Chemical-resistant protective film containing polycarboxylic acid

Abstract

The present invention provides a protective film-forming composition having good masking (protection) function resistant to wet etching liquid, high dry etching speed, good coverage of uneven substrates, small film thickness difference after embedding, and capable of forming a flat film, and a protective film manufactured using the composition, a substrate with a resist pattern, and a method for manufacturing a semiconductor device. A protective film-forming composition resistant to wet etching liquid for semiconductors, comprising: (A) a compound containing at least 3 carboxyl groups, (B) a resin or a monomer, and a solvent. Preferably, the compound (A) containing at least 3 carboxyl groups has a ring structure. Preferably, 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 heterocyclic ring.

Description

Technical Field

[0001] The present invention relates to a composition for forming a protective film having excellent resistance to a semiconductor wet etching solution in a photolithography process in semiconductor manufacturing, 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, and dry etching is mainly used as a process, but wet etching is sometimes used depending on the type of substrate. Patent Documents 1 and 2 disclose a protective film-forming composition that is resistant to aqueous hydrogen peroxide solution and contains a specific compound.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2018 / 052130

[0006] Patent Document 2: International Publication No. 2018 / 203464 Summary of the invention

[0007] Problems to be solved by the invention

[0008] 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 that is resistant to a wet etching solution during processing of the base substrate (ie, the masked portion can protect the substrate).

[0009] In such a case, the resist underlayer film is used as a protective film for the substrate. Furthermore, when the unnecessary protective film is removed by dry etching after wet etching, in order not to damage the base substrate, the protective film is required to be a protective film with a fast etching speed (high etching rate) that can be quickly removed by dry etching.

[0010] 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.

[0011] Conventionally, in order to develop resistance to SC-1 (ammonia-hydrogen peroxide solution) which is a kind of wet etching solution, a method of using a low molecular weight compound (eg, gallic acid) as an additive has been used, but this method is limited in solving the above-mentioned problems.

[0012] An object of the present invention is to solve the above-mentioned problems.

[0013] Means for solving problems

[0014] The present invention includes the following aspects. [1]

[0016] A composition for forming a protective film resistant to a wet etching solution for semiconductors, comprising:

[0017] (A) a compound containing at least 3 carboxyl groups,

[0018] (B) resin or monomer, and

[0019] Solvent. [2]

[0021] The composition for forming a protective film resistant to semiconductor wet etching liquid according to [1], wherein the compound (A) containing at least three carboxyl groups has a ring structure. Preferably, the at least three carboxyl groups are bonded to the ring structure directly or via an alkylene group having 1 to 4 carbon atoms. [3]

[0023] The composition for forming a protective film resistant to 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 heterocyclic ring. [4]

[0025] The composition for forming a protective film resistant to a semiconductor wet etching solution according to [3], wherein the aromatic ring having 6 to 40 carbon atoms is selected from benzene, naphthalene and a compound represented by formula (1),

[0026]

[0027] (In formula (1), X is a divalent organic group selected from -CH2-, -C(CH3)2-, -CO-, -SO2- and -C(CF3)2-, which is a direct bond.

[0028] 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. ), or,

[0029] According to the composition for forming a protective film resistant to a semiconductor wet etching solution as described in [3], the compound (A) containing at least 3 carboxyl groups is selected from

[0030] (i) a compound in which the aromatic ring having 6 to 40 carbon atoms is benzene or naphthalene, and

[0031] (ii) A compound represented by formula (1).

[0032]

[0033] (In formula (1), X is a divalent organic group selected from -CH2-, -C(CH3)2-, -CO-, -SO2- and -C(CF3)2-, which is a direct bond.

[0034] 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. [5]

[0036] The composition for forming a protective film resistant to a semiconductor wet etching solution according to [1], wherein the resin or monomer (B) has at least one hydroxyl group in a unit structure of the resin or in a monomer molecule. [6]

[0038] The composition for forming a protective film resistant to a semiconductor wet etching solution according to any one of [1] to [5], further comprising at least one selected from a crosslinking agent, a crosslinking catalyst and a surfactant. [7]

[0040] The composition for forming a protective film resistant to a semiconductor wet etching solution according to any one of [1] to [6], wherein the semiconductor wet etching solution contains hydrogen peroxide water. [8]

[0042] The composition for forming a protective film resistant to a semiconductor wet etching solution according to [7], wherein the hydrogen peroxide solution is an acidic hydrogen peroxide solution. [9]

[0044] A protective film resistant to a semiconductor wet etching solution, characterized in that it is a fired product of a coating film formed from the protective film-forming composition according to any one of [1] to [8].

[10]

[0046] A method for manufacturing a substrate with a resist pattern, characterized in that it comprises the following steps: a step of coating the protective film composition described in any one of [1] to [8] 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, wherein the above-mentioned manufacturing method is used for the manufacture of semiconductors.

[11]

[0048] 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 [8], 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 washing the inorganic film or the semiconductor substrate using a semiconductor wet etching solution using the dry-etched protective film as a mask.

[0049] Effects of the Invention

[0050] 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) a good masking function that is resistant to wet etching solutions when processing a base substrate, (2) a further high dry etching rate, and (3) 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

[0051] <Protective film forming composition>

[0052] The protective film-forming composition of the present application is a protective film-forming composition resistant to a semiconductor wet etching solution, comprising (A) a compound containing at least three carboxyl groups, (B) a resin or a monomer, and a solvent.

[0053] (A) The compound containing at least 3 carboxyl groups preferably contains 3 to 6 carboxyl groups, and particularly preferably contains 3 or 4 carboxyl groups.

[0054] It is preferred that the compound (A) containing at least three carboxyl groups has a ring structure.

[0055] 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 heterocyclic ring.

[0056] Examples of the "aromatic ring having 6 to 40 carbon atoms" include benzene, naphthalene, anthracene, acenaphthene, fluorene, benzo[9,10]phenanthrene, phenalene, phenanthrene, indene, indane, indacene, pyrene, Perylene, tetracene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, dibenzo[a,j]anthracene, etc.

[0057] Examples of the “aliphatic ring having 3 to 10 carbon atoms” include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirodicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, tricyclo[3.2.1.02,7]octane and spiro[3,4]octane.

[0058] It is preferred that the aromatic ring having 6 to 40 carbon atoms is selected from benzene and naphthalene, or the compound (A) is selected from the compounds represented by formula (1).

[0059]

[0060] (In formula (1), X is a divalent organic group selected from -CH2-, -C(CH3)2-, -CO-, -SO2- and -C(CF3)2-, which is a direct bond.

[0061] 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.

[0062] Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, and 2-methyl-cyclopropyl.

[0063] Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

[0064] Examples of the "heterocycle" include furan, pyrrole, pyran, imidazole, pyrazole, Azoles, thiophenes, thiazoles, thiadiazoles, imidazolines, thiazolines, imidazolines, alkane, morpholine, diazine, thiazine, triazole, tetrazole, dioxolane, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenanthracene Oxazines, xanthenes, acridines, phenazines, carbazoles and triazines.

[0065] The triazine may be a compound containing triazoneone, a compound containing triazinedione, or a compound containing triazinetrione, but is preferably a compound containing triazinetrione.

[0066] Examples of the compound having at least three carboxyl groups of the present application include the following formulas (A-1) to (A-25), but the compound is not limited thereto.

[0067]

[0068] <Resin, Monomer>

[0069] The protective film-forming composition of the present invention contains the above-mentioned (B) resin or monomer as an essential component.

[0070] As the above-mentioned resin, a polymer having a weight average molecular weight exceeding 1000 (i.e., 1001 or more) can be used. The polymer is not particularly limited, and 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 above-mentioned polymer is, for example, 100,000 or 50,000.

[0071] Furthermore, the above-mentioned resin preferably has at least one hydroxyl group in the unit structure.

[0072] The resin having at least one hydroxyl group in the unit structure may be, for example, a resin having the unit structure (2) shown below, which is a reaction product (B1) of a diepoxy compound (C) and a difunctional or higher-functional proton-generating compound (D).

[0073] The reaction product may be a substance including a unit structure represented by the following formula (2).

[0074]

[0075] (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.)

[0076] Q1 in the above formula (2) can be represented by the following formula (3).

[0077] -Z1-Q2-Z2- Formula (3)

[0078] (In formula (3), Q2 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 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. Z1 and Z2 each represent any one of -COO-, -O-, and -S-.)

[0079] Q1 in the above formula (2) can also be represented by the following formula (4).

[0080]

[0081] (In formula (4), Q3 represents the following formula (5), formula (6) or formula (7).)

[0082]

[0083] (In formula (5), formula (6) and formula (7), R9, R 10 , R 11 , R 12 and R 13 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 11 With R 12 They may also be bonded to form a ring having 3 to 6 carbon atoms.)

[0084] As diepoxy compounds (C) that form structural units represented by the above formula (2) in which m3 and m4 represent 1, examples include diglycidyl ethers having two epoxy groups and compounds having diglycidyl esters represented by the following formulas (C-1) to (C-51), but are not limited to these examples.

[0085]

[0086]

[0087] As the proton-generating compound (D) with two or more functional groups that forms the structural unit represented by the above formula (2) and in which m3 and m4 represent 0, examples include compounds having two carboxyl groups, hydroxyphenyl groups or imide groups, and acid dianhydrides represented by the following formulas (D-1) to (D-47), but are not limited to these examples.

[0088]

[0089] The unit structure of the reaction product (B1) of the diepoxy compound (C) and the bifunctional or higher-functional proton-generating compound (D) can be exemplified by the following formulae (B1-1) to (B1-38), but is not limited to these examples.

[0090]

[0091]

[0092]

[0093] The resin having at least one hydroxyl group in the unit structure may be a resin having a structure including at least one set of two hydroxyl groups adjacent to each other in the molecule at a terminal.

[0094] The structure including at least one set of two adjacent hydroxyl groups in the molecule may be a 1,2-ethanediol structure.

[0095] The 1,2-ethanediol structure may include a structure represented by formula (8).

[0096]

[0097] (In formula (8), X represents -COO-, -O-, -S- or -NR 17 -Any one of R 17 represents a hydrogen atom or a methyl group. Y represents an alkylene group having 1 to 4 carbon atoms which may be substituted. 14 , R 15 and R 16 are a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms, R 14 Can be used with R 15 or R 16 Together they form a ring.)

[0098] As R 14 With R 15 or R 16 Specific examples of the groups that form a ring together include cyclopentane, cyclohexane, and bicyclo[2,2,1]heptane.

[0099] When the ring is formed, for example, 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.

[0100] In the above formula (8), R 14 , R 15 and R 16 It may be a hydrogen atom.

[0101] In the above formula (8), Y may be a methylene group.

[0102] In the above formula (8), X may be -S-.

[0103] 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).

[0104]

[0105] In addition, the structures forming the terminal of the above polymer having a 1,2-ethanediol structure can be exemplified by the following formulas (B1-39) to (B1-50), but are not limited to these examples.

[0106]

[0107] As the monomer, a monomer having a molecular weight of 1000 or less can be used. The molecular weight of the monomer is preferably 200 to 1,000, more preferably 500 to 1,000.

[0108] Furthermore, the above-mentioned monomer preferably has at least one hydroxyl group in the monomer molecule.

[0109] Examples of the monomer (B2) having at least one hydroxyl group in the monomer include the following formulas (B2-1) to (B2-8), but the invention is not limited to these examples.

[0110] It should be noted that the monomer (B2) having at least one hydroxyl group in the monomer can be obtained, for example, by reacting a polyfunctional epoxy compound with a proton-generating compound.

[0111]

[0112] <Solvent>

[0113] The protective film-forming composition of the present invention can be prepared by dissolving the above-mentioned components in an organic solvent and used in a uniform solution state.

[0114] As the solvent of the protective film forming composition according to the present invention, any solvent that can dissolve the above-mentioned (B) resin or monomer can be used without particular limitation. In particular, since the protective film forming composition according to the present invention is used in a uniform solution state, it is recommended to use a solvent generally used in a photolithography process in combination in consideration of its coating performance.

[0115] 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.

[0116] 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.

[0117] [Crosslinking agent]

[0118] The resist underlayer film forming composition of the present invention may include a crosslinking agent component. As the crosslinking agent, melamine system, substituted urea system, or polymer system thereof, etc. may be cited. Preferably, the crosslinking agent has at least two crosslinking substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. In addition, condensates of these compounds may also be used.

[0119] As the crosslinking agent, a crosslinking agent with high heat resistance can be used. As the crosslinking agent with high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be used.

[0120] Examples of the compound include a compound having a partial structure of the following formula (2-1) and a polymer or oligomer having a repeating unit of the following formula (2-2).

[0121]

[0122] The above R 18 , R 19 , R 20 , and R 21 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups exemplified above can be used.

[0123] n3 satisfies 1≤n3≤6-n4, n4 satisfies 1≤n4≤5, n5 satisfies 1≤n5≤4-n6, and n6 satisfies 1≤n6≤3.

[0124] The compound represented by the formula (2-1) is exemplified by the following formulas (2-3) to (2-19).

[0125]

[0126] The above compounds can be obtained as products of Asahi Organic Materials Industries, Ltd. and Honshu Chemical Industries, Ltd. For example, the compound of formula (2-15) among the above crosslinking agents can be obtained as TMOM-BP from Asahi Organic Materials Industries, Ltd.

[0127] 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 generally 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 in the case where a crosslinkable substituent is present in the above-mentioned polymer of the present invention, a crosslinking reaction may occur with these crosslinkable substituents.

[0128] [Cross-linking catalyst]

[0129] 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.

[0130] Examples of the sulfonic acid compound or carboxylic acid compound include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridine Trifluoromethanesulfonate, pyridine - p-Toluenesulfonate, pyridine -4-Hydroxybenzenesulfonate, 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.

[0131] 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.).

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] When the protective film forming composition contains a crosslinking catalyst, the content thereof is usually 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.

[0137] [Surfactant]

[0138] 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 above-mentioned surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and other polyoxyethylene alkyl aryl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, etc. 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, E-F303, E-F352 (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 (Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (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, its content is usually 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.

[0139] [Protective film forming composition]

[0140] 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.

[0141] [Protective film resistant to wet etching solution for semiconductor, substrate with resist pattern, and method for manufacturing semiconductor device]

[0142] 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.

[0143] 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.

[0144] Examples of the semiconductor substrate to which the protective film-forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0145] When a semiconductor substrate having an inorganic film formed on the surface is used, the inorganic film can be 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: borophosphorus silicon glass) film, titanium nitride film, titanium oxynitride film, tungsten nitride film, gallium nitride film, and gallium arsenide film.

[0146] 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, the protective film is formed by baking using a heating means such as a hot plate. As baking conditions, it is 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, sometimes crosslinking 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, sometimes the protective film is decomposed by heat.

[0147] Exposure is performed through a mask (intermediate mask) for forming a predetermined pattern, using, for example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet rays) or EB (electron beams). For development, an alkaline developer can be used, and the development temperature can be appropriately selected from 5°C to 50°C and the development time can be appropriately selected from 10 seconds to 300 seconds. As an alkaline developer, for example, an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, a primary amine such as ethylamine, n-propylamine, a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, an alcohol amine such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, a quaternary ammonium salt such as choline, a cyclic amine such as pyrrole and piperidine 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, an organic solvent such as butyl acetate may be used instead of an alkaline developer to develop the portion of the photoresist where the alkali dissolution rate is not increased.

[0148] 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.

[0149] [Wet etching solution for semiconductors]

[0150] 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.

[0151] 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.

[0152] 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.

[0153] As the substance showing alkalinity, ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, and alkaline hydrogen peroxide water obtained by mixing organic amines such as triethanolamine with hydrogen peroxide water to make the pH alkaline. As a specific example, SC-1 (ammonia-hydrogen peroxide solution) can be mentioned. In addition, a substance that can make the pH alkaline can also be used, for example, urea is mixed with hydrogen peroxide water, and ammonia is generated by thermal decomposition of urea by heating, and finally a substance that makes the pH alkaline can be used as a wet etching solution.

[0154] Among them, acidic hydrogen peroxide water is preferred.

[0155] These chemical solutions may contain additives such as surfactants.

[0156] 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.

[0157] Example

[0158] Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

[0159] The apparatus and the like used for measuring the weight average molecular weight of the polymer obtained in the following synthesis example are shown.

[0160] Device: HLC-8320GPC manufactured by Higashikata Co., Ltd.

[0161] GPC column: Shodex〔registered trademark〕Asahipak〔registered trademark〕(Showa Denko K.K.)

[0162] Column temperature: 40°C

[0163] Flow rate: 0.35mL / min

[0164] Eluent: Tetrahydrofuran (THF)

[0165] Standard sample: Polystyrene (Tosoh Corporation)

[0166] <Synthesis example 1>

[0167] 10.00 g of resorcinol diglycidyl ether (product name: Denacol EX-201-IM, manufactured by Nagase Chemtex Co., Ltd.), 6.09 g of succinic acid, and ethyltriphenylphosphine bromide were added. A reaction flask containing 67.55 g of propylene glycol monomethyl ether was heated and stirred at 100° C. for 27 hours under a nitrogen atmosphere. The obtained reaction product corresponded to the formula (B1-27) and had a weight average molecular weight Mw of 3,000 in terms of polystyrene measured by GPC.

[0168]

[0169] <Synthesis example 2>

[0170] 25.00 g of resorcinol diglycidyl ether (product name: Denacol EX-201-IM, manufactured by Nagase Chemtex Co., Ltd., 50.0 wt% propylene glycol monomethyl ether solution), 5.06 g of succinic acid, 2.32 g of 1-thioglycerol, and tetrabutyl bromide were added. A reaction flask containing 72.49 g of propylene glycol monomethyl ether was heated and stirred at 100° C. for 21 hours under a nitrogen atmosphere. The obtained reaction product corresponded to the formula (B1-46) and had a weight average molecular weight Mw of 3,300 in terms of polystyrene measured by GPC.

[0171]

[0172] <Trial Example 1>

[0173] 5.09 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-27) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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 above formula (A-4) as an additive, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0174] <Trial Example 2>

[0175] 5.09 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-27) and pyridine as a crosslinking catalyst were added. -trifluoromethanesulfonate 0.03 g, fluorine-based surfactant (product name: Megafuk R-40, manufactured by DIC Corporation) 0.001 g as a surfactant, tetrahydrofuran-2,3,4,5-tetracarboxylic acid 0.03 g represented by the above formula (A-23) as an additive, propylene glycol monomethyl ether 12.95 g, and propylene glycol monomethyl ether acetate 1.91 g were used to prepare a solution of a protective film forming composition.

[0176] <Trial Example 3>

[0177] 5.23 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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 above formula (A-4) as an additive, 12.81 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0178] <Trial Example 4>

[0179] 5.04 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.04 g of trifluoromethanesulfonate, 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 above formula (A-4) as an additive, 12.97 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0180] <Trial Example 5>

[0181] 4.44 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46), 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, and pyridine as a crosslinking catalyst were added. -0.01 g of 4-hydroxybenzenesulfonate, 0.001 g of a fluorine-based surfactant (product name: Megaphage R-40, manufactured by DIC Corporation) as a surfactant, 0.02 g of pyromellitic acid represented by the above formula (A-4) as an additive, 13.47 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0182] <Trial Comparative Example 1>

[0183] 5.24 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -trifluoromethanesulfonate 0.03 g, fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) 0.001 g as a surfactant, propylene glycol monomethyl ether 12.83 g, and propylene glycol monomethyl ether acetate 1.91 g were added to prepare a solution of a protective film-forming composition.

[0184] <Trial Comparative Example 2>

[0185] 5.09 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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 an additive, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0186]

[0187] <Trial Comparative Example 3>

[0188] 5.09 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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-acetoacetyl-o-aminobenzoic acid represented by the following formula (F-2) as an additive, 12.95 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0189]

[0190] <Trial Comparative Example 4>

[0191] 5.09 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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 were used to prepare a solution of a protective film-forming composition.

[0192]

[0193] <Trial Comparative Example 5>

[0194] 5.09 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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 were used to prepare a solution of a protective film-forming composition.

[0195]

[0196] <Trial Comparative Example 6>

[0197] 5.09 g of a solution (solid content: 16.7 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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 were used to prepare a solution of a protective film-forming composition.

[0198]

[0199] <Trial Comparative Example 7>

[0200] 5.38 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -trifluoromethanesulfonate 0.03 g, fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) 0.001 g as a surfactant, propylene glycol monomethyl ether 12.68 g, and propylene glycol monomethyl ether acetate 1.91 g were added to prepare a solution of a protective film-forming composition.

[0201] <Trial Comparative Example 8>

[0202] 5.23 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.03 g of trifluoromethanesulfonate, 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 above formula (F-1) as an additive, 12.81 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0203] <Trial Comparative Example 9>

[0204] 5.28 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -trifluoromethanesulfonate 0.04 g, fluorine-based surfactant (product name: Megafac R-40, manufactured by DIC Corporation) 0.001 g as a surfactant, propylene glycol monomethyl ether 12.77 g, and propylene glycol monomethyl ether acetate 1.91 g were added to prepare a solution of a protective film-forming composition.

[0205] <Trial Comparative Example 10>

[0206] 5.04 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46) and pyridine as a crosslinking catalyst were added. -0.04 g of trifluoromethanesulfonate, 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 an additive, 12.97 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0207] <Trial Comparative Example 11>

[0208] 4.54 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46), 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, and pyridine as a crosslinking catalyst were added. A solution of a protective film-forming composition was prepared by adding 0.01 g of -4-hydroxybenzenesulfonate, 0.001 g of a fluorine-based surfactant (product name: Megaphage 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.

[0209] <Comparative Prototype Example 12>

[0210] 4.44 g of a solution (solid content: 16.2 wt%) of the reaction product of the above formula (B1-46), 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, and pyridine as a crosslinking catalyst were added. -0.01 g of 4-hydroxybenzenesulfonate, 0.001 g of a fluorine-based surfactant (product name: Megaphage R-40, manufactured by DIC Corporation) as a surfactant, 0.02 g of gallic acid represented by the above formula (F-1) as an additive, 13.47 g of propylene glycol monomethyl ether, and 1.91 g of propylene glycol monomethyl ether acetate were used to prepare a solution of a protective film forming composition.

[0211] [Test of resistance to acidic hydrogen peroxide water]

[0212] As an evaluation of resistance to acidic hydrogen peroxide water, the protective film-forming composition prepared in Trial Examples 1 to 5 and Trial Comparative Examples 1 to 12 was applied to a TiN (titanium nitride) vapor-deposited substrate with a film thickness of 50 nm, a TiN (titanium nitride) vapor-deposited substrate with a film thickness of 30 nm, a TiON (titanium oxynitride) vapor-deposited substrate with a film thickness of 30 nm, and a WN (tungsten nitride) vapor-deposited substrate with a film thickness of 30 nm, and heated at 250° C. for 1 minute to form a film with a film thickness of 110 nm. The protective films on the obtained substrates were set as Examples 1 to 7 and Comparative Examples 1 to 16. The details of each Example and Comparative Example are shown in Table 1.

[0213] [Table 1]

[0214]

[0215] Next, 85% phosphoric acid and 30% hydrogen peroxide water were mixed in a weight ratio of 1:1 to prepare acidic hydrogen peroxide water. Furthermore, each vapor deposition substrate coated with the protective film forming composition was immersed in the acidic hydrogen peroxide water heated to 60°C for a certain period of time. 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 was peeled off from the substrate. The time required from the moment the protective film was immersed to the moment a part or all of the protective film was peeled off was set as "peeling time of the protective film", which is shown in Tables [2-1] to [2-6]. It should be noted that the longer the peeling time of the protective film, the higher the resistance to the wet etching solution using acidic hydrogen peroxide water.

[0216] [Table 2-1]

[0217]

[0218] [Table 2-2]

[0219]

[0220] [Table 2-3]

[0221]

[0222] [Table 2-4]

[0223]

[0224] [Table 2-5]

[0225]

[0226] [Table 2-6]

[0227]

[0228] According to the above results, in each of Tables [2-1] to [2-6], even when the types of the vapor deposition substrates are different, the Examples all have longer peeling times for the protective film to acidic hydrogen peroxide water than the Comparative Examples in each table. That is, it can be said that the protective film-forming composition containing a polycarboxylic acid as an additive described in the present application shows better resistance to a wet etching solution using acidic hydrogen peroxide water than the protective film-forming composition not containing the polycarboxylic acid. That is, the protective film-forming composition containing a polycarboxylic acid as an additive is useful as a protective film resistant to wet etching for semiconductors.

[0229] Industrial Availability

[0230] The protective film-forming composition of the present invention has excellent resistance to wet etching solutions when used for substrate processing and has a high dry etching rate, so substrate processing is easy, and provides a protective film with excellent planarization properties when applied to a substrate with unevenness.

Claims

1. A composition for forming a protective film resistant to a wet etching solution for semiconductors, comprising: (A) a compound containing at least 4 carboxyl groups, (B) a resin having a unit structure of the following formula (2) which is a reaction product (B1) of a diepoxy compound (C) and a protogenic compound having two or more functional groups (D), or a monomer (B2) having at least one hydroxyl group in a monomer obtained by reacting a polyfunctional epoxy compound with a protogenic compound, and Solvents, The compound (A) containing at least 4 carboxyl groups has a ring structure selected from an aromatic ring having 6 to 40 carbon atoms, an aliphatic ring having 3 to 10 carbon atoms, and a heterocyclic ring. 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, m3 and m4 each represent 1, Q1 in the formula (2) is represented by the following formula (3) or the following formula (4), -Z1-Q2-Z2- Formula (3) In formula (3), Q2 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 which has 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 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; and Z1 and Z2 represent any one of -COO-, -O-, and -S-, respectively; In formula (4), Q3 represents the following formula (5), formula (6) or formula (7), In formula (5), formula (6) and formula (7), R9, R 10 , R 11 , R 12 and R 13 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 11 With R 12 They may be bonded to each other to form a ring having 3 to 6 carbon atoms.

2. The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 1, wherein the heterocyclic ring is selected from furan, pyrrole, pyran, imidazole, pyrazole, Azoles, thiophenes, thiazoles, thiadiazoles, imidazolines, thiazolines, imidazolines, alkane, morpholine, diazine, thiazine, triazole, tetrazole, dioxolane, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenanthracene Oxazines, xanthenes, acridines, phenazines, carbazoles and triazines. 3 . The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 2 , wherein the triazine is selected from a compound containing triazoneone, a compound containing triazinedione, and a compound containing triazinetrione. 4 . The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 1 , wherein the aromatic ring having 6 to 40 carbon atoms is selected from benzene and naphthalene.

5. The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 1, wherein the compound (A) containing at least four carboxyl groups is a compound represented by formula (1), In formula (1), X is a divalent organic group selected from -CH2-, -C(CH3)2-, -CO-, -SO2- and -C(CF3)2-, which is a direct bond. 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 from 1 to 5, n1+n2 is an integer from 4 to 10, m1 and m2 are each independently an integer from 0 to 5, and m1+m2 is an integer from 0 to 7.

6. The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 1, wherein the compound (A) containing at least 4 carboxyl groups is selected from the following compounds:

7. The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 1 or 2, wherein the unit structure of the reaction product (B1) is selected from the following formula: 8 . The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 1 , further comprising at least one selected from a cross-linking agent, a cross-linking catalyst and a surfactant. 9 . The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 1 or 2 , wherein the semiconductor wet etching solution contains hydrogen peroxide water. 10 . The composition for forming a protective film resistant to a semiconductor wet etching solution according to claim 9 , wherein the hydrogen peroxide solution is an acidic hydrogen peroxide solution.

11. A protective film resistant to wet etching solution for semiconductors, 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 10.

12. A method for manufacturing a substrate with a resist pattern, characterized in that: The manufacturing method comprises the following steps: a step of applying the protective film forming composition described in any one of claims 1 to 10 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, and then exposing and developing it to form a resist pattern. The manufacturing method is used for the manufacture of semiconductors.

13. 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 10, 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 washing the inorganic film or the semiconductor substrate using a semiconductor wet etching solution using the dry-etched protective film as a mask.

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