Semiconductor element-forming composition

Abstract

Provided is a semiconductor element-forming composition that is for use in forming circuits or the like for a semiconductor device and that satisfactorily has all of good applicability, curability of film in a short period of time, and good storage stability.　This semiconductor element-forming composition comprises: (A) a compound or a polymer having a reactive group indicated by a cyclic ether structure represented by formula (I); (B) a compound or a polymer having a reactive group that has reactivity to the reactive group in (A); (C) a basic curing agent; (D) an acidic additive; and (E) a solvent.　 (In formula (I), * represents a binding site. n represents 1 or 2. When n equals 1, X represents an ether bond, an ester bond, or an amide bond, and, when n equals 2, X represents a nitrogen atom or an amide bond.)

Description

Composition for forming semiconductor elements

[0001] The present invention relates to a composition for forming a semiconductor element, which can be used as a cavity-forming composition for forming a cavity between conductive wiring patterns, a protective film-forming composition for forming a protective film having excellent resistance to a semiconductor wet etching solution, or a resist underlayer film-forming composition in a lithography process, and also to a method for manufacturing a semiconductor element or a semiconductor device using a cured film formed from the composition for forming a semiconductor element.

[0002] With the recent technological advances in semiconductor devices, various coating-type organic materials are used in the process of forming circuits in semiconductor devices. Cavity-forming compositions for forming cavities between conductive wiring patterns, protective film-forming compositions for forming protective films that have excellent resistance to semiconductor wet etching solutions, and resist underlayer film-forming compositions in lithography processes are all compositions for forming semiconductor elements used in forming circuits in such semiconductor devices.

[0003] Compositions for forming semiconductor elements, which are used for forming circuits in semiconductor devices, are generally applied to various substrates, including silicon, and then baked to harden the composition, resulting in a cured film. In this process, only limited compositions are available that can induce a chemical reaction that satisfies the requirements of good application properties, short-term film curing, and storage stability. Compositions containing epoxy groups are promising compositions that harden in a short time during the baking process. On the other hand, compositions in which epoxy groups, reactive groups that react with them, and a basic curing agent are diluted with various solvents commonly used in the semiconductor industry may have poor storage stability due to the reactivity of the basic curing agent.

[0004] Incidentally, a method for improving the pot life of a basic curing agent is known (see Patent Document 1). It is also known to use a basic curing agent having an imidazole structure in the form of a salt with an acid (see Patent Document 2). However, neither of these patent documents describes the storage stability of the composition as a composition used for forming circuits in semiconductor devices.

[0005] Special Publication No. 2020-514456 Japanese Patent Application Publication No. 03-166221

[0006] Liquid compositions used in semiconductor circuit formation, which require coating and baking processes, are required to have high storage stability (i.e., film hardening properties and molecular weight distribution remain unchanged even after long-term storage) due to industrial demands.

[0007] Therefore, an object of the present invention is to provide a composition for forming a semiconductor element, which is used for forming circuits in a semiconductor device, and which satisfies all of the following: good coatability, film curing in a short time, and good storage stability.

[0008] As a result of intensive research conducted by the present inventors to solve the above problems, they found that by adding an acidic additive as a stabilizer to a basic curing agent in order to suppress side reactions during storage that occur due to the reaction between a reactive group represented by a highly reactive three- or four-membered cyclic ether structure and a reactive group reactive with said reactive group, it is possible to form a composition that has high storage stability that can withstand the demands of the semiconductor manufacturing industry, and thus completed the present invention.

[0009] That is, the present invention encompasses the following aspects: [1] A composition for forming a semiconductor element, comprising: (A) a compound or polymer having a reactive group represented by a cyclic ether structure represented by the following formula (I): (B) a compound or polymer having a reactive group reactive to the reactive group in (A): (C) a basic curing agent: (D) an acidic additive: and (E) a solvent. (In formula (I), * represents a bonding site, and n represents 1 or 2. When n = 1, X represents an ether bond, an ester bond, or an amide bond, and when n = 2, X represents a nitrogen atom or an amide bond.) [2] The composition for forming a semiconductor element according to [1], 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. n represents 1 or 2. When n = 1, X represents an ether bond, an ester bond, or an amide bond. When n = 2, X represents a nitrogen atom or an amide bond.) [3] The composition for forming a semiconductor element according to [1], wherein the polymer (A) is a polymer having a novolac structure 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 hydroxy group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and which may be substituted by a hydroxy group; n1 represents an integer of 0 to 3; 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 oxetanyl group; T １ When n2=1, represents an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond; T １ represents a nitrogen atom or a trivalent hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by an amide bond when n2=2.) [4] The composition for forming a semiconductor device according to any one of [1] to [3], wherein the compound or polymer (B) is a compound or polymer having a phenolic hydroxy group, or a compound having a thiol structure. [5] The composition for forming a semiconductor device according to any one of [1] to [4], wherein the basic curing agent (C) is a compound 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 optionally substituted aryl group, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of an optionally substituted triazine ring from the triazine ring, a cyano group, a hydroxy group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group; R ２ represents an alkylene group having 1 to 4 carbon atoms, R ３represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group which may be substituted; 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; 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 composition for forming a semiconductor device according to any one of [1] to [4], wherein the basic curing agent (C) is at least one compound selected from the group consisting of tertiary amine compounds represented by the following formula: [7] The composition for forming a semiconductor device according to any one of [1] to [6], wherein the acidic additive (D) is a compound containing at least one group selected from the group consisting of an imide group, a carboxy group, a sulfonyl group, and a sulfo group. [8] The composition for forming a semiconductor device according to [7], wherein the acidic additive (D) is acetic acid or maleic acid. [9] The composition for forming a semiconductor device according to any one of [1] to [8], wherein the solvent (E) contains at least one solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol, monomethyl ether acetate, isopropyl alcohol, ethyl acetate, butyl acetate, and cyclohexanone.

[10] The composition for forming a semiconductor device according to any one of [1] to [9], wherein the composition for forming a semiconductor device is used as a cavity-forming composition for forming cavities between conductive wiring patterns.

[11] The composition for forming a semiconductor device according to any one of [1] to [9], wherein the composition for forming a semiconductor device is used as a protective film-forming composition for forming a protective film having excellent resistance to a semiconductor wet etching solution.

[12] The composition for forming a semiconductor device according to any one of [1] to [9], wherein the composition for forming a semiconductor device is used as a composition for forming a resist underlayer film in a lithography process.

[13] A film for forming a semiconductor device, which is a fired product of a coating film made of the composition for forming a semiconductor device according to any one of [1] to

[12] .

[0010] According to the present invention, it is possible to provide a composition for forming a semiconductor element, which is used for forming a circuit of a semiconductor device, and which satisfies all of good coatability, film curing in a short time, and good storage stability.

[0011] The present invention will be described in detail below. Note that the following explanation of the constituent elements is an example for explaining the present invention, and the present invention is not limited to these contents.

[0012] (Composition for forming semiconductor element) The composition for forming semiconductor element of the present invention comprises: (A) a compound or polymer having a reactive group represented by a cyclic ether structure represented by the following formula (I): (B) a compound having a reactive group reactive to the reactive group in (A); (C) a basic curing agent; (D) an acidic additive; and (E) a solvent.

[0013] (In formula (I), * represents a bonding site. n represents 1 or 2. When n=1, X represents an ether bond, an ester bond, or an amide bond. When n=2, X represents a nitrogen atom or an amide bond.)

[0014] The composition for forming a semiconductor element of the present invention may further contain, as other components, a compound having a hydroxy group and at least one of a hydroxy group and a carbonyl group.

[0015] The present inventors have found that a composition for forming a semiconductor device, comprising (A) a compound or polymer having a cyclic ether structure represented by the above formula (I), (B) a compound having a reactive group reactive with the reactive group in (A), (C) a basic curing agent, (D) an acidic additive, and (E) a solvent, can satisfy all of the following: good coatability, short-term film curing ability, and good storage stability. This composition for forming a semiconductor device can be suitably used as a cavity-forming composition for forming cavities between conductive wiring patterns, a protective film-forming composition for forming a protective film having excellent resistance to semiconductor wet etching solutions, a resist underlayer film-forming composition in a lithography process (particularly a resist underlayer film-forming composition having antireflection properties), etc.

[0016] <(A) Compound or Polymer> The (A) compound or polymer used in the present invention has a reactive group represented by a cyclic ether structure (epoxy structure or oxetane structure) represented by the above formula (I). More preferred embodiments of the (A) compound or polymer include a polymer represented by the following first aspect or a compound represented by the following second aspect.

[0017] <<First Aspect>> Examples of the polymer (A) used in the present invention include the following polymers: Such polymers (hereinafter also referred to as polymers in the first aspect) include polymers having a novolac structure having a unit structure represented by the following formula (1-1), and acrylic polymers having a unit structure represented by the following formula (1-3).

[0018] As the polymer in the first embodiment, for example, a polymer having a novolac structure is 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 hydroxy group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and which may be substituted by a hydroxy group; n1 represents an integer of 0 to 3; 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 oxetanyl group; T １ When n2=1, represents an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond, or an amide bond; T １ When n2=2, represents a trivalent hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a nitrogen atom or an amide bond.

[0019] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, 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, and a 1-ethyl-n-propyl group. Cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2- Dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3 -ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples of such groups include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, a decyl group, a methoxy group, an ethoxy group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a methylamino group, a dimethylamino group, a diethylamino group, an aminomethyl group, a 1-aminoethyl group, a 2-aminoethyl group, a methylthio group, an ethylthio group, a mercaptomethyl group, a 1-mercaptoethyl group, and a 2-mercaptoethyl group.

[0020] 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, an s-butylene group, a t-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, and a 1-ethyl-n-propylene group. cyclopentylene group, 1-methyl-n-pentylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples of the cyclopropylene group include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0021] R １ An example of the alkyl group having 1 to 10 carbon atoms substituted or interrupted by a heteroatom in the formula (I) is an alkoxy group having 1 to 10 carbon atoms.

[0022] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 5-methyl-n-pentyloxy group, a 6-methyl-n-pentyloxy group, a 7-methyl-n-pentyloxy group, a 8-methyl-n-pentyloxy group, a 9-methyl-n-pentyloxy group, a 10-methyl-n-butoxy group, a 11-methyl-n-butoxy group, a 22-methyl-n-butoxy group, a 23-methyl-n-butoxy group, a 24-methyl-n-butoxy group, a 25-methyl-n-butoxy group, a 26-methyl-n-butoxy group, a 27-methyl-n-butoxy group, a 28-methyl-n-butoxy group, a 29-methyl-n-butoxy group, a 30-methyl-n-butoxy group, a 31-methyl-n-butoxy group, a 32-methyl-n-butoxy group, a 33-methyl-n-butoxy group, a 34-methyl-n-butoxy group, a 35-methyl-n-butoxy group, a 36-methyl-n- Examples of the alkyl group include an ethyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, a 1-ethyl-2-methyl-n-propoxy group, an n-heptyloxy group, an n-octyloxy group, and an n-nonyloxy group.

[0023] The unit structure represented by formula (1-1) may be one type or a combination of two or more types. For example, a copolymer having a plurality of unit structures in which Ar is the same type may be used, and copolymers having a plurality of unit structures in which Ar is different, such as a unit structure in which Ar includes a benzene ring and a unit structure in which Ar includes a naphthalene ring, are not excluded from the technical scope of the present application.

[0024] The above phrase "optionally interrupted" means, in the case of an alkylene group having 2 to 10 carbon atoms, that any carbon-to-carbon bond in the alkylene group is interrupted by a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond; and in the case of an alkylene group having one carbon atom (i.e., a methylene group), that either one of the carbons of the methylene group has a heteroatom (i.e., an ether bond in the case of oxygen, or a sulfide bond in the case of sulfur), an ester bond, or an amide bond.

[0025] T １ represents a hydrocarbon group having 1 to 10 carbon atoms (including an alkylene group and a trivalent hydrocarbon group) which may be interrupted by an ether bond, an ester bond, a nitrogen atom, or an amide bond, but does not include a combination of an ether bond and a methylene group (i.e., "-T" in formula (1-1)). １ When "-(E)n2" is a glycidyl ether group, it is preferably a combination of an ester bond and a methylene group, or a combination of an amide bond and a methylene group.

[0026] The alkyl group having 1 to 10 carbon atoms which may be substituted with a heteroatom refers to an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms have been substituted with a heteroatom (preferably a halogeno group).

[0027] L １ represents a single bond or an alkylene group having 1 to 10 carbon atoms, and is represented by the following formula (1-2): (In formula (1-2), R ２ , R ３ are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, or a cyclobutyl group; R２ , R ３ may be bonded to each other to form a ring having 3 to 6 carbon atoms). ２ , R ３ Both are hydrogen atoms (i.e., -(CR ２ R ３ )- is preferably a methylene group.

[0028] The halogeno group refers to a halogen-X (F, Cl, Br, I) that replaces hydrogen.

[0029] More preferably, E in formula (1-1) is a group having an epoxy group.

[0030] The polymer having a novolac structure in the first aspect is not particularly limited as long as it satisfies the unit structure of formula (1-1), for example. It may be one produced by a method known per se. Commercially available products may also be used. Examples of commercially available products include the heat-resistant epoxy novolac resin EOCN (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.) and the epoxy novolac resin D.E.N (registered trademark) series (manufactured by Dow Chemical Japan Co., Ltd.).

[0031] The weight average molecular weight of the polymer having a novolak structure in the first embodiment is 100 or more, 500 to 200,000, 600 to 50,000, or 700 to 10,000.

[0032] The polymer having a novolak structure in the first embodiment includes those having the following unit structure: Me represents a methyl group, and Et represents an ethyl group.

[0033] As the polymer in the first embodiment, for example, an acrylic polymer is represented by the following formula (1-3): (In formula (1-3), R １００ represents a hydrogen atom or a methyl group; n2 represents 1 or 2; E represents a group having an epoxy group or a group having an oxetanyl group; T ２ When n2=1, represents an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond, or an amide bond; T ２When n2=2, represents a trivalent hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a nitrogen atom or an amide bond.

[0034] The weight average molecular weight of the acrylic polymer in the first embodiment is 100 to 20,000, 300 to 10,000, or 500 to 5,000.

[0035] <<Second Aspect>> Examples of the compound (A) used in the present invention include the following compounds: Such a compound (hereinafter also referred to as a compound in the second aspect) is a compound that does not have a repeating structural unit, and includes a terminal group (A1), a polyvalent group (A2), and a linking group (A3), wherein the terminal group (A1) is bonded only to the linking group (A3), the polyvalent group (A2) is bonded only to the linking group (A3), the linking group (A3) is bonded to the terminal group (A1) on one side and the polyvalent group (A2) on the other side, and may optionally be bonded to another linking group (A3), and the terminal group (A1) has any of the structures of the following formula (I): (In formula (I), * represents the bonding site with the linking group (A3). n represents 1 or 2. When n = 1, X represents an ether bond, an ester bond, or an amide bond, and when n = 2, X represents a nitrogen atom or an amide bond.) The compound is one in which the polyvalent group (A2) is a divalent to tetravalent group selected from the group consisting of: -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-; and the linking group (A3) represents an aromatic hydrocarbon group.

[0036] The phrase "having no repeating structural units" means excluding so-called polymers that have repeating structural units, such as polyolefins, polyesters, polyamides, poly(meth)acrylates, etc. Preferably, the weight average molecular weight of the (A) compound is 300 or more and 1,500 or less.

[0037] The "bond" between the terminal group (A1), the polyvalent group (A2), and the linking group (A3) means a chemical bond, and usually means a covalent bond, but does not prevent it from being an ionic bond.

[0038] The polyvalent group (A2) is a divalent to tetravalent group.

[0039] Therefore, the aliphatic hydrocarbon group in the definition of the polyvalent group (A2) is a divalent to tetravalent aliphatic hydrocarbon group. Non-limiting examples of divalent aliphatic hydrocarbon groups include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, s-butylene, t-butylene, cyclobutylene, 1-methylcyclopropylene, 2-methylcyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, and 1,3-dimethyl-n-propylene. Methyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n -pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,Examples of alkylene groups include a 3-dimethyl-cyclobutylene group, a 1-n-propyl-cyclopropylene group, a 2-n-propyl-cyclopropylene group, a 1-isopropyl-cyclopropylene group, a 2-isopropyl-cyclopropylene group, a 1,2,2-trimethyl-cyclopropylene group, a 1,2,3-trimethyl-cyclopropylene group, a 2,2,3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0040] A hydrogen atom at any position of these groups can be removed and converted into a bond to give a trivalent or tetravalent group.

[0041] 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.

[0042] Examples of the aliphatic hydrocarbon group that can be combined with the aromatic hydrocarbon group having less than 10 carbon atoms include, in addition to the above alkylene groups, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, an n-pentyl group, a 1-methyln-butyl group, a 2-methyln-butyl group, a 3-methyln-butyl group, a 1,1-dimethyln-propyl group, a 1,2-dimethyln-propyl group, a 2,2-dimethyl -n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-di Methyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclohexyl group cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples of alkyl groups include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, and a decyl group.

[0043] In the definition of the polyvalent group (A2), either the aromatic hydrocarbon group or the aliphatic hydrocarbon group having less than 10 carbon atoms may be bonded to the linking group (A3).

[0044] 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, naphthacene, triphenylene, pyrene, and chrysene.

[0045] 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—.

[0046] 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.

[0047] Preferably, the compound (A) has two or more linking groups (A3).

[0048] The compound in the second aspect is preferably represented by, for example, the following formula (II): (In formula (II), Z １ , and Z ２ are each independently (In formula (I), * represents Y １ , or Y ２ represents a bonding site with Y. n represents 1 or 2. When n=1, X represents an ether bond, an ester bond, or an amide bond, and when n=2, X represents a nitrogen atom or an amide bond. １ , and Y ２ each independently represents an aromatic hydrocarbon group; １ , and X ２ are each independently -Y １ -Z １ or -Y ２ -Z２ n1 and n2 each independently represent an integer of 0 to 4, provided that either one is 1 or more; (X １ ) m1 defined as m1 represents 0 or 1, ２ ) m2 defined as m2 represents 0 or 1, and Q represents an (n1+n2)-valent group selected from the group consisting of -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-. ) Q is preferably a divalent to tetravalent group.

[0049] In formula (II), Z １ , and Z ２ represents the terminal group (A1), Q represents the polyvalent group (A2), and Y １ , and Y ２ correspond to the above linking group (A3), and the explanations, examples, etc. for them are as described above.

[0050] The compound according to the second aspect preferably includes, for example, a partial structure represented by the following formula (III): (In formula (III), Ar represents a benzene ring, a naphthalene ring, or an anthracene ring. n represents 1 or 2. When n=1, X represents an ether bond, an ester bond, or an amide bond. When n=2, X represents a nitrogen atom or an amide bond.)

[0051] Examples of the compound according to the second aspect include the following compounds:

[0052] <(B) Compound or polymer having a reactive group reactive to the reactive group in (A)> The compound or polymer (B) used in the present invention has a reactive group reactive to the reactive group in (A). More preferred embodiments of the compound or polymer (B) include a compound or polymer having a phenolic hydroxy group shown in the third aspect below, or a compound having a thiol structure shown in the fourth aspect below.

[0053] <<Third Aspect>> Examples of the (B) compound or polymer used in the present invention include the following compounds or polymers having a phenolic hydroxy group. The (B) compound or polymer having a phenolic hydroxy group is not particularly limited as long as it is a compound or polymer that does not impair the effects of the present invention. Needless to say, the (B) compound or polymer having a phenolic hydroxy group is different from the above-mentioned (A) compound or polymer.

[0054] The weight average molecular weight of the (B) compound or polymer having a phenolic hydroxy group (hereinafter also referred to as (B) compound or polymer) is not particularly limited, but is, for example, 300 to 50,000.

[0055] The compound or polymer (B) preferably has two or more phenolic hydroxy groups. More preferred embodiments of the compound or polymer (B) include, for example, the compounds or polymers shown in Aspects 3-1 to 3-3 below.

[0056] <<Aspect 3-1>> The compound or polymer (B) used in the present invention includes, for example, a compound or polymer represented by formula 2-1.

[0057] (In the formula, R ２ A each independently represents a halogeno group, a carboxy 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 hydroxy group or a halogeno group. １ and A ２ are each independently an alkylene group having 1 to 10 carbon atoms, a divalent organic group derived from a bicyclo ring compound, a biphenylene group, or -C(T ２ ) (T ３ )- or a combination thereof, ２represents a halogeno group, a carboxy 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 hydroxy group or a halogeno group; T ３ represents a hydrogen atom or a monovalent group represented by formula 2-1-a.

[0058] * in (Formula 2-1-a) represents T ３ represents the bonding site with the carbon atom to which R is attached. ２ is R in (Equation 2-1) ２ 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 an integer of 0 to 10,000,000. It is preferable that m1, n3 to n5, and r2 are 0, and m2 is 1.

[0059] The halogeno group, alkoxy group, and alkyl group in (Formula 2-1) are as described above.

[0060] Examples of bicyclocyclic compounds 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. Substitution refers to one or more hydrogen atoms of the bicyclocyclic compound being independently substituted with a halogeno group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms which may be substituted with such groups. A divalent organic group derived from a bicyclocyclic compound refers to a group having two bonds derived by removing any two hydrogen atoms from a bicyclocyclic compound.

[0061] Examples of the aryl group having 6 to 40 carbon atoms include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0062] Specific examples of the compound represented by formula 2-1 include the compounds shown below. The compound or polymer (B) may be the compound shown below.

[0063]

[0064] <<Aspect 3-2>> The compound or polymer (B) used in the present invention includes, for example, a compound represented by formula 2-2.

[0065] (In the formula, R ３ represents a halogeno group, a carboxy 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 hydroxy 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 halogeno 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.) The alkoxy group, alkyl group, and halogeno group in (Formula 2-2) are as described above.

[0066] Examples of the arylene group having 6 to 40 carbon atoms include a phenylene group, an o-methylphenylene group, an m-methylphenylene group, a p-methylphenylene group, an o-chlorophenylene group, an m-chlorophenylene group, a p-chlorophenylene group, an o-fluorophenylene group, a p-fluorophenylene group, an o-methoxyphenylene group, a p-methoxyphenylene group, a p-nitrophenylene group, a p-cyanophenylene group, an α-naphthylene group, a β-naphthylene group, an o-biphenylylene group, an m-biphenylylene group, a p-biphenylylene group, a 1-anthrylene group, a 2-anthrylene group, a 9-anthrylene group, a 1-phenanthrylene group, a 2-phenanthrylene group, a 3-phenanthrylene group, a 4-phenanthrylene group, and a 9-phenanthrylene group.

[0067] 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, an s-butylene group, a t-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, and a 1-ethyl-n-propylene group. cyclopentylene group, 1-methyl-n-pentylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples of the cyclopropylene group include a 3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group.

[0068] Specific examples of the compound represented by formula 2-2 include the compounds shown below. The compound (B) may be a compound represented by the following formula (4-1).

[0069] (In the formula, R ５ represents a halogeno group, a carboxy 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 hydroxy group or a halogeno group. In the formula, n8 represents an integer of 4, 5, 6, or 8.) The above terms are as defined above.

[0070] Specific examples of the compound represented by formula (4-1) are shown below. The compound (B) may be a compound represented by the following formula (5-1) or formula (5-1-a).

[0071] (In the formula, n9 and n10 each represent an integer of 0 or 1, and R ６ represents a halogeno group, a carboxy 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 hydroxy group or a halogeno 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 bonding site between the structure represented by formula (5-1) and the structure represented by formula (5-1-a). The above terms are as explained above.

[0072] Specific examples of the compounds represented by the following formula (5-1) and formula (5-1-a) are shown below. The compound (B) may be the compound shown below.

[0073]

[0074] <<Aspect 3-3>> The (B) 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 (B) polymer preferably has at least 3 or more repeating unit structures.

[0075] The weight average molecular weight of the polymer (B) is not particularly limited, but is, for example, 1,000 to 50,000.

[0076] The polymer (B) preferably contains a unit structure represented by the following formula 3-1: (In the formula, T ４ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogeno group. ４ represents a halogeno group, a carboxy 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 hydroxy group or a halogeno 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.) The halogeno group, alkyl group and alkoxy group are as described above.

[0077] The polymer represented by (Formula 3-1) may be a polymer containing one type of unit structure represented by (Formula 3-1), or may be a copolymer containing two or more types.

[0078] Specific examples of the polymer (B) represented by formula 3-1 include polymers containing the unit structures shown below. (In the above formula, m and n written next to the repeating units represent the molar ratio of the copolymer.

[0079] <<Fourth Aspect>> Examples of the compound (B) used in the present invention include compounds having a thiol structure. Examples of the compound having a thiol structure according to the present invention include polyfunctional thiol compounds represented by the following formula (10-1):

[0080] (In formula (10-1), R ７ represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms; X represents a single bond or an ester bond; A represents an organic group having 2 to 12 carbon atoms or a heteroatom; r １ represents an integer of 2 to 6.)

[0081] A may contain at least one heteroatom, or may contain no heteroatom. Examples of the heteroatom in A include an oxygen atom and a nitrogen atom.

[0082] Examples of compounds having a thiol structure include 1,2-ethanedithiol, 1,3-propanedithiol, 1,10-decanedithiol, 3,6-dioxaoctane-1,8-dithiol, 2,2'-oxyethanethiol, 2,3-dimercapto-1-propanol, dithioerythritol, dithiothreitol, 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithiol, and 4-chloro-1,3-benzenedithiol. 4-methyl-1,2-benzenedithiol, 4,5-dimethyl-1,2-benzenedimethanethiol, 2,3-quinoxylenedithiol, 2-dimethylamino-1,3,5-triazine-4,6-dithiol, 2-methoxy-1,3,5-triazine-4,6-dithiol, 2-dibutylamino-1,3,5-triazine-4,6-dithiol, 2-N-phenylamino-1,3,5-triazine-4,6-dithiol, dicyclohexylamino- 1,3,5-triazine-4,6-dithiol, thiocyanuric acid, bismuthiol, bis(2-mercaptoethyl)ether, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetra tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and pentaerythritol tris(3-mercaptopropyl)ether.

[0083] As the polyfunctional thiol compound represented by the above formula (10-1), commercially available products such as Karenz MT (registered trademark) PE1, Karenz MT NR1, Karenz MT BD1, TPMB, and TEMB (all manufactured by Showa Denko K.K.), and TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, and PEPT (all manufactured by SC Organic Chemical Co., Ltd.) can be used.

[0084] Examples of the polyfunctional thiol compound represented by the above formula (10-1) include the following compounds.

[0085] In the composition for forming semiconductor elements of the present invention, the content of (B) a compound or polymer having a reactive group reactive to the reactive group in (A) is, for example, such that the lower limit of the content is usually 1 mass %, preferably 5 mass %, relative to the total solid content of the composition for forming semiconductor elements, and the upper limit of the content is usually 70 mass %, preferably 50 mass %, and more preferably 30 mass %, relative to the total solid content of the composition for forming semiconductor elements.

[0086] <(C) Basic Curing Agent> Examples of the (C) basic curing agent used in the present invention include imidazole compounds, piperidine compounds, amide compounds, amine compounds, diazabicycloundecene (DBU) compounds, diazabicyclononene (DBN) compounds, phosphonium compounds, and urea compounds. Among these, imidazole compounds and diazabicycloundecene (DBU) compounds are preferred from the viewpoint of storage stability.

[0087] More preferred embodiments of the basic curing agent (C) include at least one compound selected from the group consisting of a compound represented by formula (B1) in the fifth aspect below and a tertiary amine compound represented by formula (B2) in the sixth aspect below.

[0088] <<Fifth Aspect>> Examples of the basic curing agent (C) in the present invention include imidazole compounds represented by the following formula (B1).

[0089] (In formula (B1), R １represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an optionally substituted aryl group, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of an optionally substituted triazine ring from the triazine ring, a cyano group, a hydroxy group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group; 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; 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; 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.

[0090] The optionally substituted aryl group and the optionally substituted triazine ring may have an amino group or a hydroxy group as a substituent. The alkyl group may be either linear or branched. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. R ４ or R ５ In the above, examples of the substituent in the optionally substituted alkyl group and the optionally substituted alkoxyalkyl group include a hydroxy group and a cyano group.

[0091] Specific examples of the imidazole compounds used in the present invention are shown below, but the present invention is not limited to these.

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] <<Sixth Aspect>> Examples of the basic curing agent (C) in the present invention include at least one compound selected from the group of tertiary amine compounds represented by the following formula:

[0102]

[0103] Regarding the content of the basic curing agent (C) in the composition for forming a semiconductor element of the present invention, for example, the lower limit of the content is usually 0.0001 mass %, preferably 0.01 mass %, and more preferably 0.1 mass %, relative to the total solid content of the composition for forming a semiconductor element, and the upper limit of the content is usually 50 mass %, preferably 40 mass %, and more preferably 30 mass %, relative to the total solid content of the composition for forming a semiconductor element.

[0104] <(D) Acidic Additive> The (D) acidic additive used in the present invention is a compound containing at least one group selected from an imide group, a carboxy group, a sulfonyl group, and a sulfo group. Preferred embodiments of the (D) acidic additive include acetic acid and maleic acid. Note that acidic additives having an acid dissociation constant (pKa) of 3 or less and a highly nucleophilic carboxyl group are not preferred in the present invention from the viewpoint of cleaving the epoxy group. A specific example of such an acidic additive is trifluoroacetic acid.

[0105] Specific examples of the acidic additives used in the present invention are shown below, but the present invention is not limited to these.

[0106] (In the formula R ４０ represents an alkyl group having 1 to 10 carbon atoms.

[0107]

[0108]

[0109] Regarding the content of the acidic additive (D) in the composition for forming a semiconductor element of the present invention, for example, the lower limit of the content is usually 0.0001 mass %, preferably 0.01 mass %, and more preferably 0.1 mass %, relative to the total solid content of the composition for forming a semiconductor element, and the upper limit of the content is usually 50 mass %, preferably 40 mass %, and more preferably 30 mass %, relative to the total solid content of the composition for forming a semiconductor element.

[0110] The content of the (D) acidic additive relative to the (C) basic curing agent is preferably, for example, 0.5 to 1.5 equivalents of the (D) acidic additive per equivalent of the (C) basic curing agent. Note that, when the acidic additive has a carboxy group, the above equivalent refers to the carboxy equivalent, taking into account the number of carboxy groups. For example, when acetic acid is used as the acidic additive per equivalent of the basic curing agent, acetic acid may be added in a ratio of 0.5 to 1.5 equivalents (more specifically, for example, 0.8 equivalents). Note that when maleic acid is used as the acidic additive, if maleic acid is to be added at the same carboxy equivalent as the 0.8 carboxy equivalent shown in the case of acetic acid above, since maleic acid has two carboxy groups, 0.4 equivalents of maleic acid should be added. When 0.4 equivalents of maleic acid are added, the carboxy equivalent is 0.8, since 0.4 x 2 = 0.8.

[0111] <(E) Solvent> The composition for forming a semiconductor element of the present invention can be prepared by dissolving the above-mentioned components in a solvent, preferably an organic solvent, and is used in the form of a homogeneous solution. Note that in the present invention, the solvent (E) is different from the compound shown in (other components) described below.

[0112] As the organic solvent for the composition for forming a semiconductor device according to the present invention, any organic solvent can be used without particular limitation as long as it can dissolve the solid components such as the compounds or polymers of (A) to (D) above and other optional solid components. In particular, since the composition for forming a semiconductor device according to the present invention is used in the state of a homogeneous solution, in consideration of its coating performance, it is recommended to use an organic solvent commonly used in lithography processes in combination with the composition.

[0113] Examples of organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexane-1, cyclohexane-2, cyclohexane-3, cyclohexane-4, cyclohexane-5, cyclohexane-6, cyclohexane-7, cyclohexane-8, cyclohexane-9, cyclohexane-10, cyclohexane-11, cyclohexane-12, cyclohexane-13, cyclohexane-14, cyclohexane-15, cyclohexane-16, cyclohexane-17, cyclohexane-18, cyclohexane-19, cyclohexane-20, cyclohexane-21, cyclohexane-22, cyclohexane-23, cyclohexane-24, cyclohexane-25, cyclohexane-26, cyclohexane-27, cyclohexane-28, cyclohexane-39, cyclohexane-49, cyclohexane-59, cyclohexane-60, cyclohexane-19, cyclohexane-19, cyclohexane-25, cyclohexane-26, cyclohexane-28 Examples of suitable solvents include 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, isopropyl alcohol, 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.

[0114] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, isopropyl alcohol, ethyl acetate, butyl acetate, cyclohexanone, etc. are preferred, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being particularly preferred.

[0115] The solid content of the composition for forming a semiconductor device according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the content of all components excluding the solvent from the composition for forming a semiconductor device. The proportion of the (A) compound or polymer in the solid content is preferably 1 to 100% by mass, more preferably 1 to 99.9% by mass, even more preferably 50 to 99.9% by mass, even more preferably 50 to 95% by mass, and particularly preferably 50 to 90% by mass.

[0116] <Other Components> The composition for forming a semiconductor element of the present invention may further contain, as (other components), a compound having a hydroxy group and at least one of a hydroxy group and a carbonyl group (hereinafter, may be referred to as “a compound represented by (F)” or “a compound (F)”).

[0117] The compound (F) may have, for example, 2 to 20 carbon atoms.

[0118] As the compound (F), a compound represented by the following formula (20-1), a compound represented by the following formula (20-2), or a compound represented by the following formula (20-3) is preferred.

[0119] (In formula (20-1), R １ ~R ４ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. In formula (20-2), X is -O- or -NR- (R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a hydroxy group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 13 carbon atoms which may have a substituent). n is an integer of 1 to 3. When n is 2 or 3, X may be the same or different. In formula (20-3), R １１ represents an alkyl group having 1 to 4 carbon atoms. １２ represents an alkyl group having 1 to 6 carbon atoms.

[0120] R in formula (20-1) １ ~R ４ The alkyl group and hydroxyalkyl group in the formula (20-1) may be linear, branched, or cyclic, but are preferably linear. １ ~R ３ represents a hydrogen atom, R ４ It is preferable that represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.

[0121] Examples of the aromatic ring in the aryl group having 6 to 12 carbon atoms, which may have a substituent, include a benzene ring and a naphthalene ring. Examples of the aromatic ring in the aralkyl group having 7 to 13 carbon atoms, which may have a substituent, include a benzene ring and a naphthalene ring. Examples of the substituent in the aryl group having 6 to 12 carbon atoms, which may have a substituent, and the aralkyl group having 7 to 13 carbon atoms, which may have a substituent, include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.

[0122] As R in -NR- in formula (20-2), an alkyl group having 1 to 6 carbon atoms which may have a hydroxy group, or an aryl group having 6 to 12 carbon atoms which may have a substituent, is preferred. As the alkyl group having 1 to 6 carbon atoms which may have a hydroxy group, a hydroxyalkyl group is preferred, and a 2-hydroxyethyl group is more preferred. In formula (20-2), when X is -O-, n is preferably 2. In formula (20-2), when X is -NR-, n is preferably 1.

[0123] Examples of the compound (F) include the following compounds:

[0124] The content of the (F) compound in the composition for forming a semiconductor element of the present invention is not particularly limited, but the lower limit of the content is preferably 0.5 mass %, more preferably 1 mass %, and particularly preferably 5 mass %, based on the (A) compound or polymer, and the upper limit of the content is preferably 50 mass %, more preferably 30 mass %, and particularly preferably 20 mass %, based on the (A) compound or polymer.

[0125] The content of the (F) compound in the composition for forming a semiconductor element of the present invention is not particularly limited, but the lower limit of the content is preferably 0.0001 mass %, more preferably 0.005 mass %, and particularly preferably 0.001 mass %, relative to the (E) solvent, and the upper limit of the content is preferably 50 mass %, more preferably 30 mass %, and particularly preferably 20 mass %, relative to the (E) solvent.

[0126] (Specific Methods of Using the Composition for Forming Semiconductor Devices, Semiconductor Device Forming Film, etc.) The composition for forming a semiconductor device of the present invention can be used in various forms, such as a composition for forming a resist underlayer film in a lithography process (particularly a composition for forming a resist underlayer film having an antireflection function), a composition for forming a protective film for forming a protective film having excellent resistance to a wet etching solution for semiconductors, or a cavity-forming composition for forming cavities between conductive wiring patterns.

[0127] <Use as a composition for forming a resist underlayer film or a composition for forming a protective film> Hereinafter, a method for producing a substrate having a resist pattern and a method for producing a semiconductor device using the composition for forming a semiconductor element (composition for forming a resist underlayer film) according to the present invention will be described.

[0128] The semiconductor element forming film of the present invention is a fired product of a coating film made from the semiconductor element forming composition of the present invention. The method for producing a substrate with a film for semiconductor element formation of the present invention comprises the step of applying the semiconductor element forming composition of the present invention onto a semiconductor substrate and firing it to form a semiconductor element forming film. The method for producing a substrate with a film for semiconductor element formation is used in the production of semiconductors. The method for producing a substrate with a resist pattern of the present invention comprises the step of applying the semiconductor element forming composition of the present invention or the resist underlayer film forming composition of the present invention onto a semiconductor substrate and firing it to form a semiconductor element forming film as a resist underlayer film, and the step of forming a resist film on the semiconductor element forming film, followed by exposure and development to form a resist pattern. The method for producing a substrate with a resist pattern is used in the production of semiconductors. One embodiment of the method for manufacturing a semiconductor device according to the present invention comprises the steps of forming a semiconductor element-forming film on a semiconductor substrate, which may have an inorganic film formed on its surface, using the composition for forming a semiconductor element according to the present invention, forming a resist pattern on the semiconductor element-forming film, dry-etching the semiconductor element-forming film using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and wet-etching and cleaning the inorganic film or the semiconductor substrate using the film for forming a semiconductor element after dry etching with a semiconductor wet etching solution. One embodiment of the method for manufacturing a semiconductor device according to the present invention comprises the steps of forming a resist underlayer film on a semiconductor substrate, which may have an inorganic film formed on its surface, using the composition for forming a resist underlayer film according to the present invention, 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 resist underlayer film after dry etching as a mask.

[0129] The substrate having a resist pattern according to the present invention can be produced by applying the above-mentioned composition for forming a semiconductor element (composition for forming a resist underlayer film) onto a semiconductor substrate and baking it.

[0130] Examples of semiconductor substrates to which the composition for forming a semiconductor element (composition for forming a resist underlayer film) of the present invention can be applied include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0131] When a semiconductor substrate having an inorganic film formed on its surface is used, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin-coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon films, silicon oxide films, silicon nitride films, silicon oxynitride films, borophosphosilicate glass (BPSG) films, titanium nitride films, titanium oxynitride films, tungsten nitride films, gallium nitride films, and gallium arsenide films. The semiconductor substrate may be a stepped substrate having vias (holes), trenches (grooves), or the like formed therein. For example, the via has a substantially circular shape when viewed from above, with a diameter of, for example, 2 nm to 20 nm and a depth of, for example, 50 nm to 500 nm, and the trench has a groove (recess in the substrate) with a width of, for example, 2 nm to 20 nm and a depth of, for example, 50 nm to 500 nm. The composition for forming a semiconductor device (composition for forming a resist underlayer film) of the present invention has a small weight-average molecular weight and average particle size of the compounds contained in the composition, and therefore the composition can be used to fill uneven substrates such as those described above without defects such as voids (gaps). The absence of defects such as voids is an important characteristic for the subsequent steps in semiconductor manufacturing (wet etching / dry etching of the semiconductor substrate, resist pattern formation).

[0132] The composition for forming a semiconductor device (resist underlayer film-forming composition) of the present invention is applied onto such a semiconductor substrate using an appropriate application method such as a spinner or coater. The composition is then baked using a heating means such as a hot plate to form a film for forming a semiconductor device (also referred to as a resist underlayer film or a protective film). Baking conditions are appropriately selected from a bake temperature of 100°C to 400°C and a bake time of 0.3 minutes to 60 minutes. Preferably, the bake temperature is 120°C to 350°C, the bake time is 0.5 minutes to 30 minutes, and more preferably, the bake temperature is 150°C to 300°C, and the bake time is 0.8 minutes to 10 minutes. The film thickness of the film for forming a semiconductor device is, for example, 0.001 μm to 10 μm, preferably 0.002 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm. If the baking temperature is lower than the above range, crosslinking will be insufficient, and the resulting semiconductor element formation film may not be resistant to a resist solvent or a basic hydrogen peroxide aqueous solution, whereas if the baking temperature is higher than the above range, the semiconductor element formation film may be decomposed by heat.

[0133] A resist film is formed on the semiconductor element forming film thus formed, followed by exposure and development to form a resist pattern. Exposure is carried out through a mask (reticle) for forming a predetermined pattern, and for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used. An alkaline developer is used for development, with the development temperature selected from 5°C to 50°C and the development time selected from 10 seconds to 300 seconds. Examples of alkaline developers that can be used include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant can be added to the aqueous alkali solution. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can be added to these developers. A method can also be used in which development is carried out with an organic solvent such as butyl acetate instead of an alkaline developer, and the parts of the photoresist where the alkaline dissolution rate is not improved are developed.

[0134] Next, the semiconductor element formation film (also referred to as a resist underlayer film or a protective film) is dry-etched using the formed resist pattern as a mask, to expose the surface of the inorganic film if the inorganic film is formed on the surface of the semiconductor substrate used, or to expose the surface of the semiconductor substrate if the inorganic film is not formed on the surface of the semiconductor substrate used.

[0135] Furthermore, a desired pattern is formed by wet etching using a semiconductor wet etching solution, using the semiconductor element formation film after dry etching (and also the resist pattern, if any, remaining on the semiconductor element formation film / resist underlayer film) as a mask.

[0136] As the semiconductor wet etching solution, a general chemical solution for etching semiconductor wafers can be used, and for example, either an acidic substance or a basic substance can be used.

[0137] Examples of substances that exhibit acidity include hydrogen peroxide, hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrogen fluoride, buffered hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and mixtures thereof.

[0138] Examples of substances that exhibit basicity include basic hydrogen peroxide solution, which is obtained by mixing ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, or an organic amine such as triethanolamine with hydrogen peroxide solution to make the pH basic. A specific example is SC-1 (ammonia-hydrogen peroxide solution). Other substances that can make the pH basic, such as a solution obtained by mixing urea with hydrogen peroxide solution and heating to cause thermal decomposition of the urea to generate ammonia, which ultimately makes the pH basic, can also be used as a wet etching chemical.

[0139] Among these, acidic hydrogen peroxide solution or basic hydrogen peroxide solution is preferred.

[0140] These chemical solutions may contain additives such as surfactants.

[0141] The temperature at which the semiconductor wet etching solution is used is preferably 25° C. to 90° C., and more preferably 40° C. to 80° C. The wet etching time is preferably 0.5 to 30 minutes, and more preferably 1 to 20 minutes.

[0142] <Use as a Cavity-Forming Composition> Hereinafter, a method for manufacturing a semiconductor element or a semiconductor device using the semiconductor element-forming composition according to the present invention as a cavity-forming composition will be described.

[0143] The cavity-forming composition is suitably used in the manufacture of a semiconductor device, which includes the following steps (A) to (D): step (A): applying the cavity-forming composition onto a semiconductor substrate on which a conductive wiring pattern has been formed; step (B): heating the semiconductor substrate after step (A) to form a cavity-forming film formed from the cavity-forming composition between the conductive wiring patterns; step (C): forming an insulating layer on the conductive wiring pattern and the cavity-forming film between the conductive wiring patterns after step (B); and step (D): heating the semiconductor substrate after step (C) to burn off the cavity-forming film.

[0144] Steps (A) to (D) are described below. <Step (A)> Step (A) is a step of applying the cavity-forming composition according to the present invention onto a semiconductor substrate on which a conductive wiring pattern has been formed.

[0145] Examples of semiconductor substrates include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0146] The material, size, and shape of the conductive wiring pattern are not particularly limited, and examples of the material for the conductive wiring pattern include copper, cobalt, ruthenium, molybdenum, chromium, tungsten, manganese, rhodium, nickel, palladium, platinum, silver, gold, and aluminum.

[0147] An insulating layer may be formed on the conductive wiring pattern. Examples of materials for the insulating layer include silicon dioxide, silicon oxycarbide, silicon oxynitride, silicon nitride, silicon carbon nitride (SiCN), aluminum nitride, aluminum oxynitride, and aluminum oxide. Examples of methods for forming the insulating layer include vapor deposition.

[0148] The line width of each wire in the conductive wiring pattern is not particularly limited, but may be, for example, 3 nm to 50 nm. The width of the space between each wire in the conductive wiring pattern is not particularly limited, but may be, for example, 3 nm to 50 nm.

[0149] The method for forming the conductive wiring pattern is not particularly limited, and for example, a conventionally known lithography process can be used.

[0150] The cavity-forming composition is applied onto the semiconductor substrate by a suitable application method such as using a spinner or a coater.

[0151] <Step (B)> Step (B) is a step in which, after step (A), the semiconductor substrate is heated to form a cavity-forming film made of a cavity-forming composition between the conductive wiring patterns.

[0152] The semiconductor substrate is heated using a heating means such as a hot plate. Because the cavity-forming composition contains a component that crosslinks the polymer, a crosslinked structure of the polymer is formed by heating the semiconductor substrate in step (B). As a result, a cavity-forming film is obtained that is formed from the cavity-forming composition containing the crosslinked polymer. The heating temperature here can be appropriately selected depending on the type of polymer and the type of crosslinking component contained in the cavity-forming composition, but is preferably 200 to 260°C. The heating time is not particularly limited, but is preferably 30 seconds to 2 minutes.

[0153] <Step (C)> Step (C) is a step that follows step (B) and involves forming an insulating layer on the conductive wiring patterns and the cavity-forming film between the conductive wiring patterns.

[0154] The material of the insulating layer is not particularly limited and may be an organic material or an inorganic material. When the insulating layer is made of an inorganic material, examples of the material include silicon dioxide, silicon oxycarbide, silicon oxynitride, silicon nitride, silicon carbon nitride (SiCN), aluminum nitride, aluminum oxynitride, aluminum oxide, tantalum oxide, titanium oxide, yttrium oxide, lanthanum oxide, hafnium oxide, zirconium oxide, and mixtures thereof.

[0155] The thickness of the insulating layer is not particularly limited, but may be, for example, 0.2 nm to 10 nm.

[0156] The method for forming the insulating layer is not particularly limited, but chemical vapor deposition (CVD) is preferred. That is, in step (C), the insulating layer is preferably formed by chemical vapor deposition.

[0157] <Step (D)> In step (D), which is performed after step (C), the semiconductor substrate is heated to burn off the cavity-forming film.

[0158] When the cavity-forming film is heated, the cavity-forming film is thermally decomposed and burned away due to the thermal decomposition of the polymer.

[0159] The heating temperature is not particularly limited as long as it is a temperature at which the cavity-forming film disappears, and can be appropriately selected depending on the type of polymer, etc., but is preferably 300 to 500° C. The heating time is not particularly limited, but is preferably 30 to 90 minutes.

[0160] The amount of the cavity-forming film that is burned away (decomposition rate) is preferably 100%, but does not have to be 100% and may be 99.9% or less. The decomposition rate is preferably 90% or more, more preferably 95% or more, more preferably 96% or more, more preferably 97% or more, even more preferably 98% or more, and particularly preferably 99% or more.

[0161] The contents and effects of the present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0162] The weight-average molecular weights of the compounds synthesized in the following examples of this specification were measured by gel permeation chromatography (hereinafter abbreviated as GPC) using a GPC device manufactured by Tosoh Corporation under the following conditions:

[0163] GPC column Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0164] <Explanation of terms> PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate

[0165] Example 1 0.49 g (weight average molecular weight: 3,100) of epoxy novolak resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., corresponding to the following formula (a-1)), 0.97 g of 3,7-dihydroxy-2-naphthoic acid-tri(2,3-epoxypropyl)isocyanurate copolymer (corresponding to the following formula (2-2-t)), 0.032 g of 1B2PZ (a product of Shikoku Chemical Industry Co., Ltd., corresponding to the following formula (c-1)), 0.007 g of acetic acid (a product of Kanto Chemical Co., Ltd.), 68.95 g of PGMEA, and 29.55 g of PGME were mixed to prepare a solution with a solids content of 1.5 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor device (a composition for forming a resist underlayer film). In Example 1, 0.007 / 60.05 equivalents of acetic acid were contained relative to 0.032 / 234.3 equivalents of 1B2PZ, which means that 0.85 equivalents of acetic acid were contained relative to 1 equivalent of 1B2PZ.

[0166]

[0167] Example 2 0.49 g (weight average molecular weight: 3,100) of epoxy novolak resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)), 0.97 g of 3,7-dihydroxy-2-naphthoic acid-tri(2,3-epoxypropyl)isocyanurate copolymer (corresponding to the above formula (2-2-t)), 0.031 g of 1B2PZ (a product of Shikoku Chemical Industry Co., Ltd., corresponding to the above formula (c-1)), 0.008 g of maleic acid (a product of Tokyo Chemical Industry Co., Ltd.), 68.95 g of PGMEA, and 29.55 g of PGME were mixed to prepare a solution with a solids content of 1.5 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor device (a composition for forming a resist underlayer film).

[0168] Example 3 0.48 g (weight average molecular weight: 3,100) of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)), 0.97 g of 3,7-dihydroxy-2-naphthoic acid-tri(2,3-epoxypropyl)isocyanurate copolymer (corresponding to the above formula (2-2-t)), 0.032 g of 1B2PZ (product of Shikoku Chemicals Corporation, corresponding to the above formula (c-1)), 0.016 g of trifluoromethanesulfonic acid (product of Tokyo Chemical Industry Co., Ltd.), 68.95 g of PGMEA, and 29.55 g of PGME were mixed to prepare a solution with a solids content of 1.5 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor device (composition for forming a resist underlayer film).

[0169] Comparative Example 1 0.48 g (weight average molecular weight: 3,100) of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)), 0.97 g of 3,7-dihydroxy-2-naphthoic acid-tri(2,3-epoxypropyl)isocyanurate copolymer (corresponding to the above formula (2-2-t)), 0.032 g of 1B2PZ (product of Shikoku Chemicals Corporation, corresponding to the above formula (c-1)), 0.013 g of trifluoroacetic acid (product of Tokyo Chemical Industry Co., Ltd.), 68.95 g of PGMEA, and 29.55 g of PGME were mixed to prepare a solution with a solids content of 1.5 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor device (composition for forming a resist underlayer film).

[0170] Comparative Example 2 0.49 g (weight average molecular weight: 3,100) of epoxy novolak resin EOCN-104S (a product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)), 0.97 g of 3,7-dihydroxy-2-naphthoic acid-tri(2,3-epoxypropyl)isocyanurate copolymer (corresponding to the above formula (2-2-t)), 0.040 g of 1B2PZ (a product of Shikoku Chemicals Corporation, corresponding to the above formula (c-1)), 68.95 g of PGMEA, and 29.55 g of PGME were mixed to prepare a solution with a solids content of 1.5 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor device (a composition for forming a resist underlayer film).

[0171] Example 4 2.88 g of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)) (weight average molecular weight: 3100), 0.72 g of VP-2500 (product of Nippon Soda Co., Ltd., corresponding to the following formula (b-1)) (weight average molecular weight: 3687), 0.036 g of 1B2PZ (product of Shikoku Chemical Industry Co., Ltd., corresponding to the above formula (c-1)), 0.007 g of acetic acid (product of Kanto Chemical Co., Ltd.), 0.29 g of 1,2-hexanediol (product of Tokyo Chemical Industry Co., Ltd., corresponding to the below formula (f-1)), Karenz MT (registered trademark) 0.58 g of TPMB (a product of Resonac Corporation, corresponding to the following formula (b-3)), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solids content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor element (composition for forming a protective film).

[0172] Example 5 2.88 g of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)) (weight average molecular weight: 3100), 0.72 g of VP-2500 (product of Nippon Soda Co., Ltd., corresponding to the above formula (b-1) and weight average molecular weight: 3687), 0.036 g of 1B2PZ (product of Shikoku Chemical Industry Co., Ltd., corresponding to the above formula (c-1)), 0.007 g of acetic acid (product of Kanto Chemical Co., Ltd.), 0.29 g of 1,2-hexanediol (product of Tokyo Chemical Industry Co., Ltd., corresponding to the following formula (f-1)), Karenz MT (registered trademark) 0.58 g of NR1 (a product of Resonac Corporation, corresponding to the following formula (b-4)), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solids content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor element (composition for forming a protective film).

[0173]

[0174] Example 6 2.88 g of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)) (weight average molecular weight: 3100), 0.72 g of VP-2500 (product of Nippon Soda Co., Ltd., corresponding to the above formula (b-1)) 0.036 g of 1B2PZ (product of Shikoku Chemical Industry Co., Ltd., corresponding to the above formula (c-1)), 0.007 g of acetic acid (product of Kanto Chemical Co., Ltd.), 0.29 g of 1,2-hexanediol (product of Tokyo Chemical Industry Co., Ltd., corresponding to the following formula (f-1)), Karenz MT (registered trademark) 0.58 g of PE1 (a product of Resonac Corporation, corresponding to the following formula (b-5)), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solids content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor element (composition for forming a protective film).

[0175]

[0176] Comparative Example 3 2.88 g (weight average molecular weight: 3100) of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)), 0.72 g of VP-2500 (product of Nippon Soda Co., Ltd., corresponding to the above formula (b-1) and weight average molecular weight: 3687), 0.043 g of 1B2PZ (product of Shikoku Chemicals Corporation, corresponding to the above formula (c-1)), 0.29 g of 1,2-hexanediol (product of Tokyo Chemical Industry Co., Ltd., corresponding to the following formula (f-1)), 0.58 g of Karenz MT (registered trademark) TPMB (product of Resonac Corporation, corresponding to the above formula (b-3)), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solids content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor element (composition for forming a protective film).

[0177] Comparative Example 4 2.88 g (weight average molecular weight: 3100) of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)), 0.72 g of VP-2500 (product of Nippon Soda Co., Ltd., corresponding to the above formula (b-1) and weight average molecular weight: 3687), 0.043 g of 1B2PZ (product of Shikoku Chemicals Corporation, corresponding to the above formula (c-1)), 0.29 g of 1,2-hexanediol (product of Tokyo Chemical Industry Co., Ltd., corresponding to the following formula (f-1)), 0.58 g of Karenz MT (registered trademark) NR1 (product of Resonac Corporation, corresponding to the following formula (b-4)), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solids content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor element (composition for forming a protective film).

[0178] Comparative Example 5 2.88 g (weight average molecular weight of 3100) of epoxy novolak resin EOCN-104S (product of Nippon Kayaku Co., Ltd., corresponding to the above formula (a-1)), 0.72 g of VP-2500 (product of Nippon Soda Co., Ltd., corresponding to the above formula (b-1) and weight average molecular weight of 3687), 0.043 g of 1B2PZ (product of Shikoku Chemicals Corporation, corresponding to the above formula (c-1)), 0.29 g of 1,2-hexanediol (product of Tokyo Chemical Industry Co., Ltd., corresponding to the following formula (f-1)), 0.58 g of Karenz MT (registered trademark) PE1 (product of Resonac Corporation, corresponding to the following formula (b-5)), 28.65 g of PGMEA, and 66.85 g of PGME were mixed to prepare a solution with a solids content of 4.0 mass %. The solution was filtered using a polytetrafluoroethylene microfilter with a pore size of 0.2 μm to prepare a composition for forming a semiconductor element (composition for forming a protective film).

[0179] (Test of Performance as an Antireflective Film) The resist underlayer film-forming compositions prepared in Examples 1 and 2 and Comparative Example 1 were applied to a silicon wafer using a spinner. Then, the composition was baked on a hot plate at 220°C for 1 minute to form a resist underlayer film (film thickness: 400 nm). A commercially available photoresist solution (manufactured by JSR Corporation, product name: AR2772) was applied to the resist underlayer film using a spinner and baked on a hot plate at 110°C for 90 seconds to form a photoresist film (film thickness: 0.2 μm). Next, using a Nikon Corporation scanner, NSRS307E (wavelength: 193 nm, NA: 0.85, σ: 0.62 / 0.93 (ANNULAR)), exposure was performed through a photomask set so that the photoresist line width and the width between the photoresist lines would be 65 nm after development. The resulting resist patterns were then subjected to a post-exposure bake (PEB) on a hot plate at 110°C for 90 seconds. After cooling, the resist patterns were developed using a 0.26N aqueous solution of tetramethylammonium hydroxide as a developer in an industry-standard 60-second single-puddle process to obtain photoresist patterns. The cross sections of the resulting photoresist patterns perpendicular to the substrate, i.e., silicon wafer, were observed with a scanning electron microscope (SEM) to evaluate their lithography properties. The cross-sectional shapes of the photoresist patterns prepared using the antireflective coatings of Examples 1 and 2 and Comparative Example 1 were observed to be nearly rectangular with good straight bottom shapes.

[0180] (Chemical Resistance Test) For the chemical resistance test, a silicon wafer on which a titanium nitride film (thickness: 50 nm) was formed was cut into a 3 cm square. Next, the evaluation material was applied and spin-coated, and baked at 220° C. for 60 seconds to form a chemical protection film.

[0181] (Resistance test to basic hydrogen peroxide aqueous solution) Each of the protective film-forming compositions prepared in Examples 1 to 6 and the protective film-forming compositions prepared in Comparative Examples 1 to 3 was applied to a silicon substrate having a titanium nitride film formed on its surface, and baked at 220°C to produce a coating film. The coating film was then immersed in a basic hydrogen peroxide aqueous solution having the composition shown in Table 1 below for 1 minute 30 seconds at the temperature shown in the table, and then washed with water and dried, after which the state of the coating film was visually observed. The film thickness of the applied chemical-resistant protective film and the results of the resistance test are shown in Table 2 below. "X" indicates that the film peeled off, while "◯" indicates that the film did not peel off.

[0182]

[0183]

[0184] (Storage Stability Test) The storage stability test was carried out by measuring the molecular weight distribution and epoxy value by gel permeation chromatography (hereinafter abbreviated as GPC) of samples stored at -20°C and 60°C for 3 days each. The results are from GPC measurements. As described above, the GPC measurements were carried out using a GPC device manufactured by Tosoh Corporation under the following measurement conditions. GPC column Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0185] In the GPC measurement, when the molecular weight distributions of the products stored at -20°C and 60°C were superimposed, those showing no deviation as a whole were evaluated as "Good", and those showing partial deviation were evaluated as "Poor". The evaluation results for each of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 3 below.

[0186]

[0187] As shown by the above results, the comparative example showed poor results in the storage stability test by GPC, whereas the examples showed good results. The composition for forming a semiconductor device according to the present invention exhibits good coatability and film curing in a short time, and also shows good results in storage stability.

Claims

1. A composition for forming a semiconductor element, comprising: (A) a compound or polymer having a reactive group represented by a cyclic ether structure represented by the following formula (I): (B) a compound or polymer having a reactive group reactive to the reactive group in (A): (C) a basic curing agent: (D) an acidic additive: and (E) a solvent. (In formula (I), * represents a bonding site. n represents 1 or 2. When n=1, X represents an ether bond, an ester bond, or an amide bond. When n=2, X represents a nitrogen atom or an amide bond.) 2. The composition for forming a semiconductor device according to claim 1, 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. n represents 1 or 2. When n=1, X represents an ether bond, an ester bond, or an amide bond. When n=2, X represents a nitrogen atom or an amide bond.) 3. The composition for forming a semiconductor device according to claim 1, wherein the polymer (A) is a polymer having a novolac structure 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 hydroxy group, a mercapto group which may be protected by a methyl group, an amino group which may be protected by a methyl group, a halogeno group, or an alkyl group having 1 to 10 carbon atoms which may be substituted or interrupted by a heteroatom and which may be substituted by a hydroxy group; n1 represents an integer of 0 to 3; 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 oxetanyl group, T １ When n2=1, represents an alkylene group having 1 to 10 carbon atoms which may be interrupted by an ether bond, an ester bond or an amide bond; T １ When n2=2, represents a trivalent hydrocarbon group having 1 to 10 carbon atoms which may be interrupted by a nitrogen atom or an amide bond.

4. The composition for forming a semiconductor device according to claim 1, wherein the compound or polymer (B) is a compound or polymer having a phenolic hydroxy group, or a compound having a thiol structure.

5. The composition for forming a semiconductor device according to claim 1, wherein the basic curing agent (C) is a compound 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 optionally substituted aryl group, a monovalent group obtained by removing a hydrogen atom bonded to a carbon atom of an optionally substituted triazine ring from the triazine ring, a cyano group, a hydroxy group, an amino group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group; 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; 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; 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 composition for forming a semiconductor device according to claim 1, wherein the basic curing agent (C) is at least one compound selected from the group consisting of tertiary amine compounds represented by the following formula:

7. The composition for forming a semiconductor device according to claim 1, wherein the acidic additive (D) is a compound containing at least one group selected from the group consisting of an imide group, a carboxy group, a sulfonyl group, and a sulfo group.

8. The composition for forming a semiconductor device according to claim 7, wherein the acidic additive (D) is acetic acid or maleic acid.

9. The composition for forming a semiconductor element according to claim 1, wherein the solvent (E) comprises at least one solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol, monomethyl ether acetate, isopropyl alcohol, ethyl acetate, butyl acetate, and cyclohexanone.

10. The composition for forming a semiconductor element according to claim 1, which is used as a cavity-forming composition for forming cavities between conductive wiring patterns.

11. The composition for forming a semiconductor element according to claim 1, which is used as a composition for forming a protective film for forming a protective film having excellent resistance to a wet etching solution for semiconductors.

12. The composition for forming a semiconductor device according to claim 1, which is used as a composition for forming a resist underlayer film in a lithography process.

13. A film for forming semiconductor elements, which is a fired product of a coating film made of the composition for forming semiconductor elements according to any one of claims 1 to 12.

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