Liquid medicine resistant protective film

Abstract

A composition for forming a protective film for a wet etching solution for semiconductors, the composition comprising: (A) a compound or polymer having a reactive group capable of cross-linking in the presence of a curing agent; (B) a curing agent; (C) a beta-dicarbonyl compound; and (D) a solvent.

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, and also relates to a method for manufacturing a protective film formed from the composition and a substrate with a resist pattern to which the protective film is applied, and a method for manufacturing a semiconductor device. Background Art

[0002] In semiconductor manufacturing, a photolithography process is well known in which a resist underlayer film is provided between a substrate and a resist film formed thereon to form a resist pattern of a desired shape. After the resist pattern is formed, the substrate is processed. Dry etching is mainly used as this process, but wet etching is sometimes used depending on the type of substrate. Patent Document 1 discloses a resist underlayer film material having alkaline hydrogen peroxide water resistance.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2018-173520 Summary of the invention

[0006] Problems to be solved by the invention

[0007] When a protective film for a semiconductor substrate is formed using a protective film forming composition and a base substrate is processed by wet etching using the protective film as an etching mask, the protective film is required to have a good masking function against a semiconductor wet etching solution (i.e., the masked portion can protect the substrate).

[0008] 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.

[0009] Conventionally, in order to develop resistance to SC-1 (ammonia-hydrogen peroxide solution) which is a type 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 has limited effect on solving the above-mentioned problems.

[0010] Furthermore, the protective film used for the above purpose is expected to have a function as a resist underlayer film for solving problems (shape defects, etc.) in so-called resist pattern formation.

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a protective film which can form a protective film having excellent resistance to a semiconductor wet etching solution and which can also be effectively used as a composition for forming a resist underlayer film.

[0012] Means for solving problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that a film obtained from a composition for forming a protective film containing a compound or polymer having a reactive group capable of undergoing a cross-linking reaction in the presence of a curing agent, a curing agent, and a β-dicarbonyl compound has excellent resistance to chemical solutions, thereby completing the present invention.

[0014] That is, the present invention includes the following aspects.

[0015] [1] A composition for forming a protective film for a semiconductor wet etching solution, comprising:

[0016] (A) a compound or polymer having a reactive group capable of undergoing a crosslinking reaction in the presence of a curing agent;

[0017] (B) a curing agent;

[0018] (C) β-dicarbonyl compounds; and

[0019] (D) Solvent.

[0020] [2] The protective film-forming composition according to [1], further comprising (E) a compound or polymer having a phenolic hydroxyl group.

[0021] [3] The protective film-forming composition according to [1] or [2], wherein the curing agent is a base.

[0022] [4] The protective film-forming composition according to [3], wherein the base is an imidazole compound.

[0023] [5] The protective film-forming composition according to [4], wherein the base is represented by the following formula (B1).

[0024]

[0025] (In formula (B1), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group which may be substituted, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a triazine ring which may be substituted, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, R 3 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group which may be substituted, and R 4 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and R 5represents a hydrogen atom, a formyl group, an alkyl group having 1 to 4 carbon atoms which may be substituted, or an alkoxyalkyl group having 4 or less carbon atoms which may be substituted, and n represents 0 or 1.

[0026] [6] The protective film-forming composition according to any one of [1] to [5], wherein the compound (C) is a compound represented by the following formula (C).

[0027]

[0028] (In formula (C), R A and R B Each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted aryloxy group having 5 to 18 carbon atoms. C and R D Each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted acyl group having 2 to 6 carbon atoms. A With R C Together they can form a ring structure.)

[0029] [7] The protective film-forming composition according to any one of [1] to [6], wherein the content of the compound (C) is 1 to 30% by mass relative to the compound or polymer (A).

[0030] [8] The protective film-forming composition according to any one of [1] to [7], wherein the compound or polymer (A) is a compound or polymer containing a cyclic ether having a three-membered ring structure or a four-membered ring structure.

[0031] [9] The protective film-forming composition according to [8], wherein the compound (A) is a compound having no repeating structural unit, and

[0032] comprising a terminal group (A1), a multivalent group (A2), and a linking group (A3),

[0033] The terminal group (A1) is only bonded to the linking group (A3),

[0034] The multivalent group (A2) is only bonded to the linking group (A3),

[0035] The linking group (A3) is bonded to the terminal group (A1) on one side and to the multivalent group (A2) on the other side, and can optionally be bonded to other linking groups (A3),

[0036] The terminal group (A1) is any of the structures of the following formula (I),

[0037]

[0038] (In formula (I), * represents the bonding site with the linker (A3).

[0039] X represents an ether bond, an ester bond or a nitrogen atom. When X is an ether bond or an ester bond, n=1; when X is a nitrogen atom, n=2.

[0040] The polyvalent group (A2) is selected from

[0041] -O-,

[0042] Aliphatic hydrocarbon group,

[0043] A combination of an aromatic hydrocarbon group having less than 10 carbon atoms and an aliphatic hydrocarbon group, and

[0044] Combination of an aromatic hydrocarbon group having 10 or more carbon atoms and -O-

[0045] The 2-4 valent groups in

[0046] The linking group (A3) represents an aromatic hydrocarbon group.

[0047]

[10] The protective film-forming composition according to [9], wherein the compound (A) is a compound represented by the following formula (II).

[0048]

[0049] (In formula (II),

[0050] Z 1 and Z 2 Each independently represents:

[0051]

[0052] (In formula (I), * represents 1 or Y 2 The binding part.

[0053] X represents an ether bond, an ester bond or a nitrogen atom, and when X is an ether bond or an ester bond, n=1, and when X is a nitrogen atom, n=2. )

[0054] Y 1 and Y 2 Each independently represents an aromatic hydrocarbon group,

[0055] X 1 and X 2 Each independently represents -Y 1 -Z1 or -Y 2 -Z 2 ,

[0056] n1 and n2 each independently represent an integer of 0 to 4, any of which is 1 or more,

[0057] (X 1 ) The m1 specified in m1 represents 0 or 1,

[0058] (X 2 ) The m2 specified in m2 represents 0 or 1,

[0059] Q represents a (n1+n2)-valent group selected from -O-, an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group having less than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group having more than 10 carbon atoms and O-.

[0060]

[11] The protective film-forming composition according to [9], wherein the compound (A) is a compound containing a partial structure represented by the following formula (III).

[0061]

[0062] (In formula (III), Ar represents a benzene ring, a naphthalene ring or an anthracene ring. X represents an ether bond, an ester bond or a nitrogen atom. When X is an ether bond or an ester bond, n=1; when X is a nitrogen atom, n=2.)

[0063]

[12] The protective film-forming composition according to [8], wherein the polymer (A) has a unit structure represented by the following formula (1-1).

[0064]

[0065] (In formula (1-1), Ar represents a benzene ring, a naphthalene ring or an anthracene ring, and R 1 represents a hydroxyl group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halo group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and may be substituted by a hydroxyl group, n1 represents an integer of 0 to 3, and L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, n2 represents 1 or 2, E represents a group having an epoxy group or a group having an oxetane group, and when n2=1, T 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond. When n2=2, T 1 represents a nitrogen atom or an amide bond. )

[0066]

[13] The protective film-forming composition according to any one of [2] to

[12] , wherein the (E) compound or polymer having a phenolic hydroxyl group has two or more phenolic hydroxyl groups.

[0067]

[14] The protective film-forming composition according to any one of [2] to

[13] , wherein the (E) compound or polymer having a phenolic hydroxyl group is represented by the following formula (2-1).

[0068]

[0069] (In formula (2-1), R 2 Each independently represents a halo group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halo group. 1 and A 2 Each independently represents an alkylene group having 1 to 10 carbon atoms, a divalent organic group derived from a bicyclic compound, a biphenylene group or -C(T 2 )(T 3 )-represented by a divalent organic group or a combination thereof, T 2 represents a halo group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, amino group which may be substituted with alkyl group having 1 to 3 carbon atoms, or alkyl group having 1 to 10 carbon atoms which may be substituted with hydroxyl group or a halo group, T 3 represents a hydrogen atom or a monovalent group represented by formula (2-1-a).

[0070]

[0071] (The * in formula (2-1-a) indicates the 3 The binding site of the carbon atom to which it is bound, R 2 With R in formula (2-1) 2 have the same meaning. a represents an integer of 1 to 6. n3 to n5 each independently represent an integer of 0 to 2. r2 represents an integer of 0 to 3. m1 and m2 each independently represent a number of 0 to 10,000,000.)

[0072]

[15] The protective film-forming composition according to any one of [2] to

[13] , wherein the compound or polymer (E) having a phenolic hydroxyl group is a compound represented by the following formula (2-2).

[0073]

[0074] (In formula (2-2), R 3represents a halogeno group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halogeno group. 1 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 6 to 40 carbon atoms, or an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogenated group. a represents an integer of 1 to 6. n6 represents an integer of 0 to 2. r3 represents an integer of 0 to 3.

[0075]

[16] The protective film-forming composition according to any one of [2] to

[13] , wherein the compound or polymer (E) having a phenolic hydroxyl group is a polymer having a unit structure represented by the following formula (3-1).

[0076]

[0077] (In formula (3-1), T 4 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group. 4 represents a halo group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halo group. r4 represents an integer of 0 to 3. n7 represents an integer of 0 to 2. a represents an integer of 1 to 6.

[0078]

[17] A protective film against 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

[16] .

[0079]

[18] A composition for forming a resist underlayer film, comprising:

[0080] (A) a compound or polymer having a reactive group capable of undergoing a crosslinking reaction in the presence of a curing agent;

[0081] (B) a curing agent;

[0082] (C) β-dicarbonyl compounds; and

[0083] (D) Solvent.

[0084]

[19] The resist underlayer film forming composition according to

[18] , further comprising (E) a compound or polymer having a phenolic hydroxyl group.

[0085]

[20] The resist underlayer film forming composition according to

[18] or

[19] , wherein the curing agent is a base.

[0086]

[21] The resist underlayer film forming composition according to

[20] , wherein the base is an imidazole compound.

[0087]

[22] The resist underlayer film forming composition according to

[21] , wherein the base is represented by the following formula (B1).

[0088]

[0089] (In formula (B1), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group which may be substituted, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a triazine ring which may be substituted, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, R 3 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group which may be substituted, and R 4 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and R 5 represents a hydrogen atom, a formyl group, an alkyl group having 1 to 4 carbon atoms which may be substituted, or an alkoxyalkyl group having 4 or less carbon atoms which may be substituted, and n represents 0 or 1.

[0090]

[23] The resist underlayer film forming composition according to any one of

[18] to

[22] , wherein the compound (C) is a compound represented by the following formula (C).

[0091]

[0092] (In formula (C), R A and R B Each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted aryloxy group having 5 to 18 carbon atoms. C and R D Each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted acyl group having 2 to 6 carbon atoms. A With R C Together they can form a ring structure.)

[0093]

[24] The resist underlayer film forming composition according to any one of

[18] to

[23] , wherein the content of the compound (C) is 1 to 30% by mass relative to the compound or polymer (A).

[0094]

[25] The resist underlayer film forming composition according to any one of

[18] to

[24] , wherein the compound or polymer (A) is a compound or polymer containing a cyclic ether having a 3-membered ring structure or a 4-membered ring structure.

[0095]

[26] A resist underlayer film characterized by being a fired product of a coating film formed from the resist underlayer film forming composition according to any one of

[18] to

[25] .

[0096]

[27] A method for manufacturing a substrate with a protective film, characterized in that it comprises the following steps: a step of applying the protective film-forming composition described in any one of [1] to

[16] on a semiconductor substrate having a height difference and firing it to form a protective film, wherein the above-mentioned method for manufacturing a substrate with a protective film is used to manufacture a semiconductor.

[0097]

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

[16] or the resist underlayer film forming composition described in any one of

[18] to

[25] on a semiconductor substrate and firing it to form a protective film as a resist underlayer film; and a step of forming a resist film on the protective film, followed by exposing and developing it to form a resist pattern. The above-mentioned method for manufacturing a substrate with a resist pattern is used to manufacture a semiconductor.

[0098]

[29] A method for manufacturing a semiconductor device, comprising the following steps: forming a protective film on a semiconductor substrate having an inorganic film formed on its surface using the protective film-forming composition described in any one of [1] to

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

[0099]

[30] A method for manufacturing a semiconductor device, comprising the following steps: forming a resist underlayer film on a semiconductor substrate having an inorganic film formed on its surface using the resist underlayer film forming composition described in any one of

[18] to

[25] , forming a resist pattern on the resist underlayer film, dry-etching the resist underlayer film using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and etching the inorganic film or the semiconductor substrate using the dry-etched resist underlayer film as a mask.

[0100] Effects of the Invention

[0101] According to the present invention, it is possible to provide a composition for forming a protective film which can form a protective film having excellent resistance to a semiconductor wet etching solution and which can also be effectively used as a composition for forming a resist underlayer film.

[0102] 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) It has a good masking function for wet etching liquid during base substrate processing, (2) It further reduces damage to the protective film or resist underlayer film during substrate processing by a low dry etching rate, (3) It has excellent planarization properties for uneven substrates, and (4) It has excellent embedding properties into fine groove pattern substrates. Furthermore, by having these properties (1) to (4) in a well-balanced manner, it is possible to easily perform fine processing of semiconductor substrates. DETAILED DESCRIPTION

[0103] Hereinafter, the present invention will be described in detail. It should be noted that the description of the constituent elements described below is for exemplification to illustrate the present invention, and the present invention is not limited to these contents.

[0104] (Composition for forming a protective film for a semiconductor wet etching solution)

[0105] The protective film forming composition for semiconductor wet etching solution of the present invention comprises:

[0106] (A) a compound or polymer having a reactive group capable of undergoing a crosslinking reaction in the presence of a curing agent;

[0107] (B) a curing agent;

[0108] (C) β-dicarbonyl compounds; and

[0109] (D) Solvent.

[0110] The protective film-forming composition of the present invention may further contain (E) a compound or polymer having a phenolic hydroxyl group.

[0111] The present inventors have discovered that a protective film having better resistance to semiconductor wet etching solutions can be formed by further including (C) a β-dicarbonyl compound in a protective film-forming composition comprising (A) a compound or polymer having a reactive group capable of undergoing a cross-linking reaction in the presence of a curing agent, (B) a curing agent, and (D) a solvent, thereby completing the present invention.

[0112] The reason for forming a protective film with better resistance is unclear, but the present inventors believe that the (C) β-dicarbonyl compound in the protective film reacts (eg, chelates) with the object to be protected (eg, inorganic film), thereby further improving the resistance of the protective film to the semiconductor wet etching solution.

[0113] <(A) Compound or polymer>

[0114] The (A) compound or polymer used in the present invention is not particularly limited as long as it has a reactive group capable of undergoing a crosslinking reaction in the presence of a curing agent, and can be appropriately selected depending on the purpose. For example, it is preferred that the compound or polymer is a compound or polymer containing a cyclic ether having a 3-membered ring structure or a 4-membered ring structure.

[0115] Here, examples of the cyclic ether having a three-membered ring structure include an epoxy group, and examples of the cyclic ether having a four-membered ring structure include an oxetanyl group.

[0116] As a more preferred embodiment of the (A) compound or polymer, there can be mentioned the compound represented by the following Embodiment 1 or the polymer represented by the following Embodiment 2.

[0117] <<Plan 1>>

[0118] As the (A) compound used in the present invention, for example, the following compounds can be mentioned.

[0119] Such a compound (hereinafter also referred to as a compound in the first embodiment) is a compound having no repeating structural unit, and

[0120] comprising a terminal group (A1), a multivalent group (A2), and a linking group (A3),

[0121] The terminal group (A1) is only bonded to the linking group (A3),

[0122] The multivalent group (A2) is only bonded to the linking group (A3),

[0123] The linking group (A3) is bonded to the terminal group (A1) on one side and to the multivalent group (A2) on the other side, and can optionally be bonded to other linking groups (A3),

[0124] The terminal group (A1) is any of the structures of the following formula (I),

[0125]

[0126] (In formula (I), * represents the bonding site with the linker (A3).

[0127] X represents an ether bond, an ester bond or a nitrogen atom. When X is an ether bond or an ester bond, n=1; when X is a nitrogen atom, n=2.

[0128] The polyvalent group (A2) is selected from

[0129] -O-,

[0130] Aliphatic hydrocarbon group,

[0131] A combination of an aromatic hydrocarbon group having less than 10 carbon atoms and an aliphatic hydrocarbon group, and

[0132] Combination of an aromatic hydrocarbon group having 10 or more carbon atoms and -O-

[0133] The 2-4 valent groups in

[0134] The linking group (A3) represents an aromatic hydrocarbon group.

[0135] The term “having no repeating structural unit” means excluding so-called polymers having repeating structural units such as polyolefin, polyester, polyamide, poly(meth)acrylate, etc. The weight average molecular weight of the (A) compound is preferably 300 or more and 1,500 or less.

[0136] The "bond" between the terminal group (A1), the multivalent group (A2), and the linking group (A3) refers to a chemical bond, usually a covalent bond, but may also be an ionic bond.

[0137] The polyvalent group (A2) is a divalent to tetravalent group.

[0138] Therefore, the aliphatic hydrocarbon group in the definition of the polyvalent group (A2) is a divalent to tetravalent aliphatic hydrocarbon group.

[0139] As non-limiting examples, when a divalent aliphatic hydrocarbon group is illustrated, methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, cyclobutylene, 1-methyl-cyclopropylene, 2-methyl-cyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene, cyclopentylene, 1-methyl-cyclobutylene, 2 -methyl-cyclobutylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene Butyl, 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclopentylene, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4- Alkylene groups of dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene or n-decylene.

[0140] By removing hydrogen at any position from these groups, a trivalent or tetravalent group is derived to form a bond.

[0141] Examples of the aromatic hydrocarbon group having less than 10 carbon atoms in the definition of the polyvalent group (A2) include benzene, toluene, xylene, mesitylene, cumene, styrene, and indene.

[0142] Examples of the aliphatic hydrocarbon group combined with the aromatic hydrocarbon group having less than 10 carbon atoms include, in addition to the above-mentioned alkylene group, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl -n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3 -dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, decyl and the like alkyl groups.

[0143] In the definition of the polyvalent group (A2), any of the aromatic hydrocarbon group and the aliphatic hydrocarbon group having less than 10 carbon atoms may be bonded to the linking group (A3).

[0144] Examples of the aromatic hydrocarbon group having 10 or more carbon atoms in the definition of the polyvalent group (A2) include naphthalene, azulene, anthracene, phenanthrene, tetracene, benzo[9,10]phenanthrene, pyrene, wait.

[0145] The aromatic hydrocarbon group having 10 or more carbon atoms in the definition of the polyvalent group (A2) is preferably bonded to the linking group (A3) via -O-.

[0146] Examples of the aromatic hydrocarbon group in the definition of the linking group (A3) include the above-mentioned aromatic hydrocarbon groups having less than 10 carbon atoms and the above-mentioned aromatic hydrocarbon groups having 10 or more carbon atoms.

[0147] It is preferred that the compound (A) has two or more linking groups (A3).

[0148] The compound in the first embodiment is preferably represented by the following formula (II), for example.

[0149]

[0150] (In formula (II),

[0151] Z 1 , and Z 2 Each independently represents:

[0152]

[0153] (In formula (I), * represents 1 , or Y 2 The binding part.

[0154] X represents an ether bond, an ester bond or a nitrogen atom, and when X is an ether bond or an ester bond, n=1, and when X is a nitrogen atom, n=2. )

[0155] Y 1 , and Y 2 Each independently represents an aromatic hydrocarbon group,

[0156] X 1 , and X 2 Each independently represents -Y 1 -Z 1 or -Y 2 -Z 2 ,

[0157] n1 and n2 each independently represent an integer of 0 to 4, any of which is 1 or more,

[0158] (X 1 ) The m1 specified in m1 represents 0 or 1,

[0159] (X 2 ) The m2 specified in m2 represents 0 or 1,

[0160] Q represents a (n1+n2)-valent group selected from -O-, an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group having less than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group having 10 or more carbon atoms and -O-.

[0161] Q is preferably a di- to tetravalent group.

[0162] In formula (II), Z 1 , and Z 2 corresponds to the above terminal group (A1), Q corresponds to the above multivalent group (A2), and Y 1 , and Y 2 These correspond to the above-mentioned linking group (A3), and their descriptions, examples, etc. are as described above.

[0163] The compound in the first embodiment preferably includes, for example, a partial structure represented by the following formula (III).

[0164]

[0165] (In formula (III), Ar represents a benzene ring, a naphthalene ring or an anthracene ring. X represents an ether bond, an ester bond or a nitrogen atom. When X is an ether bond or an ester bond, n=1; when X is a nitrogen atom, n=2.)

[0166] Examples of the compound in the first embodiment include the following compounds.

[0167]

[0168] <<Plan 2>>

[0169] As (A) polymer used in the present invention, the following polymers can be mentioned, for example.

[0170] Such a polymer (hereinafter also referred to as a polymer in the second embodiment) is a polymer having a unit structure represented by the following formula (1-1):

[0171]

[0172] (In formula (1-1), Ar represents a benzene ring, a naphthalene ring or an anthracene ring, and R 1 represents a hydroxyl group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halo group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and may be substituted by a hydroxyl group, n1 represents an integer of 0 to 3, and L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, n2 represents 1 or 2, E represents a group having an epoxy group or a group having an oxetane group, and when n2=1, T 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond. When n2=2, T 1 represents a nitrogen atom or an amide bond. )

[0173] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl 2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2 ,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, decyl, methoxy, ethoxy, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, methylamino, dimethylamino, diethylamino, aminomethyl, 1-aminoethyl, 2-aminoethyl, methylthio, ethylthio, mercaptomethyl, 1-mercaptoethyl, 2-mercaptoethyl, etc.

[0174] Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a cyclobutylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 1-ethyl-n-propylene group, a cyclopentylene group, a 1-methyl-cyclobutylene group, a 2-methyl-cyclopropylene group, a Butylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene , 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclopentylene, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4 -dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene or n-decylene.

[0175] R 1 An example of the alkyl group having 1 to 10 carbon atoms which is substituted or interrupted by a hetero atom is an alkoxy group having 1 to 10 carbon atoms.

[0176] Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, 4-methyl- n-Pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2,-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, n-heptyloxy, n-octyloxy and n-nonyloxy, etc.

[0177] The unit structure shown in formula (1-1) may be one or a combination of two or more. For example, it may be a copolymer having multiple unit structures in which Ar is of the same type, and copolymers having multiple unit structures in which Ar is of different types, such as a unit structure in which Ar contains a benzene ring and a unit structure having a naphthalene ring, are not excluded from the technical scope of the present application.

[0178] The term “may be interrupted” as used above means, in the case of an alkylene group having 2 to 10 carbon atoms, that any carbon-carbon atom in the alkylene group is interrupted by a heteroatom (i.e., an ether bond in the case of oxygen, a sulfide bond in the case of sulfur), an ester bond, or an amide bond, and in the case of a group having 1 carbon atom (i.e., a methylene group), that a heteroatom (i.e., an ether bond in the case of oxygen, a sulfide bond in the case of sulfur), an ester bond, or an amide bond is present on either side of the carbon of the methylene group.

[0179] When n2 = 1, T 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond, and is preferably a combination of an ether bond and a methylene group (i.e., "-T" in formula (1-1) 1 -(E)n2" is a glycidyl ether group), a combination of an ester bond and a methylene group, or a combination of an amide bond and a methylene group.

[0180] The alkyl group having 1 to 10 carbon atoms which may be substituted with a hetero atom means that one or more hydrogen atoms in the alkyl group having 1 to 10 carbon atoms are substituted with a hetero atom (preferably a halogeno group).

[0181] L 1represents a single bond or an alkylene group having 1 to 10 carbon atoms, and is preferably represented by the following formula (1-2).

[0182] -CR 2 R 3 - (1-2)

[0183] (In formula (1-2), R 2 , R 3 R independently represents a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, 2 , R 3 They may be bonded to each other to form a ring having 3 to 6 carbon atoms. Among them, R 2 , R 3 are all hydrogen atoms (i.e. -(CR 2 R 3 )- is methylene).

[0184] The halogeno group refers to a halogen -X (F, Cl, Br, I) substituted with hydrogen.

[0185] E in the formula (1-1) is more preferably a group having an epoxy group.

[0186] The polymer in the second embodiment is not particularly limited as long as it is a substance having a unit structure satisfying formula (1-1). It can be manufactured by a method known per se. Commercially available products can be used. As commercially available products, heat-resistant epoxy novolac resin EOCN (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.), epoxy novolac resin DEN (registered trademark) series (manufactured by Dai Chemikar Japan Co., Ltd.), etc. can be cited.

[0187] The weight average molecular weight of the polymer in the second embodiment is 100 or more, 500 to 200,000, 600 to 50,000, or 700 to 10,000.

[0188] Examples of the polymer in the second embodiment include those having the following unit structures.

[0189]

[0190] Me represents a methyl group, and Et represents an ethyl group.

[0191] <(B) Curing agent>

[0192] The component (B) used in the present invention is a curing agent.

[0193] The curing agent is not particularly limited as long as it can crosslink the reactive group possessed by the component (A) and can undergo a crosslinking reaction, and examples thereof include bases, thermal acid generators, phenolic curing agents, amide curing agents, amine curing agents, imidazoles, acid anhydride curing agents, organic phosphines, thiol curing agents, tertiary amines, Salts, tetraphenylborate salts, organic acid dihydrazides, halogenated boron amine coordination compounds, isocyanate curing agents, blocked isocyanate curing agents, etc.

[0194] It should be noted that, for example, 2-phenylimidazole is a base and also an imidazole. As described above, in the present invention, there may be a plurality of specific examples belonging to the lower concept of the curing agent exemplified above.

[0195] <<Alkali>>

[0196] The inventors have found that

[0197] (A') a compound or polymer having a reactive group capable of undergoing a cross-linking reaction in the presence of a base,

[0198] (B') base, and

[0199] (D) Solvent

[0200] The protective film-forming composition is a protective film-forming composition that can form a protective film with excellent resistance to a semiconductor wet etching solution, and can also be effectively used as a composition for forming a resist underlayer film, and an application has been made (Japanese Patent Application No. 2021-183272 and PCT / JP2022 / 37571 as a priority claim application). Japanese Patent Application No. 2021-183272 and PCT / JP2022 / 37571 are incorporated into this specification to the same extent as if all were expressly stated.

[0201] The present inventors have confirmed that even when the protective film-forming composition further contains (C) a β-dicarbonyl compound, a protective film having even better resistance to a semiconductor wet etching solution can be formed.

[0202] Examples of the base include imidazole compounds, (piperidine compounds, amide compounds, amine compounds, diazabicycloundecene (DBU) compounds, diazabicyclononene (DBN) compounds, Among them, imidazole compounds are preferred from the viewpoint of storage stability.

[0203] The base used in the present invention may also be in the form of a salt with an acid.

[0204] For example, the following description will be given taking imidazole compounds as an example.

[0205] Examples of the base of the component (B) in the present invention include (i) an imidazole compound represented by the following formula (B1), (ii) a salt of the imidazole compound represented by the formula (B1) and an acid, or (iii) a quaternary salt containing a cation represented by the following formula (B2).

[0206]

[0207] (In formula (B1), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group which may be substituted, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a triazine ring which may be substituted, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, R 3 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group which may be substituted, and R 4 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and R 5 represents a hydrogen atom, a formyl group, an alkyl group having 1 to 4 carbon atoms which may be substituted, or an alkoxyalkyl group having 4 or less carbon atoms which may be substituted, and n represents 0 or 1.

[0208] Examples of the substituent in the aryl group which may be substituted and the triazine ring which may be substituted include an amino group and a hydroxyl group.

[0209] The alkyl group may be linear or branched.

[0210] Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, and an anthracenyl group.

[0211] In R 4 or R 5 In the above, examples of the substituent in the alkyl group which may be substituted and the alkoxyalkyl group which may be substituted include a hydroxyl group and a cyano group.

[0212]

[0213] (In formula (B2), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group which may be substituted, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a triazine ring which may be substituted, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, R 3 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group which may be substituted, and R 4represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and R 5 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and R 6 represents an alkylene group having 1 to 4 carbon atoms, R 7 represents an alkyl group having 1 to 4 carbon atoms or an aryl group which may be substituted, m represents 0 or 1, and n represents 0 or 1. )

[0214] In formula (B2), R 1 ~R 5 The description of is the same as that of formula (B1). In formula (B2), R 7 The substituent in the aryl group which may be substituted includes amino group and hydroxyl group. 7 Specific examples of the aryl group include the same ones as mentioned above.

[0215] In the present invention, when the base of the component (B) forms a salt with a counter anion as described above, the counter anion is not particularly limited, and examples thereof include imide, halogen, carboxylate, sulfate, sulfonate, thiocyanate, aluminate, borate, phosphate, phosphinate, amide, antimonate, and methide. More specifically, (CF3SO2)2N - 、(CF3SO2)(FSO2)N - 、(FSO2)2N - 、(CF3CF2SO2)2N - 、(CN)2N - OH - , Cl - Br - ,I - 、NO3 - 、CH3COO - CF3COO - 、CF3CF2CF2COO - CF3SO3 - CF3CF2SO3 - CF3CF2CF2CF2SO3 - 、SbF6 - 、AlCl4 - 、SCN - PF6 - 、BF4 - 、[CF3OCF2CF2BF3 - ]、[(C p F 2p+1 )BF3] -(p represents an integer of 1, 2, 3, or 4), etc.

[0216] Further, for example, the anions shown below are mentioned.

[0217]

[0218] (R 40 represents an alkyl group having 1 to 10 carbon atoms. )

[0219] The base used in the present invention will be specifically shown below using imidazole compounds as examples, but the base is not limited to these.

[0220]

[0221]

[0222]

[0223] <<Thermal Acid Generator>>

[0224] Examples of the thermal acid generator include pyridine - p-Toluenesulfonate, pyridine -Trifluoromethanesulfonate, pyridine - p-Phenolsulfonate, K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689 (all manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0225] <<Phenolic curing agent>>

[0226] Examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol , tert-butylcatechol, tert-butylhydroquinone, phloroglucinol, pyrogallol, tert-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated products of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, etc.

[0227] <<Amine curing agent>>

[0228] Examples of the amine-based curing agent include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines.

[0229] Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, 1,6-hexanediamine, 2,5-dimethylhexanediamine, trimethylhexanediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, and tetrakis(hydroxyethyl)ethylenediamine.

[0230] Examples of the polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamine.

[0231] Examples of the alicyclic amines include isophoronediamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornene diamine.

[0232] Examples of the aromatic amines include tetrachloro-p-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, and α,α'-bis(4-aminophenyl)-p-diisopropylbenzene.

[0233] <<Imidazoles>>

[0234] Examples of the imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and the above imidazoles, etc.

[0235] <<Anhydride curing agent>>

[0236] Examples of the acid anhydride-based curing agent include acid anhydrides and modified products of acid anhydrides.

[0237] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyloctadecanedioic acid) anhydride, poly(phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, Hydrogenated phthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, ethylene glycol ditrimellitate dianhydride, chlorobridgeic acid, nadic anhydride, methyl nadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, etc.

[0238] As modified products of acid anhydrides, for example, substances obtained by modifying the above acid anhydrides with diols can be cited. Here, as examples of diols that can be used for modification, for example, alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol can be cited. Furthermore, copolymerized polyether diols of two or more diols and / or polyether diols among them can also be used. It should be noted that in the modified products of acid anhydrides, it is preferred to modify with less than 0.4 moles of diols relative to 1 mole of acid anhydride.

[0239] <<Organophosphine>>

[0240] Examples of the organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine.

[0241] << Salt>>

[0242] As Salts include, for example, tetraphenyl Tetraphenylborate, tetraphenyl ·Ethyl triphenyl borate, tetrabutyl Tetrabutyl borate, etc.

[0243] <<Tetraphenylboron salt>>

[0244] Examples of the tetraphenylborate salt include 2-ethyl-4-methylimidazolium tetraphenylborate and N-methylmorpholine tetraphenylborate.

[0245] As the content of the (B) curing agent in the protective film forming composition of the present invention, for example, the lower limit of the content is usually 0.0001% by mass, preferably 0.01% by mass, and more preferably 0.1% by mass, relative to the total solid content of the protective film forming composition, and the upper limit of the content is usually 50% by mass, preferably 40% by mass, and more preferably 30% by mass, relative to the total solid content of the protective film forming composition.

[0246] <(C) β-Dicarbonyl compounds>

[0247] The component (C) used in the present invention is a β-dicarbonyl compound (hereinafter sometimes referred to as "compound (C)"). The β-dicarbonyl compound is a compound having -C(=O)-CR X R Y -C(=O)-(R X and R Y Each independently represents a hydrogen atom or a monovalent group. A compound having a structure represented by ).

[0248] Examples of the number of carbon atoms of the compound (C) include 5 to 30.

[0249] As the compound (C), a compound represented by the following formula (C) is preferred.

[0250]

[0251] (In formula (C), R A and R B Each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted aryloxy group having 5 to 18 carbon atoms. C and R D Each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted acyl group having 2 to 6 carbon atoms. A With R C Together they can form a ring structure.)

[0252] As R A , R B , R C and R D The number of carbon atoms in the alkyl group having 1 to 10 carbon atoms which may be substituted may be, for example, 1 to 10, or 1 to 6.

[0253] As RA , R B , R C and R D Specific examples of the alkyl group having 1 to 10 carbon atoms include, for example, 1 Specific examples of the alkyl group having 1 to 10 carbon atoms exemplified in the description of . The alkyl group may be linear, branched, cyclic, or a combination thereof.

[0254] As R A and R B The number of carbon atoms in the alkoxy group having 1 to 10 carbon atoms which may be substituted may be, for example, 1 to 10, or 1 to 6.

[0255] As R A and R B Specific examples of the alkoxy group having 1 to 10 carbon atoms include, for example, 1 Specific examples of the alkoxy group having 1 to 10 carbon atoms are given in the description of . The alkyl group in the alkoxy group may be linear, branched, cyclic, or a combination thereof.

[0256] As R A , R B , R C and R D The aryl group of the aryl group having 5 to 18 carbon atoms which may be substituted may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon ring in the aromatic hydrocarbon group include a benzene ring and a naphthalene ring. Examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a quinoline ring, an indole ring, a benzofuran ring, a benzothiophene ring, etc. Among them, a benzene ring, a furan ring, a thiophene ring, and a pyridine ring are preferred.

[0257] As R A , R B , R C and R D The aryl group of the aralkyl group having 5 to 18 carbon atoms which may be substituted may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon ring in the aromatic hydrocarbon group include a benzene ring and a naphthalene ring. Examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a quinoline ring, an indole ring, a benzofuran ring, a benzothiophene ring, etc. Among them, a benzene ring, a furan ring, a thiophene ring, and a pyridine ring are preferred.

[0258] As R A and R B The aralkyl group having 5 to 18 carbon atoms includes benzyl group, phenethyl group and the like.

[0259] As R A and R B The aryl group of the aryloxy group having 5 to 18 carbon atoms which may be substituted may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon ring in the aromatic hydrocarbon group include a benzene ring and a naphthalene ring. Examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a quinoline ring, an indole ring, a benzofuran ring, a benzothiophene ring, etc. Among them, a benzene ring, a furan ring, a thiophene ring, and a pyridine ring are preferred.

[0260] Examples of the substituent in the optionally substituted alkyl group having 1 to 10 carbon atoms and the optionally substituted alkoxy group having 1 to 10 carbon atoms include halogen atoms, alkoxy groups, acyl groups, etc. Examples of the acyl group include acyl groups having 2 to 5 carbon atoms.

[0261] In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0262] Examples of the substituent in the optionally substituted aryl group having 5 to 18 carbon atoms, the optionally substituted aralkyl group having 5 to 18 carbon atoms and the optionally substituted aryloxy group having 5 to 18 carbon atoms include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an acyl group having 2 to 5 carbon atoms.

[0263] As R C and R D Examples of the substituent in the optionally substituted acyl group having 2 to 6 carbon atoms include a halogen atom.

[0264] R A With R C The ring structure may be formed together. The number of ring members of the formed ring structure may be, for example, 5 to 7. The formed ring structure may be, for example, a lactone ring. The atoms constituting the ring structure may contain a heteroatom. The bonds forming the ring structure may have a carbon-carbon double bond.

[0265] Examples of the substituent in the aryl group having 5 to 18 carbon atoms which may be substituted, the aralkyl group having 5 to 18 carbon atoms which may be substituted, and the aryloxy group having 5 to 18 carbon atoms which may be substituted include a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

[0266] Examples of the compound (C) include the following compounds.

[0267]

[0268] The content of the compound (C) in the protective film-forming composition of the present invention is not particularly limited, but the lower limit of the content is preferably 0.5% by mass, more preferably 1% by mass, and particularly preferably 5% by mass, relative to the compound (A) or the polymer, and the upper limit of the content is preferably 50% by mass, more preferably 30% by mass, and particularly preferably 20% by mass, relative to the compound (A) or the polymer.

[0269] The content of the compound (C) in the protective film-forming composition of the present invention is not particularly limited, but the lower limit of the content is preferably 0.0001% by mass, more preferably 0.005% by mass, and particularly preferably 0.001% by mass, relative to the (D) solvent; and the upper limit of the content is preferably 50% by mass, more preferably 30% by mass, and particularly preferably 20% by mass, relative to the (D) solvent.

[0270] <(D) Solvent>

[0271] The protective film-forming composition of the present invention can be prepared by dissolving the above-mentioned components in a solvent, preferably an organic solvent, and used in a uniform solution state. In the present invention, (D) the solvent is different from (C) the compound.

[0272] As the organic solvent of the protective film forming composition according to the present invention, any organic solvent that can dissolve the above-mentioned (A) compound or polymer, the above-mentioned (B) curing agent, other arbitrarily selected solid components, etc. 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 an organic solvent generally used in a photolithography process in combination in consideration of its coating performance.

[0273] 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, 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, 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.

[0274] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0275] 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 proportion of all components from the protective film forming composition after removing the solvent. The proportion of the above-mentioned (A) compound or polymer in the solid content is preferably 1 to 100% by mass, more preferably 1 to 99.9% by mass, further preferably 50 to 99.9% by mass, further more preferably 50 to 95% by mass, and particularly preferably 50 to 90% by mass.

[0276] <(E) Compound or polymer having phenolic hydroxyl group>

[0277] The protective film-forming composition of the present invention may further contain (E) a compound or polymer having a phenolic hydroxyl group.

[0278] The compound or polymer having a phenolic hydroxyl group (E) is not particularly limited as long as it does not impair the effects of the present invention. It goes without saying that the compound or polymer having a phenolic hydroxyl group (E) is different from the compound or polymer (A) described above.

[0279] The weight average molecular weight of the (E) compound or polymer having a phenolic hydroxyl group (hereinafter, also referred to as the (E) compound or polymer) is not particularly limited, and is, for example, 300 to 50,000.

[0280] The (E) compound or polymer preferably has two or more phenolic hydroxyl groups.

[0281] As more preferred embodiments of the compound or polymer (E), for example, there can be mentioned compounds or polymers shown in the following third to fifth embodiments.

[0282] <<Plan 3>>

[0283] Examples of the (E) compound or polymer used in the present invention include compounds or polymers represented by formula (2-1).

[0284]

[0285] (In formula (2-1), R 2 Each independently represents a halo group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halo group. 1 and A 2Each independently represents an alkylene group having 1 to 10 carbon atoms, a divalent organic group derived from a bicyclic compound, a biphenylene group or -C(T 2 )(T 3 )-represented by a divalent organic group or a combination thereof, T 2 represents a halo group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, amino group which may be substituted with alkyl group having 1 to 3 carbon atoms, or alkyl group having 1 to 10 carbon atoms which may be substituted with hydroxyl group or a halo group, T 3 represents a hydrogen atom or a monovalent group represented by formula (2-1-a).

[0286]

[0287] (The * in formula (2-1-a) indicates the 3 The bonding site of the bonded carbon atom. 2 With R in formula (2-1) 2 have the same meaning. a represents an integer of 1 to 6. n3 to n5 each independently represent an integer of 0 to 2. r2 represents an integer of 0 to 3. m1 and m2 each independently represent 0 to 10,000,000.)

[0288] It is preferred that m1, n3 to n5 and r2 are 0, and m2 is 1.

[0289] The halogeno group, alkoxy group and alkyl group in formula (2-1) are as described above.

[0290] Examples of the bicyclic compound include dicyclopentadiene, substituted dicyclopentadiene, tetracyclo[4.4.0.12,5.17,10]dodeca-3,8-diene, and substituted tetracyclo[4.4.0.12,5.17,10]dodeca-3,8-diene. The substitution means that one or more hydrogen atoms of the bicyclic compound are independently substituted by a halide, nitro, amino or hydroxyl group, or an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms which can be substituted by these groups. The divalent organic group derived from the bicyclic compound means a group having two bonds derived by removing any two hydrogen atoms from the bicyclic compound.

[0291] Examples of the aryl group having 6 to 40 carbon atoms include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl.

[0292] Specific examples of the compound represented by formula (2-1) include the following compounds.

[0293]

[0294] (E) The compound or polymer may be the following compounds.

[0295]

[0296] <<Plan 4>>

[0297] Examples of the (E) compound or polymer used in the present invention include compounds represented by formula (2-2).

[0298]

[0299] (In formula (2-2), R 3 represents a halogeno group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halogeno group. 1 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 6 to 40 carbon atoms, or an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogenated group. a represents an integer of 1 to 6. n6 represents an integer of 0 to 2. r3 represents an integer of 0 to 3.

[0300] The alkoxy group, alkyl group and halogeno group of formula (2-2) are as described above.

[0301] Examples of the arylene group having 6 to 40 carbon atoms include phenylene, o-methylphenylene, m-methylphenylene, p-methylphenylene, o-chlorophenylene, m-chlorophenylene, p-chlorophenylene, o-fluorophenylene, p-fluorophenylene, o-methoxyphenylene, p-methoxyphenylene, p-nitrophenylene, p-cyanophenylene, α-naphthylene, β-naphthylene, o-biphenylene, m-biphenylene, p-biphenylene, 1-anthrylene, 2-anthrylene, 9-anthrylene, 1-phenanthrylene, 2-phenanthrylene, 3-phenanthrylene, 4-phenanthrylene and 9-phenanthrylene.

[0302] Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a cyclobutylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, a 1-ethyl-n-propylene group, a cyclopentylene group, a 1-methyl-cyclobutylene group, a 2-methyl-cyclopropylene group, a Butylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 2,2-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene , 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclopentylene, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4 -dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene or n-decylene.

[0303] Specific examples of the compound represented by formula (2-2) include the following compounds.

[0304]

[0305] The compound (E) may be a compound represented by the following formula (4-1).

[0306]

[0307] (In formula (4-1), R 5represents a halo group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halo group. In the formula, n8 represents an integer of 4, 5, 6, or 8.)

[0308] The explanations of the above terms are as described above.

[0309] Specific examples of the compound represented by formula (4-1) are shown below.

[0310]

[0311] The compound (E) may be a compound represented by the following formula (5-1) or formula (5-1-a).

[0312]

[0313] (where n9 and n10 each represent an integer of 0 or 1, R 6 represents a halo group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halo group. a represents an integer of 1 to 6. n11 represents an integer of 1 or 2. r5 represents an integer of 0 to 3. * represents the structure represented by formula (5-1) and the bonding site with the structure represented by formula (5-1-a).

[0314] The explanations of the above terms are as described above.

[0315] Specific examples of the compounds represented by the following formula (5-1) and formula (5-1-a) are shown below.

[0316]

[0317] The compound (E) may be the following compound.

[0318]

[0319] <<Plan 5>>

[0320] The (E) compound or polymer used in the present invention is not particularly limited as long as it is a polymer that does not impair the effects of the present invention. For example, the (E) polymer preferably has at least three repeating unit structures.

[0321] The weight average molecular weight of the (E) polymer is not particularly limited, and is, for example, 1,000 to 50,000.

[0322] It is preferred that the (E) polymer includes a unit structure represented by the following (Formula 3-1).

[0323]

[0324] (In formula (3-1), T 4 R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group. 4 represents a halo group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halo group. r4 represents an integer of 0 to 3. n7 represents an integer of 0 to 2. a represents an integer of 1 to 6.

[0325] The halo group, the alkyl group and the alkoxy group are as described above.

[0326] The polymer represented by the formula (3-1) may be a polymer including one type of the unit structure represented by the formula (3-1), or may be a copolymer including two or more types.

[0327] Specific examples of the (E) polymer represented by the formula (3-1) include polymers having the unit structures described below.

[0328]

[0329] (In the above formula, m and n written next to the repeating unit represent the molar ratio of copolymerization.

[0330] (Resist underlayer film forming composition)

[0331] The resist underlayer film-forming composition of the present invention comprises:

[0332] (A) a compound or polymer having a reactive group capable of undergoing a crosslinking reaction in the presence of a curing agent;

[0333] (B) a curing agent;

[0334] (C) β-dicarbonyl compounds; and

[0335] (D) Solvent.

[0336] The protective film-forming composition of the present invention not only exhibits excellent resistance to a semiconductor wet etching solution, but can also be effectively used as a composition for forming a resist underlayer film.

[0337] The description of terms related to the resist underlayer film forming composition of the present invention is the same as the description of the protective film forming composition described above.

[0338] (Protective film, resist underlayer film, substrate with resist pattern, and method for manufacturing semiconductor device, etc.)

[0339] 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 (resist underlayer film-forming composition) according to the present invention will be described.

[0340] The protective film of the present invention is a fired product of a coating film formed from the protective film-forming composition of the present invention.

[0341] The resist underlayer film of the present invention is a fired product of a coating film of the resist underlayer film-forming composition of the present invention.

[0342] The method for producing a substrate with a protective film of the present invention comprises the steps of applying the protective film-forming composition of the present invention on a semiconductor substrate having a height difference and firing the composition to form a protective film. The method for producing a substrate with a protective film is used to produce a semiconductor.

[0343] The method for producing a substrate with a resist pattern of the present invention comprises the following steps: a step of applying the protective film-forming composition of the present invention or the resist underlayer film-forming composition of the present invention on a semiconductor substrate and firing it to form a protective film as a resist underlayer film; and a step of forming a resist film on the protective film, followed by exposure and development to form a resist pattern. The method for producing a substrate with a resist pattern is used for producing semiconductors.

[0344] One embodiment of the method for manufacturing a semiconductor device of the present invention includes 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 of the present invention, forming a resist pattern on the above-mentioned protective film, dry-etching the above-mentioned protective film using the above-mentioned resist pattern as a mask to expose the surface of the above-mentioned inorganic film or the above-mentioned semiconductor substrate, and wet-etching the above-mentioned inorganic film or the above-mentioned semiconductor substrate using a semiconductor wet etching solution using the above-mentioned protective film after dry etching as a mask and washing it.

[0345] One embodiment of the method for manufacturing a semiconductor device of the present invention includes the following steps: forming a resist underlayer film on a semiconductor substrate on which an inorganic film can be formed using the resist underlayer film forming composition of the present invention, forming a resist pattern on the above-mentioned resist underlayer film, dry-etching the above-mentioned resist underlayer film using the above-mentioned resist pattern as a mask to expose the surface of the above-mentioned inorganic film or the above-mentioned semiconductor substrate, and etching the above-mentioned inorganic film or the above-mentioned semiconductor substrate using the above-mentioned resist underlayer film after dry etching as a mask.

[0346] The substrate with a resist pattern according to the present invention can be produced by applying the protective film-forming composition (resist underlayer film-forming composition) on a semiconductor substrate and firing the coating.

[0347] Examples of semiconductor substrates to which the protective film-forming composition (resist underlayer 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.

[0348] In the case of using a semiconductor substrate having an inorganic film formed on the surface, the inorganic film is formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum evaporation method, spin coating method (spin-on glass: SOG). As the above-mentioned inorganic film, for example, 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 can be cited. The above-mentioned semiconductor substrate can be a height difference substrate formed with so-called through holes (holes), grooves (grooves), etc. For example, the through hole is roughly circular in shape when viewed from above, and the diameter of the roughly circular circle is, for example, 2nm to 20nm, and the depth is 50nm to 500nm. The groove is, for example, a groove (a recessed portion of the substrate) with a width of 2nm to 20nm and a depth of 50nm to 500nm. The protective film-forming composition (resist underlayer film-forming composition) of the present invention has a small weight average molecular weight and average particle size of the compound contained in the composition, so the composition can be embedded in the above-mentioned uneven substrate without defects such as pores (voids). For the subsequent steps of semiconductor manufacturing (wet etching / dry etching of semiconductor substrates, resist pattern formation), the absence of defects such as pores is an important characteristic.

[0349] On such a semiconductor substrate, the protective film-forming composition of the present invention (resist underlayer film-forming composition) is applied by an appropriate coating method such as a spin coater or a coater. Then, a protective film (resist underlayer film) is formed by baking by 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, crosslinking may become insufficient, and it may be difficult to obtain the resistance of the formed protective film (resist underlayer film) to the resist solvent or the alkaline hydrogen peroxide solution. On the other hand, when the temperature during baking is higher than the above range, the protective film (resist underlayer film) may be decomposed by heat.

[0350] A resist film is formed on the protective film formed as described above, and then exposure and development are performed to form a resist pattern.

[0351] Exposure is performed through a mask (photomask) for forming a predetermined pattern, using, for example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet rays) or EB (electron beams). An alkaline developer is used for development, and is appropriately selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. As an alkaline developer, for example, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc., a primary amine such as ethylamine, n-propylamine, a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, etc., an alcohol amine such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salts such as choline, cyclic amines such as pyrrole and piperidine, etc. can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol, a nonionic surfactant, etc. can also be added to the aqueous solution of the above-mentioned alkali and used. Among them, preferred developer is quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline. Further, surfactants etc. may be added to these developers. Alternatively, 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.

[0352] Next, the protective film (resist lower 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.

[0353] Furthermore, by using the protective film (resist underlayer film) after dry etching (when a resist pattern remains on the protective film / resist underlayer film, the resist pattern is also used) as a mask, wet etching is performed using a semiconductor wet etching solution to form a desired pattern.

[0354] 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.

[0355] 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.

[0356] As a substance showing alkalinity, an alkaline hydrogen peroxide solution obtained by mixing an organic amine such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, triethanolamine, etc. with hydrogen peroxide solution to make the pH alkaline can be cited. As a specific example, SC-1 (ammonia-hydrogen peroxide solution) can be cited. In addition, a substance that can make the pH alkaline, such as mixing urea with hydrogen peroxide solution, causing thermal decomposition of urea by heating to generate ammonia, and finally making the pH alkaline can also be used as a wet etching solution.

[0357] Among them, acidic hydrogen peroxide water or alkaline hydrogen peroxide water is preferred.

[0358] These liquids may contain additives such as surfactants.

[0359] 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.

[0360] Example

[0361] Hereinafter, the contents and effects of the present invention will be described in further detail with reference to Examples, but the present invention is not limited thereto.

[0362] The weight average molecular weights of the compounds synthesized in the following Examples of this specification are the results of measurements obtained by gel permeation chromatography (hereinafter referred to as GPC). The measurement was performed using a GPC apparatus manufactured by Tosoh Corporation, and the measurement conditions and the like were as follows.

[0363] GPC columns

[0364] Column temperature: 40°C

[0365] Solvent: Tetrahydrofuran (THF)

[0366] Flow rate: 1.0ml / min

[0367] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0368] <Explanation of terms>

[0369] PGME: Propylene glycol monomethyl ether

[0370] PGMEA: Propylene glycol monomethyl ether acetate

[0371] <Example 1>

[0372] 3.16 g of epoxy novolac resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass % PGMEA solution, weight average molecular weight 3100), 0.24 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 3687), 0.014 g of 1B2PZ (manufactured by Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.095 g of acetylacetone (Tokyo Chemical Industry Co., Ltd.), 0.0009 g of R-40-LM (DIC Co., Ltd.), 17.95 g of PGMEA and 8.64 g of PGME were mixed to prepare a solution having a solid content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0373] The amount of acetylacetone relative to the epoxy novolac resin EOCN-104S was 10% by mass.

[0374]

[0375]

[0376] <Example 2>

[0377] 3.16 g of epoxy novolac resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass % PGMEA solution, weight average molecular weight 3100), 0.24 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 3687), 0.014 g of 1B2MZ (manufactured by Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.095 g of dipivaloyl methane (Tokyo Chemical Industry Co., Ltd.), 0.0009 g of R-40-LM (DIC Co., Ltd.), 17.95 g of PGMEA and 8.64 g of PGME were mixed to prepare a solution having a solid content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0378] The amount of dipivaloyl methane relative to the epoxy novolac resin EOCN-104S was 10% by mass.

[0379]

[0380] <Example 3>

[0381] 3.16 g of epoxy novolac resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass % PGMEA solution, weight average molecular weight 3100), 0.24 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 3687), 0.014 g of 1B2PZ (manufactured by Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.095 g of trifluoroacetylacetone (Tokyo Chemical Industry Co., Ltd.), 0.0009 g of R-40-LM (DIC Co., Ltd.), 17.95 g of PGMEA, and 8.64 g of PGME were mixed to prepare a solution having a solid content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0382] The amount of trifluoroacetylacetone relative to the epoxy novolac resin EOCN-104S was 10% by mass.

[0383]

[0384] <Example 4>

[0385] 3.16 g of epoxy novolac resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass% PGMEA solution, weight average molecular weight 3100), 0.24 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 3687), 0.014 g of 1B2PZ (manufactured by Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.095 g of 1-phenyl-1,3-butanedione (Tokyo Chemical Industry Co., Ltd.), 0.0009 g of R-40-LM (DIC Co., Ltd.), 17.95 g of PGMEA, and 8.64 g of PGME were mixed to prepare a solution having a solid content of 4.0 mass%. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a protective film-forming composition.

[0386] The amount of 1-phenyl-1,3-butanedione relative to the epoxy novolac resin EOCN-104S was 10% by mass.

[0387]

[0388]

[0389] <Example 5>

[0390] 3.16 g of epoxy novolac resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass % PGMEA solution, weight average molecular weight 3100), 0.24 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 3687), 0.014 g of 1B2PZ (manufactured by Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.095 g of avobenzone (Tokyo Chemical Industry Co., Ltd.), 0.0009 g of R-40-LM (DIC Co., Ltd.), 17.95 g of PGMEA, and 8.64 g of PGME were mixed to prepare a solution having a solid content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0391] The amount of avobenzone relative to the epoxy novolac resin EOCN-104S was 10% by mass.

[0392]

[0393]

[0394] <Example 6>

[0395] 3.16 g of epoxy novolac resin EOCN-104S (product of Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass% PGMEA solution, weight average molecular weight of 3100), 0.24 g of VP-2500 (product of Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight of 3687), 0.014 g of 1B2PZ (product of Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.095 g of 1,3-di(2-pyridyl)-1,3-propanedione (Tokyo Chemical Industry Co., Ltd., dipyridylmethane), 0.0009 g of R-40-LM (DIC Co., Ltd.), 17.95 g of PGMEA and 8.64 g of PGME were mixed to prepare a solution with a solid content of 4.0 mass%. This solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a protective film-forming composition.

[0396] The amount of 1,3-di(2-pyridyl)-1,3-propanedione relative to the epoxy novolac resin EOCN-104S was 10% by mass.

[0397]

[0398] <Example 7>

[0399] 3.16 g of epoxy novolac resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass% PGMEA solution, weight average molecular weight 3100), 0.24 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 3687), 0.014 g of 1B2PZ (manufactured by Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.095 g of 1,3-diphenyl-1,3-propanedione (Tokyo Chemical Industry Co., Ltd., dibenzoylmethane), 0.0009 g of R-40-LM (DIC Co., Ltd.), 17.95 g of PGMEA, and 8.64 g of PGME were mixed to prepare a solution having a solid content of 4.0 mass%. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0400] The amount of 1,3-diphenyl-1,3-propanedione relative to the epoxy novolac resin EOCN-104S was 10% by mass.

[0401]

[0402] <Comparative Example 1>

[0403] <<Synthesis Example 1>>

[0404] A solution of 5.50 g of glycerol monomethacrylate (product name: Brenma GLM, manufactured by NOF Corporation), 5.09 g of 5-vinylbenzo[d][1,3]dioxole (manufactured by Cool Pharm LTD.), 0.66 g of 2,2'-azobis(isobutyronitrile) (manufactured by Tokyo Chemical Industry Co., Ltd.), and 35.99 g of propylene glycol monomethyl ether was added to a dropping funnel, and the mixture was added dropwise to a reaction flask containing 9.00 g of propylene glycol monomethyl ether at 100° C. under a nitrogen atmosphere, followed by heating and stirring for 17 hours. To the obtained solution, 11 g of a cation exchange resin (product name: Dawuex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 11 g of an anion exchange resin (product name: Anvalite [registered trademark] 15JWET, Organo Co., Ltd.) were added, and ion exchange treatment was performed at room temperature for 4 hours. The ion exchange resin was separated to obtain a resin solution corresponding to formula (F), and the weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 10,800.

[0405]

[0406] <<Preparation of protective film forming composition>>

[0407] Pyridine was added as a crosslinking acid catalyst to 6.6 g of the resin solution (solid content: 17.4 wt%) obtained in Synthesis Example 1. A solution of a protective film-forming composition was prepared by adding 0.06 g of trifluoromethanesulfonic acid (manufactured by ADEKA Corporation), 0.001 g of a surfactant (manufactured by DIC Corporation, product name: Megafac R-40, a fluorine-based surfactant), 11.5 g of PGME, and 1.9 g of PGMEA.

[0408] <Comparative Example 2>

[0409] 3.16 g of epoxy novolac resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., equivalent to formula (a-1)) (30 mass % PGMEA solution, weight average molecular weight 3100), 0.24 g of VP-2500 (manufactured by Nippon Soda Co., Ltd., equivalent to formula (a-3), weight average molecular weight 3687), 0.014 g of 1B2PZ (manufactured by Shikoku Chemical Industry Co., Ltd., equivalent to formula (b-3)), 0.0009 g of R-40-LM (manufactured by DIC Co., Ltd.), 17.95 g of PGMEA and 8.64 g of PGME were mixed to prepare a solution having a solid content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter having a pore size of 0.2 μm to prepare a composition for forming a protective film.

[0410]

[0411] (Formation of coating film)

[0412] On a silicon substrate having a titanium nitride film formed on the surface, the protective film forming composition prepared in Examples 1 to 7 and the protective film forming composition prepared in Comparative Examples 1 to 2 were each applied by spin coating and baked at 250°C for 60 seconds to produce a coating film with a thickness of 100 nm.

[0413] (Resistance test to alkaline hydrogen peroxide aqueous solution)

[0414] The coating films prepared on the silicon substrate having a titanium nitride film formed on the surface using the protective film forming compositions prepared in Examples 1 to 7 and the protective film forming compositions prepared in Comparative Examples 1 to 2 were immersed in an alkaline hydrogen peroxide aqueous solution having the composition shown in Table 1 for 4 minutes at the temperature shown in the table, and then washed with water, and the state of the dried coating films was visually observed. The results are shown in Table 2. "×" indicates a state where the film has peeled off, "△" indicates a state where partial peeling is observed, and "○" indicates a state where the film has not peeled off.

[0415] [Table 1]

[0416]

[0417] [Table 2]

[0418] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 ○ ○ ○ ○ ○ ○ ○ × △

[0419] As can be seen from the results in Table 2, the coating films produced using the protective film-forming compositions prepared in Examples 1 to 7 have improved resistance to alkaline aqueous hydrogen peroxide solutions compared to Comparative Examples 1 and 2.

[0420] In addition, although Comparative Example 2 showed a good result compared with Comparative Example 1, Examples 1 to 7 showed a better result compared with Comparative Example 1.

[0421] (Optical parameter test)

[0422] The protective film forming compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 2 were applied to silicon wafers by spin coaters. The films were baked at 250°C for 1 minute on a hot plate to form a resist underlayer film (film thickness 50 nm). Furthermore, the n value (refractive index) and k value (attenuation coefficient or absorption coefficient) at wavelengths of 193 nm and 248 nm were measured using a spectroscopic ellipsometer (JA Woollam, VUV-VASE VU-302). The results are shown in Table 3.

[0423] [Table 3]

[0424] n / k@193nm n / k@248nm Example 1 1.46 / 0.66 1.89 / 0.03 Example 2 1.46 / 0.66 1.89 / 0.03 Example 3 1.45 / 0.66 1.89 / 0.03 Example 4 1.46 / 0.65 1.89 / 0.03 Example 5 1.46 / 0.66 1.89 / 0.03 Example 6 1.46 / 0.66 1.90 / 0.02 Example 7 1.45 / 0.65 1.89 / 0.03 Comparative Example 1 1.47 / 0.32 1.91 / 0.04 Comparative Example 2 1.48 / 0.65 1.88 / 0.02

[0425] Industrial Availability

[0426] The composition for forming a protective film according to the present invention has excellent resistance when a wet etching solution is used for substrate processing, thereby providing a protective film with low damage to the protective film during substrate processing. The composition for forming a resist underlayer film according to the present invention has excellent resistance when a wet etching solution is used for substrate processing.

Claims

1. A composition for forming a protective film for a semiconductor wet etching solution, comprising: (A) a compound or polymer having a reactive group capable of undergoing a crosslinking reaction in the presence of a curing agent; (B) a curing agent; (C) β-dicarbonyl compounds; and (D) Solvent. 2 . The protective film-forming composition according to claim 1 , further comprising (E) a compound or polymer having a phenolic hydroxyl group. The protective film-forming composition according to claim 1 , wherein the curing agent is a base. The protective film-forming composition according to claim 3 , wherein the base is an imidazole compound.

5. The protective film-forming composition according to claim 4, wherein the base is represented by the following formula (B1): In formula (B1), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group which may be substituted, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a triazine ring which may be substituted, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, R 3 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group which may be substituted, and R 4 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and R 5 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and n represents 0 or 1.

6. The protective film-forming composition according to claim 1, wherein the compound (C) is a compound represented by the following formula (C): In formula (C), R A and R B Each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted, an alkoxy group having 1 to 10 carbon atoms which may be substituted, an aryl group having 5 to 18 carbon atoms which may be substituted, an aralkyl group having 5 to 18 carbon atoms which may be substituted, or an aryloxy group having 5 to 18 carbon atoms which may be substituted; R C and R D Each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted acyl group having 2 to 6 carbon atoms; R A With R C Can together form a ring structure. 7 . The protective film-forming composition according to claim 1 , wherein the content of the compound (C) is 1 to 30% by mass based on the compound or polymer (A). 8 . The protective film-forming composition according to claim 1 , wherein the compound or polymer (A) is a compound or polymer containing a cyclic ether having a three-membered ring structure or a four-membered ring structure.

9. The protective film-forming composition according to claim 8, wherein the compound (A) is a compound having no repeating structural unit, and comprising a terminal group (A1), a multivalent group (A2), and a linking group (A3), The terminal group (A1) is only bonded to the linking group (A3), The multivalent group (A2) is only bonded to the linking group (A3), The linking group (A3) is bonded to the terminal group (A1) on one side and to the multivalent group (A2) on the other side, and can optionally be bonded to other linking groups (A3), The terminal group (A1) is any of the structures of the following formula (I), In formula (I), * represents the binding site with the linker (A3); X represents an ether bond, an ester bond or a nitrogen atom, and when X is an ether bond or an ester bond, n=1, and when X is a nitrogen atom, n=2; The polyvalent group (A2) is selected from -O-、 Aliphatic hydrocarbon group, A combination of an aromatic hydrocarbon group having less than 10 carbon atoms and an aliphatic hydrocarbon group, and Combination of an aromatic hydrocarbon group having 10 or more carbon atoms and -O- The 2-4 valent groups in The linking group (A3) represents an aromatic hydrocarbon group.

10. The protective film-forming composition according to claim 9, wherein the compound (A) is a compound represented by the following formula (II): In formula (II), Z 1 and Z 2 Each independently represents: In formula (I), * represents 1 or Y 2 The binding site; X represents an ether bond, an ester bond or a nitrogen atom. When X is an ether bond or an ester bond, n=1; when X is a nitrogen atom, n=2. Y 1 and Y 2 Each independently represents an aromatic hydrocarbon group, X 1 and X 2 Each independently represents -Y 1 -Z 1 or -Y 2 -Z 2 , n1 and n2 each independently represent an integer of 0 to 4, any of which is 1 or more, (X 1 ) The m1 specified in m1 represents 0 or 1, (X 2 ) The m2 specified in m2 represents 0 or 1, Q represents a (n1+n2)-valent group selected from -O-, an aliphatic hydrocarbon group, a combination of an aromatic hydrocarbon group having less than 10 carbon atoms and an aliphatic hydrocarbon group, and a combination of an aromatic hydrocarbon group having 10 or more carbon atoms and -O-.

11. The protective film-forming composition according to claim 9, wherein the compound (A) is a compound containing a partial structure represented by the following formula (III): In formula (III), Ar represents a benzene ring, a naphthalene ring or an anthracene ring; X represents an ether bond, an ester bond or a nitrogen atom, and n=1 when X is an ether bond or an ester bond, and n=2 when X is a nitrogen atom.

12. The protective film-forming composition according to claim 8, wherein the polymer (A) is a polymer having a unit structure represented by the following formula (1-1): In formula (1-1), Ar represents a benzene ring, a naphthalene ring or an anthracene ring, and R 1 represents a hydroxyl group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halo group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and may be substituted by a hydroxyl group, n1 represents an integer of 0 to 3, and L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, n2 represents 1 or 2, E represents a group having an epoxy group or a group having an oxetane group, and when n2=1, T 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond. When n2=2, T 1 represents a nitrogen atom or an amide bond. 13 . The protective film-forming composition according to claim 2 , wherein the (E) compound or polymer having a phenolic hydroxyl group has two or more phenolic hydroxyl groups.

14. The protective film-forming composition according to claim 2, wherein the (E) compound or polymer having a phenolic hydroxyl group is represented by the following formula (2-1): In formula (2-1), R 2 A each independently represents a halo group, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halo group; 1 and A 2 Each independently represents an alkylene group having 1 to 10 carbon atoms, a divalent organic group derived from a bicyclic compound, a biphenylene group or -C(T 2 )(T 3 )-represented by a divalent organic group or a combination thereof, T 2 represents a halo group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, amino group which may be substituted with alkyl group having 1 to 3 carbon atoms, or alkyl group having 1 to 10 carbon atoms which may be substituted with hydroxyl group or a halo group, T 3 represents a hydrogen atom or a monovalent group represented by formula (2-1-a); The * in formula (2-1-a) indicates that 3 The binding site of the carbon atom to which it is bound, R 2 With R in formula (2-1) 2 have the same meaning; a represents an integer of 1 to 6; n3 to n5 each independently represent an integer of 0 to 2; r2 represents an integer of 0 to 3; m1 and m2 each independently represent a number of 0 to 10,000,000.

15. The protective film-forming composition according to claim 2, wherein the (E) compound or polymer having a phenolic hydroxyl group is a compound represented by the following formula (2-2): In formula (2-2), R 3 represents a halo group, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, alkoxy group having 1 to 9 carbon atoms, amino group which may be substituted with alkyl group having 1 to 3 carbon atoms, or alkyl group having 1 to 10 carbon atoms which may be substituted with hydroxyl group or a halo group; Q 1 represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an imino group, an arylene group having 6 to 40 carbon atoms, or an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogenated group; a represents an integer of 1 to 6; n6 represents an integer of 0 to 2; and r3 represents an integer of 0 to 3.

16. The protective film-forming composition according to claim 2, wherein the (E) compound or polymer having a phenolic hydroxyl group is a polymer having a unit structure represented by the following formula (3-1): In formula (3-1), T 4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group; R 4 represents a halide, carboxyl, nitro, cyano, methylenedioxy, acetoxy, methylthio, an alkoxy group having 1 to 9 carbon atoms, an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxyl group or a halide; R4 represents an integer of 0 to 3; N7 represents an integer of 0 to 2; and A represents an integer of 1 to 6.

17. A protective film for a semiconductor wet etching solution, 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 16.

18. A composition for forming a resist underlayer film, comprising: (A) a compound or polymer having a reactive group capable of undergoing a crosslinking reaction in the presence of a curing agent; (B) a curing agent; (C) β-dicarbonyl compounds; and (D) Solvent. 19 . The resist underlayer film-forming composition according to claim 18 , further comprising (E) a compound or polymer having a phenolic hydroxyl group. 20 . The resist underlayer film-forming composition according to claim 18 , wherein the curing agent is a base. 21 . The resist underlayer film forming composition according to claim 20 , wherein the base is an imidazole compound.

22. The resist underlayer film-forming composition according to claim 21, wherein the base is represented by the following formula (B1): In formula (B1), R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group which may be substituted, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of a triazine ring which may be substituted, a cyano group, a hydroxyl group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group, and R 2 represents an alkylene group having 1 to 4 carbon atoms, R 3 represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group which may be substituted, and R 4 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and R 5 represents a hydrogen atom, a formyl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkoxyalkyl group having 4 or less carbon atoms, and n represents 0 or 1.

23. The resist underlayer film-forming composition according to claim 18, wherein the compound (C) is a compound represented by the following formula (C): In formula (C), R A and R B Each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted, an alkoxy group having 1 to 10 carbon atoms which may be substituted, an aryl group having 5 to 18 carbon atoms which may be substituted, an aralkyl group having 5 to 18 carbon atoms which may be substituted, or an aryloxy group having 5 to 18 carbon atoms which may be substituted; R C and R D Each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 5 to 18 carbon atoms, an optionally substituted aralkyl group having 5 to 18 carbon atoms, or an optionally substituted acyl group having 2 to 6 carbon atoms; R A With R C Can together form a ring structure. 24 . The resist underlayer film-forming composition according to claim 18 , wherein a content of the compound (C) is 1 to 30% by mass based on the compound or polymer (A). 25 . The resist underlayer film-forming composition according to claim 18 , wherein the compound or polymer (A) is a compound or polymer containing a cyclic ether having a three-membered ring structure or a four-membered ring structure.

26. A resist underlayer film, characterized in that: A fired product of a coating film formed from the resist underlayer film forming composition according to claim 18.

27. A method for manufacturing a substrate with a protective film, characterized in that: The method for producing a substrate with a protective film comprises the step of applying the protective film-forming composition according to any one of claims 1 to 16 onto a semiconductor substrate having a step and firing the composition to form a protective film, wherein the method is used for producing a semiconductor.

28. A method for manufacturing a substrate with a resist pattern, characterized in that: The method comprises the following steps: a step of applying the protective film-forming composition according to any one of claims 1 to 16 or the resist underlayer film-forming composition according to any one of claims 18 to 25 onto a semiconductor substrate and firing the coating to form a protective film as a resist underlayer film; and a step of forming a resist film on the protective film, followed by exposing and developing the coating to form a resist pattern. The method for manufacturing a substrate with a resist pattern is used for manufacturing a semiconductor.

29. 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 16, forming a resist pattern on the protective film, dry-etching the protective film using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and wet-etching the inorganic film or the semiconductor substrate using a semiconductor wet etching solution and washing the protective film after dry etching as a mask.

30. A method for manufacturing a semiconductor device, comprising the following steps: forming a resist underlayer film on a semiconductor substrate having an inorganic film formed on its surface using the resist underlayer film forming composition described in any one of claims 18 to 25, forming a resist pattern on the resist underlayer film, dry-etching the resist underlayer film using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and etching the inorganic film or the semiconductor substrate using the dry-etched resist underlayer film as a mask.

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