Composition for forming resist underlayer film, resist underlayer film, method for forming resist pattern, and method for manufacturing semiconductor device

Abstract

This composition for forming a resist underlayer film contains a resin (G) having a composite unit structure, and a solvent, the composite unit structure having a unit structure (A) that has an aromatic ring and a unit structure (B) that has one or more carbon atoms, the resin (G) being obtained by a reaction for generating a covalent bond between a carbon atom constituting the aromatic ring in the unit structure (A) and a carbon atom in the unit structure (B), the unit structure (A) including a unit structure (A-I) that includes a bisphenol skeleton having three or more aromatic hydrocarbon rings, and the unit structure (B) including a unit structure (B-I) that has a quaternary carbon atom to be bonded to the carbon atom constituting the aromatic ring in the unit structure (A).

Description

Composition for forming resist underlayer film, resist underlayer film, method for forming resist pattern, and method for manufacturing semiconductor device

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a method for forming a resist pattern, and a method for manufacturing a semiconductor device.

[0002] In recent years, semiconductor manufacturing processes have progressed rapidly, and this has led to a strong demand for higher quality and improved properties of resist underlayer films (see, for example, Patent Documents 1 to 6). In particular, resist underlayer films, which are known to be made of high-carbon materials, are strongly required to be imparted with etching resistance.

[0003] US Patent Application Publication No. 2016 / 311975 Specification International Publication No. 2018 / 198960 Pamphlet Japanese Patent Application Laid-Open No. 2021-81686 Japanese Patent Application Laid-Open No. 2020-105513 International Publication No. 2013 / 146670 Pamphlet Japanese Patent Application Laid-Open No. 2016-151024

[0004] However, it is extremely difficult to prepare a material that combines properties such as solvent resistance, coatability on uneven substrates, and planarization with etching resistance, and there is still room for improvement as a material. Furthermore, in the manufacturing process of a semiconductor device, if a large amount of sublimate is generated from the resist underlayer film, problems such as contamination of the baking pan or the inside of the piping used during baking occur. The present invention has been made in view of the above circumstances, and aims to provide a composition for forming a resist underlayer film that satisfies a good balance of solvent resistance, etching resistance, coatability on uneven substrates, and planarization while suppressing the amount of sublimate generated, as well as a method for forming a resist underlayer film and a resist pattern, and a method for manufacturing a semiconductor device using the resist underlayer film composition.

[0005] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0006] That is, the present invention encompasses the following aspects. [1] A composition for forming a resist underlayer film, comprising: a resin (G) having a composite unit structure; and a solvent, wherein the composite unit structure comprises: a unit structure (A) having an aromatic ring; and a unit structure (B) having one or more carbon atoms, wherein the resin (G) is a resin obtained by a reaction to form a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B), wherein the unit structure (A) comprises a unit structure (AI) including a bisphenol skeleton having three or more aromatic hydrocarbon rings, and the unit structure (B) comprises a unit structure (BI) having a quaternary carbon atom bonded to a carbon atom constituting the aromatic ring of the unit structure (A). [2] The composition for forming a resist underlayer film according to [1], wherein the molar ratio of the unit structure (A) to the unit structure (B) is 1:1 to 1:2. [3] The composition for forming a resist underlayer film according to [1] or [2], wherein the resin (G) contains, as the composite unit structure, one or two of composite unit structures represented by the following formula (1AB) and the following formula (2AB): (In formula (1AB) and formula (2AB), R １ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms; R ２ and R ３ each independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent, and R ２ and R ３ When each represents an aromatic hydrocarbon group, they may be bonded to each other to form a fluorene ring, and R ２ and R ３each represent an aliphatic hydrocarbon group, they may be bonded to each other to form an aliphatic hydrocarbon ring, and each Ar independently represents a benzene ring or a naphthalene ring.) [4] The composition for forming a resist underlayer film according to [3], wherein in formula (1AB) and formula (2AB), the substituent that the aromatic or aliphatic hydrocarbon group may have is one or more groups selected from a halo group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxy group, a hydroxyalkyl group, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, and an ether bond-containing group. [5] In formula (1AB) and formula (2AB), ２ and R ３ each independently represent an aromatic hydrocarbon group which may have a substituent, and the aromatic hydrocarbon groups which may have a substituent are a phenyl group or a naphthyl group, and may be bonded to each other to form a fluorene ring. [6] The composition for forming a resist underlayer film according to [3] or [4], ２ and R ３each independently represent an optionally substituted aliphatic hydrocarbon group, and the optionally substituted aliphatic hydrocarbon group is an alkyl group having 1 to 10 carbon atoms. [7] The composition for forming a resist underlayer film according to any one of [1] to [6], wherein the resin (G) is a resin synthesized by polymerizing at least one compound having a bisphenol skeleton having three or more aromatic hydrocarbon rings with at least one aromatic ketone or aliphatic ketone in the presence of an acid catalyst. [8] The composition for forming a resist underlayer film according to any one of [1] to [7], wherein the solvent comprises a solvent having a boiling point of 160°C or higher. [9] The composition for forming a resist underlayer film according to any one of [1] to [8], further comprising at least one selected from the group consisting of an acid, a salt thereof, and an acid generator.

[10] The composition for forming a resist underlayer film according to any one of [1] to [9], further comprising a crosslinking agent.

[11] The composition for forming a resist underlayer film according to

[10] , wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

[12] The composition for forming a resist underlayer film according to any one of [1] to

[11] , further comprising a surfactant.

[13] A resist underlayer film on a semiconductor substrate, which is a cured product of the composition for forming a resist underlayer film according to any one of [1] to

[12] .

[14] A method for forming a resist pattern used in semiconductor production, comprising the steps of applying the composition for forming a resist underlayer film according to any one of [1] to

[12] onto a semiconductor substrate and baking the applied composition.

[15] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[12] ; forming a resist film on the resist underlayer film; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

[16] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[12] ; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

[17] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[12] ; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing a semiconductor substrate through the patterned resist underlayer film.

[18] A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to

[12] ; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film on the resist underlayer film after removing the hard mask; processing the vapor-deposited film by etching; removing the patterned resist underlayer film to leave a patterned vapor-deposited film; and processing a semiconductor substrate through the patterned vapor-deposited film.

[19] The method for manufacturing a semiconductor device according to any one of

[16] to

[18] , wherein the hard mask is formed by applying a composition containing an inorganic substance or vapor-depositing an inorganic substance.

[20] The method for manufacturing a semiconductor device according to any one of

[15] to

[19] , wherein the resist film is patterned by a nanoimprint method or a self-assembled film.

[21] The method for manufacturing a semiconductor device according to

[17] or

[18] , wherein the hard mask is removed by etching or an alkaline chemical solution.

[0007] According to the present invention, it is possible to provide a composition for forming a resist underlayer film that satisfies a good balance of solvent resistance, etching resistance, coatability onto uneven substrates, and planarization properties while suppressing the amount of sublimate generation, as well as a method for forming a resist underlayer film and a resist pattern, and a method for manufacturing a semiconductor device, which use the composition for forming a resist underlayer film.

[0008] [Composition for Forming Resist Underlayer Film] The composition for forming a resist underlayer film of the present invention comprises a resin (G) having a composite unit structure and a solvent. The composite unit structure comprises a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. The resin (G) is a resin obtained by a reaction that forms a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B). The unit structure (A) comprises a unit structure (A-I) that includes a bisphenol skeleton having three or more aromatic hydrocarbon rings. The unit structure (B) comprises a unit structure (B-I) that has a quaternary carbon atom bonded to a carbon atom constituting the aromatic ring of the unit structure (A). In this specification, the resin (G) may be referred to as a "novolac resin." By comprising the above-described unit structure (A) and unit structure (B), the resin (G) can provide a composition for forming a resist underlayer film that exhibits a good balance of solvent resistance, etching resistance, coatability on uneven substrates, and planarization properties while suppressing the amount of sublimate generation.

[0009] The unit structure (A) has, for example, at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring. The unit structure (A) does not have a heteroatom, for example, as an atom constituting an aromatic ring or an atom bonded to an aromatic ring.

[0010] The unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. The aldehyde equivalent is an organic compound capable of forming a covalent bond with an aromatic ring, and is an organic compound having a ketone group, an acetal group, a ketal group, a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom, a hydroxyl group, an alkoxy group or a halo group bonded to the α-carbon atom of an alkylaryl group, or a carbon-carbon unsaturated bond.

[0011] [I. Definitions of Terms] In this specification, definitions of main terms related to the novolac resin, which is one embodiment of the present invention, are explained below. Unless otherwise specified, the following definitions of each term apply to the novolac resin.

[0012] (I-1) "Novolac Resin" The term "novolac resin" is used in a broad sense to encompass not only phenol-formaldehyde resins (so-called novolac phenolic resins) and aniline-formaldehyde resins (so-called novolac aniline resins) in the narrow sense, but also resins formed by forming a covalent bond (substitution reaction, addition reaction, condensation reaction, addition-condensation reaction, etc.) between an organic compound having a functional group capable of forming a covalent bond with an aromatic ring (for example, an aldehyde group; a ketone group; an acetal group; a ketal group; a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (e.g., the benzylic carbon atom) of an alkylaryl group; or a carbon-carbon unsaturated bond such as in divinylbenzene or dicyclopentadiene) in the presence of an acid catalyst or under equivalent reaction conditions, and an aromatic ring in a compound having an aromatic ring (preferably having heteroatoms such as oxygen, nitrogen, and sulfur atoms as atoms constituting the aromatic ring or atoms bonded to the aromatic ring)

[0013] Therefore, the novolak resin referred to in this specification is a resin formed by linking a plurality of compounds having aromatic rings together, with an organic compound containing a carbon atom derived from the functional group (sometimes referred to as a "linking carbon atom") forming a covalent bond with an aromatic ring in a compound having an aromatic ring via the linking carbon atom.

[0014] In this specification, the terms unit structure (A) and unit structure (B) are used to refer to unit structures constituting a "novolac resin." Unit structure (A) is a unit structure derived from a compound having an aromatic ring. Unit structure (B) is a unit structure derived from a compound having a functional group that enables covalent bonding with the aromatic ring of unit structure (A).

[0015] (I-2) "Residue" A "residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or a heteroatom (such as a nitrogen atom, oxygen atom, or sulfur atom) is replaced with a bond, and may be a monovalent group or a polyvalent group. For example, replacing one hydrogen atom with one bond results in a monovalent organic group, and replacing two hydrogen atoms with bonds results in a divalent organic group.

[0016] (I-3) "Aromatic Ring" (Aromatic Group, Aryl Group, Arylene Group) The term "aromatic ring" refers to a concept that encompasses aromatic hydrocarbon rings, aromatic heterocycles, and residues thereof [sometimes referred to as "aromatic groups," "aryl groups" (in the case of monovalent groups), or "arylene groups" (in the case of divalent groups)], and encompasses not only monocyclic (aromatic monocycles) but also polycyclic (aromatic polycycles). In the case of polycycles, at least one monocycle is an aromatic monocycle, and the remaining monocycles that form a fused ring with the aromatic monocycle may be a monocyclic heterocycle (heteromonocycle) or a monocyclic alicyclic hydrocarbon (alicyclic monocycle). In this specification, heteroaryl groups are included in the aryl group. Heteroarylene groups are included in the arylene group.

[0017] Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, triphenylene, benzanthracene, pyrene, chrysene, fluorene, biphenyl, corannulene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, coronene, dibenzo[g,p]chrysene, acenaphthylene, acenaphthene, naphthacene, pentacene, and cyclooctatetraene, more typically aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene; and aromatic hydrocarbon rings such as furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, and pyrrolidone. aromatic heterocycles such as indole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindolefluorene, bisindolebenzofluorene, bisindoledibenzofluorene, purine, quinoline, isoquinoline, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, and indolocarbazole, and more typically, furan, thiophene, pyrrole, indole, phenylindole, bisindolefluorene, phenothiazine, carbazole, and indolocarbazole, but are not limited thereto.

[0018] The aromatic ring (for example, a benzene ring, a naphthalene ring, etc.) may have an optional substituent, and examples of such a substituent include the following atoms and groups: a halogen atom; a saturated or unsaturated, linear, branched, or cyclic hydrocarbon group (-R ａ ) (including alkyl groups, alkenyl groups, and alkynyl groups (e.g., propargyl groups), and aryl groups, whose hydrocarbon chains may be interrupted one or more times by oxygen atoms), -OR (wherein R is the hydrocarbon group -R ａ ) Aryloxy group -NH ２ , —NHR or —NR ２ (Two R's may be the same or different from each other), where R's are the hydrocarbon groups -R ａ - Hydroxyl group - Hydroxyalkyl group - Carboxy group - Formyl group - Cyano group - Nitro group - Ester group (for example, -CO ２ R or -OCOR, where R is the hydrocarbon group -R ａ an amide group [for example, —NHCOR, —CONHR, —NRCOR (wherein the two Rs may be the same or different), or —CONR ２ (Two R's may be the same or different from each other), where R's are the hydrocarbon groups -R ａ a sulfonyl-containing group (e.g., —SO ２ R, where R is the hydrocarbon group -R ａ or a hydroxyl group -OH.) a thiol group (-SH) a sulfide-containing group (-SR, where R is the hydrocarbon group -R ａ An organic group containing an ether bond [R １１ -O-R １１ (R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group or a pyrenyl group; a residue of an ether compound represented by the formula (I); an organic group containing an ether bond, such as a methoxy group, an ethoxy group or a phenoxy group]

[0019] The term "aromatic ring" also includes organic groups having one or more fused rings of aromatic rings (such as benzene, naphthalene, anthracene, and pyrene) with one or more fused aliphatic or heterocyclic rings. Examples of the aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene. Examples of the heterocyclic rings include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0020] The "aromatic ring" may be an organic group having a structure in which two or more aromatic rings are linked by a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２ The divalent linking group may also be a divalent group in which one hydrogen atom has been removed from any of the substituents of the aromatic rings described above.

[0021] (I-4) "Heterocycle" The term "heterocycle" encompasses both aliphatic heterocycles and aromatic heterocycles, and is a concept that encompasses not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic). In the case of a polycyclic, at least one monocyclic ring is a heteromonocyclic ring, but the remaining monocyclic rings may be aromatic hydrocarbon monocyclic or alicyclic monocyclic. For the aromatic heterocycle, the examples in (I-3) above can be referred to. As with the aromatic ring in (I-3) above, it may have a substituent.

[0022] (I-5) "Non-aromatic ring" (aliphatic ring) When the "non-aromatic ring" is a monocycle, the "non-aromatic monocycle" refers to a monocyclic hydrocarbon that does not belong to the aromatic group, and is typically a monocycle of an alicyclic compound. It may also be called an aliphatic monocycle (which may include an aliphatic heteromonocycle, or may contain an unsaturated bond as long as it does not belong to the aromatic compound). As with the aromatic ring of (I-3) above, it may have a substituent.

[0023] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0024] When the "non-aromatic ring" is a polycyclic ring, the "non-aromatic polycyclic ring" refers to a polycyclic hydrocarbon that does not belong to the aromatic group, and is typically a polycyclic ring of an alicyclic compound. It may also be called an aliphatic polycyclic ring (which may include an aliphatic heteropolycyclic ring (at least one of the monocyclic rings constituting the polycyclic ring is an aliphatic heterocyclic ring), or may contain an unsaturated bond as long as it does not belong to the aromatic compound). It includes a non-aromatic bicyclic ring, a non-aromatic tricyclic ring, and a non-aromatic tetracyclic ring.

[0025] When the "non-aromatic ring" is a bicycle, the "non-aromatic bicycle" refers to a fused ring composed of two monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of two alicyclic compounds. In this specification, it may also be referred to as an aliphatic bicycle (which may include an aliphatic heterobicycle, and may contain unsaturated bonds as long as it does not belong to the aromatic compound). Examples of non-aromatic bicycles include bicyclopentane, bicyclooctane, and bicycloheptene.

[0026] When the "non-aromatic ring" is a tricycle, the "non-aromatic tricycle" refers to a fused ring composed of three monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of three alicyclic compounds (each of which may be a heterocycle or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tricycles include tricyclooctane, tricyclononane, and tricyclodecane.

[0027] When the "non-aromatic ring" is a tetracyclic ring, the "non-aromatic tetracyclic ring" refers to a fused ring composed of four monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of four alicyclic compounds (each of which may be a heterocyclic ring or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tetracyclic rings include hexadecahydropyrene.

[0028] (I-6) The term "carbon atoms constituting a ring (moiety)" refers to the carbon atoms constituting a hydrocarbon ring (which may be an aromatic ring, an aliphatic ring, or a heterocyclic ring) in an unsubstituted state.

[0029] (I-7) The term "hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0030] (I-8) In the chemical structural formula showing the unit structure of the novolak resin in this specification, a bond (indicated by *) may be shown for convenience. However, unless otherwise specified, such a bond can be at any available bonding position in the unit structure, and does not in any way limit the bonding position in the unit structure.

[0031] <Resin (G)> The resin (G) has a composite unit structure. The resin (G) may be a polymer. The composite unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms.

[0032] The composite unit structure of the resin (G) is represented, for example, by the following formula (AB). (In formula (AB), A represents the unit structure (A), and B represents the unit structure (B).)

[0033] <<A-1: Unit Structure (A)>> The unit structure (A) has an aromatic ring. The unit structure (A) may have, for example, at least one of an oxygen atom constituting the aromatic ring, a sulfur atom constituting the aromatic ring, an oxygen atom bonded to the aromatic ring, a nitrogen atom constituting the aromatic ring, and a nitrogen atom directly bonded to the aromatic ring.

[0034] The number of carbon atoms contained in the unit structure (A) is not particularly limited, but is, for example, 4 to 100, and preferably 4 to 50.

[0035] Preferably, such aromatic rings have from 4 to 30, more preferably from 4 to 24, carbon atoms.

[0036] Preferably, such aromatic ring is one or more benzene rings, naphthalene rings, anthracene rings, or pyrene rings; or a condensed ring of a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring with a heterocycle or an aliphatic ring (such as a fluorene ring, a benzofluorene ring, a dibenzofluorene ring, an indole ring, a carbazole ring, or an indolocarbazole ring).

[0037] The aromatic ring may have any substituent, and from the viewpoint of polymerization reactivity, the substituent may contain the minimum necessary number of heteroatoms.In addition, the aromatic ring may have two or more aromatic rings connected by a linking group, and the linking group may contain the minimum necessary number of heteroatoms.Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0038] The "aromatic ring" may contain at least one heteroatom selected from N, S and O on, within or between the rings.

[0039] Examples of heteroatoms that may be contained on the ring include nitrogen atoms contained in amino groups (e.g., propargylamino groups) and cyano groups; oxygen atoms contained in oxygen-containing substituents such as formyl groups, hydroxy groups, carboxy groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups (e.g., propargyloxy groups), and aryloxy groups; and nitrogen atoms and oxygen atoms contained in nitro groups, which are oxygen-containing and nitrogen-containing substituents. Examples of heteroatoms that may be contained in the ring include oxygen atoms contained in furan and xanthene, nitrogen atoms contained in carbazole and pyrrole, and sulfur atoms contained in phenothiazine. Examples of heteroatoms that may be contained in the linking group of two or more aromatic rings include -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２Examples of the aromatic ring include a nitrogen atom, an oxygen atom, and a sulfur atom. In this specification, "an atom constituting an aromatic ring" is synonymous with "an atom contained within the ring." "An atom bonded to an aromatic ring" refers to, for example, "an atom directly bonded to the ring among atoms or groups contained on the ring" and "an atom directly bonded to the ring among atoms contained between rings." For example, the atoms constituting a benzene ring are carbon atoms. For example, the atoms constituting a pyrrole ring are carbon atoms and nitrogen atoms. For example, the oxygen atom of a hydroxyl group in phenol is not an atom constituting an aromatic ring. For example, the oxygen atom of a hydroxyl group in phenol is an atom bonded to the benzene ring, and is an atom directly bonded to the benzene ring among groups contained on the benzene ring.

[0040] <<A-2: Examples of Skeletons Constituting the Unit Structure (A)>> The unit structure (A) has, for example, a skeleton having an aromatic ring.

[0041] The skeleton having an aromatic ring is preferably an aromatic amine skeleton, a nitrogen-containing aromatic heterocyclic skeleton, or a phenol skeleton.

[0042] The unit structure (A) is, for example, a residue obtained by removing two hydrogen atoms from a skeleton having an aromatic ring. The skeleton having an aromatic ring is derived, for example, from a compound having an aromatic ring when synthesizing the resin (G). The skeleton having an aromatic ring is, for example, a residue obtained by removing two hydrogen atoms from a compound having an aromatic ring when synthesizing the resin (G).

[0043] The skeleton having an aromatic ring may have a substituent. Examples of the substituent include a halo group (halogen atom), an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxy group, a hydroxyalkyl group, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, and an ether bond-containing group. Examples of the alkyl group include a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. Examples of the alkenyl group include a linear, branched, or cyclic alkenyl group having 2 to 10 carbon atoms. Examples of the alkynyl group include a linear, branched, or cyclic alkynyl group having 2 to 10 carbon atoms. Examples of the alkoxy group include a group represented by -OR. Here, R represents a saturated or unsaturated linear, branched, or cyclic hydrocarbon group (-R ａ The alkoxy group may have, for example, 1 to 20 carbon atoms. The aryl group may have 6 to 30 carbon atoms. The aryloxy group may have 6 to 30 carbon atoms. The amino group may have -NH ２ , —NHR or —NR ２ Here, R is the hydrocarbon group -R ａ represents -NR ２ In the formula, the two R's may be the same or different. Examples of the hydroxyalkyl group include linear, branched, or cyclic hydroxyalkyl groups having 1 to 20 carbon atoms. Examples of the ester group include -CO ２ Examples of the hydrocarbon group include a group represented by -R or -OCOR. ａ The amide group is —NHCOR, —CONHR, —NRCOR, or —CONR ２ Here, R is the hydrocarbon group -R ａ When there are two R's, the two R's may be the same or different. The sulfonyl-containing group includes -SO ２Here, R is the hydrocarbon group -R ａ or a hydroxy group -OH. Examples of sulfide-containing groups include groups represented by -SR, where R is the hydrocarbon group -R ａ The ether bond-containing group is represented by R １１ -O-R １１ In this case, R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group, or a pyrenyl group. The ether bond-containing group may be an organic group containing an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group.

[0044] <<<A-3: Unit structure (A-I)>>> The unit structure (A) includes a unit structure (A-I) that includes a bisphenol skeleton having three or more aromatic hydrocarbon rings. The unit structure (A-I) has a skeleton having an aromatic ring. Here, the unit structure (A-I) is a subordinate concept of the unit structure (A) and does not refer to a partial structure of the unit structure (A). The skeleton having an aromatic ring in the unit structure (A-I) will be described below.

[0045] In this specification, the term "bisphenol skeleton" refers to a skeleton containing a structure derived from a bisphenol having three or more aromatic hydrocarbon rings, such as bisphenol P. Examples of the bisphenol skeleton include a skeleton containing a structure derived from a bisphenol represented by the following formula (1A): (In formula (1A), R １ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and each Ar independently represents a benzene ring or a naphthalene ring.

[0046] In formula (1A), when Ar is a naphthalene ring, the hydroxy group may be bonded to either of the two benzene rings constituting the naphthalene ring. Also, when the central Ar in formula (1A) is a naphthalene ring, the bond bonding to the adjacent carbon atom may extend from either of the two benzene rings constituting the naphthalene ring.

[0047] The resin (G) preferably contains, as a composite unit structure, one or two of the composite unit structures represented by the following formula (1AB) and the following formula (2AB). (In formula (1AB) and formula (2AB), R １ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms; R ２ and R ３ each independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent, and R ２ and R ３ When each represents an aromatic hydrocarbon group, they may be bonded to each other to form a fluorene ring, and R ２ and R ３ When each represents an aliphatic hydrocarbon group, they may be bonded to each other to form an aliphatic hydrocarbon ring, and each Ar independently represents a benzene ring or a naphthalene ring.

[0048] In formula (1AB) and formula (2AB), when Ar is a naphthalene ring, the hydroxy group may be bonded to either of the two benzene rings constituting the naphthalene ring. Also, when the central Ar in formula (1AB) and formula (2AB) is a naphthalene ring, the bond bonding to the adjacent carbon atom may extend from either of the two benzene rings constituting the naphthalene ring.

[0049] In formula (1AB) and formula (2AB), the bisphenol skeleton containing Ar corresponds to the unit structure (AI), and R ２ , R ３ , and R ２ and R３ The carbon atom bonded to R corresponds to the unit structure (BI) described below. ２ and R ３ The carbon atom bonded to R is a quaternary carbon atom. ２ and R ３ The carbon atom bonded to is, for example, a quaternary carbon atom bonded to a carbon atom constituting the aromatic ring of the unit structure (A-1).

[0050] 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, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl 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 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, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0051] Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, and 1-methyl-3-butenyl. nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl Examples of the alkyl group include phenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-heptenyl group, 1-octenyl group, 1-nonenyl group, and 1-decenyl group.

[0052] Examples of alkynyl groups having 2 to 10 carbon atoms include ethynyl, 1-propynyl, propargyl (2-propynyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl, and 1-decynyl.

[0053] In formula (1AB) and formula (2AB), the two benzene rings in the fluorene ring that may be formed may each independently have a substituent, may be linked to another aromatic hydrocarbon ring, or may be condensed with another aromatic hydrocarbon ring. Examples of other aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a tetraphene ring, a chrysene ring, a triphenylene ring, a pyrene ring, a pentacene ring, and a hexacene ring. Examples of substituents include a halo group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxy group, a hydroxyalkyl group, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, and an ether bond-containing group. Examples of halo groups include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of alkyl groups include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups having 2 to 10 carbon atoms. Examples of alkynyl groups include linear, branched, or cyclic alkynyl groups having 2 to 10 carbon atoms. Examples of alkoxy groups include groups represented by -OR. Here, R represents a saturated or unsaturated linear, branched, or cyclic hydrocarbon group (-R ａ The alkoxy group may have, for example, 1 to 20 carbon atoms. The aryl group may have 6 to 30 carbon atoms. The aryloxy group may have 6 to 30 carbon atoms. The amino group may have -NH ２ , —NHR or —NR ２ Here, R is the hydrocarbon group -R ａ represents -NR ２ In the formula, the two R's may be the same or different. Examples of the hydroxyalkyl group include linear, branched, or cyclic hydroxyalkyl groups having 1 to 20 carbon atoms. Examples of the ester group include -CO２ Examples of the hydrocarbon group include a group represented by -R or -OCOR. ａ The amide group is —NHCOR, —CONHR, —NRCOR, or —CONR ２ Here, R is the hydrocarbon group -R ａ When there are two R's, the two R's may be the same or different. The sulfonyl-containing group includes -SO ２ Here, R is the hydrocarbon group -R ａ or a hydroxy group -OH. Examples of sulfide-containing groups include groups represented by -SR, where R is the hydrocarbon group -R ａ The ether bond-containing group is represented by R １１ -O-R １１ In this case, R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, an anthranyl group, or a pyrenyl group. The ether bond-containing group may be an organic group containing an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group.

[0054] In formula (1AB) and formula (2AB), examples of the aliphatic hydrocarbon ring that may be formed include a cyclopropane ring, a cyclobutane ring, a cycloheptane ring, a cyclohexane ring, a bicyclopentane ring, a bicyclooctane ring, and a tricyclodecane ring.

[0055] In formula (1AB) and formula (2AB), R ２ and R ３ and each independently represent an aromatic hydrocarbon group which may have a substituent, the aromatic hydrocarbon group is preferably a phenyl group or a naphthyl group (1-naphthyl group or 2-naphthyl group). These aromatic hydrocarbon groups may be bonded to each other to form a fluorene ring.

[0056] In formula (1AB) and formula (2AB), R ２ and R ３and each independently represent an aliphatic hydrocarbon group which may have a substituent, the aliphatic hydrocarbon group is preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic.

[0057] The unit structure (A) in the resin (G) may contain a unit structure other than the unit structure (AI). Examples of unit structures other than the unit structure (AI) include a unit structure having an aromatic amine skeleton, a unit structure having a nitrogen-containing aromatic heterocyclic skeleton, and a unit structure having a phenol skeleton. The unit structures having these skeletons may include the unit structure (AI).

[0058] <<<A-4-1: Aromatic Amine Skeleton>>> The aromatic amine skeleton refers to a skeleton having an aromatic ring and a nitrogen atom bonded to the aromatic ring but not constituting a ring. Examples of the aromatic amine skeleton include skeletons represented by the following formulas (A-1a) to (A-1c). As described below, in the unit structure (A), the hydrogen atom of the NH group may be replaced with a substituent. Examples of the substituent include the substituents described in the above (I-3) "Aromatic Ring", the substituents described in the above (A-2) "Examples of Skeletons Constituting the Unit Structure (A)", and the substituents (S) represented by the below-described formulas (S1) to (S7). (In formulas (A-1a) to (A-1c), Ar １１ R each independently represents a residue of an aromatic ring. １１ each independently represents a hydrogen atom or a residue of an aromatic ring.

[0059] Ar １１ and R １１ Examples of the aromatic ring in the residue of the aromatic ring include aromatic rings represented by the following formula (G1): These aromatic rings may have a substituent.

[0060] Examples of the skeleton represented by formula (A-1a) include the following skeletons. The aromatic rings in these skeletons may have a substituent, and the hydrogen atoms of the NH groups may be replaced with substituents. The same applies to the following skeletons.

[0061] Examples of the skeleton represented by formula (A-1b) include the following skeletons:

[0062] Examples of the skeleton represented by formula (A-1c) include the following skeletons:

[0063] <<<A-4-2: Nitrogen-Containing Aromatic Heterocyclic Skeleton>>> The nitrogen-containing aromatic heterocyclic skeleton refers to a skeleton having an aromatic heterocycle having a nitrogen atom among the atoms constituting the heterocycle. Examples of the nitrogen-containing aromatic heterocycle include a pyrrole ring, an indole ring, a carbazole ring, a pyridine ring, an acridine ring, a phenoxazine ring, and a phenothiazine ring. These nitrogen-containing aromatic heterocycles may have a substituent. Examples of the nitrogen-containing aromatic heterocyclic skeleton include skeletons represented by the following formula (A-2a), (A-2b-1), (A-2b-2), (A-2c-1), (A-2c-2), (A-2c-3), (A-2c-4), (A-2d), (A-2e), (A-3a), or (A-3b). As will be described later, in the structural unit (A), the hydrogen atom of the NH group may be replaced with a substituent. (In the formula, Ar ２１ R each independently represents a residue of an aromatic ring. ２１ R each independently represents a hydrogen atom or a residue of an aromatic ring. ２２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a residue of an aromatic ring. ２２may be joined together to form an unsaturated aliphatic ring. One of the unsaturated bonds in the unsaturated aliphatic ring refers to an unsaturated bond constituting a pyrrole ring. Each R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond to L. L represents a single bond or a linking group. n1 represents 1, and n2 represents 1 or 2. In formulas (A-2b-2) and (A-2c-4), when L is a single bond, the partial structure (In1) and the partial structure (In2), and the partial structure (Ca1) and the partial structure (Ca2), respectively, are bonded by two nitrogen atoms bonding together, or by two Ar ２１ or a nitrogen atom and Ar ２１ In formula (A-2b-2) and formula (A-2c-4), when L is a linking group, L is N or Ar ２１ is bonded to

[0064] Ar ２１ , R ２１ , R ２２ and the aromatic ring in the residue of the aromatic ring of R includes, for example, an aromatic ring represented by the following formula (G2): These aromatic rings may have a substituent.

[0065] Two adjacent R ２２ Examples of the unsaturated aliphatic ring formed by combining these include the following rings: These aliphatic rings may have a substituent.

[0066] Examples of the linking group for L include a saturated hydrocarbon group having 1 to 5 carbon atoms and a valence of (n1+n2), and a residue obtained by removing (n1+n2) hydrogen atoms from an aromatic ring.

[0067] <Formula (A-2d)> (In formula (A-2d), R １１ each independently represents a hydrogen atom or an aromatic group, Ar is an aromatic ring moiety, each independently representing a benzene ring, a fused ring composed of 2 to 3 benzene rings, or a structure represented by the following formula (Ar01), ０ represents a single bond, —O—, —S—, or —NR１２ -or-CR １３ R １４ represents -, and R １２ is R １１ Same or different from R １１ is the same as the definition of R １３ and R １４ each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n is 1 or 2, when n is 1, Z represents a monovalent organic group, and when n is 2, Z represents a divalent organic group.

[0068] In the unit structure (A), R in formula (A-2d) １１ may be a substituent. １１ is a substituent or an aromatic group, R １１ represents, for example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) may be further substituted with an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, an aryl group, or a halo group, and that (iii) may have the hydrocarbon chain portion further interrupted by an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, or an arylene group.

[0069] An example of the skeleton represented by formula (A-2d) is the skeleton represented by the following formula (A-2d-1). (R in formula (A-2d-1) １１ , Ar, and X ０ respectively represent R in formula (A-2d). １１ , Ar, and X ０ It is synonymous with R ２１ is an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms.

[0070] Ar in formula (A-2d) and formula (A-2d-1) is, for example, a benzene ring or a naphthalene ring. Ar in formula (A-2d) and formula (A-2d-1) may have a structure represented by the following formula (Ar01): (R in formula (Ar01) １１ａ represents R in formula (A-2d-1). １１ is synonymous with R ２１ａ represents R in formula (A-2d-1). ２１ and Ar ａ has the same meaning as Ar in formula (A-2d-1), and X ０ａ represents X in formula (A-2d-1). ０ In the case where two carbon atoms a and b, b and c, or c and d in formula (Ar01) are bonded to each other, X in formula (A-2d) or formula (A-2d-1) ０ forms a condensed ring with the monocyclic moiety containing

[0071] Here, X ０ The monocyclic moiety containing the following formula (AP011) in formula (A-2d) represents a monocyclic ring represented by the following formula (AP011):

[0072] As the skeleton represented by formula (A-2d), a skeleton represented by formula (A-2d-1) above, a skeleton represented by formula (A-2d-2) below, or a skeleton represented by formula (A-2d-3) below is preferred. (In formula (A-2d-2) and formula (A-2d-3), R １１ , Ar, and X ０ respectively represent R in formula (A-2d). １１ , Ar, and X ０ L represents a single bond or a divalent linking group, and examples of the divalent linking group include -O-, -S-, and -SO ２ -, -CO-, -CONH-, -COO-, -NR １０１ -, - (CR １０２ R １０３ ) m １ -, -(Ar １０１ ) m ２ -, -CH ２ -(Ar １０１ ) m ２ -CH ２ - or -(cyclo-R)-. １０１, R １０２ , and R １０３ each independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10. １０１ each independently represents an arylene group having 6 to 30 carbon atoms; m ２ represents an integer of 1 to 3, which is the number of aromatic rings bonded to each other by single bonds. "cyclo-R" represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring, preferably a 6- to 8-membered ring, which may form a condensed ring with one or two benzene or naphthalene rings. R ２２ each independently represents an optionally substituted arylene group having 6 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms.

[0073] <Formula (A-2e)> (In formula (A-2e), L represents a single bond or a divalent linking group between any two carbon atoms constituting each azaaryl fused ring, R １１ and R ２１ each independently represents a hydrogen atom or a residue of an aromatic ring; R １２ and R ２２ each independently represents a substituent, n1 and n2 each independently represent R １２ and R ２２ represents the number of substituents, which may be 0, １ and Ar ２ are each independently a benzene ring or a fused ring composed of 2 to 3 benzene rings, which forms a fused ring with the pyrrole ring moiety in formula (A-2e).

[0074] In the unit structure (A), R in formula (A-2e) １１ and R ２１ may be a substituent. １１ and R ２１ is a substituent or a residue of an aromatic group, R １１ and R ２１represents, for example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) may be further substituted with an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, an aryl group, or a halo group, and that (iii) may have the hydrocarbon chain portion further interrupted by an oxygen-atom-containing substituent, a sulfur-atom-containing substituent, a nitrogen-atom-containing substituent, or an arylene group.

[0075] In formula (A-2e), L is a single bond or a divalent linking group. L may be bonded to any carbon atom constituting each azaaryl fused ring, and Ar １ and Ar ２ , i.e., in the azaaryl fused ring and However, it is preferably bonded to a carbon atom constituting the pyrrole ring moiety in the azaaryl fused ring.

[0076] Preferred linking groups (L) include —O—, —S—, and —SO ２ -, -CO-, -CONH-, -COO-, -NH-, -(CR １０２ R １０３ ) m １ -, - (Ar １０１ ) m ２ -, -CH ２ -(Ar １０１ ) m ２ -CH ２ -, and -(cyclo-R)-. １０２ and R １０３ each independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10. １０１ each represents an arylene group having 6 to 30 carbon atoms; m ２represents the number of aromatic rings bonded to each other by single bonds, an integer of 1 to 3. "cyclo-R" represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring, preferably a 6- to 8-membered ring, which may form a condensed ring with one or two benzene rings or naphthalene rings.

[0077] <Formula (A-3a) and Formula (A-3b)> (In the formula, Ar ３１ and Ar ３２ each independently represents a residue of an aromatic ring, or together with the carbon atom bound thereto represents a residue of an aromatic ring. X is —O, —S—, —NH—, —CH ２ -, -CH ２ -CH ２ - or -CH=CH-.)

[0078] Ar ３１ and Ar ３２ Examples of the aromatic ring in the aromatic ring residue include the aromatic ring represented by the above formula (G1). ３１ and Ar ３２ Examples of the aromatic ring that is formed by combining with the carbon atom to which it is bonded include a fluorene ring, a benzofluorene ring, and a dibenzofluorene ring.

[0079] Examples of the skeleton represented by formula (A-2a) include the following skeletons. The aromatic rings in these skeletons may have a substituent, and the hydrogen atoms of the NH groups may be replaced with substituents. The same applies to the following skeletons.

[0080] Examples of the skeleton represented by formula (A-2b-1) include the following skeletons:

[0081] Examples of the skeleton represented by formula (A-2b-2) include the following skeletons:

[0082] Examples of the skeleton represented by formula (A-2c-1) include the following skeletons:

[0083] Examples of the skeleton represented by formula (A-2c-2) or formula (A-2c-3) include the following skeletons:

[0084] Examples of the skeleton represented by formula (A-2c-4) include the following skeletons:

[0085] Examples of the skeleton represented by formula (A-2d) include the following skeletons:

[0086] Examples of the skeleton represented by formula (A-2e) include the following skeletons: Note that specific examples of the skeleton represented by formula (A-2d) and specific examples of the skeleton represented by formula (A-2e) may overlap.

[0087] Examples of the skeleton represented by formula (A-3a) include the following skeletons:

[0088] Examples of the skeleton represented by formula (A-3b) include the following skeletons:

[0089] Other examples of the nitrogen-containing aromatic heterocyclic skeleton include the following skeletons.

[0090] <<<A-4-3: Phenol Skeleton>>> The phenol skeleton refers to a skeleton having an aromatic ring and a hydroxy group bonded to the aromatic ring. The number of hydroxy groups bonded to the aromatic ring of the phenol skeleton is not particularly limited and may be one or more. When there are more than one hydroxy groups, the number may be 2 to 10 or 2 to 8. When there are more than one hydroxy groups, the hydroxy groups may be bonded to the same aromatic ring (for example, a benzene ring) or to different aromatic rings. In unit structure (A), the hydrogen atom of the hydroxy group bonded to the aromatic ring may be replaced with a substituent. Examples of the substituent include the substituents described in (I-3) "Aromatic Ring" above, the substituents described in (A-2) "Examples of Skeletons Constituting Unit Structure (A)" above, and the substituents (S) represented by formulas (S1) to (S7) described below.

[0091] Examples of the phenol skeleton include skeletons represented by the following formula (A-4). The aromatic ring in these skeletons may have a substituent, and the hydrogen atom of the hydroxy group may be substituted with a substituent. The same applies to the following skeletons. (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent an integer of 1 to 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent an integer of 0 to 4, provided that the sum of n3a and n3b ​​is 1 or more, the sum of n7a and n7b is 1 or more, and the sum of n8a and n8b is 1 or more.)

[0092] Examples of the phenol skeleton include skeletons represented by the following formula (A-5a), (A-5b), (A-5c), or (A-5d). (In the formula, Ar ４１ each independently represents a residue of an aromatic ring; k1 and k2 each independently represent an integer of 1 or 2. X １ is -O-, -CO-, -S-, -SO ２ - or an alkylene group optionally substituted with a halogen atom. ２１ represents a single bond, —O—, —CO—, —S—, or —SO２ When k2 is 1, X represents - or an alkylene group which may be substituted with a halogen atom. ２２ represents a single bond, —O—, —CO—, —S—, or —SO ２ When k1 is 2, X represents - or an alkylene group which may be substituted with a halogen atom. ２１ represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom; ２２ represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. １ represents a trivalent saturated hydrocarbon group. ２ represents a tetravalent saturated hydrocarbon group. m1 and m2 each independently represent an integer of 0 to 3, provided that the sum of m1 and m2 is 1 or more. m3 to m5 each independently represent an integer of 0 to 3, provided that the sum of m3 to m5 is 1 or more. m6 to m8 each independently represent an integer of 0 to 3, provided that the sum of m6 to m8 is 1 or more. m9 to m12 each independently represent an integer of 0 to 3, provided that the sum of m9 to m12 is 1 or more.

[0093] Ar ４１ Examples of the aromatic ring in the residue of the aromatic ring include aromatic rings represented by the following formula (G3): These aromatic rings may have a substituent.

[0094] X １ , and X ２ The number of carbon atoms in the alkylene group which may be substituted with a halogen atom in the formula (I) is, for example, 1 to 20. The structure of the alkylene group may be, for example, linear, branched, cyclic, or a combination of two or more thereof. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0095] Y １ , and Y ２ The number of carbon atoms in the saturated hydrocarbon group in the formula (I) is, for example, 1 to 20. The structure of the saturated hydrocarbon group may be, for example, linear, branched, or cyclic, or a combination of two or more thereof.

[0096] Examples of the phenol skeleton include skeletons represented by the following formula (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d). (In formula (A-6a), formula (A-6b-1), formula (A-6b-2), formula (A-6c), and formula (A-6d), Ar ５１ each independently represents a residue of an aromatic ring. Each n11 independently represents an integer of 1 to 4. Each p independently represents 0 or 1. When p is 1, the oxygen atom forms an ether bond to bridge the aromatic rings, and when p is 0, there is no ether bond to form a bridge between the aromatic rings. L represents a single bond or a divalent linking group.

[0097] Ar ５１ Examples of the aromatic ring in the formula (G1) include aromatic rings represented by the above formula (G1), and a benzene ring or a naphthalene ring is preferred. Examples of L include divalent groups obtained by removing two hydrogen atoms from the following structure:

[0098] n11 each independently represents 1 or 2, for example.

[0099] Examples of the phenol skeleton include skeletons represented by the following formula (A-7a), (A-7b), or (A-7c). (In formula (A-7a), formula (A-7b), and formula (A-7c), Ar ６１ each independently represents a residue of an aromatic ring; and each n21 independently represents an integer of 1 to 4.

[0100] Ar ６１ Examples of the aromatic ring in the formula (G1) include aromatic rings represented by the above formula (G1), and a benzene ring and a naphthalene ring are preferred. n21 each independently represents 1 or 2, for example.

[0101] Furthermore, examples of the phenol skeleton include skeletons represented by the following formula (A-8a-1), (A-8a-2), (A-8b), (A-8c), (A-8d), (A-8e), (A-8f), (A-8g-1), or (A-8g-2). In formula (A-8a-1), formula (A-8b), formula (A-8c), formula (A-8e), formula (A-8f), formula (A-8g-1), and formula (A-8g-2), n31 each independently represents an integer of 1 to 4. In formula (A-8a-2), n32 and n33 each independently represent an integer of 0 to 4, provided that the sum of n32 and n33 is 1 or more. In formula (A-8d), n32 and n33 each independently represent an integer of 0 to 4, provided that the sum of n32 and n33 is 1 or more. In formula (A-8b), X １ represents —O— or —NH—. ２ is —O—, —S—, or —CH ２ In formula (A-8e), X ３ is -S-, -CH ２ In formula (A-8f), X represents - or -NH-. ４ represents —CO— or —O—, and X ５ is -CH ２ represents - or -O-.)

[0102] For example, n31 each independently represents 1 or 2. n32 and n33 each independently represents 0, 1 or 2.

[0103] Examples of the skeleton represented by formula (A-4) include the following skeletons. The aromatic rings in these skeletons may have a substituent, and the hydrogen atoms of the hydroxy groups may be substituted with a substituent. The same applies to the following skeletons.

[0104] Examples of the skeleton represented by formula (A-5a) include the following skeletons:

[0105] Examples of the skeleton represented by formula (A-5b) include the following skeletons:

[0106] Examples of the skeleton represented by formula (A-5c) include the following skeletons:

[0107] Examples of the skeleton represented by formula (A-5d) include the following skeletons:

[0108] Examples of the skeleton represented by formula (A-6a) include the following skeletons:

[0109] Examples of the skeleton represented by formula (A-6b-1) or formula (A-6b-2) include the following skeletons:

[0110] Examples of the skeleton represented by formula (A-6c) include the following skeletons:

[0111] Examples of the skeleton represented by formula (A-6d) include the following skeletons:

[0112] Examples of the skeleton represented by formula (A-7a), formula (A-7b), or formula (A-7c) include the following skeletons.

[0113] Examples of the skeleton represented by formula (A-8a-1) or formula (A-8a-2) include the following skeletons:

[0114] Examples of the skeleton represented by formula (A-8b) include the following skeletons:

[0115] Examples of the skeleton represented by formula (A-8c) include the following skeletons:

[0116] Examples of the skeleton represented by formula (A-8d) include the following skeletons:

[0117] Examples of the skeleton represented by formula (A-8e) include the following skeletons:

[0118] Examples of the skeleton represented by formula (A-8f) include the following skeletons:

[0119] Examples of the skeleton represented by formula (A-8g-1) or formula (A-8g-2) include the following skeletons.

[0120] Examples of other skeletons besides the phenol skeleton include the following skeletons.

[0121] Furthermore, the H of NH in the skeleton having an aromatic ring, the H of a hydroxy group bonded to the aromatic ring in the skeleton having an aromatic ring, and the hydrogen atom bonded to the aromatic ring in the skeleton having an aromatic ring may be replaced with a substituent. Examples of the substituent include the substituents (S) represented by the following formulae (S1) to (S7).

[0122] (In formulas (S1) to (S7), R ｓａ represents a monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｂ R each independently represents a single bond or a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｃ R each independently represents a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｄ ａｌｋｙｎｙｌ each independently represents an alkynyl group having 2 to 4 carbon atoms. ｓａ each independently represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. ｓｂ each independently represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. ｓａ and X ｓｂ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or X ｓａ and X ｓｂtogether with the carbon atom bonded to the hydroxy group, form a carbonyl group. n represents an integer of 0 to 5. * represents a bond.

[0123] <R ｓａ > R ｓａ Examples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms in the formula (I) include an alkyl group having 1 to 10 carbon atoms and a monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms. The monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When the monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, all may be carbon-carbon triple bonds, or may be a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated.

[0124] <R ｓｂ , and R ｓｃ > R ｓｂ , and R ｓｃ In the formula, examples of the divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms include an alkylene group having 1 to 10 carbon atoms and a divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms. The divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When the divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, all may be carbon-carbon triple bonds, or may be a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated. R ｓｂ , and R ｓｃ Examples of the group include the following groups: (* represents a bond.)

[0125] <R ｓｄ ａｌｋｙｎｙｌ > R ｓｄ ａｌｋｙｎｙｌrepresents an alkynyl group having 2 to 4 carbon atoms. Examples of the alkynyl group having 2 to 4 carbon atoms include an ethynyl group, a 1-propynyl group, and a propargyl group (2-propynyl group).

[0126] <Ar ｓａ > Ar ｓａ The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in the formula (I) is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0127] <Ar ｓｂ > Ar ｓｂ The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms in the formula (I) is a residue obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, and biphenyl.

[0128] <X ｓａ and X ｓｂ > X ｓａ and X ｓｂ In the formula (I), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the monovalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms. A monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0129] Examples of the substituent represented by formula (S1) include the following groups. (* represents a bond.)

[0130] Examples of the substituent represented by formula (S2) include the following groups. (* represents a bond.)

[0131] Examples of the substituent represented by formula (S3) include the following groups. (* represents a bond.)

[0132] Examples of the substituent represented by formula (S4) include the following groups. (* represents a bond.)

[0133] Examples of the substituent represented by formula (S5) include the following groups. (* represents a bond.)

[0134] Examples of the substituent represented by formula (S6) include the following groups. (* represents a bond.)

[0135] Examples of the substituent represented by formula (S7) include the following groups. (* represents a bond.)

[0136] Examples of other substituents include the following groups: (* represents a bond.)

[0137] The unit structure (A) is preferably at least one selected from the following: Note that the positions of the two bonds shown in each unit structure shown below are shown merely for convenience, and each bond can extend from any possible carbon atom, and the positions are not limited thereto.

[0138] (Examples of unit structures composed of aromatic amine skeletons) -NH- can also have a structure in which the hydrogen atom on the N is substituted.

[0139]

[0140] (Examples of unit structures composed of nitrogen-containing aromatic heterocyclic skeletons)

[0141] (Example of a unit structure composed of a phenol skeleton)

[0142] <<B-1: Unit Structure (B)>> The unit structure (B) has one or more carbon atoms. The unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. The unit structure (B) is one or more types of unit structures containing a linking carbon atom bonding to an aromatic ring in the unit structure (A) [see (I-1) above], and includes, for example, a structure represented by the formula (B1), (B2), or (B3) shown below. The unit structure (B) can link two unit structures (A) by forming a covalent bond with the unit structure (A).

[0143] <<<B-2: Unit structure (BI)>>> The unit structure (B) contains a unit structure (BI). The unit structure (BI) has a quaternary carbon atom bonded to a carbon atom constituting the aromatic ring of the unit structure (A). Here, the unit structure (BI) is a subordinate concept of the unit structure (B) and does not refer to a partial structure of the unit structure (B). The unit structure (BI) will be described below.

[0144] <<<B-3: Formula (B1)>>> The unit structure (BI) includes, for example, a structure represented by the following formula (B1): The unit structure (BI) may be a structure represented by the following formula (B1): In formula (B1), R and R' each independently represent an aromatic ring having 6 to 30 carbon atoms, which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms, which may have a substituent, or a linear, branched, or cyclic alkyl group having 10 or less carbon atoms, which may have a substituent. R and R' may form a ring structure together with the carbon atom to which they are bonded. * represents a bond. The central carbon atom in formula (B1) is a quaternary carbon atom bonded to a carbon atom constituting the aromatic ring of unit structure (A).

[0145] Examples of the substituent include a hydroxy group, a carboxy group, a formyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a group in which H in a hydroxy group has been substituted with the above-mentioned substituent (S), and a halo group.

[0146] Furthermore, the two bonds in formula (B1) can be covalently bonded to the aromatic rings in the two structural units (A), respectively.

[0147] In the definitions of R and R' in formula (B1), the "aromatic ring" and "heterocycle" can be seen in (I-3) and (I-4) above.

[0148] In the definition of R and R′ in formula (B1), examples of the “alkyl group” 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, a 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-dimethyl-n-butyl group ethyl 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 cyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,Examples of the cyclopropyl group 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, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0149] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, or pyrenyl.

[0150] Examples of the ring structure formed by R and R' together with the carbon atoms to which they are bonded include structures represented by the following formulas. (In the formula, each Ar independently represents a residue of an aromatic ring. The carbon atom marked with * is the carbon atom bonded to R and R′ in formula (B1).)

[0151] Examples of the aromatic ring of Ar include aromatic rings represented by formula (G1).

[0152] The unit structure (B) containing the structure represented by formula (B1) is derived from, for example, a ketone compound. Examples of the ketone compound include compounds represented by the following formula (B-1b): (In formula (B-1b), R and R' have the same meanings as R and R' in formula (B1), respectively. In formula (B-1b), R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded.)

[0153] For example, in obtaining resin (G), the carbonyl group in formula (B-1b) is converted to *-C-* in formula (B1).

[0154] Some specific examples of the unit structure (B) containing the structure represented by formula (B1) are as follows. * basically indicates the bonding site with the unit structure (A). Needless to say, the structure may contain the exemplified structure as a part of the whole.

[0155] Examples include those having more than two bonds (*), but these excess bonds can be used for bonding to an aromatic ring in another polymer chain, for crosslinking, or for other purposes, or they can be bonds to hydrogen bonds.

[0156]

[0157] <<<B-4: Formula (B2)>>> The unit structure (B) in the resin (G) may include a unit structure other than the unit structure (BI) (hereinafter also referred to as "unit structure (B-II)"). The unit structure (B-II) includes, for example, a structure represented by the following formula (B2). The unit structure (B-II) may be a structure represented by the following formula (B2).

[0158] In formula (B2), Z ０ represents an aromatic ring residue or aliphatic ring residue having 6 to 30 carbon atoms, which may have a substituent, or an organic group in which two or more aromatic or aliphatic rings are linked by a single bond. Examples of the organic group in which two or more aromatic rings or aliphatic rings are linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and bicyclohexyl.

[0159] Examples of the substituent include a hydroxy group, a carboxy group, a formyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a group in which H in a hydroxy group has been substituted with the above-mentioned substituent (S), and a halo group.

[0160] J １ and J ２ each independently represents a divalent organic group which may have a direct bond or a substituent. The divalent organic group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, an aryl group (e.g., a phenyl group, a substituted phenyl group), or a halo group (e.g., fluorine) as a substituent. Examples of linear alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0161] The unit structure (B) containing the structure represented by formula (B2) is derived from, for example, a compound having a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom, a compound having a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (e.g., the benzylic carbon atom) of an alkylaryl group, or a compound having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0162] Examples of compounds having a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom include compounds represented by the following formula (B-2a): Compounds having a hydroxyl group, an alkoxy group, or a halo group bonded to the α-carbon atom (such as the benzylic carbon atom) of an alkylaryl group include compounds represented by the following formula (B-2b): Compounds having two carbon-carbon double bonds include compounds represented by the following formula (B-2c) or (B-2d): (In formula (B-2a), formula (B-2b), and formula (B-2b), J １ , J ２ , and Z ０ is J in formula (B2) １ , J ２ , and Z ０ In formula (B-2a), X ａ , and X ｂ each independently represents a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom. ａ , and Y ｂ each independently represents a hydroxyl group, an alkoxy group, or a halo group bonded to the α-position carbon atom (e.g., the benzyl-position carbon atom) of the alkylaryl group. In formula (B-2d), n represents an integer of 0 to 4.

[0163] For example, when obtaining resin (G), X in formula (B-2a) ａ -J １ is *-J in formula (B2). １ It is converted into ２ -X ｂ is J in formula (B2) ２For example, when resin (G) is obtained, Y in formula (B-2b) is converted to -*. ａ -J １ is *-J in formula (B2). １ It is converted into ２ -Y ｂ is J in formula (B2) ２ It is converted to -*.

[0164] An example of formula (B-2a) is the following compound:

[0165] An example of formula (B-2b) is the following compound:

[0166] An example of formula (B-2c) is the following compound:

[0167] Some specific examples of unit structures containing the structure represented by formula (B2) are as follows. * indicates the bonding site with the unit structure (A). Needless to say, the unit structure may contain the exemplified structure as a part of the whole.

[0168]

[0169] <<<B-5: Formula (B3)>>> The unit structure (B-II) includes, for example, a structure represented by the following formula (B3): The unit structure (B-II) may be a structure represented by the following formula (B3): In formula (B3), Z is a group having a monocyclic ring or a bicyclic, tricyclic, or tetracyclic fused ring, which may have a substituent, and which has 4 to 25 carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the monocyclic ring or the bicyclic, tricyclic, or tetracyclic fused ring excluding the substituent, and does not include the number of heteroatoms constituting the heterocyclic ring when the monocyclic ring or the fused ring is a heterocyclic ring.

[0170] The monocycle is a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more) (hereinafter, may be referred to as a "non-Hückel monocycle"); at least one of the monocycles constituting the bicycle, tricycle, and tetracycle is a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more), and the remaining monocycles may be either a monocycle having a π electron number that satisfies 4n+2 (n is an integer of 0 or more) or a monocycle having a π electron number that does not satisfy 4n+2 (n is an integer of 0 or more).

[0171] The monocyclic or bicyclic, tricyclic, or tetracyclic fused ring may further form a fused ring with one or more aromatic rings to form a pentacyclic or higher fused ring, and the pentacyclic or higher fused ring preferably has 40 or less carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the pentacyclic or higher fused ring excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the pentacyclic or higher fused ring is a heterocyclic ring.

[0172] X and Y may be the same or different and each represent -CR ３１ R ３２ represents a - group, and R ３１ and R ３２ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0173] x and y represent the numbers X and Y, respectively, and each independently represents 0 or 1.

[0174] In formula (B3), and in formula (B3) At least one of the above is bonded to any carbon atom constituting the non-Hückel monocycle of Z (referred to as "carbon atom Z") (when x = 1, y = 1) or extends from carbon atom Z (when x = 0, y = 0).

[0175] For example, in formula (B3), is bonded to any carbon atom constituting the non-Hückel monocyclic ring of Z (referred to as "carbon atom 1") (when x = 1) or extends from carbon atom 1 (when x = 0),

[0176] In formula (B3), is bonded to any of the carbon atoms (referred to as "carbon atom 2") constituting the non-Hückel monocycle of Z (when y = 1) or extends from carbon atom 2 (when y = 0), and carbon atom 1 and carbon atom 2 may be the same or different, and if they are different, they may belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0177] Furthermore, formula (B3) may optionally contain linking carbon atoms other than carbon atom 1 and carbon atom 2. When Z is a tricyclic or higher fused ring, the permutation position relationship between one or two non-Hückel monocycles to which carbon atoms 1 and 2 in formula (B3) belong and the remaining monocycles is arbitrary, and when carbon atom 1 and carbon atom 2 belong to different non-Hückel monocycles (referred to as "non-Hückel monocycle 1" and "non-Hückel monocycle 2," respectively), the permutation position relationship between non-Hückel monocycle 1 and non-Hückel monocycle 2 in the fused ring is also arbitrary. Some specific examples of organic groups containing a structure represented by formula (B3) are as follows. The bonding site with unit structure (A) is not particularly limited. Needless to say, a structure containing the exemplified structure as a part of the whole may also be used.

[0178] Examples include those having more than two bonds (*), but these excess bonds can be used for bonding to an aromatic ring in another polymer chain, for crosslinking, or for other purposes, or they can be bonds to hydrogen bonds.

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185] Hereinafter, in formula (B3), and in formula (B3) In this case, only one of the carbon atoms constituting the non-Hückel monocycle of Z (referred to as "carbon atom Z") is bonded (when x = 1, y = 1) or extends from carbon atom Z (when x = 0, y = 0). As a more specific structure of formula (B3) in this case, for example, in the following formula (C31), p and k which can be bonding hands are １ and k ２ Among them, p and k １ , or p and k ２ The remaining bond is bonded to a hydrogen atom.

[0186] In addition, in the following formula (C32), p and k which can be bonding hands １ , k ２ and m, p and k １ , p and k ２ , or depending on p and m, it can be a unit structure (B) represented by formula (B3). The remaining bond is bonded to a hydrogen atom.

[0187] Some specific examples of formula (B3) corresponding to formula (C31) or formula (C32) are as follows: * indicates the bonding site with the unit structure (A).

[0188] In formula (B3), a bond extends from the aromatic ring in each of these structures to another unit structure (for example, unit structure (A)), but in the specific examples below, such a bond is omitted. Needless to say, the unit structure may include the exemplified structure as a part of the whole. In the above specific examples, when there is no bond from the aromatic ring, it can be a specific example of a polymer terminal.

[0189] <<<B-6: Formula (B4)>>> The unit structure (B-II) includes, for example, a structure represented by the following formula (B4): The unit structure (B-II) may be a structure represented by the following formula (B4):

[0190] In formula (B4), R and R' each independently represent a hydrogen atom, an aromatic ring having 5 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear or branched alkyl group having 10 or less carbon atoms which may have a substituent. R and R' may form a structure having a ring structure together with the carbon atom to which they are bonded. * represents a bond.

[0191] Examples of the substituent include a hydroxy group, a carboxy group, a formyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a group in which H in a hydroxy group has been substituted with the above-mentioned substituent (S), and a halo group.

[0192] Furthermore, the two bonds in formula (B4) can be covalently bonded to the aromatic rings in the two structural units (A), respectively.

[0193] In the definitions of R and R' in formula (B4), the "aromatic ring" and "heterocycle" can be seen in (I-3) and (I-4) above.

[0194] In the definitions of R and R' in formula (B4), the "alkyl group" can be the same as the groups defined for R and R' in formula (B1).

[0195] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, or pyrenyl.

[0196] Examples of the ring structure formed by R and R' together with the carbon atoms to which they are bonded include structures represented by the following formulas. (In the formula, each Ar independently represents a residue of an aromatic ring. The carbon atom marked with * is the carbon atom bonded to R and R′ in formula (B4).)

[0197] Examples of the aromatic ring of Ar include aromatic rings represented by formula (G1).

[0198] The unit structure (B-II) including the structure represented by formula (B4) is derived from, for example, an aldehyde compound or a ketone compound. Examples of the aldehyde compound include the compound represented by formula (B-1a) above. Examples of the ketone compound include the compound represented by formula (B-1b) above.

[0199] Some specific examples of the unit structure (B-II) containing the structure represented by formula (B4) are as follows. * basically indicates the bonding site with the unit structure (A). Needless to say, the structure may contain the exemplified structure as a part of the whole.

[0200] The novolak resin having the structure represented by formula (AB) can be prepared by a known method. For example, a compound having a ring represented by H-A-H and OHC-B, O═C-B, RO-B-OR, RO-CH ２ -B-CH ２ It can be prepared by condensing an oxygen-containing compound represented by —OR, etc. In the formula, A and B are as defined above, and R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0201] The ring-containing compound and the oxygen-containing compound may each be used alone or in combination of two or more. In this condensation reaction, the oxygen-containing compound can be used in an amount of 0.1 to 10 moles, preferably 0.1 to 2 moles, per mole of the ring-containing compound.

[0202] Examples of the catalyst used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid, and carboxylic acids such as formic acid and oxalic acid. The amount of catalyst used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass per 100 parts by mass of the ring-containing compound (or the total amount of ring-containing compounds when multiple types are used).

[0203] The condensation reaction can be carried out without a solvent, but is usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrates and does not inhibit the reaction. Examples of the solvent include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, tetrahydropyran, dioxane, 1,2-dichloromethane, 1,2-dichloroethane, toluene, N-methylpyrrolidone, and dimethylformamide. The condensation reaction temperature is usually 40°C to 200°C, preferably 100°C to 180°C. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 50 hours, preferably 5 minutes to 24 hours.

[0204] The weight average molecular weight of the novolak resin according to one embodiment of the present invention is usually 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0205] The content of the resin (G) in the composition for forming a resist underlayer film is, for example, preferably 25 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 70 to 100 mass %, based on the mass of the film-forming components. Here, the film-forming components refer to the components remaining after excluding the solvent component from the composition for forming a resist underlayer film.

[0206] The molar ratio ((A):(B)) of the unit structure (A) to the unit structure (B) in the resin (G) is, for example, preferably 1:1 to 1:2, more preferably 1:1.2 to 1:2, even more preferably 1:1.4 to 1:2, and particularly preferably 1:1.5 to 1:2. The molar ratio of the unit structure (A) to the unit structure (B) in the resin (G) can also be expressed as the molar ratio of the compound (A) that serves as the raw material for the unit structure (A) to the compound (B) that serves as the raw material for the unit structure (B). The molar ratio ((A):(B)) of the compound (A) to the compound (B) is, for example, preferably 1:1 to 1:2, more preferably 1:1.2 to 1:2, even more preferably 1:1.4 to 1:2, and particularly preferably 1:1.5 to 1:2. Here, the compound (A) may be one type or two or more types. Similarly, the compound (B) may be one type or two or more types.

[0207] The content (molar ratio ((A-I) / (A))) of the unit structure (A) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and may even be 100 mol%. The content (molar ratio) of the unit structure (A) can also be expressed as the molar ratio of the compound (A-I) that is the raw material for the unit structure (A-I) in the compound (A). The molar ratio of compound (A-I) in compound (A) ((A-I) / (A)) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and may be 100 mol%.

[0208] The content (molar ratio ((B-I) / (B))) of the unit structure (B) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and may even be 100 mol%. The content (molar ratio) of the unit structure (B) can also be expressed as the molar ratio of the compound (B-I) that is the raw material for the unit structure (B-I) in the compound (B). The molar ratio of compound (B-I) in compound (B) ((B-I) / (B)) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and may be 100 mol%.

[0209] Resin (G) is preferably a resin synthesized by polymerizing at least one compound having a bisphenol skeleton with three or more aromatic hydrocarbon rings with at least one aromatic ketone or aliphatic ketone in the presence of an acid catalyst. Examples of the compound having a bisphenol skeleton include bisphenols represented by formula (1A) described in (A-3) above. Examples of aromatic ketones or aliphatic ketones include the ketone compounds described in (B-3) above, as well as compounds represented by formulas (K1) and (K2) below.

[0210]

[0211]

[0212] The acid catalyst may be at least one selected from the group consisting of acids and salts thereof, and acid generators, which will be described later.

[0213] <Solvent> The composition for forming a resist underlayer film, which is one embodiment of the present invention, contains a solvent.

[0214] The solvent is not particularly limited as long as it can dissolve the specific novolak resin and other optional components added as needed.

[0215] Examples of the solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate,Isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate Examples of suitable solvents include methyl acetoacetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

[0216] Also, solvents with boiling points of 160°C or higher can be included in combination with solvents with boiling points below 160°C.

[0217] As such a high-boiling point solvent, for example, the following compounds described in WO 2018 / 131562 (A1) can be preferably used.

[0218] [R in formula (i)] １ , R ２ and R ３each represent a hydrogen atom, an oxygen atom, a sulfur atom, or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and may be the same or different from each other and may be bonded to each other to form a ring structure.] Alternatively, 1,6-diacetoxyhexane (boiling point 260°C) and tripropylene glycol monomethyl ether (boiling point 242°C) described in JP-A No. 2021-84974, as well as various other high-boiling point solvents described in paragraph 0082 of the same publication, can be preferably used.

[0219] Alternatively, dipropylene glycol monomethyl ether acetate (boiling point 213°C), diethylene glycol monoethyl ether acetate (boiling point 217°C), diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol dimethyl ether (boiling point 171°C), dipropylene glycol monomethyl ether (boiling point 187°C), dipropylene glycol monobutyl ether (boiling point 231°C), tripropylene glycol monomethyl ether (boiling point 247°C), di ... Preferred examples of high-boiling solvents that can be used include dimethyl ether (boiling point 242°C), γ-butyrolactone (boiling point 204°C), benzyl alcohol (boiling point 205°C), propylene carbonate (boiling point 242°C), tetraethylene glycol dimethyl ether (boiling point 275°C), 1,6-diacetoxyhexane (boiling point 260°C), dipropylene glycol (boiling point 230°C), 1,3-butylene glycol diacetate (boiling point 232°C), and various other high-boiling solvents described in paragraphs 0023 to 0031 of the publication.

[0220] The composition for forming a resist underlayer film, which is one embodiment of the present invention, may contain an acid and / or a salt thereof and / or an acid generator.

[0221] Examples of the acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid.

[0222] The salt may be a salt of the above-mentioned acid, and is not limited thereto, but suitable salts include ammonia derivative salts such as trimethylamine salts and triethylamine salts, pyridine derivative salts, and morpholine derivative salts.

[0223] The acid and / or salt thereof may be used singly or in combination of two or more kinds, and the blending amount is usually 0.0001 to 20 mass %, preferably 0.0005 to 10 mass %, and more preferably 0.01 to 5 mass %, based on the total solid content.

[0224] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0225] Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0226] Photoacid generators generate acid when the resist is exposed to light. This allows the acidity of the underlayer film to be adjusted. This is one way to match the acidity of the underlayer film to that of the upper layer resist. Adjusting the acidity of the underlayer film also allows for adjustment of the pattern shape of the upper layer resist.

[0227] Examples of the photoacid generator contained in the composition for forming a resist underlayer film of the present invention include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0228] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0229] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0230] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0231] The acid generators may be used singly or in combination of two or more.

[0232] When an acid generator is used, the proportion thereof is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass, relative to 100 parts by mass of the solid content of the composition for forming a resist underlayer film.

[0233] The composition for forming a resist underlayer film, which is one embodiment of the present invention, may contain, in addition to the above, a crosslinking agent, a surfactant, a light absorbing agent, a rheology adjuster, an adhesion aid, and the like, as necessary.

[0234] Representative examples of the crosslinking agent include an aminoplast crosslinking agent and a phenoplast crosslinking agent.

[0235] As the crosslinking agent, a crosslinking agent having high heat resistance can be used, and as the crosslinking agent having high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0236] Aminoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, and polymers thereof. Crosslinking agents having at least two crosslink-forming substituents are preferred, including compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and methoxymethylated thiourea. Condensates of these compounds can also be used.

[0237] Preferably, it is at least one selected from the group consisting of tetramethoxymethyl glycoluril and hexamethoxymethyl melamine.

[0238] Some specific examples are as follows:

[0239]

[0240] Phenoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated aromatics, their polymers, and the like. Preferred crosslinking agents have at least two crosslink-forming substituents per molecule, such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Condensates of these compounds can also be used.

[0241] In addition to the above, other examples of such compounds include compounds having a partial structure of the following formula (4) and polymers or oligomers having a repeating unit of the following formula (5).

[0242] The above R １１ , R １２ , R １３ , and R １４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the above-mentioned examples of these alkyl groups can be used. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5-n1), and (n1+n2) is an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is an integer of 0 to (4-n3), and (n3+n4) is an integer of 1 to 4. Oligomers and polymers having a repeating unit structure number of 2 to 100 or 2 to 50 can be used.

[0243] Some specific examples are as follows:

[0244]

[0245]

[0246]

[0247]

[0248] The crosslinking agents, such as aminoplast crosslinking agents and phenoplast crosslinking agents, may be used alone or in combination of two or more. The aminoplast crosslinking agent may be produced by a known method or a method equivalent thereto, or a commercially available product may be used.

[0249] The amount of the crosslinking agent, such as an aminoplast crosslinking agent or a phenoplast crosslinking agent, used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, and the like, but is 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.5 mass % or more, or 1.0 mass % or more, and is 80 mass % or less, 50 mass % or less, 40 mass % or less, 20 mass % or less, or 10 mass % or less, relative to the total solids content of the composition for forming a resist underlayer film of the present invention.

[0250] The composition for forming a resist underlayer film according to the present invention can contain a surfactant in order to prevent pinholes, striations, etc., and to further improve the coatability for preventing surface irregularities.

[0251] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Examples of suitable surfactants include fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, and R-40 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), and Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0252] The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the composition for forming a resist underlayer film according to the present invention. These surfactants may be added alone or in combination of two or more.

[0253] Examples of the light absorber include commercially available light absorbers described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as C.I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; C.I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; C.I. C.I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; C.I. Disperse Violet 43; C.I. Disperse Blue 96; C.I. Fluorescent Brightening Agent 112, 135, and 163; C.I. Solvent Orange 2 and 45; C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, and 49; C.I. Pigment Green 10; C.I. Pigment Brown 2, etc. can be suitably used. The light-absorbing agent is usually blended in an amount of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the composition for forming a resist underlayer film according to the present invention.

[0254] The rheology modifier is added primarily to improve the fluidity of the resist underlayer film-forming composition, thereby improving the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes, particularly during the baking process. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di(n-butyl) maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition of the present invention.

[0255] The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the composition for forming a resist underlayer film, and particularly to prevent peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; Examples of the adhesion promoter include silanes such as silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion promoters are typically blended in an amount of less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the composition for forming a resist underlayer film according to the present invention.

[0256] The solids content of the composition for forming a resist underlayer film according to the present invention is 0.1 to 70% by mass, or 0.1 to 60% by mass. The solids content is the content of all components excluding the solvent from the composition for forming a resist underlayer film. The solids content may contain a crosslinkable resin in an amount of 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass.

[0257] [Resist Underlayer Film] The resist underlayer film can be formed, for example, as follows using the composition for forming a resist underlayer film according to the present invention.

[0258] Substrates used in the manufacture of semiconductor devices (e.g., silicon wafer substrates, silicon dioxide coated substrates (SiO ２ The resist underlayer film forming composition according to one embodiment of the present invention is applied onto a substrate (e.g., a silicon nitride substrate (SiN substrate), a silicon oxynitride substrate (SiON substrate), a titanium nitride substrate (TiN substrate), a tungsten substrate (W substrate), a glass substrate, an ITO substrate, a polyimide substrate, or a substrate coated with a low dielectric constant material (low-k material)) by a suitable application method such as a spinner or coater, and then baked using a heating means such as a hot plate to form a resist underlayer film. Baking conditions are appropriately selected from a baking temperature of 80°C to 800°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 150°C to 500°C and the baking time is 0.5 to 2 minutes. The atmospheric gas during baking may be air, or an inert gas such as nitrogen or argon. In one embodiment, an oxygen concentration of 1% or less is particularly preferred. The thickness of the underlayer film formed here is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz imprint mold (mold replica) can be produced.

[0259] Furthermore, an adhesion layer and / or a silicon-containing layer containing 99% by mass or less, or 50% by mass or less of Si can be formed by coating or vapor deposition on the resist underlayer film according to one embodiment of the present invention. For example, an adhesion layer as described in JP-A-2013-202982 or JP-A-5827180, a silicon-containing resist underlayer film (inorganic resist underlayer film) forming composition as described in WO 2009 / 104552 (A1) can be formed by spin coating, or a Si-based inorganic material film can be formed by CVD or the like.

[0260] Furthermore, by applying the composition for forming a resist underlayer film, which is one embodiment of the present invention, to a semiconductor substrate having a portion with a step and a portion without a step (a so-called stepped substrate) and baking it, the step between the portion with a step and the portion without a step can be reduced.

[0261] [Method of Forming a Resist Pattern] The method of forming a resist pattern of the present invention includes at least the step of applying the composition for forming a resist underlayer film of the present invention onto a semiconductor substrate and baking it to form a resist underlayer film. The method of forming a resist pattern of the present invention may also include the following steps: - the step of forming a resist film on the resist underlayer film; - the step of irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern; and - the step of etching the resist underlayer film using the resist pattern as a mask.

[0262] [Method for manufacturing a semiconductor device] (i) A method for manufacturing a semiconductor device, which is one aspect of the present invention, includes: a step of forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film, which is one aspect of the present invention; a step of forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; a step of etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and a step of processing a semiconductor substrate through the patterned resist underlayer film.

[0263] (ii) A method for manufacturing a semiconductor device, which is an aspect of the present invention, includes the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film-forming composition, which is an aspect of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

[0264] (iii) A method for manufacturing a semiconductor device, which is an aspect of the present invention, includes the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition, which is an aspect of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing the semiconductor substrate through the patterned resist underlayer film.

[0265] (iv) A method for manufacturing a semiconductor device according to one embodiment of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to one embodiment of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film (spacer) on the resist underlayer film after removing the hard mask; processing the vapor-deposited film (spacer) by etching; removing the patterned resist underlayer film to leave the patterned vapor-deposited film (spacer); and processing a semiconductor substrate through the patterned vapor-deposited film (spacer).

[0266] The manufacturing methods (i) to (iv) above can be used to process a semiconductor substrate.

[0267] The step of forming a resist underlayer film using the composition for forming a resist underlayer film, which is one aspect of the present invention, is as described above in [Resist Underlayer Film].

[0268] A hard mask such as a silicon-containing film may be formed as a second resist underlayer film on the resist underlayer film formed in the above steps, and a resist pattern may be formed thereon [(ii) to (iv) above].

[0269] The hard mask may be a coating film of an inorganic material or a vapor-deposited film of an inorganic material formed by a vapor deposition method such as CVD or PVD, and may be a SiON film, a SiN film, or a SiO ２ An example is a membrane.

[0270] Furthermore, an anti-reflective coating (BARC) may be formed on this hard mask, or a resist shape correction film without anti-reflective properties may be formed.

[0271] In the step of forming the resist pattern, exposure is performed through a mask (reticle) for forming a predetermined pattern or by direct writing. Examples of exposure sources that can be used include g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, and electron beam. After exposure, post-exposure baking is performed as needed. The resist is then developed with a developer (e.g., a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, butyl acetate), and then rinsed with a rinse solution or pure water to remove the used developer. Post-baking is then performed to dry the resist pattern and enhance adhesion to the underlayer.

[0272] The etching step performed after the formation of the resist pattern is performed by dry etching.

[0273] The following gases are used for processing the hard mask (silicon-containing layer), resist underlayer film, and substrate: CF ４ , CHF ３ , C.H. ２ F ２ , CH ３ F, C ４ F ６ , C ４ F ８ , O２ , N ２ O, NO ２ , H ２ , He can be used. These gases may be used alone or in combination of two or more. Furthermore, these gases may be mixed with argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon, or nitrogen trifluoride.

[0274] The resist film may be patterned by a nanoimprint method or a self-assembled film method.

[0275] In the nanoimprint method, a resist composition is molded using a patterned mold that is transparent to irradiated light, while in the self-assembled film method, a pattern is formed using a self-assembled film that naturally forms a regular structure on the nanometer order, such as a diblock polymer (e.g., polystyrene-polymethyl methacrylate).

[0276] In the nanoimprint method, before applying the curable composition that will form the resist film, a silicon-containing layer (hard mask layer) may be optionally formed on the resist underlayer film by coating or vapor deposition, and further an adhesion layer may be formed on the resist underlayer film or the silicon-containing layer (hard mask layer) by coating or vapor deposition, and the curable composition that will form the resist film may be applied on the adhesion layer.

[0277] In addition, wet etching may be performed to simplify the process and reduce damage to the processed substrate. This leads to suppression of fluctuations in processing dimensions and reduction of pattern roughness, making it possible to process the substrate with high yield. Therefore, in steps (iii) to (iv), the hard mask can be removed using either etching or an alkaline chemical solution. In particular, when an alkaline chemical solution is used, there are no restrictions on the components, but it is preferable that the alkaline component contains the following:

[0278] Examples of the alkaline component include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, and (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N , N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, 1,5-diazabicyclo[4.3.0]nonene-5, etc. Furthermore, particularly from the viewpoint of handling, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, and an inorganic base may be used in combination with the quaternary ammonium hydroxide. As the inorganic base, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, rubidium hydroxide, etc. are preferred, with potassium hydroxide being more preferred.

[0279] The present invention will be explained in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0280] The weight-average molecular weights Mw of the resins shown in Synthesis Examples 1 to 8 below are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: TSKgel Super-Multipore HZ-N (2 columns) Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0281] [Synthesis of Resins] The synthesis of resins (S1) to (S6) used in the resist underlayer film, and the synthesis of resins (S'1) to (S'2) as comparative examples, used Compound Group A, Compound Group B, Catalyst Group C, Solvent Group D, and Reprecipitation Solvent Group E shown below.

[0282] (Compound groups A, B)

[0283] (Catalyst group C) Methanesulfonic acid: C1 3-mercaptopropionic acid: C2

[0284] (Solvent group D) Propylene glycol monomethyl ether acetate (=PGMEA): D1 Propylene glycol monomethyl ether (=PGME): D2

[0285] (Reprecipitation Solvent Group E) Methanol: E1

[0286] Synthesis Example 1: 13.2 g of (A1), 6.7 g of (B1), 10.9 g of (C1), 1.2 g of (C2), and 21.4 g of (D1) were placed in a flask. The mixture was then heated to 100°C under nitrogen and reacted for approximately 20 hours. After the reaction was stopped, the mixture was reprecipitated with (E1) and dried to obtain resin (S1). The weight average molecular weight Mw measured by GPC in terms of polystyrene was approximately 1,800. The resulting resin was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a solution of the target compound.

[0287] [Synthesis Examples 2 to 8] Resins used in resist underlayer films were synthesized by changing Compound Group A, Compound Group B, Catalyst Group C, Solvent Group D, and Reprecipitation Solvent Group E. The experimental procedures were the same as in Synthesis Example 1. Synthesis was performed under the conditions listed in Table 1 below to obtain Example Resins (S1) to (S6), Comparative Resins (S'1) to (S'2), and their solutions. In Table 1, the upper column in the Compound column indicates the type of compound used in the synthesis, and the lower column indicates the mass of that compound. Similarly, the upper column in the Catalyst and Solvent columns indicates the type of catalyst or solvent, and the lower column indicates its mass. The "Temperature / Time" column indicates the reaction temperature and reaction time. In Synthesis Examples 1 and 7, Compound Group A and Compound Group B were used in a molar ratio of 1:1 ((moles of Compound Group A):(moles of Compound Group B)=1:1). In Synthesis Examples 2 to 6 and 8, Compound Group A and Compound Group B were used in a molar ratio of 1:2 ((number of moles of Compound Group A):(number of moles of Compound Group B)=1:2). When a plurality of Compound Group Bs were used as in Synthesis Examples 4 to 6, they were weighed out so that the total number of moles thereof was twice the number of moles of Compound Group A.

[0288]

[0289] The structural formulae of the resulting resins (S1) to (S6) and resins (S'1) to (S'2) are shown below.

[0290]

[0291] [Preparation of Compositions for Forming Resist Underlayer Films] Resins (S1) to (S6), (S'1) to (S'2), crosslinker (CL1), acid generator (Ad1), solvents (PGMEA (D1), PGME (D2)), and Megafac (registered trademark) R-40 (R-40, manufactured by DIC Corporation) as a surfactant were mixed in the proportions shown in Table 2 below, and the mixture was filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare compositions for forming resist underlayer films (M1 to M7, comparative M'1 to M'3). The structural formulas of the crosslinker (CL1) and the acid generator (Ad1) are shown below.

[0292]

[0293] [Elution Test in Resist Solvent] [Examples 1-7, Comparative Examples 1-3] The concentrations of the resist underlayer film-forming compositions M1-M7 and Comparative Examples M'1-M'3 were adjusted so that the film thickness obtained after baking at 400°C for 60 seconds would be approximately 100 nm. Using a Tokyo Electron Limited coater / developer (ACT-8), each resist underlayer film-forming composition was applied to a silicon wafer and baked in air at the specified temperature and for the specified time listed in Table 3 to form a 100 nm resist underlayer film. The formed resist underlayer film was immersed in a PGME / PGMEA mixed solution (mass ratio = 7 / 3), a commonly used thinner, for 60 seconds to confirm its solvent resistance. A film thickness reduction of 1% or less after immersion in the thinner was evaluated as "Good," and a film thickness reduction of more than 1% was evaluated as "Poor." The results are shown in Table 3.

[0294] [Measurement of Etching Rate] The etcher and etching gas used for the etching measurement were as follows: RIE-200NL (manufactured by Samco) CF ４ 50 sccm N ２ / O ２ 200 / 10sccm

[0295] The concentrations of the resist underlayer film-forming compositions M1 to M7 and Comparative M'1 to M'3 were adjusted so that the thickness of the film obtained by baking at 400°C for 60 seconds would be approximately 100 nm, and each was applied to a silicon wafer using a spin coater and baked. ４ or N ２ / O ２ The dry etching rate of each resist was measured using a dry etching rate measuring device. The etching resistance was evaluated as a dry etching rate ratio (dry etching rate of resist underlayer film) / (dry etching rate of KrF resist), with a ratio of less than 0.80 being evaluated as "good" and a ratio of 0.80 or more being evaluated as "poor." The results are shown in Table 3.

[0296] [Measurement of the amount of sublimation product] The concentrations of the resist underlayer film-forming compositions M1 to M7 and Comparative M'1 to M'3 were adjusted so that the film thickness obtained by baking at 400°C for 60 seconds would be approximately 100 nm, and each was applied to a silicon wafer using a spin coater. This wafer was set in a sublimation product amount measuring device integrated with a hot plate adjusted to 300°C and baked for 60 seconds, and the sublimation product was collected and quantified using a QCM sensor. For measurement, the hot plate was heated to 300°C, the pump flow rate was set to 0.24 m ３ The speed was set to / s, and the wafer was left for aging for the first 60 seconds. Immediately thereafter, the film-coated wafer was quickly placed on the hot plate through the slide opening (the test object was installed), and sublimate collection was performed from the 60-second point to the 120-second point (60 seconds). The QCM sensor used electrodes made of a compound containing silicon and aluminum, with a quartz crystal oscillator diameter (sensor diameter) of 14 mm, an electrode diameter on the quartz crystal oscillator surface of 5 mm, and a resonant frequency of 9 MHz. A sublimate amount of less than 5,000 ng over 60 seconds was evaluated as "Good," and a sublimate amount of 5,000 ng or more was evaluated as "Poor." The results are shown in Table 3.

[0297] [Test for embedding ability into uneven substrate] As a test for embedding ability into uneven substrate, a 100 nm thick SiO ２ The substrate was checked for whether a resist underlayer film had been filled into a stepped substrate having a trench width of 20 nm and a depth of 100 nm. The resist underlayer film-forming compositions M1 to M7 and comparative M'1 to M'3 were applied to the stepped substrate, and then baked at 400°C for 60 seconds to form a resist underlayer film of approximately 100 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation. A sample that was filled without voids was considered to have good fillability and was rated "Good," whereas a sample that had voids was considered to have poor fillability and was rated "Poor." The results are shown in Table 3.

[0298]

[0299] From the above, by using the resin obtained by the present invention, not only does the resin alone exhibit sufficient solvent resistance in the atmosphere, but it also exhibits sufficient etching resistance against commonly used etching gases such as fluorine-based gases and oxygen-based gases. In addition, the resin has high heat resistance, which can suppress the generation of sublimates. The self-crosslinking groups contained in the resin can increase the crosslinking initiation temperature, resulting in sufficient reflowability and good embedding properties for patterned substrates with uneven surfaces. From these perspectives, it is expected to be applicable to a wide range of semiconductor devices.

[0300] The resist underlayer film-forming composition of the present invention, which is used in a lithography process using a multilayer film, exhibits excellent etching resistance, has good planarization and embedding properties on a microfabricated substrate, and can provide an excellent resist pattern. In addition, it is possible to provide a resist underlayer film that has resistance to solvents even in an atmospheric environment, exhibits sufficient curing properties, and also has the effect of serving as an antireflective film. Furthermore, it has been found that the resist underlayer film-forming composition of the present invention has heat resistance sufficient to form a hard mask on its upper layer by vapor deposition.

Claims

1. A composition for forming a resist underlayer film, comprising: a resin (G) having a composite unit structure; and a solvent; wherein the composite unit structure comprises: a unit structure (A) having an aromatic ring; and a unit structure (B) having one or more carbon atoms; the resin (G) is a resin obtained by a reaction to form a covalent bond between a carbon atom constituting the aromatic ring of the unit structure (A) and a carbon atom in the unit structure (B); the unit structure (A) comprises a unit structure (A-I) including a bisphenol skeleton having three or more aromatic hydrocarbon rings; and the unit structure (B) comprises a unit structure (B-I) having a quaternary carbon atom bonded to a carbon atom constituting the aromatic ring of the unit structure (A).

2. The composition for forming a resist underlayer film according to claim 1, wherein the molar ratio of the unit structure (A) to the unit structure (B) is 1:1 to 1:

2.

3. The composition for forming a resist underlayer film according to claim 1, wherein the resin (G) contains, as the composite unit structure, one or two of composite unit structures represented by the following formula (1AB) and the following formula (2AB): (In formula (1AB) and formula (2AB), R １ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms; R ２ and R ３ each independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent, and R ２ and R ３ When each represents an aromatic hydrocarbon group, they may be bonded to each other to form a fluorene ring, and R ２ and R ３ When each represents an aliphatic hydrocarbon group, they may be bonded to each other to form an aliphatic hydrocarbon ring, and each Ar independently represents a benzene ring or a naphthalene ring.

4. The composition for forming a resist underlayer film according to claim 3, wherein in formula (1AB) and formula (2AB), the substituent that the aromatic or aliphatic hydrocarbon group may have is one or more groups selected from a halo group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxy group, a hydroxyalkyl group, a carboxy group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, and an ether bond-containing group.

5. In the formula (1AB) and the formula (2AB), R ２ and R ３ each independently represent an aromatic hydrocarbon group which may have a substituent, and the aromatic hydrocarbon groups which may have a substituent are a phenyl group or a naphthyl group, and may be bonded to each other to form a fluorene ring.

6. In the formula (1AB) and the formula (2AB), R ２ and R ３ each independently represent an aliphatic hydrocarbon group which may have a substituent, and the aliphatic hydrocarbon group which may have a substituent is an alkyl group having 1 to 10 carbon atoms.

7. The composition for forming a resist underlayer film according to claim 1, wherein the resin (G) is a resin synthesized by polymerizing at least one compound having a bisphenol skeleton with three or more aromatic hydrocarbon rings with at least one aromatic ketone or aliphatic ketone in the presence of an acid catalyst.

8. The composition for forming a resist underlayer film according to claim 1, wherein the solvent contains a solvent having a boiling point of 160°C or higher.

9. The composition for forming a resist underlayer film according to claim 1, further comprising at least one selected from the group consisting of acids and their salts, and acid generators.

10. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent.

11. The composition for forming a resist underlayer film according to claim 10, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

12. The composition for forming a resist underlayer film according to claim 1, further comprising a surfactant.

13. A resist underlayer film on a semiconductor substrate, which is a cured product of the composition for forming a resist underlayer film according to any one of claims 1 to 12.

14. A method for forming a resist pattern used in the manufacture of semiconductors, comprising the step of applying the composition for forming a resist underlayer film according to any one of claims 1 to 12 onto a semiconductor substrate and baking the composition to form a resist underlayer film.

15. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 12; forming a resist film on the resist underlayer film; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

16. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 12; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

17. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 12; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing a semiconductor substrate through the patterned resist underlayer film.

18. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using a composition for forming a resist underlayer film according to any one of claims 1 to 12; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film on the resist underlayer film after removing the hard mask; processing the vapor-deposited film by etching; removing the patterned resist underlayer film to leave a patterned vapor-deposited film; and processing a semiconductor substrate through the patterned vapor-deposited film.

19. The method for manufacturing a semiconductor device according to claim 16, wherein the hard mask is formed by applying a composition containing an inorganic substance or by vapor deposition of an inorganic substance.

20. The method for manufacturing a semiconductor device according to claim 15, wherein the resist film is patterned by a nanoimprint method or a self-assembled film.

21. The method for manufacturing a semiconductor device according to claim 17, wherein the hard mask is removed by either etching or an alkaline chemical solution.

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