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

Abstract

A composition for resist underlayer film formation, which contains a resin (G) having a complex structural unit and a solvent, the complex structural unit having a structural unit (A) having an aromatic ring, and a structural unit (B) having one or more carbon atoms, the resin (G) being a resin obtained by a reaction of generating a covalent bond between a carbon atom constituting the aromatic ring of the structural unit (A) and a carbon atom in the structural unit (B), the structural unit (A) containing a structural unit (A-I) containing at least a nitrogen atom and a carbon-carbon triple bond, the structural unit (B) containing a structural unit (B-I) having a non-aromatic hydrocarbon ring, the number of carbon atoms constituting the non-aromatic hydrocarbon ring of the structural unit (B-I) being 5 to 30.

Description

Technical Field

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

[0002] In recent years, with the rapid development of semiconductor technology, there has been a strong demand for higher quality and improved properties of resist underlayer films (see, for example, Patent Documents 1-6). In particular, for resist underlayer films, which are known as high-carbon materials, in addition to the requirement for reflection suppression function (having excellent optical constants to suppress reflection), there is also a strong demand for etch resistance.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: U.S. Patent Application Publication No. 2016 / 311975

[0006] Patent Document 2: International Publication No. 2018 / 198960

[0007] Patent Document 3: Japanese Patent Application Publication No. 2021-81686

[0008] Patent Document 4: Japanese Patent Application Publication No. 2020-105513

[0009] Patent Document 5: International Publication No. 2013 / 146670

[0010] Patent Document 6: Japanese Patent Application Publication No. 2016-151024 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] However, it is very difficult to produce a material that combines solvent resistance, coating properties on substrates with varying elevations, planarization properties, and etching resistance. There is still room for improvement in this material.

[0013] The present invention was made in view of the above circumstances, and aims to provide a composition for forming a resist underlayer film, which has excellent optical constants for suppressing reflection, and well balances solvent resistance, etch resistance, coating properties for substrates with high and low differences, and planarization properties. The present invention also provides a resist underlayer film using the composition for forming a resist underlayer film, a method for forming a resist pattern, and a method for manufacturing a semiconductor device.

[0014] Methods for solving problems

[0015] In order to solve the above-mentioned problems, the inventors conducted in-depth research and discovered a solution that can solve the above-mentioned problems, thereby completing the present invention with the following key points.

[0016] That is, the present invention includes the following forms.

[0017] [1]. A composition for forming a resist underlayer film, comprising a resin (G) having a composite structural unit and a solvent, The composite structural unit has: Structural units with aromatic rings (A), and Structural units (B) having one or more carbon atoms. The resin (G) is obtained by a reaction in which covalent bonds are formed between the carbon atoms constituting the aromatic ring in the structural unit (A) and the carbon atoms in the structural unit (B). The structural unit (A) comprises structural units (AI) containing at least a nitrogen atom and a carbon-carbon triple bond. The structural unit (B) comprises a structural unit (BI) having a non-aromatic hydrocarbon ring. The structural unit (BI) has 5 to 30 carbon atoms constituting the non-aromatic hydrocarbon ring.

[0018] [2]. The composition for forming a resist underlayer as described in [1], wherein the structural unit (AI) has an aromatic ring-containing skeleton, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

[0019] [3]. The composition for forming a resist underlayer as described in [1] or [2], wherein the structural unit (AI) has an aromatic ring-containing skeleton, the skeleton being at least one skeleton represented by the following formulas (A-1a), (A-1b), (A-1c), (A-2a), (A-2b-1), (A-2b-2), (A-2c-1), (A-2c-2), (A-2c-3), and (A-2c-4), and at least one hydrogen atom in the skeleton may be substituted with a substituent.

[0020] (In equations (A-1a) to (A-1c), Ar) 11 Each independently represents a residue of the aromatic ring, R 11 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0021] (In the formula, Ar) 21 Each independently represents a residue of the aromatic ring. R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring. R 22 Each of the two R groups independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or a residue of an aromatic ring. 22 They can form unsaturated aliphatic rings together. It should be noted that one of the unsaturated bonds in the unsaturated aliphatic ring refers to the unsaturated bond that constitutes the pyrrole ring. R independently represents a hydrogen atom, a residue of an aromatic ring, or a linking bond with L; L represents a single bond or a linking group; n1 represents 1; n2 represents 1 or 2. In formulas (A-2b-2) and (A-2c-4), when L is a single bond, "structural part (In1) and structural part (In2)" and "structural part (Ca1) and structural part (Ca2)" are connected together by two nitrogen atoms, or by two Ar atoms. 21 They are connected together, or through nitrogen atoms and Ar atoms. 21 When L is a linking base, in equations (A-2b-2) and (A-2c-4), L is connected to N or Ar. 21 connect.) [4]. The composition for forming a lower layer of resist as described in [3], wherein the substituent that may replace at least one hydrogen atom in the skeleton is selected from one or more groups selected from halogen group, alkyl group, alkenyl group, alkynyl group, aryl group, aryloxy group, amino group, hydroxyl group, hydroxyalkyl group, carboxyl group, formyl group, cyano group, nitro group, ester group, amide group, sulfonyl group, thiol group, thioether group and ether bond group.

[0022] [5]. A composition for forming a resist underlayer film as described in any of [1] to [4], wherein the structural unit (AI) contains a group represented by the following formula (A-10) as a group containing the carbon-carbon triple bond.

[0023] (In formula (A-10), R) 1 R represents a single bond or a divalent organic group with 1 to 20 carbon atoms. 2 (This indicates a monovalent organic group containing 1 to 20 hydrogen or carbon atoms; * indicates a linking bond.)

[0024] [6]. A composition for forming a resist underlayer film as described in any of [1] to [5], wherein the structural unit (BI) is represented by the following formula (B2),

[0025] (In formula (B2), Z 0 This refers to an organic group consisting of 5 to 30 aliphatic ring residues with substituents, or two or more aliphatic rings linked by a single bond. J 1 and J 2 Each group independently represents a divalent organic group that is directly connected or may have substituents; * indicates the connection site with structural unit (A). [7]. A composition for forming a resist underlayer film as described in any one of [1] to [6], wherein the resin (G) is a resin obtained by reacting a compound having a group containing a carbon-carbon triple bond with a resin synthesized from a reactant containing an alicyclic unsaturated compound having two or more carbon-carbon double bonds and an amine compound.

[0026] [8]. The composition for forming a resist underlayer as described in [7], wherein the amine compound has an aromatic ring-containing skeleton, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

[0027] [9]. The composition for forming a resist underlayer as described in [7] or [8], wherein the alicyclic unsaturated compound has a dicyclopentadiene structure.

[0028]

[10] . A composition for forming a resist underlayer film as described in any of [1] to [9], wherein the solvent comprises a solvent having a boiling point of 160°C or higher.

[0029]

[11] . The composition for forming a resist underlayer as described in any of [1] to

[10] further comprises at least one selected from acids and their salts, and acid-generating agents.

[0030]

[12] . A composition for forming a resist underlayer film as described in any of [1] to

[11] , further comprising a crosslinking agent.

[0031]

[13] . The composition for forming a resist underlayer film as described in

[12] , wherein the crosslinking agent is at least one selected from amino plastic crosslinking agents and phenolic plastic crosslinking agents.

[0032]

[14] . A composition for forming a resist underlayer film as described in any of [1] to

[13] , further comprising a surfactant.

[0033]

[15] . A photoresist underlayer film on a semiconductor substrate, which is a cured product of the photoresist underlayer film forming composition described in any one of [1] to

[14] .

[0034]

[16] . A method for forming a resist pattern for manufacturing a semiconductor, comprising the step of coating a resist underlayer film forming composition as described in any one of [1] to

[14] onto a semiconductor substrate and firing it to form a resist underlayer film.

[0035]

[17] . A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film composition described in any one of [1] to

[14] The process of forming a resist film on the lower resist film, The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the resist underlayer film via the resist pattern to form a patterned resist underlayer film, and... The process of processing a semiconductor substrate via the patterned resist underlayer film.

[0036]

[18] . A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film composition described in any one of [1] to

[14] The process of forming a hard mask on the underlying resist film, The next step is to form a resist film on the hard mask. The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the hard mask using the resist pattern to form a patterned hard mask. The process of etching the patterned photoresist underlayer film via the patterned hard mask to form the patterned photoresist underlayer film, and... The process of processing a semiconductor substrate via the patterned resist underlayer film.

[0037]

[19] . A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film composition described in any one of [1] to

[14] The process of forming a hard mask on the underlying resist film, The next step is to form a resist film on the hard mask. The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the hard mask using the resist pattern to form a patterned hard mask. The process of etching the resist underlayer film through the patterned hard mask to form the patterned resist underlayer film. The process of removing the hard mask, and The process of processing a semiconductor substrate via the patterned resist underlayer film.

[0038]

[20] . A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film composition described in any one of [1] to

[14] The process of forming a hard mask on the underlying resist film, The next step is to form a resist film on the hard mask. The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the hard mask using the resist pattern to form a patterned hard mask. The process of etching the resist underlayer film through the patterned hard mask to form the patterned resist underlayer film. The process of removing the hard mask, The process of forming a vapor-deposited film from the resist underlayer after the hard mask has been removed. The process of processing the vapor-deposited film by etching. The process of removing the patterned resist underlayer film, leaving the patterned vapor-deposited film, and... The process of processing a semiconductor substrate via the patterned vapor deposition film.

[0039]

[21] . A method for manufacturing a semiconductor device as described in any of

[18] to

[20] , wherein the hard mask is formed by coating an inorganic composition or by vapor deposition of an inorganic material.

[0040]

[22] . A method for manufacturing a semiconductor device as described in any of

[17] to

[21] , wherein the resist film is patterned by nanoimprinting or self-assembly of a film.

[0041]

[23] . In the method of manufacturing a semiconductor device as described in

[19] or

[20] , the removal of the hard mask is performed by etching or by an alkaline solution.

[0042] Invention Effects

[0043] According to the present invention, a composition for forming a photoresist underlayer film with excellent optical constants for suppressing reflection and a good balance of solvent resistance, etch resistance, coating properties for substrates with high and low elevation differences, and planarization properties can be provided, as well as a photoresist underlayer film obtained using the composition for forming a photoresist underlayer film, a method for forming a photoresist pattern, and a method for manufacturing a semiconductor device. Detailed Implementation

[0044] [Composition for forming the underlayer of the resist]

[0045] The composition for forming a resist underlayer film of the present invention contains a resin (G) having a composite structural unit and a solvent.

[0046] The composite structural unit has: a structural unit (A) having an aromatic ring, and a structural unit (B) having one or more carbon atoms.

[0047] Resin (G) is a resin obtained by reacting carbon atoms in structural unit (A) that form an aromatic ring with carbon atoms in structural unit (B) to form covalent bonds.

[0048] The structural unit (A) contains at least a nitrogen atom and a carbon-carbon triple bond (AI).

[0049] Structural unit (B) contains structural unit (BI) with a non-aromatic hydrocarbon ring.

[0050] The structural unit (BI) consists of a non-aromatic hydrocarbon ring with 5 to 30 carbon atoms.

[0051] In this specification, resin (G) is sometimes referred to as "phenolic varnish resin".

[0052] By including the above-mentioned structural unit (A) and structural unit (B) in the resin (G), a composition for forming a resist underlayer film can be provided, which has excellent optical constants for suppressing reflection and a good balance of solvent resistance, etch resistance, coating properties for substrates with high and low differences, and planarization properties.

[0053] The structural unit (A) has, for example, at least one of the following: an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom attached to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom attached to an aromatic ring.

[0054] Structural unit (A), for example, as the atoms that make up the aromatic ring and the atoms connected to the aromatic ring, does not have heteroatoms.

[0055] Structural unit (B) is, for example, a structural unit derived from an aldehyde compound or aldehyde equivalent.

[0056] Aldehyde equivalents refer to organic compounds that can form covalent bonds with aromatic rings and have a ketone group, acetal group, ketal group, hydroxyl or alkoxy group attached to a secondary or tertiary carbon atom, hydroxyl or alkoxy or halogen group attached to the α-carbon atom of an alkylaryl group, or a carbon-carbon unsaturated bond.

[0057] [I. Definition of Terms]

[0058] The definitions of key terms related to one aspect of the phenolic varnish resin of this application in this specification are explained below. Unless otherwise specified, the definitions of the following terms apply to phenolic varnish resin.

[0059] (I-1) "Phenolic varnish resin"

[0060] "Phenolic varnish resin" not only includes phenol-formaldehyde resin (the so-called phenolic varnish type phenolic resin) and aniline-formaldehyde resin (the so-called phenolic varnish type aniline resin) in the narrow sense, but also broadly includes the following resins and is used in a broader sense: Generally, in the presence of an acid catalyst or under equivalent reaction conditions, a resin is formed by the formation of a covalent bond between an organic compound having a functional group capable of forming a covalent bond with an aromatic ring (e.g., aldehyde, ketone, acetal, ketal, hydroxyl or alkoxy group attached to a secondary or tertiary carbon atom, hydroxyl or alkoxy group attached to the α-carbon atom (benzyl carbon atom, etc.) of an alkylaryl group, or a carbon-carbon unsaturated bond such as divinylbenzene or dicyclopentadiene) 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 attached to the aromatic ring). This process involves substitution reactions, addition reactions, condensation reactions, or addition-condensation reactions.

[0061] Therefore, the phenolic varnish resin described in this application is formed by linking multiple compounds with aromatic rings together to form a resin through an organic compound containing carbon atoms (sometimes referred to as "linking carbon atoms") derived from the functional group, which in turn form covalent bonds with the aromatic rings in the compound having aromatic rings via the linking carbon atoms.

[0062] In this specification, the terms structural unit (A) and structural unit (B) are used as structural units constituting "phenolic varnish resin". Structural unit (A) is a structural unit derived from a compound having an aromatic ring. Structural unit (B) is a structural unit derived from a compound having a functional group that can form a covalent bond with the aromatic ring of structural unit (A).

[0063] (I-2) "Residues"

[0064] "Residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or heteroatom (nitrogen atom, oxygen atom, sulfur atom, etc.) is replaced by a linking bond. It can be a monovalent group or a polyvalent group. For example, if one hydrogen atom is replaced by one linking bond, a monovalent organic group is formed; if two hydrogen atoms are replaced by linking bonds, a divalent organic group is formed.

[0065] (I-3) "Aromatic ring" (aromatic group, aryl group, arylene group)

[0066] "Aromatic ring" is a concept encompassing aromatic hydrocarbon rings, aromatic heterocycles, and their residues [sometimes also referred to as "aromatic group," "aryl" (in the case of a monovalent group), or "arylene" (in the case of a divalent group)], and includes not only monocyclic (aromatic monocycles) but also polycyclic (aromatic polycycles). In the case of a polycyclic form, at least one monocycle is an aromatic monocycle, but the remaining monocycles forming a condensation ring with the aromatic monocycle can be monocyclic heterocycles (heterocyclic monocycles) or monocyclic alicyclic hydrocarbons (alicyclic monocycles).

[0067] In this specification, heteroaryl groups are included within aryl groups. Heteroarylene groups are included within arylene groups.

[0068] Aromatic rings include: benzene, indene, naphthalene, azurite, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, trimethylbenzene, benzo[k]anthracene, pyrene, α, fluorene, biphenyl, corannulene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, coronene, dibenzo[g,p]α, acenaphthylene, acenaphthene, tetraphenylene, pentaphenylene, cyclooctatetraene, etc. More typically, aromatic rings include: benzene, naphthalene, anthracene, etc. Aromatic hydrocarbon rings such as pyrene, as well as aromatic heterocycles such as furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindole fluorene, bisindole benzo[a]fluorene, bisindole dibenzo[a]fluorene, purine, quinoline, isoquinoline, chromene, thiamethoxam, phenothiazine, phenoxazine, xanthones, acridine, phenothiazine, carbazole, indole[a]carbazole, etc. More typical examples include: furan, thiophene, pyrrole, indole, phenylindole, bisindole fluorene, phenothiazine, carbazole, indole[a]carbazole, but not limited to these.

[0069] Aromatic rings (such as benzene rings, naphthalene rings, etc.) may have substituents, and examples of such substituents include the following atoms and groups.

[0070] Halogen atoms Saturated or unsaturated straight-chain, branched, or cyclic hydrocarbon groups (-Ra) whose hydrocarbon chains can be interrupted more than once by an oxygen atom (including alkyl, alkenyl, and alkynyl groups (e.g., propargyl), as well as aryl groups, etc.) -OR (here, R represents the hydrocarbon group -R) a ) Aryloxy -NH2, -NHR, or -NR2 (the two Rs can be the same or different), where R represents the hydrocarbon group -R. a .

[0071] hydroxyl hydroxyalkyl carboxyl formyl group cyano Nitro Ester group (e.g., -CO2R or -OCOR, where R represents the hydrocarbon group -R) a ) Amide group [e.g., -NHCOR, -CONHR, -NRCOR (the two Rs can be the same or different) or -CONR2 (the two Rs can be the same or different), where R represents the hydrocarbon group -R] a ] A sulfonyl group (e.g., -SO2R, where R represents the hydrocarbon group -R) a or hydroxyl group (-OH) Thiol group (-SH) The sulfide-containing group (-SR, where R represents the hydrocarbon group -R) a ) Organic groups containing ether bonds [from R] 11 -OR 11 (R) 11 Each of the following can independently represent the residues of ether compounds represented by alkyl groups (such as methyl, ethyl, etc., with 1 to 6 carbon atoms) and aryl groups (such as phenyl, naphthyl, anthraceneyl, pyrene, etc.), including organic groups containing ether bonds such as methoxy, ethoxy, and phenoxy groups. "Aromatic ring" further includes an organic group having a condensed ring having "one or more aromatic rings (benzene, naphthalene, anthracene, pyrene, etc.)" and "one or more aliphatic rings or heterocycles". Examples of aliphatic rings include: cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene; examples of heterocycles include: furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0072] An "aromatic ring" can be an organic group having a structure in which two or more aromatic rings are linked by a divalent linker. Examples of divalent linkers include: alkylene, arylene, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, -SO2-, etc. Furthermore, a divalent linker can also be a divalent group obtained by removing a hydrogen atom from any substituent of the aromatic ring.

[0073] (I-4) "Heterocyclic ring"

[0074] The concept of "heterocycle" encompasses both aliphatic and aromatic heterocycles, and includes not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic). In the case of a polycyclic form, at least one monocycle is a heteromonocyclic ring, but the remaining monocycles can be aromatic hydrocarbon monocycles or alicyclic monocycles. For example, an aromatic heterocycle can be seen in (I-3). Like the aromatic ring in (I-3), it may also have substituents.

[0075] (I-5) "Non-aromatic ring" (aliphatic ring)

[0076] When the "non-aromatic ring" is a monocyclic ring, "non-aromatic monocyclic ring" refers to a monocyclic hydrocarbon that is not aromatic, typically referring to a monocyclic alicyclic compound. It can also be called an aliphatic monocyclic ring (which may include aliphatic heterocyclic rings; as long as it is not an aromatic compound, it may also contain unsaturated bonds). Similar to the aromatic ring described in (I-3), it may also have substituents.

[0077] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include: cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, cycloheptene, etc.

[0078] When the "non-aromatic ring" is a polycyclic ring, "non-aromatic polycyclic" refers to polycyclic hydrocarbons that are not aromatic, typically alicyclic compounds. It can also be called aliphatic polycyclic [which may include aliphatic heterocyclic rings (at least one of the monocyclic rings constituting the polycyclic ring is an aliphatic heterocyclic ring), and may also contain unsaturated bonds as long as it is not an aromatic compound]. It includes non-aromatic bicyclic, non-aromatic tricyclic, and non-aromatic tetracyclic rings.

[0079] When the "non-aromatic ring" is a bicyclic ring, it refers to a condensation ring composed of two monocyclic hydrocarbons that are not aromatic, typically a condensation ring of two alicyclic compounds. In this specification, it is sometimes also referred to as an aliphatic bicyclic ring (which may include aliphatic heterocyclic rings, and may also contain unsaturated bonds as long as they are not aromatic compounds). Examples of non-aromatic bicyclic rings include: bicyclopentane, bicyclooctane, and bicycloheptene.

[0080] When the "non-aromatic ring" is a tricyclic ring, it refers to a condensation ring composed of three monocyclic hydrocarbons that are not aromatic. Typically, it is a condensation ring of three alicyclic compounds (each of which can be a heterocycle, and as long as it is not an aromatic compound, it may also contain unsaturated bonds). Examples of non-aromatic tricyclic rings include: tricyclooctane, tricyclononane, and tricyclodecane.

[0081] When the "non-aromatic ring" is a tetracyclic ring, it refers to a condensation ring composed of four monocyclic hydrocarbons that are not aromatic. Typically, it is a condensation ring of four alicyclic compounds (each of which can be a heterocycle, and as long as it is not an aromatic compound, it may also contain unsaturated bonds). Examples of non-aromatic tetracyclic rings include hexadecylhydropyrene.

[0082] (I-6)

[0083] "The carbon atoms constituting (part of) the ring" refers to the carbon atoms constituting the ring in the case of a hydrocarbon ring in an unsubstituted state (which may be an aromatic ring, an aliphatic ring, or a heterocyclic ring).

[0084] (I-7)

[0085] "Hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon, including saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0086] (I-8)

[0087] In this application specification, in the chemical structural formula of the structural unit of the phenolic varnish resin, sometimes connecting bonds (indicated by *) are described for convenience. Unless otherwise stated, the connecting bonds can be selected at any connection position in the structural unit that can be connected, and there is no limitation on the connection position in the structural unit.

[0088] <Resin (G)>

[0089] Resin (G) has a composite structural unit.

[0090] The composite structural unit has a structural unit containing an aromatic ring (A) and a structural unit having one or more carbon atoms (B).

[0091] The composite structural unit of resin (G) is represented, for example, by the following formula (AB).

[0092]

[0093] (In formula (AB), A represents structural unit (A), and B represents structural unit (B).)

[0094] <<A-1: Structural Unit (A)>>

[0095] Structural unit (A) has an aromatic ring.

[0096] The structural unit (A) may, for example, have at least one of the following: an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom connected to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom directly connected to an aromatic ring.

[0097] The number of carbon atoms in the structural unit (A) is not particularly limited, but is, for example, 4 to 100, preferably 4 to 50.

[0098] The aromatic ring preferably has 4 to 30 carbon atoms, more preferably 4 to 24 carbon atoms.

[0099] The aromatic ring is preferably one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or condensation rings of "benzene rings, naphthalene rings, anthracene rings, pyrene rings" and "heterocyclic or aliphatic rings" (fluorene ring, benzo[a]fluorene ring, dibenzo[a]fluorene ring, indole ring, carbazole ring, indole[a]carbazole ring, etc.).

[0100] Aromatic rings may have any substituents, but from the viewpoint of polymerization reactivity, the substituents may contain a necessary minimum number of heteroatoms. Furthermore, two or more aromatic rings may be linked by a linking group, which may contain a necessary minimum number of heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0101] An aromatic ring may contain at least one heteroatom selected from N, S and O on, inside or between the rings.

[0102] Examples of heteroatoms that can be contained in a ring include: nitrogen atoms contained in amino groups (e.g., propargylamino) and cyano groups; oxygen atoms contained in formyl, hydroxy, carboxyl, alkoxy, alkenoxy, alkynoxy (e.g., propargyloxy), and aryloxy groups as oxygen-containing substituents; and nitrogen and oxygen atoms contained in nitro groups as oxygen-containing and nitrogen-containing substituents.

[0103] Examples of heteroatoms that can be contained within a ring include, for example, oxygen atoms in furan and thiamethoxam, nitrogen atoms in carbazole and pyrrole, and sulfur atoms in phenothiazines.

[0104] Examples of heteroatoms that can be contained in a linking group of two or more aromatic rings include nitrogen, oxygen, and sulfur atoms contained in -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO2-.

[0105] In this specification, "atoms constituting an aromatic ring" and "atoms contained within a ring" have the same meaning. "Atoms connected to an aromatic ring" refers to, for example, "atoms directly connected to the ring among atoms or groups contained on the ring" and "atoms directly connected to the ring among atoms contained between the rings".

[0106] For example, the atoms that make up the benzene ring are carbon atoms.

[0107] For example, the atoms that make up the pyrrole ring are carbon and nitrogen atoms.

[0108] For example, the oxygen atom of the hydroxyl group in phenol is not an atom that forms an aromatic ring.

[0109] For example, the oxygen atom of the hydroxyl group in phenol is an atom that is attached to the benzene ring, and it is an atom that is directly attached to the benzene ring among the groups contained on the benzene ring.

[0110] <<A-2: Example of the structural skeleton of structural unit (A)>>

[0111] Structural unit (A) for example has a skeleton containing aromatic rings.

[0112] The preferred skeletons with aromatic rings are aromatic amine skeletons, nitrogen-containing aromatic heterocyclic skeletons, and phenol skeletons.

[0113] Structural unit (A) is, for example, a residue from a skeleton with an aromatic ring after removing two hydrogen atoms.

[0114] The aromatic ring skeleton is derived, for example, from compounds with aromatic rings in the synthesis of resin (G). The aromatic ring skeleton is, for example, from residues remaining after removing two hydrogen atoms from compounds with aromatic rings in the synthesis of resin (G).

[0115] A skeleton with an aromatic ring may have substituents.

[0116] Examples of substituents include: halogen groups (halogen atoms), alkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl groups, thiol groups, thioether groups, and groups containing ether bonds.

[0117] Alkyl groups can be listed as straight-chain, branched, or cyclic alkyl groups having 1 to 20 carbon atoms.

[0118] Examples of alkenyl groups include straight-chain, branched, or cyclic alkenyl groups with 2 to 10 carbon atoms.

[0119] Examples of alkyne groups include straight-chain, branched, or cyclic alkyne groups with 2 to 10 carbon atoms.

[0120] Alkoxy groups can be categorized by -OR. Here, R represents a saturated or unsaturated straight-chain, branched, or cyclic hydrocarbon group that can be interrupted more than once in the middle of the hydrocarbon chain (-R). a Examples of carbon atoms that can be represented by an alkoxy group range from 1 to 20.

[0121] Aryl groups with 6 to 30 carbon atoms can be listed as aryl groups.

[0122] Aryloxy groups with 6 to 30 carbon atoms can be listed as examples.

[0123] Amino groups can be represented by -NH2, -NHR, or -NR2. Wherein, R represents the hydrocarbon group -R. a Furthermore, in -NR2, the two Rs can be the same or different.

[0124] Examples of hydroxyalkyl groups include straight-chain, branched, or cyclic hydroxyalkyl groups with 1 to 20 carbon atoms.

[0125] Examples of ester groups include those represented by -CO2R or -OCOR, where R represents the hydrocarbon group -R. a .

[0126] Examples of amide groups include those represented by -NHCOR, -CONHR, -NRCOR, or -CONR2. Wherein, R represents the hydrocarbon group -R. a When there are two Rs, the two Rs can be the same or different.

[0127] Examples of sulfonyl groups include those represented by -SO2R, where R represents the hydrocarbon group -R. a Or hydroxyl group -OH.

[0128] Groups represented by -SR can be listed as sulfide-containing groups. Wherein, R represents the hydrocarbon group -R. a .

[0129] Examples of groups containing ether bonds include R. 11 -OR 11 This represents the residues of an ether compound containing an ether bond. Wherein, R... 11Each can independently represent an alkyl group with 1 to 6 carbon atoms, such as methyl or ethyl, and an aryl group, such as phenyl, naphthyl, anthraceneyl, or pyrene. Groups containing ether bonds can be, for example, organic groups containing ether bonds, such as methoxy, ethoxy, or phenoxy groups.

[0130] <<A-3: Structural Unit (AI)>>

[0131] Structural unit (A) comprises structural units (AI) containing at least a nitrogen atom and a carbon-carbon triple bond. Structural unit (AI) contains at least one carbon-carbon triple bond and has a framework containing an aromatic ring. Note that structural unit (AI) is a subordinate concept of structural unit (A) and does not refer to a portion of the structure of structural unit (A).

[0132] The following will describe the skeleton with aromatic rings in the structural unit (AI).

[0133] <<<A-3-1: Aromatic Amine Skeleton>>>

[0134] The aromatic amine skeleton refers to a skeleton that has an aromatic ring and nitrogen atoms connected to the aromatic ring but not forming a ring.

[0135] Examples of aromatic amine skeletons include those represented by the following formulas (A-1a) to (A-1c).

[0136] Furthermore, as described later, in the structural unit (AI), the hydrogen atom of the NH group can be replaced by a substituent. Examples of substituents include the substituents described in (I-3) "Aromatic Ring", the substituents described in (A-2) "Examples of the Structural Framework of Structural Unit (A)", and the substituents (S) represented by formulas (S1) to (S7) described later.

[0137]

[0138] (In equations (A-1a) to (A-1c), Ar) 11 Each residue independently represents an aromatic ring residue. R 11 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0139] As Ar 11 and R 11 The aromatic ring in the residues of the aromatic ring can be exemplified by, for example, an aromatic ring represented by the following formula (G1). These aromatic rings may have substituents.

[0140]

[0141] Examples of skeletons represented by formula (A-1a) include the following. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the NH group may be substituted. The same applies to the following skeletons.

[0142]

[0143] The skeleton represented by equation (A-1b) can be listed as follows.

[0144]

[0145] Examples of skeletons that can be represented by equation (A-1c) include the following skeletons.

[0146]

[0147] <<<A-3-2: Nitrogen-containing aromatic heterocyclic skeleton>>>

[0148] Nitrogen-containing aromatic heterocyclic skeletons refer to skeletons that have "aromatic heterocycles with nitrogen atoms among the atoms constituting the heterocycle".

[0149] Examples of nitrogen-containing aromatic heterocycles include: pyrrole rings, indole rings, carbazole rings, pyridine rings, acridine rings, phenoxazine rings, phenothiazine rings, etc. These nitrogen-containing aromatic heterocycles may have substituents.

[0150] Examples of nitrogen-containing aromatic heterocyclic skeletons include those represented by the following formulas (A-2a), (A-2b-1), (A-2b-2), (A-2c-1), (A-2c-2), (A-2c-3), (A-2c-4), (A-2d), (A-2e), (A-3a), or (A-3b).

[0151] Furthermore, as described later, in the structural unit (AI), the hydrogen atom of the NH group can be replaced by a substituent. Examples of substituents include the substituents described in (I-3) "Aromatic Ring", the substituents described in (A-2) "Examples of the Structural Unit (A)", and the substituents (S) represented by formulas (S1) to (S7) described later.

[0152]

[0153] (In the formula, Ar) 21 Each of them independently represents a residue of the aromatic ring.

[0154] R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0155] R 22 Each R represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or a residue of an aromatic ring. Two adjacent R... 22 They can form unsaturated aliphatic rings together. It should be noted that one of the unsaturated bonds in the unsaturated aliphatic ring refers to the unsaturated bond that constitutes the pyrrole ring.

[0156] R independently represents a hydrogen atom, a residue of an aromatic ring, or a linker bond connected to L. L represents a single bond or a linker group. n1 represents 1, and n2 represents 1 or 2. In formulas (A-2b-2) and (A-2c-4), when L is a single bond, "structural part (In1) and structural part (In2)" and "structural part (Ca1) and structural part (Ca2)" are connected together by two nitrogen atoms, or by two Ar atoms. 21 They are connected together, or through nitrogen atoms and Ar atoms. 21 They are connected together. In equations (A-2b-2) and (A-2c-4), when L is the connecting basis, L is connected to N or Ar. 21 connect.)

[0157] As Ar 21 R 21 R 22 The aromatic rings in the residues of the aromatic ring of R can be exemplified by, for example, aromatic rings represented by the following formula (G2). These aromatic rings may have substituents.

[0158]

[0159] As two adjacent R 22 The unsaturated aliphatic rings formed together can be exemplified by the following rings. These aliphatic rings may have substituents.

[0160]

[0161] Examples of linking groups in L include (n1+n2) valence saturated hydrocarbon groups with 1 to 5 carbon atoms, and residues after removing (n1+n2) hydrogen atoms from an aromatic ring.

[0162] <Formula (A-2d)>

[0163] (In formula (A-2d), R 11 Each can independently represent a hydrogen atom or an aromatic group. Ar represents the aromatic ring portion, each of which is an independent benzene ring, a condensed ring composed of 2 to 3 benzene rings, or a structure represented by the following formula (Ar01). X 0 Indicates single bond, -O-, -S-, -NR 12 -or-CR 13 R 14 -, R 12 With R 11 They can be the same, or different, and related to R. 11 The definitions are the same, 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; when n is 2, Z represents a divalent organic group. Furthermore, in the structural unit (AI), R in equation (A-2d) 11 It can be a substituent.

[0164] When R 11 In the case of substituents or aromatic groups, R 11 For example, it means: (i) Hydroxymethyl, (ii) aryl groups with 6 to 30 carbon atoms, or (iii) a straight-chain, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a straight-chain, 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. However, (ii) and (iii) may be further substituted with oxygen-containing substituents, sulfur-containing substituents, nitrogen-containing substituents, aryl or halogen groups, or the hydrocarbon chain portion in (iii) may be further interrupted by oxygen-containing substituents, sulfur-containing substituents, nitrogen-containing substituents, or arylene groups.

[0165] As a skeleton represented by formula (A-2d), examples of skeletons represented by the following formula (A-2d-1) can be listed.

[0166]

[0167] (R in equation (A-2d-1)) 11 Ar and X 0 Each with R in equation (A-2d) 11 Ar and X 0 They have the same meaning. R 21 It can be an aryl group with 6 to 30 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkynyl group with 2 to 10 carbon atoms.

[0168] Ar in formulas (A-2d) and (A-2d-1) can be, for example, a benzene ring or a naphthalene ring.

[0169] Ar in equations (A-2d) and (A-2d-1) can also be a structure represented by the following equation (Ar01).

[0170]

[0171] (R in equation (Ar01)) 11a R in equation (A-2d-1) 11 The meaning is the same, R 21a R in equation (A-2d-1) 21 The same meaning, Ar a As in equation (A-2d-1), X has the same meaning. 0a X in equation (A-2d-1) 0 They have the same meaning.

[0172] In formula (Ar01), the two carbon atoms "a and b", "b and c", or "c and d" can be combined with the atoms containing X in formula (A-2d) or formula (A-2d-1). 0 The single-ring portion forms a condensation ring.

[0173] Here, X is contained. 0 The single-loop part refers to the single loop in formula (A-2d) represented by the following formula (AP011).

[0174]

[0175] As the skeleton represented by formula (A-2d), the skeleton represented by formula (A-2d-1), the skeleton represented by formula (A-2d-2), and the skeleton represented by formula (A-2d-3) are preferred.

[0176]

[0177] (In equations (A-2d-2) and (A-2d-3), R) 11 Ar and X 0 Each with R in equation (A-2d) 11 Ar and X 0 They have the same meaning.

[0178] L represents a single bond or a divalent linker. As a divalent linker, it can represent, for example, -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, -NR. 101 -、-(CR 102 R 103 )m 1 -、-(Ar101 )m 2 -, -CH2-(Ar 101 )m 2 -CH2- or -(cyclo-R)-. R 101 R 102 and R 103 Each independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or an aryl group with 6 to 30 carbon atoms, m 1 Represents integers from 1 to 10. Furthermore, Ar 101 Each independently represents an arylene group with 6 to 30 carbon atoms, m 2 The number of aromatic rings connected by single bonds is an integer from 1 to 3. "cyclo-R" indicates a 5- to 8-membered ring, preferably a 6- to 8-membered ring, of a divalent alicyclic hydrocarbon group that can form a condensation ring with one or two benzene or naphthalene rings.

[0179] R 22 Each can independently represent an arylene group with 6 to 30 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkyne group with 2 to 10 carbon atoms that can be substituted.

[0180] <Formula (A-2e)>

[0181] (In formula (A-2e), L represents a single bond or divalent linker between any two carbon atoms constituting each aziraryl condensation ring.) R 11 and R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring. R 12 and R 22 Each substituent can be represented independently. n1 and n2 each independently represent R 12 and R 22 The number of substituents can also be 0. Ar 1 and Ar 2 Each of these can be independently a benzene ring that forms a condensation ring with the pyrrole ring portion in formula (A-2e), or a condensation ring composed of 2 to 3 benzene rings. Furthermore, in the structural unit (AI), R in equation (A-2e) 11 and R 21 It can be a substituent.

[0182] When R 11 and R 21 In the case of residues that are substituents or aromatic groups, R 11 and R 21 For example, it means: (i) Hydroxymethyl, (ii) aryl groups with 6 to 30 carbon atoms, or (iii) a straight-chain, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a straight-chain, 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. However, (ii) and (iii) may be further substituted with oxygen-containing substituents, sulfur-containing substituents, nitrogen-containing substituents, aryl or halogen groups, or the hydrocarbon chain portion of (iii) may be further interrupted by oxygen-containing substituents, sulfur-containing substituents, nitrogen-containing substituents, or arylene groups.

[0183] In formula (A-2e), L is a single bond or a divalent linker. L can be linked to any carbon atom that constitutes the various aziridine condensation rings, or to Ar. 1 and Ar 2 That is, the nitrogen-containing aryl condensation ring constitutes and The aromatic carbon atoms are linked, but preferably the carbon atoms that form the pyrrole ring in the azaaryl condensation ring are linked.

[0184] Preferred linker groups (L) are selected from -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, -NH-, and -(CR). 102 R 103 )m 1 -、-(Ar 101 )m 2 -, -CH2-(Ar 101 )m 2 -CH2- and -(cyclo-R)-. R 102 and R 103 Each independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or an aryl group with 6 to 30 carbon atoms, m 1 Represents integers from 1 to 10. Furthermore, Ar 101 Each represents an arylene group with 6 to 30 carbon atoms, m 2 The number of aromatic rings connected by single bonds is an integer from 1 to 3. "cyclo-R" indicates a 5- to 8-membered ring, preferably a 6- to 8-membered ring, of a divalent alicyclic hydrocarbon group that can form a condensation ring with one or two benzene or naphthalene rings.

[0185] <Equations (A-3a) and (A-3b)>

[0186] (In the formula, Ar) 31 and Ar 32Each residue independently represents a residue of the aromatic ring, or together with the carbon atom to which it is attached, represents a residue of the aromatic ring. X represents -O, -S-, -NH-, -CH2-, -CH2-CH2-, or -CH=CH-.

[0187] As Ar 31 and Ar 32 The aromatic ring in the residues of the aromatic ring can be exemplified by, for example, the aromatic ring represented by the formula (G1).

[0188] As Ar 31 and Ar 32 Aromatic rings formed together with the carbon atoms they are attached to can be exemplified by, for example, fluorene rings, benzo[a]fluorene rings, and dibenzo[a]fluorene rings.

[0189] Examples of skeletons represented by formula (A-2a) include the following. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the NH group may be substituted. The same applies to the following skeletons.

[0190]

[0191] As a skeleton represented by equation (A-2b-1), the following skeletons can be listed as examples.

[0192]

[0193] Examples of skeletons that can be represented by equation (A-2b-2) include the following skeletons.

[0194]

[0195] Examples of skeletons that can be represented by equation (A-2c-1) include the following skeletons.

[0196]

[0197] Examples of skeletons that can be represented by equation (A-2c-2) or equation (A-2c-3) include the following skeletons.

[0198]

[0199] Examples of skeletons that can be represented by equation (A-2c-4) include the following skeletons.

[0200]

[0201] Examples of skeletons that can be represented by formula (A-2d) include the following skeletons.

[0202]

[0203] As a skeleton represented by equation (A-2e), the following skeletons can be listed as examples.

[0204] Furthermore, there may be instances where specific examples of the skeleton represented by equation (A-2d) and specific examples of the skeleton represented by equation (A-2e) overlap.

[0205]

[0206] Examples of skeletons that can be represented by equation (A-3a) include the following skeletons.

[0207]

[0208] Examples of skeletons that can be represented by equation (A-3b) include the following skeletons.

[0209]

[0210] Other skeletons that serve as nitrogen-containing aromatic heterocyclic skeletons include, for example, the following skeletons.

[0211]

[0212] Furthermore, the H atom of NH in the aforementioned aromatic ring skeleton, the H atom of hydroxyl group attached to the aromatic ring in the aromatic ring skeleton, and the hydrogen atom attached to the aromatic ring in the aromatic ring skeleton can be substituted by substituents.

[0213] Examples of substituents (S) can be exemplified by the substituents (S) represented by the following formulas (S1) to (S7).

[0214]

[0215] (In equations (S1) to (S7),) R sa It represents a monovalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0216] R sbEach can independently represent a single bond or a divalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0217] R sc Each group independently represents a divalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0218] R sd alkynyl Each group independently represents an alkynyl group with 2 to 4 carbon atoms.

[0219] Ar sa Each group independently represents a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0220] Ar sb Each group independently represents a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0221] X sa and X sb Each independently represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms, or X sa and X sb Together with the carbon atom attached to the hydroxyl group, it forms a carbonyl group.

[0222] n represents an integer from 0 to 5.

[0223] * indicates a connection key.

[0224] <R sa >

[0225] As R sa The monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms can be exemplified by alkyl groups with 1 to 10 carbon atoms and monovalent unsaturated hydrocarbon groups with 2 to 10 carbon atoms.

[0226] A monovalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When the monovalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has more than two carbon-carbon multiple bonds, these multiple bonds can all be carbon-carbon double bonds, all be carbon-carbon triple bonds, or a mixture of carbon-carbon double and triple bonds. The more than two carbon-carbon multiple bonds can be conjugated or non-conjugated.

[0227] <R sb and R sc >

[0228] R sb and R sc The divalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms in the group can be exemplified by alkylene groups with 1 to 10 carbon atoms and divalent unsaturated hydrocarbon groups with 2 to 10 carbon atoms.

[0229] A divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms, possessing one or more carbon-carbon multiple bonds. When this type of group has two or more carbon-carbon multiple bonds, these bonds can all be carbon-carbon double bonds, carbon-carbon triple bonds, or a mixture of both. The two or more carbon-carbon multiple bonds can be conjugated or non-conjugated.

[0230] As R sb and R sc Examples of such groups include the following.

[0231]

[0232] (* indicates a connection key.)

[0233] <R sd alkynyl >

[0234] R sd alkynyl This refers to an alkynyl group with 2 to 4 carbon atoms. Examples of alkynyl groups with 2 to 4 carbon atoms include ethynyl, 1-propynyl, and propynyl (2-propynyl).

[0235] <Ar sa >

[0236] Ar sa A monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon with 6 to 20 carbon atoms. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, 2,3-dihydro-1H-perinaphthane, pyrene, fluorene, and biphenyl.

[0237] <Ar sb >

[0238] Ar sb A divalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue obtained by removing two hydrogen atoms from an aromatic hydrocarbon with 6 to 20 carbon atoms. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, and biphenyl.

[0239] <X sa and X sb >

[0240] As X sa and X sb Monovalent hydrocarbon groups with 1 to 20 carbon atoms can be exemplified by, for example, monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0241] Examples of monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms include alkyl groups with 1 to 10 carbon atoms.

[0242] A monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon with 6 to 20 carbon atoms. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, 2,3-dihydro-1H-phenanthrene, pyrene, fluorene, and biphenyl.

[0243] Examples of substituents represented by formula (S1) include the following groups.

[0244]

[0245] (* indicates a connection key.)

[0246] Examples of substituents represented by formula (S2) include the following groups.

[0247]

[0248] (* indicates a connection key.)

[0249] Examples of substituents represented by formula (S3) include the following groups.

[0250]

[0251] (* indicates a connection key.)

[0252] Examples of substituents represented by formula (S4) include the following groups.

[0253]

[0254] (* indicates a connection key.)

[0255] Examples of substituents represented by formula (S5) include the following groups.

[0256]

[0257] (* indicates a connection key.)

[0258] Examples of substituents represented by formula (S6) include the following groups.

[0259]

[0260] (* indicates a connection key.)

[0261] Examples of substituents represented by formula (S7) include the following groups.

[0262]

[0263] (* indicates a connection key.)

[0264] Other substituents include, for example, the following groups.

[0265]

[0266] (* indicates a connection key.)

[0267] The structural unit (AI), in addition to the skeleton described above, also contains carbon-carbon triple bonds. The carbon-carbon triple bonds can be those contained in the substituents mentioned above, or they can be those contained in the groups represented by the following formula (A-10).

[0268]

[0269] (In formula (A-10), R) 1 R represents a single bond or a divalent organic group with 1 to 20 carbon atoms. 2 (This indicates a monovalent organic group containing 1 to 20 hydrogen or carbon atoms; * indicates a linking bond.)

[0270] In formula (A-10), the connecting bond is preferably connected to a nitrogen atom.

[0271] As R 1 Examples of linear or branched alkylene groups having 1 to 20 carbon atoms that can be substituted by hydroxyl, aryl (phenyl, substituted phenyl, etc.) or halogen (e.g., fluorine) as substituents include, for example, methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0272] As R 2 Examples include straight-chain or branched alkyl, alkenyl, alkynyl, aryl, etc., with 1 to 20 carbon atoms, which can be substituted by hydroxyl, aryl (phenyl, substituted phenyl, etc.) or halogen (e.g. fluorine) as substituents.

[0273] Examples of alkyl groups include those in the following formula (B1).

[0274] Examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.

[0275] Examples of alkyne groups include ethynyl, 1-propynyl, propynyl (2-propynyl), etc. In addition, alkyne groups can be those formed by replacing the double bonds of the alkenyl groups listed above with triple bonds.

[0276] As a structural unit (AI), it is preferably selected from at least one of the following. Furthermore, the positions of the two connecting bonds represented in each of the structural units described below are indicated for convenience only, and can extend from any possible carbon atom, and their positions are not limited.

[0277] (Examples of structural units composed of aromatic amine skeletons)

[0278] (An example of a structural unit composed of a nitrogen-containing aromatic heterocyclic framework)

[0279] The structural unit (A) in the resin (G) may contain structural units other than the structural unit (AI).

[0280] Examples of structural units other than structural units (AI) include structural units with phenolic skeletons.

[0281] <<<A-4: Phenolic skeleton>>>

[0282] The phenolic skeleton refers to a skeleton that has an aromatic ring and hydroxyl groups attached to the aromatic ring.

[0283] There is no particular limitation on the number of hydroxyl groups attached to aromatic rings in the phenolic skeleton; it can be one or more. In the case of multiple hydroxyl groups, the number can be 2–10 or 2–8. In the case of multiple hydroxyl groups, the hydroxyl groups can be attached to the same aromatic ring (e.g., a benzene ring) or to different aromatic rings.

[0284] Furthermore, in structural unit (A), the hydrogen atom of the hydroxyl group connected to the aromatic ring can be replaced by a substituent. Examples of substituents include the substituents described in (I-3) "Aromatic Ring", the substituents described in (A-2) "Examples of the Structural Framework of Structural Unit (A)", and the substituents (S) represented by formulas (S1) to (S7).

[0285] Examples of phenolic skeletons, such as those represented by the following formula (A-4), can be listed. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the hydroxyl groups may be substituted. The same applies to the following skeletons.

[0286]

[0287] (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent integers from 1 to 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent integers from 0 to 4. Among them, 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.)

[0288] Furthermore, examples of phenolic skeletons can be listed, such as those represented by the following formulas (A-5a), (A-5b), (A-5c), or (A-5d).

[0289]

[0290] (In the formula, Ar) 41 Each of them independently represents a residue of the aromatic ring.

[0291] k1 and k2 each independently represent an integer of 1 or 2.

[0292] X 1 It represents -O-, -CO-, -S-, -SO2-, or alkylene groups that can be substituted with halogen atoms.

[0293] When k1 is 1, X 2 1 It represents a single bond, -O-, -CO-, -S-, -SO2-, or an alkylene group that can be substituted by a halogen atom.

[0294] When k2 is 1, X 22 It represents a single bond, -O-, -CO-, -S-, -SO2-, or an alkylene group that can be substituted by a halogen atom.

[0295] When k1 is 2, X 21 This indicates a trivalent saturated hydrocarbon group that can be replaced by a halogen atom.

[0296] When k2 is 2, X 22 This indicates a trivalent saturated hydrocarbon group that can be replaced by a halogen atom.

[0297] Y 1 It represents a trivalent saturated hydrocarbon group.

[0298] Y 2 It represents a tetravalent saturated hydrocarbon group.

[0299] m1 and m2 each independently represent integers from 0 to 3. The sum of m1 and m2 is 1 or higher.

[0300] m3 to m5 each independently represent integers from 0 to 3. The sum of m3 to m5 is 1 or higher.

[0301] m6 to m8 each independently represent integers from 0 to 3. The sum of m6 to m8 is 1 or higher.

[0302] m9 to m12 each independently represent integers from 0 to 3. The sum of m9 to m12 is 1 or higher.

[0303] As Ar 41The aromatic ring in the residues of the aromatic ring can be exemplified by, for example, an aromatic ring represented by the following formula (G3). These aromatic rings may have substituents.

[0304]

[0305] As X 1 and X 2 The number of carbon atoms in the alkylene group that can be replaced by halogen atoms can be listed, for example, from 1 to 20. The structures of the alkylene group can be listed, for example, linear, branched, and cyclic, as well as combinations of two or more of these. The halogen atoms can be listed, for example, fluorine, chlorine, bromine, and iodine atoms.

[0306] As Y 1 and Y 2 The number of carbon atoms in the saturated hydrocarbon group can be, for example, 1 to 20. The structures of the saturated hydrocarbon group can be, for example, straight-chain, branched, and cyclic, as well as combinations of two or more of these.

[0307] Furthermore, examples of phenolic skeletons can be listed, such as those represented by the following formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d).

[0308]

[0309] (In equations (A-6a), (A-6b-1), (A-6b-2), (A-6c), and (A-6d), Ar) 51 Each element independently represents a residue of the aromatic ring. n11 independently represents an integer from 1 to 4. p independently represents 0 or 1. When p is 1, the oxygen atom forms a bridging structure between aromatic rings in the form of an ether bond; when p is 0, no ether bonds form a bridging structure between aromatic rings. L represents a single bond or a divalent linker.

[0310] As Ar 51 The aromatic ring in the formula (G1) can be exemplified by, for example, the aromatic ring represented by the above formula (G1), preferably a benzene ring or a naphthalene ring.

[0311] As L, examples include divalent groups obtained by removing two hydrogen atoms from the following structure.

[0312]

[0313] n11, for example, can represent 1 or 2 independently.

[0314] Furthermore, examples of phenolic skeletons can be listed, such as those represented by the following formulas (A-7a), (A-7b), or (A-7c).

[0315]

[0316] (In equations (A-7a), (A-7b), and (A-7c), Ar) 61 Each element independently represents a residue of the aromatic ring. n21 independently represents an integer from 1 to 4.

[0317] As Ar 61 The aromatic ring in the formula (G1) can be exemplified by, for example, the aromatic ring represented by the above formula (G1), preferably a benzene ring or a naphthalene ring.

[0318] n21, for example, can represent 1 or 2 independently.

[0319] Furthermore, examples of phenolic skeletons can be listed, such as those represented by the following formulas (A-8a-1), (A-8a-2), (A-8b), (A-8c), (A-8d), (A-8e), (A-8f), (A-8g-1), or (A-8g-2).

[0320]

[0321] In equations (A-8a-1), (A-8b), (A-8c), (A-8e), (A-8f), (A-8g-1), and (A-8g-2), n31 independently represents an integer from 1 to 4.

[0322] In equation (A-8a-2), n32 and n33 each independently represent integers from 0 to 4. The sum of n32 and n33 is 1 or greater.

[0323] In equation (A-8d), n32 and n33 each independently represent integers from 0 to 4. The sum of n32 and n33 is 1 or more.

[0324] In formula (A-8b), X 1 It represents -O- or -NH-.

[0325] In formula (A-8d), X 2 It represents -O-, -S-, or -CH2-.

[0326] In equation (A-8e), X 3 It represents -S-, -CH2-, or -NH-.

[0327] In formula (A-8f), X 4X represents -CO- or -O-. 5 (This indicates -CH2- or -O-.)

[0328] n31, for example, can represent 1 or 2 independently.

[0329] n32 and n33, for example, can each independently represent 0, 1, or 2.

[0330] Examples of skeletons represented by formula (A-4) include the following. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the hydroxyl groups may be substituted. The same applies to the following skeletons.

[0331]

[0332] As a skeleton represented by equation (A-5a), the following skeletons can be listed as examples.

[0333]

[0334] As a skeleton represented by formula (A-5b), the following skeletons can be listed as examples.

[0335]

[0336] As a skeleton represented by formula (A-5c), the following skeletons can be listed as examples.

[0337]

[0338] As a skeleton represented by formula (A-5d), the following skeletons can be listed as examples.

[0339]

[0340] As a skeleton represented by equation (A-6a), the following skeletons can be listed as examples.

[0341]

[0342] As a skeleton represented by formula (A-6b-1) or formula (A-6b-2), the following skeletons can be listed as examples.

[0343]

[0344] As a skeleton represented by formula (A-6c), the following skeletons can be listed as examples.

[0345]

[0346] As a skeleton represented by formula (A-6d), the following skeletons can be listed as examples.

[0347]

[0348] As a skeleton represented by equation (A-7a), equation (A-7b), or equation (A-7c), the following skeletons can be listed as examples.

[0349]

[0350] As a skeleton represented by formula (A-8a-1) or formula (A-8a-2), the following skeletons can be listed as examples.

[0351]

[0352] As a skeleton represented by equation (A-8b), the following skeletons can be listed as examples.

[0353]

[0354] As a skeleton represented by formula (A-8c), the following skeletons can be listed as examples.

[0355]

[0356] As a skeleton represented by formula (A-8d), the following skeletons can be listed as examples.

[0357]

[0358] As a skeleton represented by equation (A-8e), the following skeletons can be listed as examples.

[0359]

[0360] As a skeleton represented by formula (A-8f), the following skeletons can be listed as examples.

[0361]

[0362] Examples of skeletons that can be represented by formula (A-8g-1) or formula (A-8g-2) include the following skeletons.

[0363]

[0364] Other skeletons that can serve as the phenol skeleton include, for example, the following skeletons.

[0365]

[0366] Furthermore, the H atoms of the hydroxyl groups attached to the aromatic rings in the phenolic skeleton and the hydrogen atoms attached to the aromatic rings in the phenolic skeleton can be substituted by substituents.

[0367] Examples of such substituents include the substituents (S) represented by formulas (S1) to (S7) above.

[0368] (Examples of structural units composed of phenolic skeletons)

[0369] <<B-1: Structural Unit (B)>>

[0370] Structural unit (B) has more than one carbon atom.

[0371] Structural unit (B) is, for example, a structural unit derived from aldehyde compounds or aldehyde equivalents.

[0372] Structural unit (B) is one or more structural units containing a linking carbon atom connected to an aromatic ring in structural unit (A) [refer to (I-1)], for example, containing a structure represented by (B1), (B2) or (B3) described later. Structural unit (B) can connect two structural units (A) by forming a covalent bond with structural unit (A).

[0373] <<B-2: Structural Unit (BI)>>

[0374] Structural unit (B) contains structural unit (BI). Structural unit (B) has a non-aromatic hydrocarbon ring.

[0375] The number of carbon atoms in the non-aromatic hydrocarbon ring constituting the structural unit (BI) is 5 to 30, preferably 5 to 25, more preferably 5 to 20, even more preferably 5 to 15, and particularly preferably 5 to 10.

[0376] Here, structural unit (BI) is a subordinate concept of structural unit (B), and does not refer to a part of the structure of structural unit (B).

[0377] The following will explain the structural unit (BI).

[0378] <<<B-3: Equation (B1)>>>

[0379] A structural unit (BI) may contain, for example, a structure represented by the following formula (B1). A structural unit (BI) may also be a structure represented by the following formula (B1).

[0380]

[0381] In formula (B1), R and R' each independently represent a hydrogen atom or a cyclic alkyl group with 10 or fewer carbon atoms that may have substituents. R and R' can form a ring structure together with the carbon atoms they are attached to. R and R' cannot both be hydrogen atoms simultaneously. * indicates a linking bond.

[0382] Examples of substituents include: hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, aryl, aryloxy, cyano, groups in which the H of the hydroxyl group is replaced by the above substituents (S), halogens, etc.

[0383] Furthermore, the two connecting bonds in equation (B1) can form covalent bonds with each aromatic ring in the two structural units (A), respectively.

[0384] In the definition of R and R' in formula (B1), examples of "alkyl" include: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2- Methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n- Butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2, 4-Dimethyl-cyclobutyl, 3,3-Dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, n-octyl, n-nonyl, n-decyl.

[0385] The structural unit (BI) containing the structure represented by formula (B1) originates from, for example, aldehyde compounds and ketone compounds.

[0386] Examples of aldehyde compounds include those represented by the following formula (B-1a).

[0387] Examples of ketone compounds include those represented by the following formula (B-1b).

[0388]

[0389] In formulas (B-1a) and (B-1b), R and R' have the same meaning as R and R' in formula (B1). R is a group other than a hydrogen atom.

[0390] In formula (B-1b), R and R' can form a ring structure together with the carbon atoms they are attached to.

[0391] For example, when obtaining resin (G), the carbonyl group in formulas (B-1a) and (B-1b) is converted into *-C-* in formula (B1).

[0392] If we were to list some specific examples of structural units (BI) containing structures represented by equation (B1), the following would be provided. *Basically represents the connection point with structural unit (A). Needless to say, it could also be a structure that includes the illustrated structure as part of a whole.

[0393]

[0394] <<<B-4: Equation (B2)>>>

[0395] A structural unit (BI) may contain a structure represented by the following formula (B2). A structural unit (BI) may be a structure represented by the following formula (B2).

[0396]

[0397] In formula (B2), Z 0 This refers to an organic group consisting of 5 to 30 aliphatic ring residues that may have substituents, or two or more aliphatic rings linked by a single bond. Examples of organic groups consisting of two or more aliphatic rings linked by a single bond include divalent residues such as dicyclohexyl.

[0398] Examples of substituents include: hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, cyano, groups in which the H of the hydroxyl group is replaced by the above-mentioned substituents (S), halogens, etc.

[0399] J1 and J 2 Each of these terms independently represents a divalent organic group that is directly connected or may have substituents. The divalent organic group is preferably a straight-chain or branched alkylene group with 1 to 6 carbon atoms, which may be replaced by a hydroxyl group or a halogen group (e.g., fluorine) as a substituent. Examples of straight-chain alkylene groups include: methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0400] Structural units (BI) containing the structure represented by formula (B2) are derived, for example, from: compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom, compounds having an alkoxy or halogen group, or compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0401] As compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom, examples include compounds represented by the following formula (B-2a).

[0402] As compounds having two carbon-carbon double bonds, examples include compounds represented by the following formula (B-2c) or the following formula (B-2d).

[0403]

[0404] (In equations (B-2a) and (B-2c), J) 1 J 2 and Z 0 Each with J in equation (B2) 1 J 2 and Z 0 They have the same meaning.

[0405] In equation (B-2a), X a and X b Each can be used independently to represent a hydroxyl or alkoxy group attached to a secondary or tertiary carbon atom.

[0406] In equation (B-2d), n represents an integer from 0 to 4.

[0407] For example, when obtaining resin (G), X in formula (B-2a) a -J 1 Transform into *-J in equation (B2) 1 J 2 -X b Transform into J in equation (B2) 2 -*.

[0408] Specific examples of structural units containing structures represented by equation (B2) are given below. * indicates the connection point with structural unit A. Needless to say, this can also be a structural unit that includes the illustrated structure as part of a whole.

[0409]

[0410] <<<B-5: Equation (B3)>>>

[0411] In formula (B3), Z is a group having a single-ring, bicyclic, tricyclic, or tetracyclic condensed ring with 5 to 30 carbon atoms, which may have substituents. Furthermore, the number of carbon atoms referred to here refers only to the number of carbon atoms constituting the "cyclic skeleton of the single-ring, bicyclic, tricyclic, or tetracyclic condensed ring with substituents removed," and does not include the number of heteroatoms constituting the heterocycle when the single-ring or condensed ring is a heterocycle.

[0412] The single ring is a single ring whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0) (hereinafter sometimes referred to as "non-Hückel single ring"). The single rings constituting the two-ring, three-ring and four-ring are single rings whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0).

[0413] X and Y can be the same or different, representing -CR 31 R 32 -base, R 31 and R 32 They can be the same or different, representing hydrocarbon groups with 1 to 6 hydrogen or carbon atoms.

[0414] x and y represent the quantities of X and Y, respectively, and each independently represents 0 or 1.

[0415] In formula (B3) In the formula (B3) At least one of them is connected to any carbon atom (referred to as "carbon atom Z") of the non-Hückel monocycle constituting Z (in the case of x=1, y=1), or extends from carbon atom Z (in the case of x=0, y=0).

[0416] For example, in equation (B3) It is connected to any carbon atom (referred to as "carbon atom 1") of the non-Hückel monocycle constituting Z (in the case of x=1) or extends from carbon atom 1 (in the case of x=0). In formula (B3) It is connected to any carbon atom (referred to as "carbon atom 2") constituting the non-Hückel monocycle of Z (in the case of y=1) or extends from carbon atom 2 (in the case of y=0). Carbon atom 1 and carbon atom 2 can be the same or different. Different cases can belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0417] In addition, formula (B3) may optionally contain connecting carbon atoms other than carbon atom 1 and carbon atom 2.

[0418] Furthermore, when Z is a condensation ring with three or more rings, the arrangement of carbon atoms 1 and 2 in formula (B3) within the condensation ring of one or two non-Hückel rings and the remaining rings is arbitrary. When carbon atoms 1 and 2 belong to different non-Hückel rings (referred to as "non-Hückel ring 1" and "non-Hückel ring 2" respectively), the arrangement of non-Hückel ring 1 and non-Hückel ring 2 within the condensation ring is also arbitrary.

[0419] Specific examples of organic groups containing structures represented by formula (B3) are provided below. There are no particular limitations on the connection sites with structural unit (A). Of course, the illustrated structure can also exist as a part of the whole.

[0420] In addition, although there are examples where the number of connecting bonds (*) exceeds 2, the remaining connecting bonds can be used to connect with aromatic rings in another polymer chain, crosslink, etc., or can be connecting bonds with hydrogen bonds.

[0421]

[0422] <<<B-6: Equation (B4)>>>

[0423] The structural unit (B) in the resin (G) may also contain structural units other than structural unit (BI) (hereinafter also referred to as "structural unit (B-II)").

[0424] Structural unit (B-II) may contain, for example, a structure represented by the following formula (B4). Structural unit (B) may also be a structure represented by the following formula (B4).

[0425]

[0426] In formula (B4), R and R' each independently represent a hydrogen atom, an aromatic ring with 5 to 30 carbon atoms (possibly with substituents), a heterocyclic ring with 3 to 30 carbon atoms (possibly with substituents), or a straight-chain or branched alkyl group with 10 or fewer carbon atoms (possibly with substituents). R and R' can form a ring structure together with the carbon atoms they are attached to. * indicates a linking bond.

[0427] Examples of substituents include: hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, aryl, aryloxy, cyano, groups in which the H of the hydroxyl group is replaced by the above substituents (S), halogens, etc.

[0428] Furthermore, the two connecting bonds in equation (B4) can each form covalent bonds with the aromatic rings in the two structural units (A).

[0429] In the definitions of R and R' in formula (B4), "aromatic ring" and "heterocyclic ring" can be referred to in (I-3) and (I-4).

[0430] In the definition of R and R' in formula (B4), the same groups as R and R' in formula (B1) can be listed as "alkyl".

[0431] R and R' are preferably phenyl, naphthyl, anthraceneyl, phenanthryl, tetraphenyl, or pyrene, each independently.

[0432] As a ring structure formed by R and R' together with the carbon atoms they are attached to, examples of structures represented by the following formula can be cited.

[0433]

[0434] (In the formula, Ar independently represents the residues of the aromatic ring. The carbon atom represented by * is the carbon atom connected to R and R' in formula (B4).)

[0435] As an aromatic ring of Ar, examples of aromatic rings represented by formula (G1) can be listed.

[0436] The structural unit (B-II) containing the structure represented by formula (B4) originates from, for example, aldehyde compounds and ketone compounds.

[0437] Examples of aldehyde compounds include those represented by the above formula (B-1a).

[0438] Examples of ketone compounds include those represented by the above formula (B-1b).

[0439] To provide specific examples of structural units (B-II) containing the structure represented by equation (B4), see the following description. *Basically represents the connection point with structural unit (A). Of course, it could also be a structure in which the illustrated structure is part of a whole.

[0440]

[0441] <<<B-7: Equation (B5)>>>

[0442] Structural unit (B-II) may contain, for example, a structure represented by the following formula (B5). Structural unit (B-II) may also be a structure represented by the following formula (B5).

[0443]

[0444] In equation (B5), Z 0 This refers to an organic group consisting of 5 to 30 carbon atoms, including aromatic ring residues, aliphatic ring residues, or two or more aromatic or aliphatic rings linked by a single bond. Examples of organic groups consisting of two or more aromatic or aliphatic rings linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and dicyclohexyl.

[0445] Examples of substituents include: hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, aryl, aryloxy, cyano, groups in which the H of the hydroxyl group is replaced by the above substituents (S), halogens, etc.

[0446] J 1 and J 2 Each of these terms independently represents a divalent organic group that is directly connected or may have substituents. The divalent organic group is preferably a straight-chain or branched alkylene group having 1 to 6 carbon atoms, which may be replaced by a hydroxyl group, an aryl group (phenyl, substituted phenyl, etc.), or a halogen group (e.g., fluorine) as a substituent. Examples of straight-chain alkylene groups include: methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0447] Structural units (B-II) containing the structure represented by formula (B5) are derived, for example, from: compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom; compounds having a hydroxyl or alkoxy group bonded to an α-carbon atom (such as a benzyl carbon atom); and compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0448] Compounds having a hydroxyl group, alkoxy group, or halogen group attached to the α-carbon atom of an alkylaryl group (such as a benzyl carbon atom) can be exemplified by compounds represented by the following formula (B-2b).

[0449] Examples of compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom include compounds represented by the above formula (B-2a).

[0450] Examples of compounds having two carbon-carbon double bonds include those represented by the above formulas (B-2c) or (B-2d).

[0451]

[0452] (In formula (B-2b), J)1 J 2 and Z 0 Each with J in equation (B5) 1 J 2 and Z 0 They have the same meaning.

[0453] In equation (B-2b), Y a and Y b Each of these groups independently represents a hydroxyl, alkoxy, or halogen group attached to the α-carbon atom of an alkylaryl group (or the carbon atom at the benzyl position, etc.).

[0454] For example, when obtaining resin (G), Y in formula (B-2b) a -J 1 Transform into *-J in formula (B5) 1 J 2 -Y b Transform into J in equation (B5) 2 -*.

[0455] An example of formula (B-2a) is the following compound.

[0456]

[0457] An example of formula (B-2b) is the following compound.

[0458]

[0459] An example of formula (B-2c) is the following compound.

[0460]

[0461] Specific examples of structural units (B-II) containing structures represented by equation (B5) are given below. *Basically represents the connection point with structural unit (A). Needless to say, it can also be a structural unit that includes the illustrated structure as part of a whole.

[0462]

[0463] <<<B-8: Equation (B6)>>>

[0464] In formula (B6), Z is a group having a single-ring, bicyclic, tricyclic, or tetracyclic condensed ring with 4 to 25 carbon atoms, which may have substituents. Furthermore, the number of carbon atoms referred to here refers only to the number of carbon atoms constituting the "ring skeleton of the single-ring, bicyclic, tricyclic, or tetracyclic condensed ring with substituents removed," excluding the number of heteroatoms constituting the heterocycle when the single-ring or condensed ring is a heterocycle.

[0465] The single ring is a single ring whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0) (hereinafter sometimes referred to as a "non-Hückel single ring"). At least one single ring constituting the two-ring, three-ring and four-ring is a single ring whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0). The remaining single rings can be single rings whose number of π electrons satisfies 4n+2 (n is an integer greater than or equal to 0) or single rings whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0).

[0466] The monocyclic, bicyclic, tricyclic, or tetracyclic condensation ring can further form a condensation ring with one or more aromatic rings to form a condensation ring with five or more rings. The number of carbon atoms in the condensation ring with five or more rings is preferably 40 or less. The number of carbon atoms referred to here refers only to the number of carbon atoms constituting the "ring skeleton of the condensation ring with five or more rings after removing substituents", and does not include the number of heteroatoms constituting the heterocycle when the condensation ring with five or more rings is a heterocycle.

[0467] X and Y can be the same or different, representing -CR 31 R 32 -base, R 31 and R 32 They can be the same or different, representing hydrocarbon groups with 1 to 6 hydrogen or carbon atoms.

[0468] x and y represent the quantities of X and Y, respectively, and each independently represents 0 or 1.

[0469] In formula (B6) In the formula (B6) At least one of them is connected to any carbon atom (referred to as "carbon atom Z") of the non-Hückel monocycle constituting Z (in the case of x=1, y=1) or extends from carbon atom Z (in the case of x=0, y=0).

[0470] For example, in equation (B6) It is connected to any carbon atom (referred to as "carbon atom 1") of the non-Hückel monocycle constituting Z (in the case of x=1) or extends from carbon atom 1 (in the case of x=0). In formula (B6) It is connected to any carbon atom (referred to as "carbon atom 2") constituting the non-Hückel monocycle of Z (in the case of y=1) or extends from carbon atom 2 (in the case of y=0). Carbon atom 1 and carbon atom 2 can be the same or different. Different cases can belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0471] In addition, formula (B6) may optionally contain connecting carbon atoms other than carbon atom 1 and carbon atom 2.

[0472] Furthermore, when Z is a condensation ring with three or more rings, the arrangement of carbon atoms 1 and 2 in formula (B6) within the condensation ring of one or two non-Hückel monocycles and the remaining monocycles is arbitrary. When carbon atoms 1 and 2 belong to different non-Hückel monocycles (referred to as "non-Hückel monocycle 1" and "non-Hückel monocycle 2" respectively), the arrangement of non-Hückel monocycle 1 and non-Hückel monocycle 2 within the condensation ring is also arbitrary.

[0473] Specific examples of organic groups containing structures represented by formula (B6) are provided below. There are no particular limitations on the connection sites with structural unit (A). Of course, the illustrated structure can also exist as a part of the whole.

[0474] In addition, there are examples where the number of connecting bonds (*) exceeds 2. These remaining connecting bonds can be used to connect with aromatic rings in another polymer chain, crosslink, etc., or they can be connecting bonds with hydrogen bonds.

[0475]

[0476] The following will explain the following situation: In equation (B6), only those in equation (B6) In the formula (B6) One is connected to any carbon atom (referred to as "carbon atom Z") of the non-Hückel monocycle constituting Z (in the case of x=1, y=1) or extends from carbon atom Z (in the case of x=0, y=0).

[0477] As a more specific structure of equation (B6) in this case, for example, in equation (C31) below, among p, k1, and k2, which can serve as connecting bonds, the structural unit (B-II) represented by equation (B6) can be formed by "p with k1" or "p with k2". The remaining connecting bonds are connected to hydrogen atoms.

[0478]

[0479] Furthermore, in the following formula (C32), among p, k1, k2, and m, which can serve as connecting bonds, a structural unit (B-II) represented by formula (B6) can be formed by "p with k1", "p with k2", or "p with m". The remaining connecting bonds are connected to hydrogen atoms.

[0480]

[0481] If we were to list some more specific examples of equation (B6) that are equivalent to equation (C31) or equation (C32), they would be described below. * indicates the connection point with structural unit (A).

[0482] In equation (B6), there are additional connecting bonds extending from the aromatic rings in these structures to connect with other structural units (e.g., structural unit (A)), but these connecting bonds are omitted in the specific examples below. Of course, the illustrated structures may also exist as structural units within a part of the whole.

[0483]

[0484] Furthermore, in the above specific examples, if there are no connecting bonds extending from the aromatic ring, it can be considered a specific example of a polymer end.

[0485] The composite structural unit in resin (G) may also include structural units other than structural unit (A) and structural unit (B).

[0486] However, resin (G) does not contain resins synthesized solely from carbazole and dicyclopentadiene.

[0487] The resin (G) contains at least one carbon-carbon triple bond. Examples of carbon-carbon triple bonds include those contained in the substituents mentioned above, carbon-carbon triple bonds contained in groups represented by formula (A-10), etc., but there are no particular limitations.

[0488] Examples of resins (G) include: resins obtained by reacting a "compound having a group containing a carbon-carbon triple bond" with a "resin synthesized from reactants containing an alicyclic unsaturated compound having two or more carbon-carbon double bonds and an amine compound", and resins obtained by reacting an "alicyclic unsaturated compound having two or more carbon-carbon double bonds" with an "amine compound having a group containing a carbon-carbon triple bond".

[0489] As the resin (G), it is preferably a resin obtained by reacting a "compound having a group containing a carbon-carbon triple bond" with a "resin synthesized from a reaction raw material containing an alicyclic unsaturated compound having two or more carbon-carbon double bonds and an amine compound".

[0490] Examples of alicyclic unsaturated compounds having two or more carbon-carbon double bonds include compounds with a dicyclopentadiene structure, compounds with a tricyclopentadiene structure, and compounds with a tetracyclopentadiene structure.

[0491] Examples of amine compounds include compounds having an aromatic ring skeleton, wherein the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

[0492] Compounds having a group containing a carbon-carbon triple bond can be listed as compounds having substituents (S) represented by the formulas (S1) to (S7) above. For example, a halogenated propargyl group (e.g., propargyl bromide) is preferably used as a compound having a substituent (S).

[0493] Phenolic varnish resins having the structure represented by formula (AB) can be formulated using known methods. For example, they can be formulated by condensing a cyclic compound represented by HAH with an oxygen-containing compound represented by OHC-B, O=CB, RO-B-OR, RO-CH2-B-CH2-OR, etc. In these formulas, A and B have the same meanings as described above. R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0494] One or more cyclic and oxygen-containing compounds may be used in combination. In this condensation reaction, the ratio of oxygen-containing compound to cyclic compound can be 0.1 to 10 moles, preferably 0.1 to 2 moles.

[0495] The catalysts used in the condensation reaction may include, for example, inorganic 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, and is typically 0.001 to 10,000 parts by mass relative to 100 parts by mass of the cyclic compound (or their total amount if there are multiple compounds), preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass.

[0496] Condensation reactions can be carried out even in the absence of a solvent, but are usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction matrix and does not hinder the reaction. Examples 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, dimethylformamide, etc. The condensation reaction temperature is typically 40°C to 200°C, preferably 100°C to 180°C. The reaction time varies depending on the reaction temperature, typically from 5 minutes to 50 hours, preferably from 5 minutes to 24 hours.

[0497] The weight-average molecular weight of the phenolic varnish resin of one form of the present invention is typically 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0498] Methods for introducing carbon-carbon triple bonds into resin (G) include, for example, adding a compound containing a carbon-carbon triple bond group to a resin synthesized from a reaction raw material containing an alicyclic unsaturated compound having two or more carbon-carbon double bonds and an amine compound, and reacting it under nitrogen at 20 to 100°C for 1 to 72 hours.

[0499] The mixing ratio of a resin synthesized from reactants containing alicyclic unsaturated compounds having two or more carbon-carbon double bonds and amine compounds, and a compound having groups containing carbon-carbon triple bonds, is preferably, for example, 1:10 to 10:1 by mass.

[0500] The content of resin (G) in the composition for forming the lower layer of the resist film is preferably 25 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass, relative to the mass of the film-forming component.

[0501] Here, the film-forming component refers to the component remaining after removing the solvent component from the composition for forming the underlying film of the resist.

[0502] The molar ratio of structural unit (A) to structural unit (B) in resin (G) is preferably 30:70 to 50:50, more preferably 40:60 to 50:50, and even more preferably 50:55 to 50:50.

[0503] Furthermore, the molar ratio of structural unit (A) to structural unit (B) in resin (G) can also be expressed as the molar ratio of compound (A) which is the raw material for structural unit (A) to compound (B) which is the raw material for structural unit (B).

[0504] The molar ratio of compound (A) to compound (B) is preferably 30:70 to 50:50, more preferably 40:60 to 50:50, and even more preferably 50:55 to 50:50. Compound (A) may be one or more compounds. Similarly, compound (B) may be one or more compounds.

[0505] The proportion (molar ratio) of structural unit (AI) in structural unit (A) is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, more preferably 40 mol% or more, more preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, and may also be 100 mol%.

[0506] Furthermore, the molar ratio of structural units (AI) in structural unit (A) can also be expressed by the molar ratio of compounds (AI) in compound (A) that serve as raw materials for structural units (AI).

[0507] The molar ratio of compound (AI) in compound (A) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and may also be 100 mol%.

[0508] The proportion (molar ratio) of structural unit (BI) in structural unit (B) is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, more preferably 40 mol% or more, more preferably 50 mol% or more, more preferably 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, and may also be 100 mol%.

[0509] Furthermore, the molar ratio of structural unit (BI) in structural unit (B) can also be expressed by the molar ratio of compound (BI) in compound (B) that serves as the raw material for structural unit (BI).

[0510] The molar ratio of compound (B) to compound (BI) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and may also be 100 mol%.

[0511] <Solvent>

[0512] One embodiment of the resist underlayer film formation composition of the present invention contains a solvent.

[0513] There are no particular limitations on the solvent, as long as it can dissolve the specific phenolic varnish resin and any other ingredients added as needed.

[0514] Examples of solvents include: methyl acetate cellosolve, ethyl acetate cellosolve, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl methanol, 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 ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate. Ethyl acetate, 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 dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate Ester, 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 Hydroxyethyl Acetate, Methyl 2-Hydroxy-2-methylpropionate, Ethyl 2-Hydroxy-2-methylpropionate, Methyl 3-Methoxy-2-methylpropionate, Methyl 2-Hydroxy-3-methylbutyrate, Ethyl Methoxyethyl Acetate, Ethyl Ethoxyethyl Acetate Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxyacetate, propyl 3-methoxyacetate, methyl-3-methoxybutyl acetate, methyl-3-methoxybutyl propionate, 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, etc. These solvents can be used alone or in combination of two or more.

[0515] In addition, it can combine solvents with boiling points above 160°C and solvents with boiling points below 160°C.

[0516] As such a high-boiling-point solvent, the following compounds described in International Publication No. 2018 / 131562 (A1) are preferred, for example.

[0517]

[0518] [R in equation (i)] 1 R 2 and R 3 Each alkyl group represents a hydrogen atom and has 1 to 20 carbon atoms, which can be interrupted by an oxygen atom, a sulfur atom, or an amide bond. These groups can be the same or different, and can also be connected to form a ring structure.

[0519] Alternatively, 1,6-diacetoxyhexane (boiling point 260°C), tripropylene glycol monomethyl ether (boiling point 242°C), and various high-boiling point solvents described in paragraph 0082 of Japanese Patent Application Publication No. 2021-84974 may be preferred.

[0520] Alternatively, the following may be preferred: 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), and tripropylene glycol monomethyl ether (boiling point 247°C), as described in Japanese Patent Application Publication No. 2019-20701. 2℃), γ-butyrolactone (boiling point 204℃), benzyl alcohol (boiling point 205℃), propylene carbonate (boiling point 242℃), tetraethylene glycol dimethyl ether (boiling point 275℃), 1,6-diacetoxyhexane (boiling point 260℃), dipropylene glycol (boiling point 230℃), 1,3-butanediol diacetate (boiling point 232℃), and various high-boiling solvents described in paragraphs 0023 to 0031 of this publication.

[0521] One embodiment of the composition for forming a resist underlayer film according to this application may contain "acid and / or its salt" and / or "acid-generating agent".

[0522] Examples of acids include: p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-hydroxybenzenesulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, etc.

[0523] Salts of the aforementioned acids may also be used as salts. There are no particular limitations on the salt; salts of ammonia derivatives such as trimethylamine and triethylamine, as well as salts of pyridine derivatives and morpholine derivatives, may be used appropriately.

[0524] The acid and / or its salt may be used alone or in combination of two or more. The mixing amount is typically 0.0001 to 20% by mass relative to all solid components, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass.

[0525] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents.

[0526] Examples of heat-generating acid agents include: 2,4,4,6-tetrabromocyclohexadienone, methyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic alkyl sulfonates.

[0527] Photoacid generators produce acid during resist exposure. This allows adjustment of the acidity of the underlying film. This is a method for matching the acidity of the underlying film with that of the upper resist layer. Furthermore, the pattern shape of the resist formed on the upper layer can be adjusted by regulating the acidity of the underlying film.

[0528] Examples of photoacid-generating agents contained in the composition for forming the lower layer of the resist film according to the present invention include: onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0529] Examples of ononium salt compounds include: diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0530] Examples of sulfonylimide compounds include: N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0531] Examples of disulfonyl diazonium compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium, etc.

[0532] Acid-producing agents can be used alone or in combination of two or more.

[0533] When an acid-generating agent is used, its proportion relative to 100 parts by weight of the solid component of the composition for forming the lower layer of the resist is 0.01 to 10 parts by weight, or 0.1 to 8 parts by weight, or 0.5 to 5 parts by weight.

[0534] In addition to the above, the composition for forming a resist underlayer film of one embodiment of the present invention may also contain crosslinking agents, surfactants, light absorbers, rheology modifiers, adhesive aids, etc., as needed.

[0535] Representative crosslinking agents include aminoplast crosslinking agents and phenolplast crosslinking agents.

[0536] The aforementioned crosslinking agent can be a crosslinking agent with high heat resistance. As a crosslinking agent with high heat resistance, a compound containing a crosslinking-forming substituent with an aromatic ring (e.g., benzene ring, naphthalene ring) is preferred.

[0537] Examples of crosslinking agents for amino plastics include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanidine, glycourea, urea, and their polymers. Crosslinking agents having at least two crosslinking-forming substituents are preferred, and are compounds such as methoxymethylated glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanidine, butoxymethylated benzoguanidine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds may also be used.

[0538] Preferably, it is selected from at least one of tetramethoxymethyl glycosuria and hexamethoxymethyl melamine.

[0539] If we were to provide some specific examples, they would be as follows.

[0540]

[0541] Examples of phenolic plastic crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated aromatic compounds and their polymers. Preferably, crosslinking agents have at least two crosslinking-forming substituents in one molecule, and are compounds 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 may also be used.

[0542] In addition to those mentioned above, compounds having the structural part of the following formula (4) and polymers or oligomers having repeating units of the following formula (5) can also be listed as such compounds.

[0543]

[0544] The above R 11 R 12 R 13 and R 14 The alkyl group consists of 1 to 10 hydrogen or carbon atoms, and the examples shown above can be used. n1 is an integer from 1 to 4, n2 is an integer from 1 to (5 - n1), and (n1 + n2) represents an integer from 2 to 5. n3 is an integer from 1 to 4, n4 is from 0 to (4 - n3), and (n3 + n4) represents an integer from 1 to 4. As oligomers and polymers, the number of repeating structural units can be in the range of 2 to 100 or 2 to 50.

[0545] If we were to list some specific examples, they would be as follows.

[0546]

[0547] Crosslinking agents such as amino plastic crosslinking agents and phenolic plastic crosslinking agents can be used alone or in combination of two or more. Amino plastic crosslinking agents can be manufactured by methods known to them or similar methods; in addition, commercially available products can also be used.

[0548] Furthermore, the amount of crosslinking agents used, such as amino plastic crosslinking agents and phenolic plastic crosslinking agents, varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., and is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, and is 80% by mass or less, 50% by mass or less, 40% by mass or less, 20% by mass or less, or 10% by mass or less, relative to all solid components of the resist lower film forming composition of the present invention.

[0549] To avoid pinholes and streaks, and to further improve the coating properties for uneven surfaces, a surfactant may be mixed into the resist lower film forming composition of the present invention.

[0550] Examples of surfactants include... The following nonionic surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate. The following fluorinated surfactants include: EFTOP EF301, EF303, EF352 (manufactured by Tohkem Products Co., Ltd., trade name), MEGAFACE F171, F173, R-30, R-40 (manufactured by Dai Nippon Ink Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), etc. Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0551] The amount of these surfactants mixed in the composition for forming the lower layer of the resist film according to the present invention is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to all solid components of the composition. These surfactants may be added individually or in combination of two or more.

[0552] Light absorbers such as those listed in "Technology and Markets of Industrial Pigments" (CMC publication) and "Dye Handbook" (edited by the Organic Synthetic Chemistry Society) are suitable, including commercially available light absorbers such as CI 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, and CI Disperse Orange 1, 5, 13, 25, 29, 30, and 31. 44, 57, 72 and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Disperse Violet 43; CI Disperse Blue 96; CI Fluorescent Whitening Agent 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The mixing ratio of the above-mentioned light absorbers is generally 10% by mass or less, preferably 5% by mass or less, relative to all solid components of the resist underlayer film forming composition of the present invention.

[0553] Rheology modifiers are primarily added to improve the flowability of the composition for forming the lower resist film, especially to improve the uniformity of the film thickness of the lower resist film during the baking process and to improve the filling ability of the composition for forming the lower resist film to the pores. Specific examples include: phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecanyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyl decyl 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; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. The mixing ratio of these rheology modifiers is typically less than 30 by mass relative to all the solid components of the resist underlayer film forming composition of the present invention.

[0554] Adhesion aids are primarily added to improve the adhesion between the substrate or resist and the composition used for forming the underlying film of the resist, especially during development to prevent resist peeling. Specific examples include: chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; and alkoxysilanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium. The compounds include silazanes such as azoles, silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidyl etheroxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. The mixing ratio of these adhesive aids is typically less than 5% by mass, preferably less than 2% by mass, relative to all solid components of the resist underlayer film forming composition of the present invention.

[0555] The solid content of the resist underlayer film forming composition of the present invention is 0.1 to 70% by mass or 0.1 to 60% by mass. The solid content is the proportion of all components in the resist underlayer film forming composition after removing the solvent. The solid content may contain 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass of a crosslinkable resin.

[0556] [Resist underlayer film]

[0557] The resist underlayer film can be formed using the resist underlayer film forming composition of the present invention, and for example as follows.

[0558] The resist underlayer film forming composition of one aspect of the present invention is applied to a substrate (e.g., silicon wafer substrate, silicon dioxide coated substrate (SiO2 substrate), silicon nitride substrate (SiN substrate), silicon oxynitride substrate (SiON substrate), titanium nitride substrate (TiN substrate), tungsten substrate (W substrate), glass substrate, ITO substrate, polyimide substrate, and low-k material coated substrate, etc.) used in the manufacture of semiconductor devices using a suitable coating method such as a heating plate. Then, the substrate is fired using a heating means such as a heating plate, thereby forming the resist underlayer film. The firing conditions are preferably selected from a firing temperature of 80°C to 800°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 500°C and the firing time is 0.5 to 2 minutes. Air, or inert gases such as nitrogen and argon, can be used as the atmosphere gas during firing. In one aspect, an oxygen concentration of 1% or less is particularly preferred. The thickness of the lower layer film formed is, for example, 10–1000 nm, 20–500 nm, 30–400 nm, or 50–300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz embossing mold (mold replica) can be made.

[0559] Furthermore, an adhesive layer and / or a silicon-containing layer containing 99% by mass or less or 50% by mass or less of Si can also be formed on the resist underlayer film of one aspect of the present invention by coating or vapor deposition. For example, in addition to the adhesive layer described in Japanese Patent Application Publication No. 2013-202982 and Japanese Patent No. 5827180, and the method of forming a silicon-containing resist underlayer film (inorganic resist underlayer film) composition described in International Publication No. 2009 / 104552 (A1) by spin coating, Si-based inorganic material films can also be formed by CVD or the like.

[0560] Furthermore, by coating a resist underlayer film forming composition of one aspect of the present invention onto a semiconductor substrate (so-called high-low difference substrate) having a portion with a high-low difference and a portion without a high-low difference and then firing it, the high-low difference between the portion with a high-low difference and the portion without a high-low difference can be reduced.

[0561] [Method for manufacturing semiconductor devices]

[0562] (i)

[0563] A method for manufacturing a semiconductor device according to one aspect of the present invention includes: The process of forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film formation composition of one aspect of the present invention. The process of forming a resist film on the underlying resist film. The process of irradiating a photoresist film with light or an electron beam and then developing it to form a photoresist pattern. The process of etching the resist underlayer film via a resist pattern to form a patterned resist underlayer film, and... The process of processing a semiconductor substrate through a patterned resist underlayer film.

[0564] (ii)

[0565] Furthermore, a method for manufacturing a semiconductor device according to one aspect of the present invention includes: The process of forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film formation composition of one aspect of the present invention. The process of forming a hard mask on the underlying resist film. The next step is to form a resist film on the hard mask. The process of irradiating a photoresist film with light or an electron beam and then developing it to form a photoresist pattern. The process of etching a hard mask using a resist pattern to form a patterned hard mask. The process of etching the resist underlayer film through a patterned hard mask to form a patterned resist underlayer film, and... The process of processing a semiconductor substrate through a patterned resist underlayer film.

[0566] (iii)

[0567] Furthermore, a method for manufacturing a semiconductor device according to one aspect of the present invention includes: The process of forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film formation composition of one aspect of the present invention. The process of forming a hard mask on the underlying resist film. The next step is to form a resist film on the hard mask. The process of irradiating a photoresist film with light or an electron beam and then developing it to form a photoresist pattern. The process of etching a hard mask using a resist pattern to form a patterned hard mask. The process of forming a patterned resist underlayer film by etching the resist underlayer film through a patterned hard mask. The process of removing the hard mask, and The process of processing a semiconductor substrate through a patterned resist underlayer film.

[0568] (iv)

[0569] Furthermore, a method for manufacturing a semiconductor device according to one aspect of the present invention includes: The process of forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film formation composition of one aspect of the present invention. The process of forming a hard mask on the underlying resist film. The next step is to form a resist film on the hard mask. The process of irradiating a photoresist film with light or an electron beam and then developing it to form a photoresist pattern. The process of etching a hard mask using a resist pattern to form a patterned hard mask. The process of forming a patterned resist underlayer film by etching the resist underlayer film through a patterned hard mask. The process of removing the hard mask, The process of forming a vapor-deposited film (spacer) on the resist underlayer after the hard mask has been removed. The process of etching to process the vapor-deposited film (spacer). The process of removing the patterned resist underlayer, leaving the patterned vapor-deposited film (spacers), and... The process of processing a semiconductor substrate by means of a patterned vapor-deposited film (spacer).

[0570] The semiconductor substrate can be processed using the manufacturing methods described in (i) to (iv).

[0571] The process of forming a photoresist underlayer film using a composition for forming a photoresist underlayer film of one aspect of the present invention is as described in the section on [Photoresist Underlayer Film].

[0572] Alternatively, a silicon-containing film or other hard mask can be formed on the resist underlayer film formed by the process described above as a second resist underlayer film, and then a resist pattern can be formed on it [as described in (ii) to (iv)].

[0573] Hard masks can be coatings of inorganic materials or vapor-deposited films of inorganic materials formed by vapor deposition methods such as CVD and PVD. Examples include SiON films, SiN films, or SiO2 films.

[0574] An anti-reflective coating (BARC) can be further formed on this hard mask, or a resist shape correction film without anti-reflective capability can be formed.

[0575] In the process of forming the resist pattern, exposure is performed either by using a mask (reticle) to form the specified pattern or by direct drawing. Exposure sources can include, for example, gamma rays, i-rays, KrF excimer lasers, ArF excimer lasers, EUV, and electron beams. After exposure, post-exposure baking is performed as needed. Subsequently, development is carried out with a developer (e.g., 2.38% by mass tetramethylammonium hydroxide aqueous solution, butyl acetate), and further rinsed with a cleaning solution or pure water to remove the developer used. Finally, post-baking is performed to dry the resist pattern and improve adhesion to the substrate.

[0576] The etching process performed after the resist pattern is formed is carried out by dry etching.

[0577] Furthermore, the following gases can be used for processing hard masks (silicon-containing layers), resist underlayers, and substrates: CF4, CHF3, CH2F2, CH3F, C4F6, C4F8, O2, N2O, NO2, H2, and He. These gases can be used alone or in mixtures of two or more. Argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon, or nitrogen trifluoride can also be mixed with these gases.

[0578] The resist film can also be patterned using nanoimprinting or self-assembly film methods.

[0579] In nanoimprinting, a resist composition is formed using a mold (mold) that is transparent to light and has a pattern. In contrast, in self-assembled film methods, patterns are formed using self-assembled films made from diblock polymers (such as polystyrene-polymethyl methacrylate) that can naturally form nanoscale regular structures.

[0580] In nanoimprint lithography, a silicon-containing layer (hard mask layer) may be optionally formed on a photoresist underlayer by coating or vapor deposition before the application of a curable composition that becomes a photoresist film. A bonding layer may then be formed on the photoresist underlayer or the silicon-containing layer (hard mask layer) by coating or vapor deposition, and the curable composition that becomes a photoresist film may be applied on the bonding layer.

[0581] Furthermore, wet etching is sometimes performed to simplify the process and reduce damage to the substrate. This suppresses dimensional variations and reduces pattern roughness, enabling high-yield substrate processing. Therefore, in (iii) to (iv), the hard mask can be removed by etching or with an alkaline solution. Especially when using an alkaline solution, while there are no restrictions on the composition, the following components are preferred as the alkaline component.

[0582] Examples of alkaline components include: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, and 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, especially from an operability point of view, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, and inorganic bases can also be used in combination with quaternary ammonium hydroxides. The inorganic base is preferably an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, or rubidium hydroxide, and potassium hydroxide is more preferred.

[0583] Example

[0584] The following examples will be used to illustrate the content of the present invention, but the present invention is not limited thereto.

[0585] The weight-average molecular weight Mw and Mw / Mn (polydispersity) of the polymers shown in Synthetic Examples 1-9, Synthetic Examples 1'-9', and Comparative Synthetic Examples 1-3 below were determined by gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus manufactured by Tosoh Corporation, and the determination conditions are as follows.

[0586] GPC column: TSKgel Super-MultiporeHZ-N (2 columns)

[0587] Column temperature: 40℃

[0588] Solvent: Tetrahydrofuran (THF)

[0589] Flow rate: 0.35 ml / min

[0590] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0591] 〇 Polymer Synthesis

[0592] In the synthesis of the polymers (S1) to (S8) used as the lower layer film of the resist, and in the synthesis of the comparative examples (SS1) to (SS3), the following compound groups A, B, C, D, E, F, and G were used.

[0593] ○ Compound groups A to C

[0594] ○ Catalyst group D, solvent group E, reprecipitation solvent group F, separation solvent group G

[0595] Mesylate: D1

[0596] Tetrabutylammonium iodide: D2

[0597] Propylene glycol monomethyl ether acetate (PGMEA): E1

[0598] Tetrahydrofuran (THF): E2

[0599] 25% sodium hydroxide aqueous solution: E3

[0600] Methanol: F1

[0601] Methanol / Water: F2

[0602] Butyl acetate / water: G1

[0603] [Synthesis Examples 1 to 9]

[0604] 10.0 g of Al, 3.2 g of Cl, 0.8 g of D1, and 20.9 g of E1 were placed in a flask. The mixture was then heated to reflux under nitrogen and the reaction was allowed to proceed for approximately 22 hours. After the reaction was stopped, the mixture was reprecipitated using F1 and dried to obtain resin (S1). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 4,800. Resins S2 to S9 were synthesized using the same procedure. The amounts of compounds added as raw materials for each resin, the synthesis conditions, etc., are shown in Table 1.

[0605] [Table 1]

[0606] The structural formulas of the obtained resins S1 to S9 are shown below.

[0607]

[0608] [Synthesis Examples 1' to 9']

[0609] 15.0 g of S1, 9.9 g of C9, 0.5 g of D2, 38.1 g of E2, and 17.2 g of E3 were placed in a flask. The mixture was heated to 55°C under nitrogen and the reaction was allowed to proceed for approximately 14 hours. After the reaction was stopped, the mixture was repeatedly separated with water using G1 to concentrate the organic layer. The organic layer was then reprecipitated using F2 and dried to obtain resin (S'1). The weight-average molecular weight (Mw) measured by GPC to polystyrene was approximately 5,000. The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain a solution of the target compound. Furthermore, the solvent used to redissolve the resin was varied depending on the solubility of the polymer. In addition, ion exchange resin treatment was performed as needed. Resins S'2 to S'9 were synthesized using the same procedure. The amounts of compounds added as raw materials for each resin, the synthesis conditions, etc., are shown in Table 2.

[0610] [Table 2]

[0611] The structural formulas, weight-average molecular weights Mw and Mw / Mn (polydispersity) of the obtained resins S'1 to S'9 are shown below.

[0612]

[0613] [Compare Synthesis Examples 1-3]

[0614] Comparative resins SS1 to SS3 were synthesized using the same procedures as in Synthesis Examples 1 to 9. The amounts of compounds added as raw materials for each resin, the synthesis conditions, etc., are shown in Table 3.

[0615] [Table 3]

[0616] The structural formulas and weight-average molecular weights (Mw) of the obtained resins SS1 to SS3 are shown below.

[0617]

[0618] Modulation of the underlayer film of the resist

[0619] Resins (S1) to (S9), (S'1) to (S'9), and (SS1 to SS3), crosslinking agent (CL1), acid-generating agent (Ad1), solvents (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CYH)), and surfactant MEGAFACE R-40 (manufactured by DIC Corporation, H1) were mixed according to the proportions shown in Table 4 below, and filtered using a 0.1µm polytetrafluoroethylene microfilter to prepare compositions for forming the lower layer of the resist film (M1 to M10, comparative M1 to comparative M12). Furthermore, the values ​​shown in Table 4 represent the weight proportions of the crosslinking agent, acid-generating agent, and surfactant when the weight of the resin is 100 parts. Regarding the solvents, the values ​​represent the weight proportions of each solvent when the total solvent weight is 100% by weight, independent of the resin weight. In Table 4, "-" indicates that the aforementioned components are not present.

[0620] The structures of the crosslinking agent (CL1) and the acid-producing agent (Ad1) are shown below.

[0621]

[0622] [Table 4]

[0623] [Dissolution test of the resist solvent]

[0624] [Examples 1-10, Comparative Examples 1-12]

[0625] The resist underlayer film forming compositions of M1 to M10 or comparative M1 to M12 were coated onto a silicon wafer using a spin coater. The wafers were then fired at atmospheric pressure according to the specified temperature and time as described in Table 5 to form a resist underlayer film with a thickness of approximately 200 nm. The formed resist underlayer film was then immersed in a PGME / PGMEA mixed solution (mass ratio = 7 / 3) of a general-purpose diluent for 60 seconds, spin-dried, and fired at 100°C for 30 seconds. Solvent resistance was confirmed by comparing the film thickness before and after diluent immersion. A reduction in film thickness of less than 1% was classified as "0", and a reduction exceeding 1% was classified as "×".

[0626] Furthermore, the aforementioned composition for forming the lower layer film was coated onto a silicon wafer using a coating and developing apparatus (ACT-8) manufactured by Tokyo Powertech Co., Ltd., and fired under nitrogen at the specified temperature and time as described in Table 5 to form a 200 nm resist lower layer film. Similarly, the film was immersed in a PGME / PGMEA mixed solution (mass ratio = 7 / 3) for 60 seconds, rotary dried, and fired at 100°C for 30 seconds. The solvent resistance was confirmed by comparing the film thickness before and after diluent immersion. A film thickness reduction rate of less than 1% before and after diluent immersion was defined as "0", and a reduction rate exceeding 1% was defined as "×". The results are shown in Table 5. Furthermore, the comparison here is for the same polymer backbone, comparing the results with and without the introduction of propargyl groups.

[0627] [Table 5]

[0628] As shown in Table 5, Comparative Examples 1-9 without propargyl groups did not exhibit sufficient curing properties under nitrogen and could not form a cured film (residual film rate ≤10%). On the other hand, by introducing propargyl groups, a cured film that can be used as a substrate film for photoresist can be obtained not only under atmospheric conditions but also under nitrogen. In the case of propargyl groups, sufficient curing properties can be exhibited even with suppressed dosage, and the material properties are not impaired by the addition of crosslinking agents. As mentioned above, there were no samples cured under nitrogen in Comparative Examples 1-9, so there were no comparison objects in the subsequent evaluation. Therefore, as comparative examples cured under nitrogen, samples mixed with additives (crosslinking agent and acid catalyst) (Comparative Examples 10-12) were prepared. The subsequent evaluation was based on comparing the samples cured under nitrogen with each other, and Comparative Examples 10-12 were used as comparison objects.

[0629] [Determination of Etching Rate]

[0630] The resist underlayer film formation compositions of Examples 1-10 or Comparative Examples 10-12 were coated onto silicon wafers using a spin coater. The resist underlayer films were formed at the specified temperatures and times as described in Table 6 on a hot plate. The dry etching rate was measured using O2 / N2 gas or CF4 gas as the etching gas. The etching rate was determined by comparing the film thickness before and after etching. Cases where the etching rate was slower than any of Comparative Examples 10-12 were marked as "0", and cases where the rate was faster were marked as "×". The results are shown in Table 6.

[0631] The etching machine and etching gas used in the etching measurement are as follows.

[0632] RIE-200NL (Made by Samco): CF450sccm

[0633] RIE-200NL (Made by Samco): O2 / N 210sccm / 200sccm

[0634] [Table 6]

[0635] As shown in Tables 5 and 6, by introducing propargyl groups, sufficient curability can be obtained not only in an atmospheric atmosphere but also in a nitrogen atmosphere. Furthermore, a cured film can be obtained even without using a crosslinking agent containing a large number of heteroatoms, thus obtaining a film with higher etching resistance than a resist underlayer film containing heteroatoms.

Claims

1. A composition for forming a resist underlayer film, comprising a resin (G) having a composite structural unit and a solvent, The composite structural unit has: Structural units with aromatic rings (A), and Structural units (B) having one or more carbon atoms. The resin (G) is obtained by a reaction in which covalent bonds are formed between the carbon atoms constituting the aromatic ring in the structural unit (A) and the carbon atoms in the structural unit (B). The structural unit (A) comprises structural units (AI) containing at least a nitrogen atom and a carbon-carbon triple bond. The structural unit (B) comprises a structural unit (BI) having a non-aromatic hydrocarbon ring. The structural unit (BI) has 5 to 30 carbon atoms constituting the non-aromatic hydrocarbon ring.

2. The composition for forming a resist underlayer film as claimed in claim 1, wherein the structural unit (AI) has an aromatic ring-containing skeleton, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

3. The composition for forming a resist underlayer film according to claim 1, wherein the structural unit (AI) has a framework containing an aromatic ring, the framework being at least one framework represented by formula (A-1a), (A-1b), (A-1c), (A-2a), (A-2b-1), (A-2b-2), (A-2c-1), (A-2c-2), (A-2c-3), and (A-2c-4), and at least one hydrogen atom in the framework may be substituted with a substituent. In equations (A-1a) to (A-1c), Ar 11 Each independently represents a residue of the aromatic ring, R 11 Each can independently represent a hydrogen atom or a residue of an aromatic ring. In the formula, Ar 21 Each independently represents a residue of the aromatic ring. R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring. R 22 Each of the two R groups independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or a residue of an aromatic ring. 22 They can form unsaturated aliphatic rings together. It should be noted that one of the unsaturated bonds in the unsaturated aliphatic ring refers to the unsaturated bond that constitutes the pyrrole ring. R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond with L; L represents a single bond or a linker; n1 represents 1; n2 represents 1 or 2. In formulas (A-2b-2) and (A-2c-4), when L is a single bond, "structural part (In1) and structural part (In2)" and "structural part (Ca1) and structural part (Ca2)" are connected together by two nitrogen atoms, or by two Ar atoms. 21 They are connected together, or through nitrogen atoms and Ar atoms. 21 When L is a linking base, in equations (A-2b-2) and (A-2c-4), L is connected to N or Ar. 21 connect.

4. The composition for forming a lower layer of resist film as claimed in claim 3, wherein the substituent that may replace at least one hydrogen atom in the skeleton is selected from one or more groups selected from halogen groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl groups, thiol groups, thioether groups, and ether-bonded groups.

5. The composition for forming a resist underlayer film as claimed in claim 1, wherein the structural unit (AI) contains a group represented by the following formula (A-10) as a group containing the carbon-carbon triple bond. In formula (A-10), R 1 R represents a single bond or a divalent organic group with 1 to 20 carbon atoms. 2 * indicates a monovalent organic group containing 1 to 20 hydrogen or carbon atoms, and * indicates a linking bond.

6. The composition for forming a resist underlayer film as claimed in claim 1, wherein the structural unit (BI) is a structure represented by the following formula (B2). In formula (B2), Z 0 This refers to an organic group consisting of 5 to 30 aliphatic ring residues with substituents, or two or more aliphatic rings linked by a single bond. J 1 and J 2 Each of these represents a divalent organic group that is directly connected or may have substituents, and * indicates the connection site with structural unit (A).

7. The composition for forming a resist underlayer as claimed in claim 1, wherein the resin (G) is a resin obtained by reacting a compound having a group containing a carbon-carbon triple bond with a resin synthesized from a reaction raw material containing an alicyclic unsaturated compound having two or more carbon-carbon double bonds and an amine compound.

8. The composition for forming a resist underlayer film as claimed in claim 7, wherein the amine compound has an aromatic ring-containing skeleton, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

9. The composition for forming a resist underlayer as described in claim 7, wherein the alicyclic unsaturated compound has a dicyclopentadiene structure.

10. The composition for forming a resist underlayer film as claimed in claim 1, wherein the solvent comprises a solvent having a boiling point of 160°C or higher.

11. The composition for forming a resist underlayer as claimed in claim 1, further comprising at least one selected from acids and their salts, and acid-generating agents.

12. The composition for forming a resist underlayer film as claimed in claim 1, further comprising a crosslinking agent.

13. The composition for forming a resist underlayer film as claimed in claim 12, wherein the crosslinking agent is at least one selected from amino plastic crosslinking agents and phenolic plastic crosslinking agents.

14. The composition for forming a resist underlayer as claimed in claim 1, further comprising a surfactant.

15. A resist underlayer film on a semiconductor substrate, which is a cured product of the resist underlayer film forming composition according to any one of claims 1 to 14.

16. A method for forming a resist pattern for manufacturing a semiconductor, comprising the steps of coating a resist underlayer film forming composition according to any one of claims 1 to 14 onto a semiconductor substrate and firing it to form a resist underlayer film.

17. A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film formation composition according to any one of claims 1 to 14 The process of forming a resist film on the lower resist film, The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the resist underlayer film via the resist pattern to form a patterned resist underlayer film, and... The process of processing a semiconductor substrate via the patterned resist underlayer film.

18. A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film formation composition according to any one of claims 1 to 14 The process of forming a hard mask on the underlying resist film, The next step is to form a resist film on the hard mask. The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the hard mask using the resist pattern to form a patterned hard mask. The process of etching the patterned photoresist underlayer film via the patterned hard mask to form the patterned photoresist underlayer film, and... The process of processing a semiconductor substrate via the patterned resist underlayer film.

19. A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film formation composition according to any one of claims 1 to 14 The process of forming a hard mask on the underlying resist film, The next step is to form a resist film on the hard mask. The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the hard mask using the resist pattern to form a patterned hard mask. The process of etching the resist underlayer film through the patterned hard mask to form the patterned resist underlayer film. The process of removing the hard mask, and The process of processing a semiconductor substrate via the patterned resist underlayer film.

20. A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film formation composition according to any one of claims 1 to 14 The process of forming a hard mask on the underlying resist film, The next step is to form a resist film on the hard mask. The process of irradiating the resist film with light or an electron beam and then developing it to form a resist pattern. The process of etching the hard mask using the resist pattern to form a patterned hard mask. The process of etching the resist underlayer film through the patterned hard mask to form the patterned resist underlayer film. The process of removing the hard mask, The process of forming a vapor-deposited film from the resist underlayer after the hard mask has been removed. The process of processing the vapor-deposited film by etching. The process of removing the patterned resist underlayer film, leaving the patterned vapor-deposited film, and... The process of processing a semiconductor substrate via the patterned vapor deposition film.

21. The method of manufacturing a semiconductor device as claimed in claim 18, wherein the hard mask is formed by coating an inorganic composition or by vapor-depositing an inorganic material.

22. The method of manufacturing a semiconductor device as claimed in claim 17, wherein the resist film is patterned by nanoimprinting or self-assembly of a film.

23. The method of manufacturing a semiconductor device as claimed in claim 19, wherein the removal of the hard mask is performed by etching or using an alkaline solution.

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