Nitrogen atom-containing substrate coating agent composition, resist underlayer film, layered product, method for forming resist pattern, and method for producing semiconductor device

Abstract

Provided is a nitrogen atom-containing substrate coating agent composition that contains: a resin (G) having a conjugated unit structure; and a solvent. The conjugated unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. The resin (G) is obtained through a reaction that generates a covalent bond between a carbon atom that constitutes the aromatic ring in the unit structure (A) and a carbon atom in the unit structure (B). The unit structure (A) includes at least a unit structure (A-I) that contains a nitrogen atom. The nitrogen atom-containing substrate is a substrate comprising a compound having a bond between a nitrogen atom and a metal atom or a metalloid atom or a substrate having a nitrogen atom-containing film comprising a compound having a bond between a nitrogen atom and a metal atom or a metalloid atom. The resin (G) is not a resin synthesized only from indole and 1-naphthoaldehyde.

Description

Nitrogen atom-containing substrate coating composition, resist underlayer film, laminate, method for forming resist pattern, and method for manufacturing semiconductor device

[0001] The present invention relates to a nitrogen atom-containing substrate coating composition, a resist underlayer film, a laminate, a method for forming a resist pattern, and a method for manufacturing a semiconductor device.

[0002] Rapid advances in semiconductor manufacturing processes have led to a strong demand for higher quality and improved properties of resist underlayer films. For example, it has been found that when a substrate used as the base for a resist underlayer film contains nitrogen atoms, the diffusion of amine components inhibits the resolution of the resist (see Patent Documents 1 to 3). Typically, resist films are exposed and developed immediately after formation. However, due to manufacturing process constraints, the development process may be delayed for an extended period of time after the resist film is formed. This process has been found to cause problems with the resolution of the resist, compared to when the resist film is exposed immediately after coating. Furthermore, when a resist underlayer film is used in existing processes to suppress the diffusion of amine components, the formation of a resist underlayer film changes the reflectivity during or after resist resolution, resulting in deterioration of the pattern shape and increased process load during pattern processing. Therefore, it is desirable to make the resist underlayer film as thin as possible.

[0003] JP 2008-39811 A JP 2008-39815 A JP 2010-134437 A

[0004] Therefore, the problem to be solved by the present invention is to provide a suitable coating composition that, when used on a nitrogen atom-containing substrate, can maintain stable resolution even after long-term storage after forming a resist film, and does not affect reflectance or pattern processing.

[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 coating composition for a nitrogen-atom-containing substrate, 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) containing at least a nitrogen atom, the nitrogen-atom-containing substrate is a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, and the resin (G) is not a resin synthesized only from indole and 1-naphthaldehyde. [2] The nitrogen-atom-containing substrate coating composition according to [1], wherein the unit structure (A-I) has a skeleton having an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton. [3] The nitrogen-atom-containing substrate coating composition according to [1] or [2], wherein the unit structure (A-I) includes a unit structure not containing a carbazole skeleton. [4] The nitrogen-atom-containing substrate coating composition according to any of [1] to [3], wherein the unit structure (A-I) has a skeleton having an aromatic ring, and the skeleton is at least one of skeletons represented by the following formula (A-1a), (A-1b), (A-1c), (A-2a), (A-2b-1), and (A-2b-2), wherein at least one hydrogen atom in the skeleton may be substituted with a substituent. (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. (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. ２２ may 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 formula (A-2b-2), when L is a single bond, the partial structure (In1) and the partial structure (In2) 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), when L is a linking group, L is N or Ar. ２１and bonded to the same.) [5] The nitrogen-atom-containing substrate coating composition according to [4], wherein the substituent in the skeleton in which at least one hydrogen atom may be replaced 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. [6] The nitrogen-atom-containing substrate coating composition according to any one of [1] to [5], wherein the unit structure (B) includes a unit structure (B-I) derived from an aldehyde compound or an aldehyde equivalent. [7] The nitrogen-atom-containing substrate coating composition according to any one of [1] to [6], wherein the resin (G) is a resin synthesized from reaction raw materials containing an amine compound and an aldehyde compound or an aldehyde equivalent. [8] The nitrogen-atom-containing substrate coating composition according to [7], wherein the amine compound has a skeleton containing an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton. [9] The nitrogen-atom-containing substrate coating composition according to any one of [1] to [8], wherein the solvent contains a solvent having a boiling point of 160°C or higher.

[10] The nitrogen-atom-containing substrate coating composition according to any one of [1] to [9], further containing at least one selected from the group consisting of acids and salts thereof, and acid generators.

[11] The nitrogen-atom-containing substrate coating composition according to any one of [1] to

[10] , further containing a crosslinking agent.

[12] The nitrogen-atom-containing substrate coating composition according to

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

[13] The nitrogen-atom-containing substrate coating composition according to any one of [1] to

[12] , further containing a surfactant.

[14] The nitrogen-atom-containing substrate coating composition according to any one of [1] to

[13] , which is used for forming a resist underlayer film.

[15] A resist underlayer film on a nitrogen-atom-containing substrate, the resist underlayer film being a cured product of the nitrogen-atom-containing substrate coating composition according to any one of [1] to

[14] .

[16] The resist underlayer film according to

[15] , having a film thickness of less than 10 nm.

[17] A laminate comprising the nitrogen-atom-containing substrate, which is a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, and the resist underlayer film according to

[15] or

[16] .

[18] The laminate according to

[17] , wherein the resist underlayer film is a nitrogen-atom-containing film and the nitrogen-atom-containing film constitutes the outermost layer of the nitrogen-atom-containing substrate.

[19] The laminate according to

[17] or

[18] , wherein the metal atom or metalloid atom is (i) silicon, (ii) titanium, or (iii) tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[20] The laminate according to any one of

[17] to

[19] , wherein the compound having a bond between a metal atom or a metalloid atom and a nitrogen atom is SiON, SiN, TiON, or TiN.

[21] A method for forming a resist pattern used in semiconductor production, comprising the steps of applying the nitrogen-atom-containing substrate coating composition according to any one of [1] to

[14] onto a nitrogen-atom-containing semiconductor substrate and baking the composition to form a resist underlayer film.

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

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

[23] A method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a nitrogen-atom-containing semiconductor substrate using the nitrogen-atom-containing substrate coating composition according to any one of [1] to

[14] ; a step of forming a hard mask on the resist underlayer film; a step of further forming a resist film on the hard mask; 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 hard mask through the resist pattern to form a patterned hard mask; a step of etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and a step of processing the nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

[24] A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a nitrogen-atom-containing semiconductor substrate using the nitrogen-atom-containing substrate coating composition according to any one of [1] to

[14] ; 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 nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

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

[14] ; 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 the nitrogen-atom-containing semiconductor substrate through the patterned vapor-deposited film.

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

[23] to

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

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

[22] to

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

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

[24] or

[25] , 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 suitable coating composition that can maintain stable resolution even after long-term storage after forming a resist film and does not affect reflectance or pattern processing, thereby making it possible to reduce the process load.

[0008] When the novolak resin of the present invention is applied to a substrate containing nitrogen atoms, even in an ultrathin film of less than 10 nm, it is capable of suppressing the diffusion of amine components contained in the substrate. When a resist film is formed on a resist underlayer film containing the resin, a resist pattern with a beautiful vertical shape can be formed without impairing the resolution of the resist film. Furthermore, since the ability to obtain a vertical resist pattern means that the diffusion of amine components from the underlayer film, i.e., the substrate, is suppressed, it can be said that excellent resolution is exhibited even when the resist film is exposed long after formation. Furthermore, even when applied in an ultrathin film, the resin exhibits good coatability on various substrate types and uneven substrates, and exhibits sufficient curing properties, thereby suppressing film thickness variations within the same wafer.

[0009] [Nitrogen-Atom-Containing Substrate Coating Composition] The nitrogen-atom-containing substrate coating composition of the present invention (hereinafter also simply referred to as "coating composition") contains a resin (G) having a composite unit structure and a solvent. The composite unit structure contains 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) contains a unit structure (A-I) that contains at least a nitrogen atom. The nitrogen-atom-containing substrate is a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom. The resin (G) is not a resin synthesized only from indole and 1-naphthaldehyde. In this specification, the resin (G) may also be referred to as a "novolac resin." By including the unit structure (A) and the unit structure (B), the resin (G) can provide a suitable coating composition that can maintain stable resolution even after long-term storage following resist film formation and does not affect reflectance or pattern processing.

[0010] The coating composition is a coating agent used for forming a coating film on a nitrogen-containing substrate. Preferably, when used for forming a resist underlayer film, it can provide the advantage of being able to form a resist pattern with a beautiful vertical shape without impairing the resolution of the resist film, even when exposed long after the resist film is formed. Normally, using a thick-film material as a resist underlayer film is thought to be able to suppress the diffusion of amine components in the nitrogen-containing substrate, but this increases the process load and material costs in subsequent processing, and further leads to deterioration of the resist shape due to deterioration of the antireflection ability. Therefore, it is very important to achieve the diffusion of amine components while avoiding the above-mentioned adverse effects. The coating composition of the present invention can fully provide the above-mentioned advantages even when used for forming an ultra-thin resist underlayer film with a film thickness of less than 10 nm.

[0011] Without being bound by theory, it is believed that the reason why the novolac resin of the present invention suppresses the diffusion of amine components is different from the prevention of diffusion by neutralizing amine components with an acidic additive as shown in the patent documents. The novolac resin has many aromatic rings with a high carbon content in its skeleton and is highly rigid, which significantly reduces the intermolecular gaps through which amine components, which are contaminants from the substrate, can diffuse, thereby preventing the diffusion of the amine components.

[0012] 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.

[0013] The unit structure (B) preferably includes a unit structure (BI) 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.

[0014] The nitrogen-atom-containing substrate is a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom. Examples of the metal atom or metalloid atom include (i) silicon, (ii) titanium, or (iii) tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[0015] Typical examples of compounds having a bond between a metal atom or a metalloid atom and a nitrogen atom include SiON, SiN, TiON, and TiN.

[0016] The effects of the coating composition, which is one aspect of the present invention, can be most effectively exhibited in an aspect in which the coating composition is directly applied to a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom; or in an aspect in which the coating composition is applied to a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, the nitrogen-atom-containing film forming the outermost layer of the substrate.

[0017] [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.

[0018] (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)

[0019] 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.

[0020] 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).

[0021] (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.

[0022] (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.

[0023] 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.

[0024] 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 represents 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]

[0025] 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.

[0026] 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.

[0027] (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.

[0028] (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.

[0029] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] (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.

[0035] (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.

[0036] (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.

[0037] <Resin (G)> Resin (G) has a composite unit structure. The composite unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms.

[0038] 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).)

[0039] <<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.

[0040] 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.

[0041] Preferably, such aromatic rings have from 4 to 30, more preferably from 4 to 24, carbon atoms.

[0042] 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).

[0043] 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.

[0044] The "aromatic ring" may contain at least one heteroatom selected from N, S and O on, within or between the rings.

[0045] 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.

[0046] <<A-2: Examples of Skeletons Constituting the Unit Structure (A)>> The unit structure (A) has, for example, a skeleton having an aromatic ring.

[0047] The skeleton having an aromatic ring is preferably an aromatic amine skeleton, a nitrogen-containing aromatic heterocyclic skeleton, or a phenol skeleton.

[0048] 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).

[0049] 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 linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Examples of the alkenyl group include linear, branched, or cyclic alkenyl groups having 2 to 10 carbon atoms. Examples of the alkynyl group include linear, branched, or cyclic alkynyl groups 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 Here, R is the hydrocarbon group -R 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.

[0050] <<A-3: Unit structure (AI)>> The unit structure (A) includes a unit structure (AI) containing at least a nitrogen atom. The unit structure (AI) has a skeleton having an aromatic ring. Here, the unit structure (AI) 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 (AI) will be described below.

[0051] <<<A-3-1: 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-I), 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.

[0052] Ar １１ and R１１ 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.

[0053] 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 atom of the NH group may be replaced with a substituent. The same applies to the following skeletons.

[0054] Examples of the skeleton represented by formula (A-1b) include the following skeletons:

[0055] Examples of the skeleton represented by formula (A-1c) include the following skeletons:

[0056] <<<A-3-2: 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 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-2d), (A-2e), (A-3a), or (A-3b). As will be described later, in the unit structure (A-I), the hydrogen atom of the NH group may be replaced by 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 unit structure (A)", and the substituents (S) represented by formulas (S1) to (S7) described later. (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. ２２each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a residue of an aromatic ring. ２２ may 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 formula (A-2b-2), when L is a single bond, the partial structure (In1) and the partial structure (In2) 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), when L is a linking group, L is N or Ar. ２１ is bonded to

[0057] 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.

[0058] 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.

[0059] 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.

[0060] <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 —NR １２ -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.

[0061] In the structural unit (AI), 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-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent, an aryl group, or a halo group, and that (iii) may have the hydrocarbon chain portion further interrupted by an oxygen-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent, or an arylene group.

[0062] Examples of the skeleton represented by formula (A-2d) include the skeleton represented by formula (A-2d-1) below. (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.

[0063] 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

[0064] 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):

[0065] 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.

[0066] <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; 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).

[0067] In the unit structure (AI), 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-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent, an aryl group, or a halo group, and that (iii) may have the hydrocarbon chain portion further interrupted by an oxygen-containing substituent, a sulfur-containing substituent, a nitrogen-containing substituent, or an arylene group.

[0068] 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.

[0069] 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.

[0070] <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-.)

[0071] Ar ３１ and Ar ３２ Examples of the aromatic ring in the residue of the aromatic ring of Ar 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.

[0072] Resin (G) preferably contains, as unit structure (AI), a unit structure that does not contain a carbazole skeleton. Here, the term "carbazole skeleton" refers to a skeleton containing a carbazole ring. Examples of the carbazole skeleton include skeletons represented by the following formula (A-2c-1), (A-2c-2), (A-2c-3), or (A-2c-4): (In the formula, Ar ２１ R each independently represents a residue of an aromatic ring. ２１each independently represents a hydrogen atom or a residue of an aromatic 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 formula (A-2c-4), when L is a single bond, partial structure (Ca1) and partial structure (Ca2) are bonded by bonding two nitrogen atoms together, or by bonding two Ar ２１ or a nitrogen atom and Ar ２１ In formula (A-2c-4), when L is a linking group, L is N or Ar. ２１ is bonded to

[0073] 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.

[0074] Examples of the skeleton represented by formula (A-2b-1) include the following skeletons:

[0075] Examples of the skeleton represented by formula (A-2b-2) include the following skeletons:

[0076] Examples of the skeleton represented by formula (A-2c-1) include the following skeletons:

[0077] Examples of the skeleton represented by formula (A-2c-2) or formula (A-2c-3) include the following skeletons:

[0078] Examples of the skeleton represented by formula (A-2c-4) include the following skeletons:

[0079] Examples of the skeleton represented by formula (A-2d) include the following skeletons:

[0080] 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.

[0081] Examples of the skeleton represented by formula (A-3a) include the following skeletons:

[0082] Examples of the skeleton represented by formula (A-3b) include the following skeletons:

[0083] Other examples of the nitrogen-containing aromatic heterocyclic skeleton include the following skeletons.

[0084] 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 substituted with a substituent. Examples of the substituent include the substituents (S) represented by the following formulae (S1) to (S7).

[0085] (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 ｓｂ together with the carbon atom bonded to the hydroxy group, form a carbonyl group. n represents an integer of 0 to 5. * represents a bond.

[0086] <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.

[0087] <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.)

[0088] <R ｓｄ ａｌｋｙｎｙｌ > R ｓｄ ａｌｋｙｎｙｌ represents 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).

[0089] <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.

[0090] <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.

[0091] <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.

[0092] Examples of the substituent represented by formula (S1) include the following groups. (* represents a bond.)

[0093] Examples of the substituent represented by formula (S2) include the following groups. (* represents a bond.)

[0094] Examples of the substituent represented by formula (S3) include the following groups. (* represents a bond.)

[0095] Examples of the substituent represented by formula (S4) include the following groups. (* represents a bond.)

[0096] Examples of the substituent represented by formula (S5) include the following groups. (* represents a bond.)

[0097] Examples of the substituent represented by formula (S6) include the following groups. (* represents a bond.)

[0098] Examples of the substituent represented by formula (S7) include the following groups. (* represents a bond.)

[0099] Examples of other substituents include the following groups: (* represents a bond.)

[0100] The structural unit (AI) is preferably at least one selected from the following: Note that the positions of the two bonds shown in each structural unit described below are shown merely for convenience, and each bond can extend from any possible carbon atom, and the positions are not limited thereto.

[0101] (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.

[0102]

[0103] (Examples of unit structures composed of nitrogen-containing aromatic heterocyclic skeletons)

[0104] The unit structure (A) in the resin (G) may contain a unit structure other than the unit structure (AI). Examples of the unit structure other than the unit structure (AI) include a unit structure having a phenol skeleton.

[0105] <<<A-4: 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) above.

[0106] 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.)

[0107] 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 ４１each 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 —SO ２ 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.

[0108] 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.

[0109] X １ , and X ２The 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.

[0110] 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.

[0111] 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.

[0112] 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:

[0113] n11 each independently represents 1 or 2, for example.

[0114] 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.

[0115] 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.

[0116] 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-.)

[0117] For example, n31 each independently represents 1 or 2. n32 and n33 each independently represents 0, 1 or 2.

[0118] 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.

[0119] Examples of the skeleton represented by formula (A-5a) include the following skeletons:

[0120] Examples of the skeleton represented by formula (A-5b) include the following skeletons:

[0121] Examples of the skeleton represented by formula (A-5c) include the following skeletons:

[0122] Examples of the skeleton represented by formula (A-5d) include the following skeletons:

[0123] Examples of the skeleton represented by formula (A-6a) include the following skeletons:

[0124] Examples of the skeleton represented by formula (A-6b-1) or formula (A-6b-2) include the following skeletons:

[0125] Examples of the skeleton represented by formula (A-6c) include the following skeletons:

[0126] Examples of the skeleton represented by formula (A-6d) include the following skeletons:

[0127] Examples of the skeleton represented by formula (A-7a), formula (A-7b), or formula (A-7c) include the following skeletons.

[0128] Examples of the skeleton represented by formula (A-8a-1) or formula (A-8a-2) include the following skeletons:

[0129] Examples of the skeleton represented by formula (A-8b) include the following skeletons:

[0130] Examples of the skeleton represented by formula (A-8c) include the following skeletons:

[0131] Examples of the skeleton represented by formula (A-8d) include the following skeletons:

[0132] Examples of the skeleton represented by formula (A-8e) include the following skeletons:

[0133] Examples of the skeleton represented by formula (A-8f) include the following skeletons:

[0134] Examples of the skeleton represented by formula (A-8g-1) or formula (A-8g-2) include the following skeletons.

[0135] Examples of other skeletons besides the phenol skeleton include the following skeletons.

[0136] Furthermore, the H of the hydroxy group bonded to the aromatic ring in the phenol skeleton and the hydrogen atom bonded to the aromatic ring in the phenol skeleton may be replaced with a substituent, such as the substituents (S) represented by the above formulae (S1) to (S7).

[0137] (Example of a unit structure composed of a phenol skeleton)

[0138] <<B-1: Unit Structure (B)>> The unit structure (B) has one or more carbon atoms. The unit structure (B) is preferably, for example, a unit structure (BI) 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).

[0139] <<B-2: Unit structure (BI)>> The unit structure (B) preferably includes a unit structure (BI). The unit structure (BI) is derived from an aldehyde compound or an aldehyde equivalent. 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.

[0140] <<<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 a hydrogen atom, 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 structure having a ring structure together with the carbon atom to which they are bonded. * represents a bond.

[0141] 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.

[0142] Furthermore, the two bonds in formula (B1) can be covalently bonded to the aromatic rings in the two structural units (A), respectively.

[0143] 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.

[0144] 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.

[0145] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, or pyrenyl. More preferably, R is a hydrogen atom and R' is naphthalenyl.

[0146] 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).)

[0147] Examples of the aromatic ring of Ar include aromatic rings represented by formula (G1).

[0148] The unit structure (BI) containing the structure represented by formula (B1) is derived from, for example, an aldehyde compound or a ketone compound. Examples of the aldehyde compound include a compound represented by the following formula (B-1a). Examples of the ketone compound include a compound represented by the following formula (B-1b). (In formula (B-1a) and formula (B-1b), R and R' have the same meanings as R and R' in formula (B1), respectively, with the proviso that R is other than a hydrogen atom. 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.)

[0149] For example, in obtaining resin (G), the carbonyl groups in formula (B-1a) and formula (B-1b) are converted to *-C-* in formula (B1).

[0150] Some specific examples of the unit structure (BI) 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.

[0151]

[0152] <<<B-4: Formula (B2)>>> The unit structure (BI) includes, for example, a structure represented by the following formula (B2): The unit structure (BI) may be a structure represented by the following formula (B2):

[0153] 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.

[0154] 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.

[0155] 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.

[0156] The structural unit (BI) 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.

[0157] 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.

[0158] 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 -*.

[0159] An example of formula (B-2a) is the following compound:

[0160] An example of formula (B-2b) is the following compound:

[0161] An example of formula (B-2c) is the following compound:

[0162] 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.

[0163]

[0164] The unit structure (B-I) includes, for example, a structure represented by the following formula (B3). The unit structure (B-I) may be a structure represented by the following formula (B3). The unit structure (B-I) including the structure represented by formula (B3) 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-position 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.

[0165] <<<B-5: 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.

[0166] 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).

[0167] 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.

[0168] 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.

[0169] x and y represent the numbers X and Y, respectively, and each independently represents 0 or 1.

[0170] 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).

[0171] 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),

[0172] 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.

[0173] 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.

[0174] 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.

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] 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.

[0182] 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 (BI) represented by formula (B3). The remaining bond is bonded to a hydrogen atom.

[0183] 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).

[0184] 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.

[0185] The composite unit structure in resin (G) may contain a unit structure other than unit structure (A) and unit structure (B), provided that resin (G) does not include a resin synthesized from only indole and 1-naphthaldehyde.

[0186] Resin (G) is preferably a resin synthesized from reaction raw materials containing an amine compound and an aldehyde compound or an aldehyde equivalent. Examples of the amine compound include compounds having a skeleton with an aromatic ring, the skeleton being at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton. Examples of the aldehyde compound include the compound represented by formula (B-1a) above. Examples of the aldehyde equivalent include the compounds represented by formula (B-1b), formula (B-2a), formula (B-2b), formula (B-2c), or formula (B-2d) above.

[0187] 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., where A and B are as defined above, and R represents a hydrogen atom, halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0188] 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.

[0189] 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).

[0190] 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.

[0191] 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.

[0192] The content of the resin (G) in the coating composition 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 coating composition.

[0193] The molar ratio of unit structure (A) to unit structure (B) in resin (G) is, for example, preferably 30:70 to 70:30, more preferably 30:70 to 50:50, even more preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50. The molar ratio of unit structure (A) to unit structure (B) in resin (G) can also be expressed as the molar ratio of compound (A) serving as the raw material for unit structure (A) to compound (B) serving as the raw material for unit structure (B). The molar ratio of compound (A) to compound (B) is, for example, preferably 30:70 to 70:30, more preferably 30:70 to 50:50, even more preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50. Here, compound (A) may be one type, or two or more types. Similarly, the compound (B) may be one type or two or more types.

[0194] The content (molar ratio) 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) 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%.

[0195] The content (molar ratio) 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) 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%.

[0196] <Solvent> The coating composition of one embodiment of the present invention contains a solvent.

[0197] The solvent is not particularly limited as long as it can dissolve the specific novolak resin and other optional components added as needed.

[0198] 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.

[0199] Also, solvents with boiling points of 160°C or higher can be included in combination with solvents with boiling points below 160°C.

[0200] As such a high-boiling point solvent, for example, the following compounds described in WO 2018 / 131562 (A1) can be preferably used.

[0201] [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.

[0202] 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.

[0203] The coating composition, which is one embodiment of the present invention, may contain an acid and / or a salt thereof and / or an acid generator.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0208] 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.

[0209] 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.

[0210] Examples of the photoacid generator contained in the coating composition of the present invention include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0211] 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.

[0212] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0213] 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.

[0214] The acid generators may be used singly or in combination of two or more.

[0215] 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, per 100 parts by mass of the solid content of the coating composition.

[0216] The coating composition according to one embodiment of the present invention may contain, in addition to the above, a crosslinking agent, a surfactant, a light absorbing agent, a rheology modifier, an adhesive aid, and the like, as needed.

[0217] Representative examples of the crosslinking agent include an aminoplast crosslinking agent and a phenoplast crosslinking agent.

[0218] As the crosslinking agent, a crosslinking agent having high heat resistance can be used. 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.

[0219] 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.

[0220] Preferably, it is at least one selected from the group consisting of tetramethoxymethyl glycoluril and hexamethoxymethyl melamine.

[0221] Some specific examples are as follows:

[0222]

[0223] 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.

[0224] 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).

[0225] 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.

[0226] Some specific examples are as follows:

[0227]

[0228]

[0229]

[0230]

[0231] 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.

[0232] The amount of 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, based on the total solids content of the coating composition of the present invention.

[0233] The coating composition of the present invention can contain a surfactant in order to prevent pinholes, striations, etc., and to further improve coating properties for preventing surface irregularities.

[0234] 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.).

[0235] The amount of these surfactants to be added is usually 2.0% by mass or less, and preferably 1.0% by mass or less, based on the total solid content of the coating composition of the present invention. These surfactants may be added alone or in combination of two or more.

[0236] 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 coating composition according to the present invention.

[0237] Rheology modifiers are added primarily to improve the fluidity of the coating composition, particularly in the baking process, to improve the film thickness uniformity of the resist underlayer film and the ability of the coating composition to fill holes. 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 incorporated in an amount of less than 30% by mass based on the total solids content of the coating composition of the present invention.

[0238] The adhesion promoter is added mainly for the purpose of improving the adhesion between the coating composition and the nitrogen atom-containing substrate or resist, and particularly to prevent the resist from peeling off 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 adhesive aid 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 aids are typically blended in an amount of less than 5 mass %, preferably less than 2 mass %, based on the total solids content of the coating composition of the present invention.

[0239] The solids content of the coating composition according to the present invention is preferably 0.1 to 70% by mass, or 0.1 to 60% by mass. The solids content is the content of all components of the coating composition excluding the solvent. The crosslinkable resin may be contained in the solids content in an amount of 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, or 50 to 90% by mass.

[0240] [Resist Underlayer Film] A resist underlayer film can be formed on a nitrogen-atom-containing substrate using the nitrogen-atom-containing substrate coating composition of one embodiment of the present invention. That is, a resist underlayer film can be formed on the nitrogen-atom-containing substrate as a baked product (cured product) of a coating film made from the nitrogen-atom-containing substrate coating composition. Another embodiment of the present invention is a method for producing a two- or more-layer laminate comprising a nitrogen-atom-containing substrate and a resist underlayer film, the method comprising the steps of applying the nitrogen-atom-containing substrate coating composition to at least one surface of the nitrogen-atom-containing substrate and baking the resulting coating film to form a resist underlayer film. The laminate may have a resist film laminated on the surface of the resist underlayer film opposite the nitrogen-atom-containing substrate (laminated in the order of substrate / resist underlayer film / resist film). Another embodiment of the present invention is the use of the nitrogen-atom-containing substrate coating composition for forming a resist underlayer film on a nitrogen-atom-containing substrate. Another embodiment of the present invention is a two- or more-layer laminate comprising a nitrogen-atom-containing substrate and a resist underlayer film. Another aspect of the present invention is a laminate comprising the resist underlayer film and the resist film laminated in this order on at least one surface of a nitrogen-atom-containing substrate. Another aspect of the present invention is the use of the nitrogen-atom-containing substrate coating composition in the production of such a laminate or a semiconductor device.

[0241] More specifically, a nitrogen-atom-containing substrate coating composition according to one embodiment of the present invention is applied to a nitrogen-atom-containing substrate (e.g., a silicon nitride substrate (SiN substrate), a silicon oxynitride substrate (SiON substrate), a titanium nitride substrate (TiN substrate), or a titanium oxynitride substrate (TiON)) among substrates used in the manufacture of semiconductor devices by a suitable application method such as a spinner or coater, and then baked using a heating means such as a hot plate, thereby forming a resist underlayer film on the nitrogen-atom-containing substrate. 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 (more preferably 150°C to 400°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, it is particularly preferable that the oxygen concentration is 1% or less.

[0242] Here, the film thickness of the resist underlayer film formed can be, for example, 10 to 1000 nm, or 20 to 500 nm, or 30 to 400 nm, or 50 to 300 nm. However, from the viewpoint of cost and manufacturing, an ultra-thin film with a film thickness of less than 10 nm is preferable. The film thickness is preferably 1 to less than 10 nm, and more preferably 3 to less than 10 nm. Even in such an ultra-thin film, the nitrogen-atom-containing substrate coating agent composition according to one embodiment of the present invention has good coatability due to the incorporation of the specific novolac resin, and can maintain resist resolution comparable to that immediately after the resist film is formed, even when exposed long after the resist film is formed.

[0243] 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.

[0244] Furthermore, by applying the coating composition of 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.

[0245] [Laminate] The laminate of the present invention comprises a nitrogen-atom-containing substrate and the resist underlayer film of the present invention. The nitrogen-atom-containing substrate is a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom. The resist underlayer film of the present invention is a cured product of the nitrogen-atom-containing substrate coating composition of the present invention. The resist underlayer film of the present invention is disposed, for example, on a nitrogen-atom-containing substrate.

[0246] In the laminate according to one aspect of the present invention, it is preferred that the cured product of the nitrogen-atom-containing substrate coating composition is a nitrogen-atom-containing film, and that the nitrogen-atom-containing film constitutes the outermost layer of the nitrogen-atom-containing substrate.

[0247] In the laminate according to one embodiment of the present invention, the metal atoms or metalloid atoms contained in the nitrogen-atom-containing substrate are preferably (i) silicon, (ii) titanium, or (iii) tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or alloys thereof.

[0248] In the laminate according to one aspect of the present invention, the compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, which is contained in the nitrogen-atom-containing substrate, is preferably SiON, SiN, TiON, or TiN.

[0249] [Pattern Forming Method] The pattern forming method of the present invention includes at least a step of applying a nitrogen-atom-containing substrate coating composition onto a nitrogen-atom-containing semiconductor substrate and baking the composition to form a resist underlayer film. The pattern forming method of the present invention may also include the following steps: a step of forming a resist film on the resist underlayer film; a step of irradiating the resist film with light or an electron beam and then developing the resist film to obtain a resist pattern; and a step of etching the resist underlayer film using the resist pattern as a mask.

[0250] [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 nitrogen-atom-containing semiconductor substrate using the coating composition, 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 the nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

[0251] (ii) 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 nitrogen-atom-containing semiconductor substrate using the coating 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; and processing the nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

[0252] (iii) 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 nitrogen-atom-containing semiconductor substrate using the coating 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; and processing the nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

[0253] (iv) A method for producing a semiconductor device according to one embodiment of the present invention includes the steps of: forming a resist underlayer film on a nitrogen-atom-containing semiconductor substrate using the coating 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 the nitrogen-atom-containing semiconductor substrate through the patterned vapor-deposited film (spacer).

[0254] The manufacturing methods (i) to (iv) above can be used to process a nitrogen atom-containing semiconductor substrate.

[0255] In this specification, the term "nitrogen-atom-containing semiconductor substrate" refers to a semiconductor substrate having the above-mentioned nitrogen-atom-containing film thereon. Examples of the nitrogen-atom-containing semiconductor substrate include a semiconductor substrate having a nitrogen-atom-containing film thereon, such as a SiON film, a SiN film, a TiON film, or a TiN film, and a silicon substrate (Si substrate) having a nitrogen-atom-containing film thereon.

[0256] The step of forming a resist underlayer film using the coating composition of one embodiment of the present invention is as described above in [Resist Underlayer Film].

[0257] 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].

[0258] 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.

[0259] 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.

[0260] 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.

[0261] The etching step performed after the formation of the resist pattern is performed by dry etching.

[0262] 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 , O ２ , 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.

[0263] The resist film may be patterned by a nanoimprint method or a self-assembled film method.

[0264] 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).

[0265] 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.

[0266] 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:

[0267] 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.

[0268] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0269] The weight average molecular weights Mw and Mw / Mn (polydispersity) of the resins shown in the following Synthesis Examples 1 to 16 and Comparative Synthesis Examples 1 to 4 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)

[0270] Synthesis of Resins Resins (S1) to (S9) used in the resist underlayer film, and resin (SS1) used as a comparative example, were synthesized using compound groups A to C, catalyst group D, solvent group E, reprecipitation solvent group F, and separation solvent group G shown below.

[0271] ○Compound groups A to C

[0272] Catalyst group D, solvent group E, reprecipitation solvent group F, separation solvent group G Methanesulfonic acid: D1 Tetrabutylammonium iodide: D2 Mercaptopropionic acid: D3

[0273] Propylene glycol monomethyl ether acetate (=PGMEA): E1 Propylene glycol monomethyl ether (=PGME): E2 N-methyl-2-pyrrolidone: E3 Cyclohexanone: E4 25% aqueous sodium hydroxide solution: E5 Tetrahydrofuran (=THF): E6

[0274] Methanol: F1 Methanol / water: F2 Butyl acetate / water: G1

[0275] Synthesis Example 1: 5.0 g of A1, 2.46 g of B1, 0.37 g of D1, and 18.3 g of PGMEA were placed in a flask. The mixture was then heated to 150°C under nitrogen and allowed to react for approximately 20 hours. After the reaction was stopped, the mixture was reprecipitated in a mixed solvent (F2) of methanol and water and dried to obtain resin (S1). The weight-average molecular weight Mw measured in polystyrene equivalent terms by GPC was approximately 1,300. The resulting resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and an anion exchange resin for 4 hours to obtain a solution of the target compound. Resins that were insoluble in PGMEA were dissolved in PGME or cyclohexanone (CYH) and similarly subjected to ion exchange. The amounts of compounds used as raw materials for the resin, synthesis conditions, etc. are shown in Table 1.

[0276] [Synthesis Examples 2 to 12] Resins (S2) to (S11) and (SS1) were synthesized using the same procedure as in Synthesis Example 1. Polymers that were insoluble in PGMEA were dissolved in PGME or CYH, and ion exchange was similarly carried out. The amounts of the compounds used as raw materials for each resin, the synthesis conditions, etc. are shown in Table 1.

[0277]

[0278] The structural formulae of the resulting resins (S1) to (S11) and resin (SS1) are shown below.

[0279]

[0280] Synthesis Example 6' 6.50 g of S6, 4.42 g of C1, 0.23 g of D2, 7.53 g of E5, and 16.7 g of E6 were placed in a flask. The mixture was heated to 55°C under nitrogen and allowed to react for approximately 23 hours. After the reaction was stopped, the liquid separation operation was repeated using a mixed solvent (G1) of butyl acetate and water, and the organic phase was concentrated, reprecipitated using F2, and dried to obtain resin (S6'). The weight average molecular weight Mw measured by GPC in terms of polystyrene was approximately 1,150. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and an anion exchange resin for 4 hours to obtain a solution of the target compound. The amounts of compounds used as raw materials for the resin, the synthesis conditions, etc. are shown in Table 2.

[0281] [Synthesis Examples 7' to 11'] Resins (S7') to (S11') were synthesized using the same procedure as in Synthesis Example 1'. Polymers that were insoluble in PGMEA were dissolved in PGME or CYH, and ion exchange was similarly carried out. The amounts of compounds used as raw materials for each resin, the synthesis conditions, etc. are shown in Table 2.

[0282]

[0283] The structural formulae of the resulting resins (S6') to (S11') are shown below.

[0284]

[0285] Preparation of Resist Underlayer Films Resins (S1) to (S5), resins (S6′) to (S11′), resin (SS1), crosslinking agent (CL1), acid generator (Ad1), solvents (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CYH)), and Megafac R-30 (manufactured by DIC Corporation, H1) as a surfactant were mixed in the proportions shown in Table 3 below (the crosslinking agent, acid generator, and surfactant are shown in parts by weight relative to 100 parts by weight of resin; the solvent is shown in % by weight relative to 100% total weight of solvent, independent of the weight of resin), and the mixture was filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare resist underlayer film materials (M1 to M11, Comparative M1), which are nitrogen atom-containing substrate coating agent compositions.

[0286] The structural formulae of the crosslinking agents (CL1) to (CL2) and the acid generators (Ad1) to (Ad2) are shown below. In the formulae, R represents a methyl group or a methoxyisopropyl group (-CH(CH ３ ) CH ２ OCH ３ A plurality of R's may be the same or different.

[0287]

[0288]

[0289] [Examples 1 to 11, Comparative Example 1] [Coatability Evaluation 1] The resist underlayer film materials M1 to M11 and Comparative M1 were each applied to various substrates (SiON substrates or Si substrates) without any steps using a spin coater, and baked in an air atmosphere at the predetermined temperature for the predetermined time shown in Table 4 to form a resist underlayer film so that the resulting film had a thickness of 5 nm. The surface of the formed resist underlayer film was visually inspected to evaluate its coatability. Cases where the coating was successful without pinholes, unevenness, or repelling were judged as "Good," and cases where this was not the case were judged as "Poor." The results are shown in Table 4. Note that the results are shown for reference to demonstrate that the coating properties of the materials are equivalent to those of conventional materials even on Si substrates that do not contain nitrogen atoms.

[0290]

[0291] [Coatability Evaluation 2] The resist underlayer film materials M1 to M11 and Comparative M1 were each coated onto various substrates using a Tokyo Electron Limited coater / developer (ACT®-8 or Lithius® Pro) and baked in an air atmosphere at the specified temperatures and times listed in Table 5 to form 5-nm-thick resist underlayer films. The nitrogen-atom-containing substrates (SiON substrates) on which SiON films (silicon oxynitride films) were deposited were coated using the ACT®-8, while the silicon wafers (Si substrates) were coated using the Lithius® Pro. The resist underlayer films thus formed were evaluated for in-plane film thickness uniformity (film thickness uniformity) by measuring the film thickness across the entire wafer at a total of 49 radial and concentric points. A film with a smaller ratio of film thickness variation ((maximum film thickness) - (minimum film thickness)) to the average film thickness at 49 points than that of Comparative Example 1 was evaluated as "Good," while Comparative Example 1 was evaluated as "Poor." A smaller variation in film thickness means higher uniformity of film thickness within the wafer surface. The results are shown in Table 5. The results are also shown for reference to demonstrate that the coating properties on Si substrates that do not contain nitrogen atoms are equivalent to those of conventional materials.

[0292] [Coatability Evaluation 3] The resist underlayer film materials M1 to M11 and Comparative M1 were each applied to a nitrogen-containing substrate (SiON substrate) on which SiON had been vapor-deposited using a Tokyo Electron Limited coater and developer (ACT (registered trademark)-8). The material was then baked in an air atmosphere at the specified temperature for the specified time shown in Table 5 to form a 5-nm-thick resist underlayer film. The surface roughness was then evaluated using an AFM (atomic force microscope) to evaluate the coatability. As a result of the AFM observation, a rating of "Good" was given when there were no problems with coatability, and a rating of "Poor" was given when film roughness such as pinholes or repelling was observed. The results are shown in Table 5. The results are also shown for reference to demonstrate that the material has the same coatability as conventional materials even on Si substrates that do not contain nitrogen atoms. A "-" in the table indicates that the evaluation was not performed.

[0293]

[0294] From Tables 4 and 5, it can be seen that the nitrogen atom-containing substrate coating composition of the present invention, like the conventional material composition, exhibited excellent coatability on the nitrogen atom-containing substrate as well as on the silicon wafer.

[0295] [Lithography Evaluation] Using a Tokyo Electron Limited coater / developer (ACT®-8), resist underlayer film materials M1 to M11 and Comparative M1 were each coated onto a nitrogen-atom-containing substrate (SiON substrate) having a SiON film formed thereon, so that the resulting film had a thickness of 5 nm. The coating and developing apparatus was then baked in an air atmosphere at the predetermined temperature and time shown in Table 6 to form a resist underlayer film. In addition to Comparative Example 1, various substrates not having a resist underlayer film formed thereon were also prepared, and tests were also conducted on Comparative Examples 2 to 4. A commercially available ArF (argon fluoride) resist solution (product name: SAIL X-206, manufactured by Shin-Etsu Chemical Co., Ltd.) was coated onto these resist underlayer films and baked at 85°C for 60 seconds to form a photoresist film with a thickness of 100 nm. After the above-described treatment, the resist film was left to stand for 48 hours without development. Using an ArF scanner (NSR-S307E, wavelength 193 nm, NA=0.85, σ=0.93 / 0.85) manufactured by Nikon Corporation, the resist was exposed through a mask set so that after development the photoresist line width and the width between the lines would be 0.1 μm, i.e., dense lines with a line and space (L / S) of 0.1 μm = 1 / 1 were formed. Thereafter, the resist was baked on a hot plate at 95° C. for 60 seconds, cooled, and then developed using butyl acetate for 60 seconds to form a positive-negative pattern on the resist underlayer film.

[0296] The pattern size immediately after resist pattern formation was observed using a CD-SEM (critical dimension SEM, manufactured by Hitachi High-Technologies Corporation). The dimensions of a resist pattern developed immediately after resist film formation and a resist pattern developed 48 hours later were compared, and the pattern size was confirmed again using the same wafer after 48 hours had passed. A case in which the pattern size variation was less than 4 nm (Comparative Example 1) was judged as "Good," and a case in which the variation was 4 nm or more (Comparative Example 1) was judged as "Poor." Next, a chip on which the target pattern size had been formed was fractured and observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation. A case in which the resist shape was vertical without being affected by poisoning thought to be due to the nitrogen atom-containing substrate was judged as "Good," and a case in which the resist shape was non-vertical due to the poisoning was judged as "Poor." The results are shown in Table 6. In Table 6, "-" means that the composition (nitrogen atom-containing substrate coating agent composition) was not applied to the substrate.

[0297]

[0298] As described above, the novolak resins of Examples 1 to 11 exhibit excellent curing properties in an air atmosphere even at film thicknesses of less than 10 nm, allowing them to be used as ultrathin resist underlayer films. Furthermore, these effects are not impaired even when triple bonds are introduced into the NH groups. Furthermore, even at film thicknesses of less than 10 nm, they exhibit excellent coatability for various vapor deposition film types, resulting in high in-plane film thickness uniformity. Furthermore, the structure of the resins of these Examples is capable of blocking amine components diffusing from nitrogen-containing substrates such as SiON, SiN, and TiN. This allows the resist dimensions and shape to be maintained in a vertical shape, similar to a pattern developed immediately after resist film formation, even when development is performed long after the resist film is formed. Furthermore, the formed resist pattern exhibits excellent pattern retention, with no pattern size fluctuations over time. Therefore, it is expected that these materials will be widely applicable to coating nitrogen-containing substrates in a variety of semiconductor manufacturing processes.

Claims

1. A nitrogen-atom-containing substrate coating composition comprising a resin (G) having a complex unit structure and a solvent, wherein the complex 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) containing at least a nitrogen atom; the nitrogen-atom-containing substrate is a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom; and the resin (G) is not a resin synthesized only from indole and 1-naphthaldehyde.

2. The nitrogen-atom-containing substrate coating composition according to claim 1, wherein the unit structure (AI) has a skeleton having an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

3. The coating composition for a nitrogen-atom-containing substrate according to claim 1, wherein the unit structure (AI) includes a unit structure that does not contain a carbazole skeleton.

4. The nitrogen-atom-containing substrate coating composition according to claim 1, wherein the unit structure (A-I) has a skeleton having an aromatic ring, and the skeleton is at least one of skeletons represented by the following formula (A-1a), (A-1b), (A-1c), (A-2a), (A-2b-1), and (A-2b-2), and at least one hydrogen atom in the skeleton may be substituted with a substituent. (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. (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. ２２ may 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 formula (A-2b-2), when L is a single bond, the partial structure (In1) and the partial structure (In2) 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), when L is a linking group, L is N or Ar. ２１ is bonded to 5. The nitrogen-atom-containing substrate coating composition according to claim 4, wherein the substituent in the skeleton, in which at least one hydrogen atom may be replaced, 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.

6. The coating composition for a nitrogen-atom-containing substrate according to claim 1, wherein the unit structure (B) includes a unit structure (BI) derived from an aldehyde compound or an aldehyde equivalent.

7. The nitrogen atom-containing substrate coating composition according to claim 1, wherein the resin (G) is a resin synthesized from reaction raw materials containing an amine compound and an aldehyde compound or an aldehyde equivalent.

8. The nitrogen-atom-containing substrate coating composition according to claim 7, wherein the amine compound has a skeleton containing an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

9. The nitrogen atom-containing substrate coating composition according to claim 1, wherein the solvent contains a solvent having a boiling point of 160°C or higher.

10. The nitrogen-atom-containing substrate coating composition according to claim 1, further comprising at least one selected from the group consisting of acids and their salts, and acid generators.

11. The nitrogen atom-containing substrate coating composition according to claim 1, further comprising a crosslinking agent.

12. The nitrogen atom-containing substrate coating composition according to claim 11, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

13. The nitrogen atom-containing substrate coating composition according to claim 1, further comprising a surfactant.

14. The nitrogen atom-containing substrate coating composition according to claim 1, which is used for forming a resist underlayer film.

15. A resist underlayer film on a nitrogen-atom-containing substrate, which is a cured product of the nitrogen-atom-containing substrate coating composition according to any one of claims 1 to 14.

16. The resist underlayer film according to claim 15, which has a film thickness of less than 10 nm.

17. A laminate comprising a nitrogen-atom-containing substrate that is a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen-atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, and the nitrogen-atom-containing substrate and the resist underlayer film according to claim 15.

18. The laminate according to claim 17, wherein the resist underlayer film is a nitrogen atom-containing film, and the nitrogen atom-containing film constitutes the outermost layer of the nitrogen atom-containing substrate.

19. The laminate of claim 17, wherein the metal or metalloid atom is (i) silicon, (ii) titanium, or (iii) tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

20. The laminate according to claim 17, wherein the compound having a bond between a metal atom or a metalloid atom and a nitrogen atom is SiON, SiN, TiON or TiN.

21. A method for forming a resist pattern used in the manufacture of semiconductors, comprising the steps of applying the nitrogen-atom-containing substrate coating composition according to any one of claims 1 to 14 onto a nitrogen-atom-containing semiconductor substrate and baking the composition to form a resist underlayer film.

22. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a nitrogen-atom-containing semiconductor substrate using a nitrogen-atom-containing substrate coating composition according to any one of claims 1 to 14; 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 the nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

23. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a nitrogen-atom-containing semiconductor substrate using a nitrogen-atom-containing substrate coating composition according to any one of claims 1 to 14; 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 the nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

24. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a nitrogen-atom-containing semiconductor substrate using a nitrogen-atom-containing substrate coating composition according to any one of claims 1 to 14; 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 nitrogen-atom-containing semiconductor substrate through the patterned resist underlayer film.

25. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a nitrogen-atom-containing semiconductor substrate using the nitrogen-atom-containing substrate coating composition according to any one of claims 1 to 14; 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 the nitrogen-atom-containing semiconductor substrate through the patterned vapor-deposited film.

26. The method for manufacturing a semiconductor device according to claim 23, wherein the hard mask is formed by applying a composition containing an inorganic substance or by vapor deposition of an inorganic substance.

27. The method for manufacturing a semiconductor device according to claim 22, wherein the resist film is patterned by a nanoimprint method or a self-assembled film.

28. The method for manufacturing a semiconductor device according to claim 24, wherein the hard mask is removed by either etching or an alkaline chemical solution.

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