor wet etching liquid, wherein the reaction product (P) of a diepoxy compound (B) and a proton-generating compound (C) with two or more functional groups contains the structure shown in the following formula (1): (In formula (1), Ar represents an aromatic group having 6 to 40 carbon atoms, n represents an integer from 2 to 10, -Y- represents -OCO-, -O- or -S-, and * represents a bonding portion to the molecular end of the above-mentioned reaction product (P)), and the above-mentioned protective film-forming composition also contains an organic solvent (S). *-Y-Ar-(OH) n (1)

Description

Technical Field

[0001] The present invention relates to a composition for forming a protective film having particularly excellent resistance to a semiconductor wet etching solution in a photolithography process in semiconductor manufacturing, and also relates to a method for manufacturing a substrate with a resist pattern to which the protective film is applied, and a method for manufacturing a semiconductor device. Background Art

[0002] In semiconductor manufacturing, a photolithography process is well known in which a resist underlayer film is provided between a substrate and a resist film formed thereon to form a resist pattern of a desired shape. After the resist pattern is formed, the substrate is processed. Dry etching is mainly used as this process, but wet etching is sometimes used depending on the type of substrate. Patent Document 1 discloses a protective film-forming composition for alkaline hydrogen peroxide aqueous solution containing a specific crosslinking agent.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2017 / 191767 Summary of the invention

[0006] Problems to be solved by the invention

[0007] When a base substrate is processed by wet etching using a resist underlayer film as an etching mask, the resist underlayer film is required to have a good masking function against a wet etching solution during processing of the base substrate (ie, the masked portion can protect the substrate).

[0008] In such a case, the resist lower film is used as a protective film for the substrate. Further, when the unnecessary protective film is removed by dry etching after wet etching, in order not to damage the base substrate, the protective film requires a protective film with a fast etching speed (high etching rate) that can be quickly removed by dry etching.

[0009] Furthermore, there is a demand for a protective film-forming composition which has good coverage even on a so-called uneven substrate, has a small difference in film thickness after embedding, and can form a flat film.

[0010] Conventionally, a method of using a low molecular weight compound (eg, gallic acid) as an additive to develop resistance to SC-1 (ammonia-hydrogen peroxide solution), which is a type of wet etching solution, has been used, but this method has limited effect on solving the above-mentioned problems.

[0011] An object of the present invention is to solve the above-mentioned problems.

[0012] Means for solving problems

[0013] The present invention includes the following aspects. [1]

[0015] A protective film forming composition for a semiconductor wet etching solution, wherein a reaction product (P) of a diepoxy compound (B) and a proton-generating compound (C) having two or more functional groups comprises a structure represented by the following formula (1), and the protective film forming composition further comprises an organic solvent (S).

[0016] *-Y-Ar-(OH) n Formula (1)

[0017] (In formula (1), Ar represents an aromatic group having 6 to 40 carbon atoms, n represents an integer of 2 to 10, -Y- represents -OCO-, -O- or -S-, and * represents a bonded portion to the molecular terminal of the above reaction product (P)) [2]

[0019] The protective film-forming composition according to [1], wherein the bifunctional or higher-functional proton-generating compound (C) has a functional group selected from a hydroxyl group, a carboxyl group, a thiol group, an amino group and an imide group. [3]

[0021] The protective film-forming composition according to [1], wherein the bifunctional or higher-functional proton-generating compound (C) is an acid dianhydride. [4]

[0023] The protective film-forming composition according to any one of [1] to [3], wherein the reaction product (P) contains a structural unit represented by the following formula (2).

[0024]

[0025] (In formula (2), Q1 and Q2 represent a divalent organic group, and A1 to A6 represent a hydrogen atom, a methyl group or an ethyl group.) [5]

[0027] According to the protective film-forming composition according to claim 4, Q1 in the above formula (2) is represented by the following formula (3).

[0028] -Z1-R2-Z1- Formula (3)

[0029] (In formula (3), R2 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or a divalent organic group having at least one alicyclic hydrocarbon ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 14 carbon atoms, which may be interrupted by -O-, -S- or -SS-, and the divalent organic group may be substituted by at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a methylene group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. Z1 and Z2 each represent any one of -COO-, -OCO-, -O-, and -S-.) [6]

[0031] According to the protective film forming composition according to claim 4 or 5, Q2 in the above formula (2) is represented by the following formula (4).

[0032]

[0033] (In the above formula (4), R1 represents a direct bond or an alkylene group having 1 to 5 carbon atoms, n1 and m represent an integer of 0 or 1, and Z2 is represented by the following formula (5), formula (6) or formula (7),

[0034]

[0035] (In the above formula (6), X is represented by the following formula (8), formula (9) or formula (10),

[0036]

[0037] (In formula (8), formula (9) and formula (10), R 11 , R 12 , R 13 , R 14 and R 15 Each independently represents 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, wherein the phenyl group may be substituted by at least one selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 6 carbon atoms and an alkylthio group having 1 to 6 carbon atoms, and R 13 With R 14 They can combine with each other to form a ring with 3 to 6 carbon atoms.) [7]

[0039] The protective film forming composition according to any one of [1] to [6], wherein Ar contains a benzene, naphthalene, and anthracene structure. [8]

[0041] The protective film-forming composition according to any one of [1] to [7], wherein n is an integer of 2 to 4. [9]

[0043] The protective film-forming composition according to any one of [1] to [8], further comprising a crosslinking agent (K).

[10]

[0045] The protective film-forming composition according to [9], wherein the crosslinking agent (K) is a compound selected from the group consisting of a compound represented by the following formula (11) or (12), a melamine compound, a guanamine compound, a glycoluril compound, and a urea compound.

[0046]

[0047] (In equations (11) and (12), Q 2 Represents a single bond or an m2-valent organic group. 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group, R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0048] n9 represents an integer of 1≤n9≤3, n10 represents an integer of 2≤n10≤5, n11 represents an integer of 0≤n11≤3, n12 represents an integer of 0≤n12≤3, and 3≤(n9+n10+n11+n12)≤6.

[0049] n13 represents an integer of 1≤n13≤3, n14 represents an integer of 1≤n14≤4, n15 represents an integer of 0≤n15≤3, n16 represents an integer of 0≤n16≤3, and 2≤(n13+n14+n15+n16)≤5. m2 represents an integer of 2 to 10.

[11]

[0051] The protective film-forming composition according to any one of [1] to

[10] , further comprising a crosslinking catalyst.

[12]

[0053] The protective film-forming composition according to any one of [1] to

[11] , further comprising a surfactant.

[13]

[0055] A protective film characterized by being a fired product of a coating film formed from the protective film-forming composition according to any one of [1] to

[13] .

[14]

[0057] A method for manufacturing a substrate with a resist pattern, characterized in that it is used in semiconductor manufacturing, and the method for manufacturing a substrate with a resist pattern comprises the following steps: a step of applying the protective film forming composition described in any one of [1] to

[13] on a semiconductor substrate and firing it to form a protective film as a resist underlayer film; and a step of forming a resist film on the protective film, followed by exposing and developing it to form a resist pattern.

[15]

[0059] A method for manufacturing a semiconductor device, comprising the following steps: forming a protective film on a semiconductor substrate on which an inorganic film can be formed using the protective film forming composition described in any one of [1] to

[13] , forming a resist pattern on the protective film, dry-etching the protective film using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and wet-etching the inorganic film or the semiconductor substrate using a semiconductor wet etching solution using the dry-etched protective film as a mask, and then cleaning the protective film.

[0060] Effects of the Invention

[0061] The protective film-forming composition of the present invention is required to have the following properties in a well-balanced manner in the photolithography process in semiconductor manufacturing. (1) having a good masking function for a wet etching solution when processing a base substrate, (2) having a further high dry etching rate, and (3) having excellent planarization properties for a high-height substrate. By having these properties (1) to (3) in a well-balanced manner, microfabrication of a semiconductor substrate can be easily performed. DETAILED DESCRIPTION

[0062] 《Explanation of Terminology》

[0063] The terms used in the present invention have the following definitions unless otherwise specified.

[0064] Examples of the “alkylene group having 1 to 10 carbon atoms” include a methylene group, an ethylene group, a n-propylene group, an isopropylene group, a cyclopropylene group, a n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a cyclobutylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 1-ethyl-n-propylene group, a cyclopentylene group, a 1-methyl-cyclobutylene group, a 2-methyl- Cyclobutylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclopentylene, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4 -dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene or n-decylene.

[0065] Examples of the “alkyl group having 1 to 10 carbon atoms” include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-n-butyl, 1 ,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-butyl 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl , 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.

[0066] Examples of the “aryl group having 6 to 40 carbon atoms” include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl.

[0067] Examples of the “alkenyl group having 2 to 10 carbon atoms” include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3- butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3- dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, etc.

[0068] The "alkenylene group having 2 to 6 carbon atoms" refers to a group obtained by removing one hydrogen atom from the alkenyl group having 2 to 6 carbon atoms in the above-mentioned "alkenyl group having 2 to 10 carbon atoms" to obtain a divalent group.

[0069] Examples of the "alicyclic hydrocarbon ring having 3 to 10 carbon atoms" include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, tricyclo[3.2.1.0 2,7 ]octane, spiro[3,4]octane, etc.

[0070] The "aromatic hydrocarbon ring having 6 to 14 carbon atoms" refers to a group having an aromatic hydrocarbon ring having 6 to 14 carbon atoms among the above-mentioned "aryl groups having 6 to 40 carbon atoms".

[0071] The "alkynyl group having 2 to 6 carbon atoms" refers to a group in which the double bond of the alkenyl group having 2 to 6 carbon atoms among the above-mentioned "alkenyl group having 2 to 10 carbon atoms" is converted into a triple bond.

[0072] Examples of the “alkoxy group having 1 to 20 carbon atoms” include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy , 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, cyclopentyloxy, cyclohexyloxy, norbornyloxy, adamantyloxy, adamantylmethyloxy, adamantylethyloxy, tetracyclodecanyloxy, tricyclodecanyloxy, and the like.

[0073] Examples of the "alkoxycarbonyl group having 1 to 6 carbon atoms" include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl and the like.

[0074] Examples of the "alkylthio group having 1 to 6 carbon atoms" include methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio.

[0075] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0076] <Protective film forming composition>

[0077] The protective film forming composition of the present application is the following protective film forming composition for semiconductor wet etching solution, which contains a reaction product (P) of a diepoxy compound (B) and a proton-generating compound (C) with two or more functional groups, and also contains an organic solvent (S), and the reaction product (P) contains a structure represented by the following formula (1) at the end.

[0078] *-Y-Ar-(OH) n Formula (1)

[0079] (In formula (1), Ar represents an aromatic group having 6 to 40 carbon atoms, n represents an integer of 2 to 10, -Y- represents -OCO-, -O- or -S-, and * represents a bonded portion to the molecular terminal of the above reaction product (P))

[0080] The functional group possessed by the bifunctional or higher-functional proton-generating compound (C) is a functional group that generates a proton, and specifically, is preferably selected from a hydroxyl group, a carboxyl group, a thiol group, an amino group, and an imide group.

[0081] The above-mentioned bifunctional or higher-functional proton-generating compound (C) may be an acid dianhydride.

[0082] The protective film forming composition of the present application is a reaction product (P) of a diepoxy compound (B) and a proton-generating compound (C) having two or more functional groups, preferably a reaction product (P) of a diepoxy compound (B) and a proton-generating compound (C) having two, three or four functional groups, preferably a reaction product (P) of a diepoxy compound (B) and a proton-generating compound (C) having two or three functional groups, and preferably a reaction product (P) of a diepoxy compound (B) and a proton-generating compound (C) having two functional groups.

[0083] The reaction product (P) preferably contains a structural unit represented by the following formula (2).

[0084]

[0085] (In formula (4), Q1 and Q2 represent a divalent organic group, and A1 to A6 represent a hydrogen atom, a methyl group or an ethyl group.)

[0086] Q1 in the above formula (2) is preferably represented by the following formula (3).

[0087] -Z1-R2-Z1- Formula (3)

[0088] (In formula (3), R2 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or a divalent organic group having at least one alicyclic hydrocarbon ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 14 carbon atoms, which may be interrupted by -O-, -S- or -SS-, and the divalent organic group may be substituted by at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a methylene group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. Z1 and Z2 each represent any one of -COO-, -OCO-, -O-, and -S-.)

[0089] Q2 in the above formula (2) is preferably represented by the following formula (4).

[0090]

[0091] (In the above formula (4), R1 represents a direct bond or an alkylene group having 1 to 5 carbon atoms, n1 and m represent an integer of 0 or 1, and Z2 is represented by the following formula (5), formula (6) or formula (7),

[0092]

[0093] (In the above formula (6), X is represented by the following formula (8), formula (9) or formula (10),

[0094]

[0095] (In formula (8), formula (9) and formula (10), R 11 , R 12 , R 13 , R 14 and R 15 Each independently represents 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, wherein the phenyl group may be substituted by at least one selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 6 carbon atoms and an alkylthio group having 1 to 6 carbon atoms, and R 13 With R 14 They can combine with each other to form a ring with 3 to 6 carbon atoms.)

[0096] Examples of the "ring having 3 to 6 carbon atoms" include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene and cyclohexane.

[0097] The above Ar preferably contains benzene, naphthalene and anthracene structures.

[0098] The above n is preferably an integer of 2-4.

[0099] Specific examples of the diepoxy compound (B) of the present application include the following compounds (a-1) to (a-24).

[0100]

[0101]

[0102] Specific examples of the bifunctional or higher-functional proton-generating compound (C) of the present application include the following compounds (b-1) to (b-27).

[0103]

[0104] The protective film-forming composition of the present application may be obtained by reacting the diepoxy compound (B), the difunctional or higher-functional proton-generating compound (C), and the following compounds (c-1) to (c-17).

[0105]

[0106] The protective film-forming composition of the present application may further contain a crosslinking agent (K).

[0107] The crosslinking agent (K) may be a compound selected from the group consisting of compounds described in WO2014 / 208542 and represented by the following formula (11) or (12), melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds.

[0108]

[0109] (In equations (11) and (12), Q 2 Represents a single bond or an m2-valent organic group. 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group, R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0110] n9 represents an integer of 1≤n9≤3, n10 represents an integer of 2≤n10≤5, n11 represents an integer of 0≤n11≤3, n12 represents an integer of 0≤n12≤3, and 3≤(n9+n10+n11+n12)≤6.

[0111] n13 represents an integer of 1≤n13≤3, n14 represents an integer of 1≤n14≤4, n15 represents an integer of 0≤n15≤3, n16 represents an integer of 0≤n16≤3, and 2≤(n13+n14+n15+n16)≤5. m2 represents an integer of 2 to 10.

[0112] Specific examples of the melamine compound include, but are not limited to, hexamethylolmelamine, hexamethoxymethylmelamine, compounds obtained by methoxymethylating 1 to 6 methylol groups of hexamethylolmelamine, or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds obtained by acyloxymethylating 1 to 6 methylol groups of hexamethylolmelamine, or mixtures thereof. Specific examples of the epoxy compound include, for example, tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like.

[0113] Specific examples of the guanamine compounds include, but are not limited to, tetrakishydroxymethylguanamine, tetramethoxymethylguanamine, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetrakishydroxymethylguanamine, or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds obtained by acyloxymethylating 1 to 4 hydroxymethyl groups of tetrakishydroxymethylguanamine, or mixtures thereof.

[0114] Specific examples of glycoluril compounds include, for example, tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril, or mixtures thereof, compounds obtained by acyloxymethylating 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril, or mixtures thereof. Specific examples of urea compounds include, for example, tetrakishydroxymethyl urea, tetramethoxymethyl urea, compounds obtained by methoxymethylating 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl urea, or mixtures thereof, and tetramethoxyethyl urea.

[0115] Specific examples of the compound containing an alkenyl ether group include, but are not limited to, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0116] Among them, glycoluril compounds are preferred, and specifically, tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are methoxymethylated or mixtures thereof, compounds in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are acyloxymethylated or mixtures thereof are preferred, and tetramethoxymethyl glycoluril is preferred.

[0117] Further, examples of the crosslinking agent (K) include a compound having a partial structure of the following formula (5-1) and a polymer or oligomer having a repeating unit of the following formula (5-2).

[0118]

[0119] The above R 11 , R 12 , R 13 , and R 14 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups exemplified above can be used.

[0120] m1 is 1≤m1≤6-m2, m2 is 1≤m2≤5, m3 is 1≤m3≤4-m2, and m4 is 1≤m4≤3.

[0121] The compounds, polymers and oligomers of formula (5-1) and formula (5-2) are exemplified below.

[0122]

[0123]

[0124] The above compounds can be obtained as products of Asahi Organic Materials Industries, Ltd. and Honshu Chemical Industries, Ltd. For example, among the above crosslinking agents, the compound of formula (6-22) can be obtained as TMOM-BP from Asahi Organic Materials Industries, Ltd.

[0125] The amount of the crosslinking agent added varies depending on the coating solvent used, the base 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 protective film-forming composition. These crosslinking agents may also undergo a crosslinking reaction caused by self-condensation, but when there is a crosslinking substituent in the above-mentioned polymer of the present invention, a crosslinking reaction may occur with these crosslinking substituents.

[0126] [Cross-linking catalyst]

[0127] In order to promote the crosslinking reaction, the protective film forming composition of the present invention may contain a crosslinking catalyst as an optional component. As the crosslinking catalyst, in addition to acidic compounds and basic compounds, compounds that generate acid or base by heat can also be used, but crosslinking acid catalysts are preferred. As acidic compounds, sulfonic acid compounds or carboxylic acid compounds can be used, and as compounds that generate acid by heat, thermal acid generators can be used.

[0128] Examples of the sulfonic acid compound or carboxylic acid compound include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine Trifluoromethanesulfonate (pyridine Trifluoromethanesulfonic acid), pyridine - p-Toluenesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, pyridine -4-Phenolsulfonate, benzene disulfonic acid, 1-naphthalenesulfonic acid, 4-nitrobenzenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid.

[0129] Examples of the thermal acid generator include K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, and K-PURE 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.).

[0130] These crosslinking catalysts may be used alone or in combination of two or more. In addition, as the basic compound, an amine compound or an ammonium hydroxide compound may be used, and as the compound that generates a base by heat, urea may be used.

[0131] As the amine compound, for example, tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, tri-n-octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane, and aromatic amines such as pyridine and 4-dimethylaminopyridine can be mentioned. In addition, primary amines such as benzylamine and n-butylamine, and secondary amines such as diethylamine and di-n-butylamine can also be mentioned as the amine compound. These amine compounds can be used alone or in combination of two or more.

[0132] Examples of the ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide.

[0133] In addition, as the compound that generates a base by heat, for example, a compound having a thermally unstable group such as an amide group, a carbamate group or an aziridine group, which generates an amine by heating, can be used. In addition, urea, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyldimethylphenylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltributylammonium chloride, and choline chloride can also be cited as the compound that generates a base by heat.

[0134] When the protective film forming composition contains a crosslinking catalyst, the content thereof is 0.0001 to 20% by mass, preferably 0.01 to 15% by mass, and more preferably 0.1 to 10% by mass, based on the total solid content of the protective film forming composition.

[0135] [Surfactant]

[0136] In order to improve the coating property on the semiconductor substrate, the protective film forming composition of the present invention may contain a surfactant as an optional component. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and other polyoxyethylene alkyl aryl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, and the like. sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., nonionic surfactants, EFTTOP (Registered Trademark) Standards: EF301, EEF303, EEF352 (Mitsubishi Mitsubishi Electric Made by Kosei Co., Ltd.), Mikake F171, Mikake F173,メガファックR-30、メガファックR-40、メガファックR-40-LM(DI C Co., Ltd.), Fluoro FC430, Fluoro FC431 (Sumitomo Solar Co., Ltd. Fluorine-based surfactants such as Asahi Glass Co., Ltd., Asahigard AG710, S-382, S-101, S-102, S-103, S-104, S-105, and S-106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more. When the protective 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 protective film-forming composition.

[0137] [Organic solvent (S)]

[0138] The protective film-forming composition of the present invention can be prepared by dissolving the above-mentioned components in an organic solvent (S) and can be used in a uniform solution state.

[0139] As the organic solvent (S) of the protective film forming composition of the present invention, any solvent that can dissolve the compound containing at least one group of two adjacent hydroxyl groups in the molecule or a polymer thereof can be used without particular limitation. In particular, since the protective film forming composition of the present invention is used in a uniform solution state, it is recommended to use an organic solvent generally used in a photolithography process in combination if its coating performance is taken into consideration.

[0140] Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, and 2-hydroxyisobutyric acid. Methyl ester, ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0141] 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.

[0142] [Other ingredients]

[0143] The protective film forming composition of the present invention may contain a light absorber, a rheology modifier, an adhesion promoter, etc. The rheology modifier is effective in improving the fluidity of the protective film forming composition. The adhesion promoter is effective in improving the adhesion between the semiconductor substrate or the resist and the underlying film.

[0144] As the light absorber, for example, commercially available light absorbers described in "Technology and Market of Industrial Pigments" (published by CMC) and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry) can be suitably used, for example, CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Disperse Violet 43; CI Disperse Blue 96; CI Fluorescent Brightener 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The light absorber is usually blended in a ratio of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the protective film-forming composition.

[0145] The rheology modifier is mainly added to improve the fluidity of the protective film forming composition, especially in the baking process, to improve the uniformity of the film thickness of the protective film and to improve the filling property of the protective film forming composition into the hole. As a specific example, phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, di-n-butyl maleate, diethyl maleate, dinonyl maleate and other maleic acid derivatives, oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, or stearic acid derivatives such as n-butyl stearate and glyceryl stearate can be cited. These rheology modifiers are usually mixed in a ratio of less than 30% by mass relative to the total solid content of the protective film forming composition.

[0146] The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate or the resist and the protective film-forming composition, and in particular, for the purpose of preventing the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylhydroxymethylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylhydroxymethylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; silanes such as hydroxymethyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole. Heterocyclic compounds such as azole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine, urea such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion promoters are usually mixed in a ratio of less than 5% by mass, preferably less than 2% by mass, relative to the total solid content of the protective film forming composition.

[0147] [Protective film forming composition]

[0148] The solid content of the protective film forming composition of the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the content ratio of all components after removing the solvent from the protective film forming composition. The proportion of the polymer in the solid content is preferably in the order of 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.

[0149] [Substrate with resist pattern and method for manufacturing semiconductor device]

[0150] Hereinafter, a method for producing a substrate with a resist pattern and a method for producing a semiconductor device using the protective film-forming composition according to the present invention will be described.

[0151] The substrate with a resist pattern according to the present invention can be produced by applying the protective film-forming composition on a semiconductor substrate and firing the coating.

[0152] Examples of semiconductor substrates to which the protective film-forming composition of the present invention can be applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0153] When a semiconductor substrate having an inorganic film formed on the surface is used, the inorganic film is formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum evaporation method, spin coating method (spin-on glass: SOG). Examples of the inorganic film include polycrystalline silicon film, silicon oxide film, silicon nitride film, silicon oxynitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium oxynitride film, tungsten nitride film, gallium nitride film, and gallium arsenide film.

[0154] On such a semiconductor substrate, the protective film forming composition of the present invention is applied by a suitable coating method such as a spin coater or a coater. Then, a heating means such as a hot plate is used to bake to form a protective film. As baking conditions, it can be 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, the baking time is 0.5 minutes to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C, and the baking time is 0.8 minutes to 10 minutes. As the film thickness of the protective film formed, for example, it is 0.001μm to 10μm, preferably 0.002μm to 1μm, and more preferably 0.005μm to 0.5μm. When the temperature during baking is lower than the above range, crosslinking sometimes becomes insufficient, and it is not easy to obtain the resistance of the formed protective film to the resist solvent or the alkaline hydrogen peroxide aqueous solution. On the other hand, when the temperature during baking is higher than the above range, the protective film is sometimes decomposed by heat.

[0155] Exposure is performed through a mask (photomask) for forming a prescribed pattern, using, for example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet rays) or EB (electron beams). An alkaline developer is used for development, and is appropriately selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. As an alkaline developer, for example, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc., a primary amine such as ethylamine, n-propylamine, a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, etc., an alcohol amine such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, cyclic amines such as pyrrole and piperidine, etc. can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol, a nonionic surfactant, etc. can also be added to the aqueous solution of the above-mentioned alkali and used. Among them, preferred developer is quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline. Further, surfactants etc. may be added to these developers. Alternatively, a method may be used in which an organic solvent such as butyl acetate is used to develop the portion of the photoresist where the alkali dissolution rate is not increased, instead of an alkaline developer.

[0156] 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, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.

[0157] Furthermore, wet etching is performed using a semiconductor wet etching solution using the protective film after dry etching (when a resist pattern remains on the protective film, the resist pattern is also used) as a mask, thereby forming a desired pattern.

[0158] As the semiconductor wet etching solution, a general chemical solution used for etching a semiconductor wafer can be used, and for example, either an acidic substance or an alkaline substance can be used.

[0159] Examples of the acidic substance include hydrogen peroxide, hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrogen fluoride, buffered hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and a mixed solution thereof.

[0160] As a substance showing alkalinity, an alkaline hydrogen peroxide solution obtained by mixing an organic amine such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, triethanolamine, etc. with hydrogen peroxide solution to make the pH alkaline can be cited. As a specific example, SC-1 (ammonia-hydrogen peroxide solution) can be cited. In addition, a substance that can make the pH alkaline, for example, a substance that can make the pH alkaline by mixing urea with hydrogen peroxide solution, causing thermal decomposition of urea by heating to generate ammonia, and finally making the pH alkaline can also be used as a wet etching solution.

[0161] Among them, acidic hydrogen peroxide water or alkaline hydrogen peroxide water is preferred.

[0162] These chemical solutions may contain additives such as surfactants.

[0163] The use temperature of the semiconductor wet etching solution is preferably 25° C. to 90° C., more preferably 40° C. to 80° C. The wet etching time is preferably 0.5 minute to 30 minutes, more preferably 1 minute to 20 minutes.

[0164] Example

[0165] Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0166] The weight average molecular weights of the polymers shown in Synthesis Examples 1 to 4 in the present specification are the results of measurements by gel permeation chromatography (hereinafter referred to as GPC). The measurement was performed using a GPC apparatus manufactured by Tosoh Corporation, and the measurement conditions and the like were as follows.

[0167] GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801〔Registered trademark〕(Showa Denko K.K.)

[0168] Column temperature: 40°C

[0169] Solvent: Tetrahydrofuran (THF)

[0170] Flow rate: 1.0ml / min

[0171] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0172] <Synthesis example 1>

[0173] 20.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd., product name: MA-DGIC), 12.69 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., product name: DTDPA), 4.22 g of gallic acid hydrate and tetrabutyl bromide as a catalyst were mixed. 1.81 g was dissolved in 58.09 g of propylene glycol monomethyl ether and reacted at 105° C. for 24 hours to obtain a solution containing a reaction product (solid content 40% by mass). The repeating unit and terminal structure of the obtained reaction product are represented by formula (D-1). GPC analysis of the obtained reaction product was performed, and the result showed that the weight average molecular weight was 3100 in terms of standard polystyrene.

[0174]

[0175] <Synthesis example 2>

[0176] 20.00 g of diglycidyl terephthalate (Naga Sechem Textiles Co., Ltd., product name EX-711), 12.33 g of 3,3'-dithiodipropionic acid (Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 4.11 g of gallic acid hydrate and tetrabutyl bromide as a catalyst were mixed. 1.76 g was dissolved in 57.29 g of propylene glycol monomethyl ether and reacted at 105° C. for 24 hours to obtain a solution containing a reaction product (solid content 40% by mass). The repeating unit and terminal structure of the obtained reaction product are represented by formula (D-2). GPC analysis of the obtained reaction product was performed, and the result showed that the weight average molecular weight was 3900 in terms of standard polystyrene.

[0177]

[0178] <Synthesis example 3>

[0179] 20.00 g of 1,3'-diglycidylhydantoin (manufactured by Shikoku Chemical Industry Co., Ltd.), 12.69 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 4.23 g of gallic acid hydrate and tetrabutyl bromide as a catalyst were mixed. 1.81 g was dissolved in 58.09 g of propylene glycol monomethyl ether and reacted at 105° C. for 24 hours to obtain a solution containing a reaction product (solid content 40% by mass). The repeating unit and terminal structure of the obtained reaction product are represented by formula (D-3). GPC analysis of the obtained reaction product was performed, and the result showed that the weight average molecular weight was 3900 in terms of standard polystyrene.

[0180]

[0181] <Synthesis example 4>

[0182] 20.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd., product name MA-DGIC), 16.42 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., product name: DTDPA), and ethyltriphenylphosphine bromide as a catalyst were mixed. 0.659 g was dissolved in 92.71 g of propylene glycol monomethyl ether and reacted at 105° C. for 24 hours to obtain a solution containing a reaction product (solid content 20% by mass). The obtained reaction product had a repeating unit of formula (D-4). GPC analysis of the obtained reaction product was performed, and the result showed that the weight average molecular weight was 4600 in terms of standard polystyrene.

[0183]

[0184] The present invention will be described in more detail below by way of examples. However, the present invention is not limited to the following examples. In addition, as the alkaline hydrogen peroxide aqueous solution, a liquid having a composition shown in Table 1 below was used, but the alkaline hydrogen peroxide aqueous solution used in the present invention is not limited to this composition.

[0185] <Example 1>

[0186] Pyridine was added to 27.62 g of the polymer-containing solution obtained in Synthesis Example 1. 0.552 g of trifluoromethanesulfonic acid, 18.84 g of propylene glycol monomethyl ether acetate, and 152.99 g of propylene glycol monomethyl ether were mixed to prepare a solution, and the solution was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a protective film-forming composition.

[0187] <Example 2>

[0188] Pyridine was added to 27.62 g of the polymer-containing solution obtained in Synthesis Example 2. 0.552 g of trifluoromethanesulfonic acid, 18.84 g of propylene glycol monomethyl ether acetate, and 152.99 g of propylene glycol monomethyl ether were mixed to prepare a solution, and the solution was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a protective film-forming composition.

[0189] <Example 3>

[0190] Pyridine was added to 27.62 g of the polymer-containing solution obtained in Synthesis Example 3. 0.552 g of trifluoromethanesulfonic acid, 18.84 g of propylene glycol monomethyl ether acetate, and 152.99 g of propylene glycol monomethyl ether were mixed to prepare a solution, and the solution was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a protective film-forming composition.

[0191] <Example 4>

[0192] Pyridine was added to 27.62 g of the polymer-containing solution obtained in Synthesis Example 1. 0.552 g of trifluoromethanesulfonic acid, 1.105 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 18.84 g of propylene glycol monomethyl ether acetate, and 152.99 g of propylene glycol monomethyl ether were prepared into a solution, and the solution was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a protective film-forming composition.

[0193] <Comparative Example 1>

[0194] Pyridine was added to 55.24 g of the polymer-containing solution obtained in Synthesis Example 4. 0.552 g of trifluoromethanesulfonic acid, 18.84 g of propylene glycol monomethyl ether acetate, and 125.37 g of propylene glycol monomethyl ether were mixed to prepare a solution, and the solution was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a protective film-forming composition.

[0195] (Formation of coating film)

[0196] The protective film-forming compositions prepared in Examples 1 to 3 and the film-forming composition prepared in Comparative Example 1 were applied by spin coating on a silicon substrate having a titanium nitride film formed on the surface, and baked at 220° C. for 60 seconds to prepare a coating film having a thickness of 100 nm.

[0197] (Resistance test to alkaline hydrogen peroxide aqueous solution)

[0198] The coating films prepared on the silicon substrate having a titanium nitride film formed on the surface using the protective film forming compositions prepared in Examples 1 to 3 and the film forming compositions prepared in Comparative Example 1 were immersed in an alkaline hydrogen peroxide aqueous solution having the composition shown in Table 1 below at the temperature shown in the table for 1 minute, then washed with water, and the state of the coating films after drying was visually observed. The results are shown in Table 2 below. "○" in Table 2 indicates that no peeling of the coating film was observed even after the 1-minute treatment, and "×" indicates that peeling was observed in part or all of the coating film after the 1-minute treatment.

[0199] [Table 1]

[0200] Table 1

[0201] Composition and treatment temperature of alkaline hydrogen peroxide aqueous solution

[0202]

[0203] [Table 2]

[0204] Table 2

[0205] Results of the resistance test Example 1 ○ Example 2 ○ Example 3 ○ Example 4 ○ Comparative Example 1 ×

[0206] From the results in Table 2 above, it is shown that the coating films produced using the protective film-forming compositions prepared in Examples 1 to 3 have sufficient resistance to alkaline aqueous hydrogen peroxide solutions. In other words, it is known that these coating films can serve as protective films against alkaline aqueous hydrogen peroxide solutions. On the other hand, it is shown that the coating film produced using the film-forming composition prepared in Comparative Example 1 does not have resistance to alkaline aqueous hydrogen peroxide solutions, and it is clear that these coating films cannot serve as protective films against alkaline aqueous hydrogen peroxide solutions.

[0207] Industrial Availability

[0208] The protective film-forming composition of the present invention has excellent resistance to wet etching liquid when used for substrate processing and has a high dry etching rate, so that substrate processing is easy and a protective film with excellent planarization properties when applied to a substrate with unevenness is provided.

Claims

1. A composition for forming a protective film for a semiconductor wet etching solution, wherein: The reaction product (P) of the diepoxy compound (B) and the difunctional or higher-functional proton-generating compound (C) comprises a structure represented by the following formula (1), and the protective film-forming composition further comprises an organic solvent (S). *-Y-Ar-(OH) n Formula (1) In the formula (1), Ar represents an aromatic group having 6 to 40 carbon atoms, n represents an integer of 2 to 10, -Y- represents -OCO-, -O- or -S-, and * represents a portion that is bonded to the molecular terminal of the reaction product (P). The reaction product (P) is a reaction product (P) produced by reacting the diepoxy compound (B), the bifunctional or higher-functional proton-generating compound (C), and further the following compounds (c-1) and (c-3) to (c-17). 2 . The protective film-forming composition according to claim 1 , wherein the bifunctional or higher-functional proton-generating compound (C) has a functional group selected from a hydroxyl group, a carboxyl group, a thiol group, an amino group and an imide group. 3 . The protective film-forming composition according to claim 1 , wherein the bifunctional or higher-functional proton-generating compound (C) is an acid dianhydride.

4. The protective film-forming composition according to claim 1, wherein the reaction product (P) comprises a structural unit represented by the following formula (2): In formula (2), Q1 and Q2 represent a divalent organic group, and A1 to A6 represent a hydrogen atom, a methyl group or an ethyl group.

5. A composition for forming a protective film for a semiconductor wet etching solution, wherein: The reaction product (P) of the diepoxy compound (B) and the difunctional or higher-functional proton-generating compound (C) comprises a structure represented by the following formula (1), and the protective film-forming composition further comprises an organic solvent (S). *-Y-Ar-(OH) n Formula (1) In the formula (1), Ar represents an aromatic group having 6 to 40 carbon atoms, n represents an integer of 2 to 10, -Y- represents -OCO-, -O- or -S-, and * represents a portion that is bonded to the molecular terminal of the reaction product (P). The reaction product (P) comprises a structural unit represented by the following formula (2): In formula (2), Q1 and Q2 represent divalent organic groups, A1 to A6 represent hydrogen atoms, methyl groups or ethyl groups, Q1 in the formula (2) is represented by the following formula (3): -Z1-R2-Z1- Formula (3) In formula (3), R2 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or a divalent organic group having at least one aromatic hydrocarbon ring having 6 to 14 carbon atoms, which may be interrupted by -O-, -S- or -SS-, and the divalent organic group may be substituted by at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a methylene group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; Z1 and Z2 each represent any one of -COO-, -OCO-, -O-, and -S-.

6. The protective film-forming composition according to claim 4, wherein Q1 in the formula (2) is represented by the following formula (3): -Z1-R2-Z1- Formula (3) In formula (3), R2 represents a divalent organic group which is a direct bond or may be interrupted by -O-, -S- or -SS-, and which is an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or having at least one alicyclic hydrocarbon ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 14 carbon atoms, and the divalent organic group may be substituted by at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a methylene group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; and Z1 and Z2 each represent any one of -COO-, -OCO-, -O-, and -S-.

7. The protective film-forming composition according to claim 4 or 5, wherein Q2 in the formula (2) is represented by the following formula (4): In the formula (4), R1 represents a direct bond or an alkylene group having 1 to 5 carbon atoms, n1 and m represent integers of 0 or 1, and Z2 is represented by the following formula (5), formula (6) or formula (7), In the above formula (6), X is represented by the following formula (8), formula (9) or formula (10), In formula (8), formula (9) and formula (10), R 11 , R 12 , R 13 , R 14 and R 15 Each independently represents 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, wherein the phenyl group may be substituted by at least one selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group, an alkoxy group having 1 to 6 carbon atoms and an alkylthio group having 1 to 6 carbon atoms, and R 13 With R 14 They may be bonded to each other to form a ring having 3 to 6 carbon atoms. 8 . The protective film-forming composition according to claim 1 , wherein Ar comprises a benzene, naphthalene, and anthracene structure. 9 . The protective film-forming composition according to claim 1 , wherein n is an integer of 2 to 4.

10. The protective film-forming composition according to claim 1 or 5, wherein the diepoxy compound (B) is represented by the following formulas (a-1) to (a-24):

11. The protective film-forming composition according to claim 1 or 5, wherein the bifunctional or higher-functional proton-generating compound (C) is represented by the following formulas (b-1) to (b-27): 12 . The protective film-forming composition according to claim 1 , further comprising a crosslinking agent (K).

13. The protective film-forming composition according to claim 12, wherein the crosslinking agent (K) is a compound selected from the group consisting of a compound represented by the following formula (11) or (12), a melamine compound, a guanamine compound, a glycoluril compound and a urea compound. In equations (11) and (12), Q 2 Represents a single bond or an m2-valent organic group; R 8 , R 9 , R 11 and R 12 Each represents a hydrogen atom or a methyl group, R 7 and R 10 each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms; n9 represents an integer of 1≤n9≤3, n10 represents an integer of 2≤n10≤5, n11 represents an integer of 0≤n11≤3, n12 represents an integer of 0≤n12≤3, and 3≤(n9+n10+n11+n12)≤6; n13 represents an integer of 1≤n13≤3, n14 represents an integer of 1≤n14≤4, n15 represents an integer of 0≤n15≤3, n16 represents an integer of 0≤n16≤3, and 2≤(n13+n14+n15+n16)≤5; m2 represents an integer of 2-10. 14 . The protective film-forming composition according to claim 1 , further comprising a cross-linking catalyst. 15 . The protective film-forming composition according to claim 1 , further comprising a surfactant.

16. A protective film, characterized in that: A fired product of a coating film formed from the protective film-forming composition according to any one of claims 1 to 15.

17. A method for manufacturing a substrate with a resist pattern, characterized in that: The method for manufacturing a substrate with a resist pattern used in the manufacture of semiconductors comprises the following steps: a step of applying the protective film-forming composition described in any one of claims 1 to 15 on a semiconductor substrate and firing it to form a protective film as a resist underlayer film; a step of forming a resist film on the protective film, followed by exposing and developing it to form a resist pattern.

18. A method for manufacturing a semiconductor device, comprising the following steps: forming a protective film on a semiconductor substrate on which an inorganic film can be formed using the protective film-forming composition described in any one of claims 1 to 15, forming a resist pattern on the protective film, dry-etching the protective film using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and wet-etching the inorganic film or the semiconductor substrate using a semiconductor wet etching solution using the dry-etched protective film as a mask and then cleaning it.

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