Polycarboxylic acid-containing chemical-resistant protective film

Abstract

The purpose of the present invention is to provide: a protective film forming composition which has a good mask (protection) function against a wet etching liquid and a high dry etching rate during processing of a semiconductor substrate and also has good coverage even for a stepped substrate, and from which a flat film can be formed due to a small difference in film thickness after being embedded; a protective film produced using said composition; a substrate with a resist pattern; and a method for producing a semiconductor device. This composition for forming a film for protecting against a semiconductor wet etching solution contains: (A) a compound having three or more carboxyl groups; (B) a resin or a monomer; and a solvent. The compound (A) having three or more carboxyl groups preferably has a ring structure. This ring structure is preferably selected from among an aromatic ring having 6-40 carbon atoms, an aliphatic ring having 3-10 carbon atoms, and a heterocyclic ring.

Description

[Technical field]

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

[0002] In semiconductor manufacturing, a lithography process is widely 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 forming the resist pattern, the substrate is processed, and dry etching is mainly used as the process, but wet etching may be used depending on the type of substrate. Patent Documents 1 and 2 disclose protective film-forming compositions for aqueous hydrogen peroxide solutions containing specific compounds. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 052130 [Patent Document 2] International Publication No. 2018 / 203464 Summary of the Invention [Problem to be solved by the invention]

[0004] When a resist underlayer film is used as an etching mask to process the underlying substrate by wet etching, the resist underlayer film is required to have good masking function against the wet etching solution during processing of the underlying substrate (i.e., the masked portion can protect the substrate).

[0005] In such a case, the resist underlayer film is used as a protective film for the substrate. Furthermore, when the unnecessary protective film is to be removed by dry etching after wet etching, the protective film is required to have a high etching speed (high etching rate) so that it can be quickly removed by dry etching without damaging the underlying substrate.

[0006] Furthermore, there is a demand for a protective film-forming composition that has good coverage even for so-called uneven substrates, has a small difference in film thickness after filling, and is capable of forming a flat film.

[0007] In the past, a method of adding a low molecular weight compound (e.g., gallic acid) as an additive was used to impart resistance to SC-1 (ammonia-hydrogen peroxide solution), a type of wet etching chemical, but this had limitations in solving the above problems.

[0008] An object of the present invention is to solve the above problems. [Means for solving the problem]

[0009] The present invention encompasses the following: [1] (A) a compound containing at least three carboxy groups; (B) a resin or monomer, and A composition for forming a protective film against a wet etching solution for semiconductors, comprising a solvent.

[0010] [2] The protective film-forming composition for a semiconductor wet etching solution according to [1], wherein the compound (A) containing at least three carboxy groups has a ring structure. Preferably, the at least three carboxy groups are bonded to the ring structure directly or via an alkylene group having 1 to 4 carbon atoms.

[0011] [3] The protective film-forming composition for a semiconductor wet etching solution according to [2], wherein the ring structure is selected from an aromatic ring having 6 to 40 carbon atoms, an aliphatic ring having 3 to 10 carbon atoms, and a heterocycle.

[0012] [4] The aromatic ring having 6 to 40 carbon atoms is selected from benzene, naphthalene, and the formula (1): [ka] (In formula (1), X is a divalent organic group selected from a direct bond, -CH2-, -C(CH3)2-, -CO-, -SO2-, and -C(CF3)2-; R1 and R2 are each independently a monovalent organic group selected from an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyano group, a nitro group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms, n1 and n2 are each independently an integer of 1 to 9, n1+n2 is an integer of 3 to 10, and m1 and m2 are each independently an integer of 0 to 7, and m1+m2 is an integer of 0 to 7. The compound (A) containing at least three carboxy groups is (i) Compounds in which the aromatic ring having 6 to 40 carbon atoms is benzene or naphthalene, and (ii) Equation (1): [ka] (In formula (1), X is a divalent organic group selected from a direct bond, -CH2-, -C(CH3)2-, -CO-, -SO2-, and -C(CF3)2-; R1 and R2 are each independently a monovalent organic group selected from an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyano group, a nitro group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms; n1 and n2 are each independently an integer of 1 to 9, n1+n2 is an integer of 3 to 10; m1 and m2 are each independently an integer of 0 to 7, and m1+m2 is an integer of 0 to 7. The protective film-forming composition for a semiconductor wet etching solution according to [3], selected from the following:

[0013] [5] The protective film-forming composition for a semiconductor wet etching solution according to [1], wherein the resin or monomer (B) has at least one hydroxy group within the unit structure of the resin or within the monomer molecule.

[0014] [6] The protective film-forming composition for a semiconductor wet etching liquid according to any one of [1] to [5], further comprising at least one selected from the group consisting of a crosslinking agent, a crosslinking catalyst, and a surfactant.

[0015] [7] The above semiconductor for The protective film-forming composition for a wet etching solution for semiconductors according to any one of [1] to [6], wherein the wet etching solution contains hydrogen peroxide.

[0016] [8] The protective film-forming composition for a semiconductor wet etching solution according to [7], wherein the hydrogen peroxide solution is an acidic hydrogen peroxide solution.

[0017] [9] A protective film against a wet etching solution for semiconductors, comprising a fired product of a coating film made of the protective film-forming composition according to any one of [1] to [8].

[0018]

[10] [1] to [8] The protective film according to any one of the above. formationA method for producing a substrate having a resist pattern, comprising the steps of applying a composition onto a semiconductor substrate and baking the composition to form a protective film as a resist underlayer film, forming a resist film on the protective film, and then exposing and developing the resist film to form a resist pattern, the method being characterized in that the substrate is used in the production of semiconductors.

[0019]

[11] A method for manufacturing a semiconductor device, comprising the steps of forming a protective film on a semiconductor substrate, on whose surface an inorganic film may be formed, using the protective film-forming composition according to any one of [1] to [8], forming a resist pattern on the protective film, dry-etching the protective film using the resist pattern as a mask to expose a surface of the inorganic film or the semiconductor substrate, and wet-etching and / or cleaning the inorganic film or the semiconductor substrate using a semiconductor wet etching solution using the protective film after dry etching as a mask. Effect of the Invention

[0020] The protective film-forming composition of the present invention is required to have, for example, the following properties in a well-balanced manner in the lithography process in semiconductor manufacturing: (1) good masking function against a wet etching solution during processing of the base substrate, (2) high dry etching rate, and (3) excellent planarization ability for uneven substrates. By having a good balance of the properties (1) to (3), fine processing of semiconductor substrates can be easily performed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] <Protective film forming composition> The protective film-forming composition of the present application comprises: (A) a compound containing at least three carboxy groups; (B) A protective film-forming composition for a semiconductor wet etching solution, comprising a resin or a monomer, and a solvent. (A) The compound containing at least three or more carboxy groups preferably contains 3 to 6 carboxy groups, and particularly preferably contains 3 or 4 carboxy groups.

[0022] The compound (A) containing at least three carboxy groups preferably has a ring structure.

[0023] The ring structure is preferably selected from an aromatic ring having 6 to 40 carbon atoms, an aliphatic ring having 3 to 10 carbon atoms, and a heterocycle.

[0024] Examples of the "aromatic ring having 6 to 40 carbon atoms" include 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, and the like.

[0025] Examples of the "aliphatic 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[3.2.1.02,7]octane, spiro[3,4]octane, and the like.

[0026] The aromatic ring having 6 to 40 carbon atoms is selected from benzene and naphthalene, or the compound (A) is represented by the formula (1): [ka] (In formula (1), X is a divalent organic group selected from a direct bond, -CH2-, -C(CH3)2-, -CO-, -SO2-, and -C(CF3)2-; R1 and R2 are each independently a monovalent organic group selected from an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyano group, a nitro group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms; n1 and n2 are each independently an integer of 1 to 9, n1+n2 is an integer of 3 to 10; and m1 and m2 are each independently an integer of 0 to 7, m1+m2 is an integer of 0 to 7.

[0027] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, and a 2-methyl-cyclopropyl group.

[0028] Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group.

[0029] Examples of the above-mentioned "heterocycle" include furan, pyrrole, pyran, imidazole, pyrazole, oxazole, thiophene, thiazole, thiadiazole, imidazolidine, thiazolidine, imidazoline, dioxane, morpholine, diazine, thiazine, triazole, tetrazole, dioxolane, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole and triazine.

[0030] The triazine may be a compound containing a triazineone, a compound containing a triazinedione or a compound containing a triazinetrione, with a compound containing a triazinetrione being preferred.

[0031] Examples of the compound having at least three carboxy groups according to the present invention include, but are not limited to, the following formulae (A-1) to (A-25). [ka]

[0032] <Resin, Monomer> The protective film-forming composition of the present invention contains the above-mentioned (B) resin or monomer as an essential component.

[0033] As the resin, a polymer having a weight average molecular weight of more than 1000 (i.e., 1001 or more) can be used. The polymer is not particularly limited, but examples thereof include polyester, polyether, polyetheretherketone, polyamide, polyimide, novolac resin, maleimide resin, acrylic resin, and methacrylic resin. The upper limit of the weight average molecular weight of the polymer is, for example, 100,000 or 50,000.

[0034] Furthermore, the resin preferably has at least one hydroxy group in its unit structure.

[0035] The resin having at least one hydroxy group in the unit structure may be, for example, a resin having the following unit structure (2), which is a reaction product (B1) of a diepoxy compound (C) and a difunctional or higher proton-generating compound (D).

[0036] The reaction product is represented by the following formula (2): [ka] (In formula (2), R3, R4, R5, R6, R7, and R8 each independently represent a hydrogen atom, a methyl group, or an ethyl group, Q1 represents a divalent organic group between two carbon atoms, and m3 and m4 each independently represent 0 or 1.) The unit structure may be represented by the following formula:

[0037] Q1 in the formula (2) is represented by the following formula (3): [ka] (In formula (3), Q2 represents a direct bond, an alkylene group having 1 to 10 carbon atoms which may be interrupted by -O-, -S- or -SS-, 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, and the divalent organic group may be substituted with 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 hydroxy group, a nitro group, a cyano group, a methylidene group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. Z1 and Z2 each represent -COO-, -O-, or -S-.) It may be expressed as:

[0038] Q1 in the formula (2) is the following formula (4): [ka] (In formula (4), Q3 represents the following formula (5), formula (6), or formula (7).) [ka] (In formula (5), formula (6) and formula (7), R 10 , R 11 , R 12 and R 13each 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, the phenyl group being optionally substituted with at least one selected from the group consisting of 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; R 11 and R 12 may be bonded to each other to form a ring having 3 to 6 carbon atoms. It may be expressed as:

[0039] Examples of the diepoxy compound (C) forming a structural unit represented by the formula (2) in which m3 and m4 each represent 1 include compounds having a diglycidyl ether or diglycidyl ester having two epoxy groups represented by the following formulae (C-1) to (C-51), but are not limited to these examples.

[0040] [ka] [ka] [ka]

[0041] Examples of the di- or higher functional proton-generating compound (D) forming a structural unit represented by the formula (2) in which m3 and m4 are 0 include compounds having two carboxyl groups, hydroxyphenyl groups, or imide groups, and acid dianhydrides, which are represented by the following formulae (D-1) to (D-47), but are not limited to these examples.

[0042] [ka] [ka]

[0043] Furthermore, examples of the unit structure of the reaction product (B1) of the diepoxy compound (C) and the difunctional or higher proton-generating compound (D) include, but are not limited to, the following formulas (B1-1) to (B1-38).

[0044] [ka] [ka] [ka] [ka]

[0045] The resin having at least one hydroxy group in the unit structure may be a resin having at its terminal a structure containing at least one pair of two hydroxy groups adjacent to each other in the molecule.

[0046] The structure containing at least one pair of two adjacent hydroxyl groups in the molecule may be a 1,2-ethanediol structure.

[0047] The 1,2-ethanediol structure has the formula (8): [ka] (In the formula (8), X is -COO-, -O-, -S- or -NR 17 - represents either R 17 represents a hydrogen atom or a methyl group; Y represents an optionally substituted alkylene group having 1 to 4 carbon atoms; R 14 , R 15 and R 16each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 40 carbon atoms; R 14 is R 15 or R 16 may form a ring together with The structure may include:

[0048] R 14 is R 15 or R 16 Specific examples of a ring formed together with the above include cyclopentane, cyclohexane, and bicyclo[2,2,1]heptane.

[0049] The ring can be derived by reacting a compound such as cyclopentane-1,2-diol, cyclohexane-1,2-diol, or bicyclo[2,2,1]heptane-1,2-diol with the polymer terminal.

[0050] The above formula ( 8 ), R 14 , R 15 and R 16 may be a hydrogen atom. The above formula ( 8 ) wherein Y may be a methylene group. The above formula ( 8 ) in which X may be -S-.

[0051] Examples of the compound that forms the terminal of the polymer having a 1,2-ethanediol structure include compounds represented by the following formulae (E-1) to (E-4). [ka]

[0052] Furthermore, examples of the structure forming the terminal of the polymer having a 1,2-ethanediol structure include those represented by the following formulae (B1-39) to (B1-50), but are not limited to these examples. [ka]

[0053] The monomer that can be used has a molecular weight of not more than 1000. The molecular weight of the monomer is preferably 200 to 1,000, and more preferably 500 to 1,000.

[0054] Furthermore, the monomer preferably has at least one hydroxy group in the monomer molecule.

[0055] Examples of the monomer (B2) having at least one hydroxy group therein include those represented by the following formulae (B2-1) to (B2-8), but are not limited to these examples.

[0056] The monomer (B2) having at least one hydroxy group therein can be obtained, for example, by reacting a polyfunctional epoxy compound with a proton-generating compound. [ka]

[0057] <Solvent> The protective film-forming composition of the present invention can be prepared by dissolving the above-mentioned components in an organic solvent, and is used in the state of a homogeneous solution.

[0058] As the solvent for the protective film-forming composition according to the present invention, any solvent that can dissolve the above (B) resin or monomer can be used without any particular limitation. In particular, since the protective film-forming composition according to the present invention is used in a homogeneous solution state, in consideration of its coating performance, it is recommended to use a solvent that is generally used in lithography processes in combination.

[0059] 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, and cyclohexanone. Examples of the solvent include cyclopentane, 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 alone or in combination of two or more.

[0060] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, etc. are preferred, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being particularly preferred.

[0061] [Crosslinking agent] The resist underlayer film forming composition of the present invention may contain a crosslinking agent component. Examples of the crosslinking agent include melamine-based, substituted urea-based, and polymers thereof. A crosslinking agent having at least two crosslinking-forming substituents is preferred, and is a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds may also be used.

[0062] In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As the crosslinking agent having high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be used.

[0063] The compound may be a compound having a partial structure of the following formula (2-1), or a polymer or oligomer having a repeating unit of the following formula (2-2). [ka]

[0064] Above R 18 , R 19 , R 20 , and R 21 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups mentioned above can be used.

[0065] n3 satisfies 1≦n3≦6-n4, n4 satisfies 1≦n4≦5, n5 satisfies 1≦n5≦4-n6, and n6 satisfies 1≦n6≦3.

[0066] Examples of the compound represented by formula (2-1) are the following formulas (2-3) to (2-19). [ka]

[0067] The above compounds are available as products of Asahi Yukizai Kogyo Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (2-15) is available from Asahi Yukizai Kogyo Co., Ltd. under the trade name TMOM-BP.

[0068] 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 usually 0.001 to 80 mass %, preferably 0.01 to 50 mass %, and more preferably 0.1 to 40 mass % based on the total solid content of the protective film-forming composition. These crosslinking agents may cause a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the above-mentioned polymer of the present invention, they can cause a crosslinking reaction with the crosslinkable substituents.

[0069] [Crosslinking catalyst] The protective film-forming composition of the present invention may contain a crosslinking catalyst as an optional component in order to promote the crosslinking reaction. As the crosslinking catalyst, in addition to an acidic compound or a basic compound, a compound that generates an acid or a base by heat may be used, but a crosslinking acid catalyst is preferable. As the acidic compound, a sulfonic acid compound or a carboxylic acid compound may be used, and as a compound that generates an acid by heat, a thermal acid generator may be used.

[0070] 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-phenolsulfonic acid, pyridinium-4-phenolsulfonate, benzenedisulfonic acid, 1-naphthalenesulfonic acid, 4-nitrobenzenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0071] Examples of thermal acid generators include K-PURE (registered trademark) 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.).

[0072] These crosslinking catalysts can be used alone or in combination of two or more. As the basic compound, an amine compound or an ammonium hydroxide compound can be used, and as the compound that generates a base by heat, urea can be used.

[0073] Examples of the amine compound include tertiary amines such as triethanolamine, tributanolamine, trimethylamine, triethylamine, tri-normal propylamine, triisopropylamine, tri-normal butylamine, tri-tert-butylamine, tri-normal octylamine, triisopropanolamine, phenyldiethanolamine, stearyldiethanolamine, and diazabicyclooctane, and aromatic amines such as pyridine and 4-dimethylaminopyridine.Other examples of the amine compound include primary amines such as benzylamine and normal butylamine, and secondary amines such as diethylamine and di-normal butylamine.These amine compounds can be used alone or in combination of two or more.

[0074] Examples of ammonium hydroxide compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, phenyltrimethylammonium hydroxide, and phenyltriethylammonium hydroxide.

[0075] As a compound that generates a base by heat, for example, a compound that has a thermolabile group such as an amide group, a urethane group, or an aziridine group and generates an amine by heating can be used. Other examples of the compound that generates a base by heat include urea, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyldimethylphenylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltributylammonium chloride, and choline chloride.

[0076] When the protective film-forming composition contains a crosslinking catalyst, the content thereof is usually 0.0001 to 20 mass %, preferably 0.01 to 15 mass %, and more preferably 0.1 to 10 mass %, based on the total solid content of the protective film-forming composition.

[0077] [Surfactants] The protective film-forming composition of the present invention may contain a surfactant as an optional component to improve the coating property on the semiconductor substrate. Examples of the surfactant 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, polyoxyethylene sorbitan monostearate ... Examples of suitable surfactants include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as F-TOP (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, R-30, R-40, and R-40-LM (manufactured by DIC Corporation), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710, Surflon (registered trademark) 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 alone or in combination of two or more. When the protective film-forming composition contains a surfactant, the content of the surfactant is usually 0.0001 to 10 mass %, preferably 0.01 to 5 mass %, based on the total solid content of the protective film-forming composition.

[0078] [Protective film forming composition] The solid content of the protective film-forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the content of all components excluding the solvent from the protective film-forming composition. The proportion of the polymer in the solid content is preferably 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, in that order.

[0079] [Protective film against wet etching solution for semiconductors, substrate with resist pattern, and method for manufacturing semiconductor device] Hereinafter, a method for producing a substrate having 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.

[0080] The substrate having a resist pattern according to the present invention can be produced by applying the above-mentioned protective film-forming composition onto a semiconductor substrate and baking it.

[0081] 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.

[0082] 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 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.

[0083] The protective film-forming composition of the present invention is applied onto such a semiconductor substrate by a suitable application method such as a spinner or coater. Then, the 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., 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. The thickness of the protective film formed 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 becomes insufficient, and the formed protective film may not be resistant to a resist solvent or a basic hydrogen peroxide aqueous solution. On the other hand, if the baking temperature is higher than the above range, the protective film may be decomposed by heat.

[0084] Exposure is performed through a mask (reticle) for forming a predetermined pattern, and for example, i-rays, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used. An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C and the development time is appropriately selected from 10 seconds to 300 seconds. As the alkaline developer, for example, aqueous solutions of alkalines such as inorganic alkalines such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, 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, cyclic amines such as pyrrole and piperidine, etc. can be used. Furthermore, an appropriate amount of alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants can be added to the aqueous solutions of the alkalines. Among these, the preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline. Furthermore, a surfactant or the like can be added to these developers. Instead of the alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate to develop the part of the photoresist where the alkaline dissolution rate is not improved.

[0085] Next, the protective film is dry-etched using the formed resist pattern as a mask, whereby 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.

[0086] [Wet etching solution for semiconductors] Furthermore, the protective film after dry etching (and the resist pattern if any remains on the protective film) is used as a mask to perform wet etching using a wet etching solution for semiconductors, thereby forming a desired pattern.

[0087] As the wet etching solution for semiconductors, a general chemical solution for etching semiconductor wafers can be used, and for example, either an acidic substance or a basic substance can be used.

[0088] Examples of substances that exhibit acidity 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 mixtures of these.

[0089] Examples of substances that exhibit basicity include basic hydrogen peroxide solution, which is obtained by mixing an organic amine such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, or triethanolamine with hydrogen peroxide solution to make the pH basic. A specific example is SC-1 (ammonia-hydrogen peroxide solution). Other substances that can make the pH basic, such as mixing urea with hydrogen peroxide solution and heating to cause thermal decomposition of the urea to generate ammonia, and finally making the pH basic, can also be used as a wet etching chemical.

[0090] Among these, acidic hydrogen peroxide solution is preferable.

[0091] These chemical solutions may contain additives such as a surfactant.

[0092] The temperature of the semiconductor wet etching solution is preferably 25° C. to 90° C., and more preferably 40° C. to 80° C. The wet etching time is preferably 0.5 to 30 minutes, and more preferably 1 to 20 minutes. EXAMPLES

[0093] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these.

[0094] The apparatuses used for measuring the weight average molecular weight of the polymers obtained in the following synthesis examples are shown below. Equipment: Tosoh Corporation HLC-8320GPC GPC column: Shodex (registered trademark) Asahipak (registered trademark) (Showa Denko K.K.) Column temperature: 40℃ Flow rate: 0.35mL / min Eluent: tetrahydrofuran (THF) Standard sample: Polystyrene (Tosoh Corporation)

[0095] <Synthesis Example 1> A reaction flask containing 10.00 g of resorcinol diglycidyl ether (product name: Denacol EX-201-IM, Nagase ChemteX Corporation), 6.09 g of succinic acid, 0.80 g of ethyltriphenylphosphonium bromide, and 67.55 g of propylene glycol monomethyl ether was heated and stirred at 100° C. for 27 hours under a nitrogen atmosphere. The resulting reaction product was represented by formula (B1-27), and had a weight average molecular weight Mw of 3000 as measured by GPC in terms of polystyrene. [ka]

[0096] <Synthesis Example 2> A reaction flask containing 25.00 g of resorcinol diglycidyl ether (product name: Denacol EX-201-IM, Nagase ChemteX Corporation, 50.0 wt% propylene glycol monomethyl ether solution), 5.06 g of succinic acid, 2.32 g of 1-thioglycerol, 1.36 g of tetrabutylphosphonium bromide, and 72.49 g of propylene glycol monomethyl ether was heated and stirred at 100° C. for 21 hours under a nitrogen atmosphere. The resulting reaction product was represented by formula (B1-46), and had a weight average molecular weight Mw of 3,300 as measured by GPC in terms of polystyrene. [ka]

[0097] <Prototype example 1> A solution of a protective film-forming composition was prepared by adding 5.09 g of a solution of the reaction product corresponding to the formula (B1-27) (solid content: 16.7 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of pyromellitic acid represented by the formula (A-4) as additives, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0098] <Prototype Example 2> A solution of a protective film-forming composition was prepared by adding 5.09 g of a solution of the reaction product corresponding to the formula (B1-27) (solid content: 16.7% by weight), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of tetrahydrofuran-2,3,4,5-tetracarboxylic acid represented by the formula (A-23) as an additive, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0099] <Prototype 3> A solution of a protective film-forming composition was prepared by adding 5.23 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.2 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of pyromellitic acid represented by the formula (A-4) as an additive, 12.81 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0100] <Prototype 4> A solution of a protective film-forming composition was prepared by adding 5.04 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.2 wt%), 0.04 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.04 g of pyromellitic acid represented by the formula (A-4) as an additive, 12.97 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0101] <Prototype 5> A solution of a protective film-forming composition was prepared by adding 4.44 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.2 wt%), 0.14 g of 3,3',5,5'-tetrakis(methoxymethyl)-4,4'-dihydroxybiphenyl (product name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, 0.01 g of pyridinium-4-hydroxybenzenesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.02 g of pyromellitic acid represented by the formula (A-4) as an additive, 13.47 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0102] <Comparative prototype 1> A solution of a protective film-forming composition was prepared by adding 5.24 g of a solution of the reaction product corresponding to the above formula (B1-46) (solid content: 16.7 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 12.83 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0103] <Prototype comparison example 2> A solution of a protective film-forming composition was prepared by adding 5.09 g of a solution of the reaction product corresponding to the above formula (B1-46) (solid content: 16.7% by weight), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of gallic acid represented by the following formula (F-1) as additives, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate. [ka]

[0104] <Comparative prototype 3> A solution of a protective film-forming composition was prepared by adding 5.09 g of a solution of the reaction product corresponding to the above formula (B1-46) (solid content: 16.7 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of N-acetoacetylanthranilic acid represented by the following formula (F-2) as additives, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate. [ka]

[0105] <Comparative prototype 4> A solution of a protective film-forming composition was prepared by adding 5.09 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.7 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of picolinic acid represented by the following formula (F-3) as an additive, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate. [ka]

[0106] <Comparative prototype 5> A solution of a protective film-forming composition was prepared by adding 5.09 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.7 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of 2,6-pyridinedicarboxylic acid represented by the following formula (F-4) as an additive, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate. [ka]

[0107] <Comparative prototype 6> A solution of a protective film-forming composition was prepared by adding 5.09 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.7 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of 2,3-pyrazinedicarboxylic acid represented by the following formula (F-5) as an additive, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate. [ka]

[0108] <Comparative prototype 7> A solution of a protective film-forming composition was prepared by adding 5.38 g of a solution of the reaction product corresponding to the above formula (B1-46) (solid content: 16.2 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 12.68 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0109] <Comparative prototype example 8> A solution of a protective film-forming composition was prepared by adding 5.23 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.2 wt%), 0.03 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.03 g of gallic acid represented by the formula (F-1) as additives, 12.81 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0110] <Comparative prototype 9> A solution of a protective film-forming composition was prepared by adding 5.28 g of a solution of the reaction product corresponding to the above formula (B1-46) (solid content: 16.2 wt%), 0.04 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 12.77 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0111] <Comparative prototype 10> A solution of a protective film-forming composition was prepared by adding 5.04 g of a solution of the reaction product corresponding to the above formula (B1-46) (solid content: 16.2 wt%), 0.04 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.04 g of gallic acid represented by the above formula (F-1) as additives, 12.97 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0112] <Comparative prototype 11> A solution of a protective film-forming composition was prepared by adding 4.54 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.2 wt%), 0.15 g of 3,3',5,5'-tetrakis(methoxymethyl)-4,4'-dihydroxybiphenyl (product name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, 0.01 g of pyridinium-4-hydroxybenzenesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 13.38 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0113] < Prototype comparison Example 12> A solution of a protective film-forming composition was prepared by adding 4.44 g of a solution of the reaction product corresponding to the formula (B1-46) (solid content: 16.2 wt%), 0.14 g of 3,3',5,5'-tetrakis(methoxymethyl)-4,4'-dihydroxybiphenyl (product name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, 0.01 g of pyridinium-4-hydroxybenzenesulfonate as a crosslinking catalyst, 0.001 g of a fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) as a surfactant, 0.02 g of gallic acid represented by the formula (F-1) as additives, 13.47 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate.

[0114] [Acid hydrogen peroxide resistance test] To evaluate resistance to acidic hydrogen peroxide water, the protective film-forming compositions prepared in Prototype Examples 1 to 5 and Prototype Comparative Examples 1 to 12 were applied to a 50 nm thick TiN (titanium nitride) vapor-deposited substrate, a 30 nm thick TiN (titanium nitride) vapor-deposited substrate, a 30 nm thick TiON (titanium oxynitride) vapor-deposited substrate, and a 30 nm thick WN (tungsten nitride) vapor-deposited substrate, and heated at 250° C. for 1 minute to form a film having a thickness of 110 nm. The obtained protective films on each substrate were designated as Examples 1 to 7 and Comparative Examples 1 to 16. Details of each Example and Comparative Example are shown in Table 1.

[0115] [Table 1]

[0116] Next, 85% phosphoric acid and 30% hydrogen peroxide were mixed in a weight ratio of 1:1 to prepare an acidic hydrogen peroxide solution. Then, each deposition substrate coated with the protective film-forming composition was immersed for a certain period of time in this acidic hydrogen peroxide solution heated to 60°C. After immersion, the substrate was washed with water, dried, and the state of the protective film was visually confirmed to measure the time until the protective film peeled off from the substrate. The time required from immediately after immersion in the protective film until a part or all of the protective film peeled off was defined as the "protective film peeling time", which is shown in Tables [2-1] to [2-6]. It can be said that the longer the protective film peeling time, the higher the resistance to the wet etching solution using the acidic hydrogen peroxide solution.

[0117] [Table 2-1]

[0118] [Table 2-2]

[0119] [Table 2-3]

[0120] [Table 2-4]

[0121] [Table 2-5]

[0122] [Table 2-6]

[0123] From the above results, in each of Tables [2-1] to [2-6], even when the deposition substrate type was different, the protective film peeling time for the examples in the respective tables against acidic hydrogen peroxide solution was longer than that for the comparative examples in the respective tables. In other words, it can be said that the protective film-forming composition containing the polyvalent carboxylic acid described in the present application as an additive exhibits better resistance to a wet etching solution using acidic hydrogen peroxide solution than a protective film-forming composition that does not contain the polyvalent carboxylic acid. In other words, the protective film-forming composition containing the polyvalent carboxylic acid as an additive is useful as a protective film against wet etching for semiconductors. [Industrial Applicability]

[0124] The protective film-forming composition of the present invention has excellent resistance when a wet etching solution is applied to substrate processing and a high dry etching rate, making substrate processing easy, and provides a protective film that has excellent planarization properties when applied to a substrate with a step.

Claims

1. (A) a compound containing at least four carboxy groups; (B) a resin or monomer, and A composition for forming a protective film against a wet etching solution for semiconductors, comprising a solvent.

2. (A) a compound containing at least three carboxy groups, (B) a reaction product (B1) of a diepoxy compound (C) and a difunctional or higher proton-generating compound (D), or a monomer (B2) obtained by reacting a polyfunctional epoxy compound with a proton-generating compound, and A composition for forming a protective film against a wet etching solution for semiconductors, comprising a solvent.

3. A protective film forming composition for a semiconductor wet etching solution as described in claim 1, wherein the compound (A) containing at least four carboxy groups has a ring structure.

4. A protective film forming composition for a semiconductor wet etching solution as described in claim 2, wherein the compound (A) containing at least three carboxy groups has a ring structure.

5. A protective film forming composition for a semiconductor wet etching solution described in claim 3, wherein the ring structure is selected from an aromatic ring having 6 to 40 carbon atoms, an aliphatic ring having 3 to 10 carbon atoms, and a heterocycle.

6. A protective film forming composition for a semiconductor wet etching solution described in claim 4, wherein the ring structure is selected from an aromatic ring having 6 to 40 carbon atoms, an aliphatic ring having 3 to 10 carbon atoms, and a heterocycle.

7. The aromatic ring having 6 to 40 carbon atoms is selected from the group consisting of benzene, naphthalene and the formula (1): 【Chemistry 1】 In formula (1), X is a divalent organic group selected from a direct bond, -CH 2 -, -C(CH 3 ) 2 -, -CO-, -SO 2 - and -C(CF 3 ) 2 -; R 1 and R 2 are each independently a monovalent organic group selected from an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a cyano group, a nitro group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms; n 1 and n 2 are each independently an integer of 1 to 5, n 1 + n 2 is an integer of 3 to 10, and m 1 and m 2 are each independently an integer of 0 to 5, and m 1 + m 2 is an integer of 0 to 7. The protective film-forming composition for a semiconductor wet etching solution according to claim 5,

8. The aromatic ring having 6 to 40 carbon atoms is selected from the group consisting of benzene, naphthalene and the formula (1): 【Chemistry 1】 In formula (1), X is a divalent organic group selected from a direct bond, -CH 2 -, -C(CH 3 ) 2 -, -CO-, -SO 2 - and -C(CF 3 ) 2 -; R 1 and R 2 are each independently a monovalent organic group selected from an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a cyano group, a nitro group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms; n 1 and n 2 are each independently an integer of 1 to 5, n 1 + n 2 is an integer of 3 to 10, and m 1 and m 2 are each independently an integer of 0 to 5, and m 1 + m 2 is an integer of 0 to 7. The protective film-forming composition for a semiconductor wet etching solution according to claim 6,

9. A protective film forming composition for a semiconductor wet etching solution as described in claim 1, wherein the resin or monomer (B) has at least one hydroxy group within the unit structure of the resin or within the monomer molecule.

10. A protective film forming composition for a semiconductor wet etching solution as described in claim 2, wherein a reaction product (B1) of the diepoxy compound (C) with a difunctional or higher proton generating compound (D), or a monomer obtained by reacting a polyfunctional epoxy compound with a proton generating compound, has at least one hydroxy group within the unit structure of the reaction product or within the monomer molecule.

11. A protective film forming composition for a semiconductor wet etching solution described in any one of claims 1 to 10, further comprising at least one selected from the group consisting of a crosslinking agent, a crosslinking catalyst, and a surfactant.

12. A protective film forming composition for a semiconductor wet etching solution described in any one of claims 1 to 10, wherein the semiconductor wet etching solution contains hydrogen peroxide.

13. A protective film forming composition for a semiconductor wet etching solution as described in claim 12, wherein the hydrogen peroxide solution is an acidic hydrogen peroxide solution.

14. A protective film against a wet etching solution for semiconductors, characterized in that it is a fired product of a coating film made of the protective film forming composition according to any one of claims 1 to 13.

15. A method for manufacturing a substrate with a resist pattern, comprising the steps of applying a protective film-forming composition described in any one of claims 1 to 13 onto a semiconductor substrate and baking the composition to form a protective film as a resist underlayer film, forming a resist film on the protective film, and then exposing and developing the resist film to form a resist pattern, the method being used in the manufacture of semiconductors.

16. A method for manufacturing a semiconductor device, comprising the steps of forming a protective film on a semiconductor substrate, on whose surface an inorganic film may be formed, using a protective film forming composition described in any one of claims 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 and / or cleaning the inorganic film or the semiconductor substrate using a semiconductor wet etching solution using the protective film after dry etching as a mask.

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