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

Abstract

Provided is a composition for forming a resist underlayer film, containing: a resin (G) having an indole structure in a side chain, and a solvent. The resin (G) is not a resin in which the indole structure is bonded to a carbon atom at the 9-position of a fluorene ring via a carbon-carbon double bond.

Description

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

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

[0002] In recent years, semiconductor manufacturing processes have advanced rapidly, and consequently, there is a strong demand for higher quality and improved properties of resist underlayer films (see, for example, Patent Documents 1 to 6). In particular, resist underlayer films, which are known to be made of high-carbon materials, are strongly required to have not only reflection suppression function (having excellent optical constants to suppress reflection) but also etching resistance.

[0003] U.S. Patent Application Publication No. 2016 / 311975 Specification International Publication No. 2018 / 198960 Brochure JP 2021-81686 JP 2020-105513 International Publication No. 2013 / 146670 Brochure JP 2016-151024

[0004] In the manufacturing process of semiconductor devices, if a large amount of sublimation material is generated from the resist underlayer film, problems such as contamination of the baker tray and piping used during firing can occur. The present invention has been made in view of the above circumstances, and aims to provide a resist underlayer film formation composition that can suppress the generation of sublimation material, as well as a method for forming a resist underlayer film and a resist pattern using the resist underlayer film formation composition, and a method for manufacturing a semiconductor device.

[0005] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, found that they could solve the above problems, and completed the present invention having the following gist.

[0006] In other words, the present invention encompasses the following embodiments: [1] A resist underlayer film forming composition comprising a resin (G) having an indole structure in its side chain and a solvent, wherein the resin (G) is not a resin in which an indole structure is bonded to the carbon atom at position 9 of a fluorene ring via a carbon-carbon double bond. [2] The resist underlayer film forming composition according to [1], wherein the resin (G) has a composite unit structure, the composite unit structure having a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms, and the resin (G) is a resin obtained by a reaction that generates a covalent bond between the carbon atoms constituting the aromatic ring of the unit structure (A) and the carbon atoms in the unit structure (B). [3] The resist underlayer film forming composition according to [2], wherein the unit structure (A) comprises a unit structure (A-I) containing at least a nitrogen atom, the unit structure (A-I) has a skeleton having an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton. [4] The resist underlayer film forming composition according to [2], wherein the unit structure (A) comprises a unit structure (A-II) containing a phenolic hydroxyl group, the unit structure (A-II) has a skeleton having an aromatic ring, and the skeleton is a phenol skeleton. [5] The resist underlayer film forming composition according to any one of [1] to [4], wherein the indole structure is at least one of the following formulas (C-1), (C-2), (C-3), (C-4), (C-5), (C-6), and (C-7), and in the indole structure, at least one hydrogen atom may be replaced by a substituent. (In formulas (C-1) to (C-7), L １ R represents a single bond or an alkylene group with 1 to 3 carbon atoms. １ Ar represents a hydrogen atom, a phenyl group, or a naphthyl group. １ Ar represents a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or biphenyl ring. ２ and Ar ３(Each represents independently a benzene ring or a naphthalene ring, and * represents a bond.) [6] The resist underlayer film forming composition according to [5], wherein the substituent in the indole structure, which may replace at least one hydrogen atom, is one or more groups selected from halogen atoms, alkyl groups, alkenyl groups, alkynyl 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-containing groups, thiol groups, sulfide-containing groups, and ether bond-containing groups. [7] The resist underlayer film forming composition according to any one of [1] to [6], wherein the solvent comprises a solvent with a boiling point of 160°C or higher. [8] The resist underlayer film forming composition according to any one of [1] to [7], further comprising at least one selected from the group consisting of acids and salts thereof, and acid generators. [9] The resist underlayer film forming composition according to any one of [1] to [8], further comprising a crosslinking agent.

[10] The resist underlayer film forming composition according to [9], wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

[11] The resist underlayer film forming composition according to any one of [1] to

[10] , further comprising a surfactant.

[12] 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 [1] to

[11] .

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

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

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

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

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

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

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

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

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

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

[18] A method for manufacturing a semiconductor device according to any one of

[15] to

[17] , wherein the hard mask is formed by coating a composition containing an inorganic substance or by vapor deposition of an inorganic substance.

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

[14] to

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

[20] A method for manufacturing a semiconductor device according to

[16] or

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

[0007] According to the present invention, it is possible to provide a resist underlayer film formation composition that can suppress the amount of sublimation generated, as well as a resist underlayer film formation method, a resist pattern formation method, and a semiconductor device manufacturing method using the resist underlayer film formation composition.

[0008] [Composition for Forming Resist Underlayer Film] The composition for forming a resist underlayer film of the present invention contains a resin (G) having an indole structure in its side chain and a solvent. The resin (G) is not a resin in which an indole structure is bonded to the 9-position carbon atom of the fluorene ring via a carbon-carbon double bond. In the present specification, "having an indole structure in the side chain" means that at least one hydrogen atom of the aromatic hydrocarbon ring constituting the main chain of the resin is substituted with an organic group having an indole structure.

[0009] Note that the "9-position carbon atom of the fluorene ring" refers to the carbon atom marked with "*" in the following structure.

[0010] (Indole Structure) In the present specification, the "indole structure" refers to an organic group containing indole in its structure. At least one hydrogen atom of indole in the indole structure may be substituted with an alkyl group, a phenyl group, or the like. The pyrrole ring or benzene ring in indole may be condensed with a naphthalene ring or another benzene ring.

[0011] Examples of the indole structure include at least one of the structures represented by the following formula (C-1), formula (C-2), formula (C-3), formula (C-4), formula (C-5), formula (C-6), and formula (C-7).

[0012] (In formulas (C-1) to (C-7), L １ represents a single bond or an alkylene group having 1 to 3 carbon atoms, R １ represents a hydrogen atom, a phenyl group, or a naphthyl group, Ar １ represents a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or a biphenyl ring, Ar ２ and Ar ３ each independently represent a benzene ring or a naphthalene ring, and * represents a bond.)

[0013] As L １ a single bond or a methylene group is preferable. As R １ a hydrogen atom is preferable. As Ar １A benzene ring or a naphthalene ring is preferred. ２ and Ar ３ A benzene ring is preferred as the element. ２ and Ar ３ They may be the same or they may be different. L in equation (C-7) １ Ar ３ Rather, Ar ２ They may be bound together.

[0014] At least one hydrogen atom in the indole structure may be substituted with a substituent. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxy groups, hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, and ether-bond-containing groups.

[0015] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups having 2 to 10 carbon atoms. Examples of alkynyl groups include linear, branched, or cyclic alkynyl groups having 2 to 10 carbon atoms. Examples of alkoxy groups include groups represented by -OR, where R is a saturated or unsaturated linear, branched, or cyclic hydrocarbon group (-R) which may be interrupted once or more by an oxygen atom in the hydrocarbon chain. ａ ) represents. Examples of the number of carbon atoms in an alkoxy group include 1 to 20. Examples of aryl groups include aryl groups with 6 to 30 carbon atoms. Examples of aryloxy groups include aryloxy groups with 6 to 30 carbon atoms. Examples of amino groups include -NH ２ , -NHR or -NR ２ A group represented by the hydrocarbon group -R is an example. Here, R is the hydrocarbon group -R ａ Represents -NR ２In this, the two Rs may be the same or different. Examples of hydroxyalkyl groups include linear, branched, or cyclic hydroxyalkyl groups having 1 to 20 carbon atoms. Examples of ester groups include -CO ２ A group represented by R or -OCOR is an example. Here, R is the hydrocarbon group -R ａ This represents the amide group, which can be -NHCOR, -CONHR, -NRCOR, or -CONR. ２ A group represented by the hydrocarbon group -R is an example. Here, R is the hydrocarbon group -R ａ This represents a group, and if there are two Rs, the two Rs may be the same or different. Examples of sulfonyl-containing groups include -SO ２ A group represented by R is an example. Here, R is the hydrocarbon group -R ａ Alternatively, it represents a hydroxyl group -OH. Examples of sulfide-containing groups include groups represented by -SR, where R is the hydrocarbon group -R. ａ This represents the ether bond-containing group, R １１ -O-R １１ Examples include residues of ether compounds containing an ether bond represented by . Here, R １１ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, anthranyl group, or a pyrenyl group. The ether bond-containing group may be an organic group containing an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group.

[0016] Examples of alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. 1,1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, and n-icosyl group. These alkyl groups may be linear, branched, or cyclic.

[0017] Examples of alkenyl groups having 2 to 10 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, and 1-methyl-3-butenyl group. Nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group Xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl Examples include penyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0018] Examples of alkynyl groups having 2 to 10 carbon atoms include the ethynyl group, 1-propynyl group, propargyl group (2-propynyl group), etc., in which the carbon-carbon double bond of the alkenyl group listed above as "alkenyl group" is replaced by a carbon-carbon triple bond.

[0019] Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, and 4-methyl-n-pentyloxy. Examples include ethyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, cyclohexyloxy group, phenoxy group, benzyloxy group, and 1-naphthyloxy group.

[0020] Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, o-xylyl, biphenyl, naphthyl, anthracenyl, phenantrenyl, chrysenyl, triphenylenyl, and pyrenyl groups.

[0021] Specific examples of indole structures are shown below, but indole structures are not limited to these. At least one hydrogen atom in these indole structures may be substituted with the substituents described above.

[0022] Examples of indole structures represented by formula (C-1) include the following structures. * represents a bond. Note that between the nitrogen atom and * in the following structures is L in formula (C-1). １ This may include.

[0023]

[0024] Examples of indole structures represented by formula (C-2) include the following structures. * represents a bond. Note that between the nitrogen atom and * in the following structures is L in formula (C-2). １ This may include.

[0025]

[0026] Examples of indole structures represented by formula (C-3) include the following structures. * represents a bond. Note that between the carbon atom and * in the following structures, there is L in formula (C-3). １ This may include.

[0027]

[0028] Examples of indole structures represented by formula (C-4) include the following structures. * represents a bond. Note that between the carbon atom and * in the following structures, there is L in formula (C-4). １ This may include.

[0029]

[0030] Examples of indole structures represented by formula (C-5) include the following structures. * represents a bond. Note that between the carbon atom and * in the following structures is L in formula (C-5). １ This may include.

[0031]

[0032] Examples of indole structures represented by formula (C-6) include the following structures. * represents a bond. Note that between the carbon atom and * in the following structures, there is L in formula (C-6). １ This may include.

[0033]

[0034] Examples of indole structures represented by formula (C-7) include the following structures. * represents a bond. Note that between the carbon atom and * in the following structures, there is L in formula (C-7). １ This may include.

[0035]

[0036] The method for introducing the indole structure into the side chain is not particularly limited, but one example is to mix a monomer that is a raw material for the resin with a compound represented by the following formulas (C-1a) to (C-7a), heat it under nitrogen until reflux occurs, and react it for a predetermined time.

[0037] (In formulas (C-1a) to (C-7a), L ２ These are hydroxyl groups, -OR, and -C=CH ２ ien-CH ２ -C=CH ２ This represents R, where R represents an alkyl group having 1 to 3 carbon atoms. In formulas (C-1a) to (C-7a), L １ , R １ Ar １ Ar ２ and Ar ３ These are L in equations (C-1) to (C-7), respectively. １ , R １ Ar １ Ar ２ and Ar ３ This is synonymous with [the above]. (* represents a binding action.)

[0038] In formulas (C-1a) to (C-7a), L ２ A hydroxyl group is preferred. In formulas (C-1a) to (C-7a), L １ A single bond or a methylene group is preferred. In formulas (C-1a) to (C-7a), R １ Hydrogen atoms are preferred as such. In formulas (C-1a) to (C-7a), Ar １ A benzene ring or a naphthalene ring is preferred as the element. In formulas (C-1a) to (C-7a), Ar ２ and Ar ３ A benzene ring is preferred as the element. ２ and Ar ３ They may be the same or they may be different. L in equation (C-7a) １ Ar ３ Rather, Ar ２ They may be bound together.

[0039] <Resin (G)> Resin (G) is not particularly limited as long as it has an indole structure in its side chains. Examples of resin (G) include novolac resin, vinyl resin, polyester resin, polyether resin, polyimide resin, and polyamide resin. Examples of vinyl resins include polystyrene resin, polyacrylic resin, polymethacrylic resin, and polyacrylamide resin. From the viewpoint of suitably obtaining the effects of the present invention, novolac resin is preferred as resin (G).

[0040] [I. Definitions of Terms] In this specification, the definitions of the main terms relating to novolac resin, which is one aspect of the present invention, are described below. Unless otherwise specified, the following definitions of terms apply to novolac resin.

[0041] (I-1) "Novolac Resin" The term "novolac resin" is used in a broad sense to broadly encompass resins formed by the covalent bonding (substitution reaction, addition reaction, condensation reaction, or addition-condensation reaction, etc.) between an organic compound having a functional group that enables covalent bonding with an aromatic ring [for example, an aldehyde group; a ketone group; an acetal group; a ketal group; a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, alkoxy group or halo group bonded to the α-carbon atom (benzyl carbon atom, etc.) of an alkylaryl group; a carbon-carbon unsaturated bond such as that found in divinylbenzene or dicyclopentadiene] and an aromatic ring in a compound having an aromatic ring (preferably having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as atoms constituting the aromatic ring or atoms bonded to the aromatic ring).

[0042] Therefore, the novolac resin referred to in this specification is formed by linking multiple compounds having aromatic rings, through which an organic compound containing carbon atoms derived from the functional group (sometimes called a "linked carbon atom") forms a covalent bond with the aromatic ring in a compound having an aromatic ring via the linked carbon atoms, thereby forming a resin.

[0043] In this specification, the terms unit structure (A) and unit structure (B) are used to refer to the unit structures constituting "novolac resin". Unit structure (A) is a unit structure derived from a compound having an aromatic ring. Unit structure (B) is a unit structure derived from a compound having a functional group that enables covalent bonding with the aromatic ring of unit structure (A).

[0044] (I-2) "Residue" A "residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or heteroatom (such as a nitrogen atom, oxygen atom, or sulfur atom) is replaced by a bonding position. It may be a monovalent or polyvalent group. For example, replacing one hydrogen atom with one bonding position results in a monovalent organic group, while replacing two hydrogen atoms with bonding positions results in a divalent organic group.

[0045] (I-3) "Aromatic Ring" (Aromatic Group, Aryl Group, Arylene Group) The term "aromatic ring" is a concept that encompasses aromatic hydrocarbon rings, aromatic heterocycles, and their residues [sometimes called "aromatic group," "aryl group" (in the case of a monovalent group), or "arylene group" (in the case of a divalent group)], and includes not only monocyclic (aromatic monocyclic) but also polycyclic (aromatic polycyclic). In the case of a polycyclic, at least one monocycle is an aromatic monocycle, but the remaining monocycles that form a fused ring with the aromatic monocycle may be monocyclic heterocycles (heteromonocycles) or monocyclic alicyclic hydrocarbons (alicyclic monocycles). In this specification, heteroaryl groups are included in aryl groups. Heteroarylene groups are included in arylene groups.

[0046] Aromatic rings include aromatic hydrocarbon rings such as benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, triphenylene, benzoanthracene, pyrene, chrysene, fluorene, biphenyl, corannellene, perylene, fluorantene, benzo[k]fluorantene, benzo[b]fluorantene, benzo[gh]perylene, coronene, dibenzo[g,p]chrysene, acenaphthylene, acenaphthene, naphthacene, pentacene, cyclooctatetraene, and more typically aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene; and furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, pyro Aromatic heterocyclic compounds such as furan, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindolefluorene, bisindolebenzofluorene, bisindoledibenzofluorene, purine, quinoline, isoquinoline, chromene, thiantrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, and indolocarbazole are examples, but are not limited to these.

[0047] Aromatic rings (e.g., benzene rings, naphthalene rings, etc.) may optionally have substituents, but examples of such substituents include the following atoms and groups: • Halogen atoms • Saturated or unsaturated linear, branched or cyclic hydrocarbon groups (-R) which may be interrupted once or more by oxygen atoms in the hydrocarbon chain. ａ ) (including alkyl groups, alkenyl groups, and alkynyl groups (e.g., propargyl groups), and aryl groups, which may be interrupted once or more by oxygen atoms in the middle of the hydrocarbon chain.), -OR (where R is the hydrocarbon group -R) ａ (Represents:) ・Aryloxy group・-NH ２ , -NHR or -NR ２(The two Rs may be the same or different from each other), where R is the hydrocarbon group -R ａ Represents: hydroxyl group, hydroxyalkyl group, carboxyl group, formyl group, cyano group, nitro group, ester group (for example, -CO ２ R or -OCOR, where R is the hydrocarbon group -R ａ (This represents...) ・Amide group [for example, -NHCOR, -CONHR, -NRCOR (the two Rs may be the same or different) or -CONR ２ (The two Rs may be the same or different from each other), where R is the hydrocarbon group -R ａ This represents: 】 ・Sulfonyl-containing group (e.g., -SO ２ R, where R is the hydrocarbon group -R ａ ) Or it represents a hydroxyl group -OH. ) ・Thiol group (-SH) ・Sulfide-containing group (-SR, where R is the hydrocarbon group -R) ａ (This represents...) ・Organic group containing an ether bond [R １１ -O-R １１ (R １１ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, anthranyl group, or a pyrenyl group. ) Residues of ether compounds represented by ; for example, organic groups containing ether bonds, including methoxy, ethoxy, and phenoxy groups.

[0048] The term "aromatic ring" further includes organic groups having a fused ring of one or more aromatic rings (such as benzene, naphthalene, anthracene, and pyrene) and one or more aliphatic or heterocyclic rings. Examples of aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene, while examples of heterocyclic rings include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0049] An "aromatic ring" may also be an organic group having a structure in which two or more aromatic rings are linked by a divalent linking group. Examples of divalent linking groups include alkylene groups, arylene groups, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２ - are some examples. In addition, the divalent linking group may be a divalent group obtained by removing one hydrogen atom from any substituent of the aromatic ring mentioned above.

[0050] (I-4) "Heterocycle" The term "heterocycle" encompasses both aliphatic heterocycles and aromatic heterocycles, and includes not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic) compounds. In the case of polycyclic compounds, at least one monocycle is a heteromonocycle, but the remaining monocycles may be aromatic hydrocarbon monocycles or alicyclic monocycles. Examples of aromatic heterocycles can be found in (I-3) above. Similar to the aromatic rings in (I-3) above, they may have substituents.

[0051] (I-5) "Non-aromatic ring" (aliphatic ring) When the "non-aromatic ring" is a monocyclic ring, the "non-aromatic monocyclic ring" refers to a monocyclic hydrocarbon that does not belong to the aromatic group, and is typically a monocyclic alicyclic compound. It may also be called an aliphatic monocyclic ring (which may include aliphatic heterocyclic rings, and may contain unsaturated bonds as long as it does not belong to the aromatic compound). Similar to the aromatic ring in (I-3) above, it may have substituents.

[0052] Examples of non-aromatic monocyclic compounds (aliphatic rings, aliphatic monocyclic compounds) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0053] When the "non-aromatic ring" is polycyclic, "non-aromatic polycyclic" refers to a polycyclic hydrocarbon that does not belong to the aromatic group, and is typically a polycyclic alicyclic compound. It may also be called an aliphatic polycyclic [which may include aliphatic heterocyclics (where at least one of the monocyclic rings is an aliphatic heterocyclic ring), or it may contain unsaturated bonds as long as it does not belong to the aromatic compound]. It includes non-aromatic dicyclic, non-aromatic tricyclic, and non-aromatic tetracyclic compounds.

[0054] When "non-aromatic ring" refers to a bicyclic non-aromatic ring, it is a fused ring composed of two monocyclic hydrocarbons that do not belong to the aromatic group, and is typically a fused ring of two alicyclic compounds. In this specification, it may also be called an aliphatic bicyclic ring (which may include aliphatic heterocyclic rings, and may contain unsaturated bonds as long as they do not belong to the aromatic group). Examples of non-aromatic bicyclic rings include bicyclopentane, bicyclooctane, and bicycloheptene.

[0055] When "non-aromatic ring" refers to a tricyclic compound, it is a fused ring composed of three monocyclic hydrocarbons that do not belong to the aromatic group. Typically, it is a fused ring of three alicyclic compounds (each of which may be a heterocyclic compound, and may contain unsaturated bonds as long as they do not belong to the aromatic group). Examples of non-aromatic tricyclic compounds include tricyclooctane, tricyclononane, and tricyclodecane.

[0056] When "non-aromatic ring" refers to a tetracyclic compound, it is a fused ring composed of four monocyclic hydrocarbons that do not belong to the aromatic group. Typically, it is a fused ring of four alicyclic compounds (each of which may be a heterocyclic compound, and may contain unsaturated bonds as long as they do not belong to the aromatic group). Examples of non-aromatic tetracyclic compounds include hexadecahydropyrene.

[0057] (I-6) "Carbon atoms constituting a ring (part)" means carbon atoms constituting a hydrocarbon ring (which may be an aromatic ring, an aliphatic ring, or a heterocycle) in an unsubstituted state.

[0058] (I-7) A "hydrocarbon group" is a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0059] (I-8) In the chemical structural formulas showing the unit structure of novolac resin in this specification, bonds (indicated by *) may be shown for convenience, but unless otherwise specified, such bonds can take any bondable position in the unit structure and do not limit the bondable position in the unit structure in any way.

[0060] <<Novolac Resin>> The novolac resin of this embodiment has a composite unit structure. The composite unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms.

[0061] The composite unit structure of the novolac resin in this embodiment can be represented, for example, by the following formula (AB). (In equation (AB), A represents unit structure (A), and B represents unit structure (B).)

[0062] <<<A-1: Unit Structure (A)>>> Unit structure (A) has an aromatic ring. Unit structure (A) may have, for example, at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom directly attached to an aromatic ring.

[0063] The number of carbon atoms in the unit structure (A) is not particularly limited, but for example, it is 4 to 100, and preferably 4 to 50.

[0064] Preferably, such aromatic ring has 4 to 30 carbon atoms, more preferably 4 to 24 carbon atoms.

[0065] Preferably, such aromatic rings are one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings; or fused rings of a benzene ring, naphthalene ring, anthracene ring, pyrene ring and a heterocycle or aliphatic ring (such as a fluorene ring, benzofluorene ring, dibenzofluorene ring, indole ring, carbazole ring, indrocarbazole ring, etc.).

[0066] The aromatic ring may optionally have substituents, but from the viewpoint of polymerization reactivity, the substituent may contain the minimum necessary amount of heteroatoms. Furthermore, two or more aromatic rings may be linked by a linking group, and the linking group may contain the minimum necessary amount of heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and the like.

[0067] The "aromatic ring" may contain at least one heteroatom selected from N, S, and O on, within, or between the rings.

[0068] Examples of heteroatoms that may be contained on the ring include nitrogen atoms in amino groups (e.g., propargylamino group) and cyano groups; oxygen atoms in oxygen-containing substituents such as formyl group, hydroxyl group, carboxyl group, alkoxy group, alkenyloxy group, alkynyloxy group (e.g., propargyloxy group), and aryloxy group; and nitrogen and oxygen atoms in oxygen-containing substituents and nitrogen-containing substituents such as nitro group. Examples of heteroatoms that may be contained within the ring include oxygen atoms in furan and xanthene, nitrogen atoms in carbazole and pyrrole, and sulfur atoms in phenothiazine. Examples of heteroatoms that may be contained in the linking group of two or more aromatic rings include -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２ Examples of atoms contained in the compound include nitrogen atoms, oxygen atoms, and sulfur atoms. In this specification, "atoms constituting an aromatic ring" is synonymous with "atoms contained within the ring." "Atoms bonded to an aromatic ring" refers, for example, to "atoms or groups contained on the ring that are directly bonded to the ring" and "atoms contained between rings that are directly bonded to the ring." For example, the atoms constituting a benzene ring are carbon atoms. For example, the atoms constituting a pyrrole ring are carbon atoms and nitrogen atoms. For example, the oxygen atom of the hydroxyl group in phenol is not an atom constituting an aromatic ring. For example, the oxygen atom of the hydroxyl group in phenol is an atom bonded to a benzene ring and is an atom of a group contained on a benzene ring that is directly bonded to the benzene ring.

[0069] <<<A-2: Examples of the skeleton constituting the unit structure (A)>>> The unit structure (A) has, for example, a skeleton having aromatic rings.

[0070] Preferred aromatic ring skeletons include aromatic amine skeletons, nitrogen-containing aromatic heterocyclic skeletons, and phenol skeletons.

[0071] The unit structure (A) is, for example, a residue obtained by removing two hydrogen atoms from a skeleton having an aromatic ring. The skeleton having an aromatic ring originates, for example, from a compound having an aromatic ring used in the synthesis of novolac resins. The skeleton having an aromatic ring is, for example, a residue obtained by removing two hydrogen atoms from a compound having an aromatic ring used in the synthesis of novolac resins.

[0072] The aromatic ring skeleton may have substituents. Examples of substituents include those similar to those described above for the (indole structure).

[0073] <<<A-3: Unit Structure (A-I)>>> It is preferable that unit structure (A) includes unit structure (A-I) which contains at least a nitrogen atom. Unit structure (A-I) has a skeleton having an aromatic ring. Here, unit structure (A-I) is a sub-concept of unit structure (A) and does not refer to a substructure of unit structure (A). The skeleton having an aromatic ring in unit structure (A-I) will be described below.

[0074] <<<<A-3-1: Aromatic Amine Skeleton>>>> An aromatic amine skeleton refers to a skeleton having an aromatic ring and a nitrogen atom bonded to the aromatic ring but not constituting a ring. Examples of aromatic amine skeletons include those represented by the following formulas (A-1a) to (A-1c). As will be described later, in the unit structure (A-I), the hydrogen atom of the NH group may be replaced by a substituent. Examples of substituents include those described above in (indole structure), and substituents (S) represented by the following formulas (S1) to (S7). (In formulas (A-1a) to (A-1c), Ar １１ Each of these independently represents a residue of an aromatic ring. １１ Each of these independently represents a hydrogen atom or an aromatic ring residue.

[0075] Ar １１ and R １１ Examples of aromatic rings in the residues of the aromatic ring include aromatic rings represented by the following formula (G1). These aromatic rings may have substituents.

[0076] As the skeleton represented by the formula (A-1a), for example, the following skeletons can be mentioned. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the NH group may be replaced by substituents. The same applies to the following skeletons.

[0077] As the skeleton represented by the formula (A-1b), for example, the following skeletons can be mentioned.

[0078] As the skeleton represented by the formula (A-1c), for example, the following skeletons can be mentioned.

[0079] <<<<A-3-2: Nitrogen-containing aromatic heterocyclic skeleton>>>> The nitrogen-containing aromatic heterocyclic skeleton refers to a skeleton having an aromatic heterocyclic ring having a nitrogen atom in the atoms constituting the heterocyclic ring. Examples of the nitrogen-containing aromatic heterocyclic ring include a pyrrole ring, an indole ring, a pyridine ring, an acridine ring, a phenoxazine ring, a phenothiazine ring, and the like. These nitrogen-containing aromatic heterocyclic rings may have substituents. Examples of the nitrogen-containing aromatic heterocyclic skeleton include a skeleton represented by the following formula (A-2a), the following formula (A-2b-1), the following formula (A-2b-2), the following formula (A-2d), the following formula (A-2e), the following formula (A-3a), or the following formula (A-3b). As described later, in the unit structure (A-I), the hydrogen atoms of the NH group may be replaced by substituents. Examples of the substituents include the substituents described in the above (indole structure), the substituents (S) represented by the following formulas (S1) to (S7) described later, and the like. (In the formula, Ar ２１ each independently represents a residue of an aromatic ring. R ２１ each independently represents a hydrogen atom or a residue of an aromatic ring. R ２２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or a residue of an aromatic ring. Two adjacent R ２２may together form an unsaturated aliphatic ring. One of the unsaturated bonds in the unsaturated aliphatic ring refers to the unsaturated bond constituting the pyrrole ring. Each R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond to L. L represents a single bond or a linking group. n1 represents 1, and n2 represents 1 or 2. In formula (A-2b-2), when L is a single bond, the substructure (In1) and the substructure (In2) are bonded either by bonding of two nitrogen atoms, by bonding of two Ar ２１ to each other, or by bonding of a nitrogen atom and Ar ２１ . In formula (A-2b-2), when L is a linking group, L is bonded to N or Ar ２１ . )

[0080] Ar ２１ , R ２１ , R ２２ , and the aromatic rings in the residues of the aromatic rings of R include, for example, the aromatic rings represented by the following formula (G2). These aromatic rings may have substituents.

[0081] The unsaturated aliphatic rings formed by two adjacent R ２２ together include, for example, the following rings. These aliphatic rings may have substituents.

[0082] Examples of the linking group in L include a saturated hydrocarbon group having (n1 + n2) valences with 1 to 5 carbon atoms and a residue obtained by removing (n1 + n2) hydrogen atoms from an aromatic ring.

[0083] <Formula (A-2d)>[[]] (In formula (A-2d), Each R １１ independently represents a hydrogen atom or an aromatic group, Ar is an aromatic ring portion and independently represents a benzene ring, a condensed ring composed of 2 to 3 benzene rings, or a structure represented by the following formula (Ar01), X ０ is a single bond, -O-, -S-, -NR １２ -, or -CR １３ R １４- represents R １２ R １１ Same as or different from R １１ It is the same as the definition of R １３ and R １４ Each of the following represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, where n is 1 or 2. When n is 1, Z represents a monovalent organic group, and when n is 2, Z represents a divalent organic group.

[0084] Furthermore, in the unit structure (A-I), R in formula (A-2d) １１ R may be a substituent. １１ If R is a substituent or aromatic group, １１ For example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) are further substituted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, an aryl group, or a halo group, or (iii) may have its hydrocarbon chain further interrupted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, or an arylene group.

[0085] An example of a skeleton represented by formula (A-2d) is the skeleton represented by the following formula (A-2d-1). (R in equation (A-2d-1)) １１ , Ar, and X ０ These are R in equation (A-2d), respectively. １１ , Ar, and X ０ This is synonymous with R. ２１ (These are aryl groups with 6 to 30 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, or alkynyl groups with 2 to 10 carbon atoms.)

[0086] In formulas (A-2d) and (A-2d-1), Ar is, for example, a benzene ring or a naphthalene ring. The Ar in formulas (A-2d) and (A-2d-1) may also be a structure represented by the following formula (Ar01). (R in equation (Ar01)) １１ａ R in equation (A-2d-1) １１ It is synonymous with R ２１ａ R in equation (A-2d-1) ２１ It is synonymous with Ar ａ This is equivalent to Ar in equation (A-2d-1), and X ０ａ X in equation (A-2d-1) ０ This is equivalent to: In formula (Ar01), two carbon atoms a and b, b and c, or c and d, X in formula (A-2d) or formula (A-2d-1) ０ (It forms a fused ring with a monocyclic portion containing the element.)

[0087] Here, X ０ The monocyclic portion containing refers to the monocyclic portion represented by the following formula (AP011) in formula (A-2d).

[0088] The skeleton represented by formula (A-2d) is preferably the skeleton represented by formula (A-2d-1) above, the skeleton represented by formula (A-2d-2) below, or the skeleton represented by formula (A-2d-3) below. (In equations (A-2d-2) and (A-2d-3), R １１ , Ar, and X ０ These are R in equation (A-2d), respectively. １１ , Ar, and X ０ This is synonymous with L. L represents a single bond or a divalent linking group, and examples of divalent linking groups include -O-, -S-, and -SO. ２ -, -CO-, -CONH-, -COO-, -NR １０１ -, - (CR １０２ R １０３ )m １ -, - (Ar １０１ )m ２ -ien-CH ２ - (Ar １０１ )m ２ -CH ２ R represents - or - (cyclo-R). １０１ , R １０２ , and R １０３ Each of these independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １represents integers from 1 to 10. And Ar １０１ Each of these independently represents an arylene group with 6 to 30 carbon atoms; m ２ R represents an integer from 1 to 3, which is the number of aromatic rings that are bonded to each other by single bonds. "cyclo-R" represents a divalent alicyclic hydrocarbon group of 5 to 8 members, preferably 6 to 8 members, which may form a fused ring with one or two benzene rings or naphthalene rings. ２２ Each of these independently represents an arylene group having 6 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms, which may be substituted.

[0089] <Formula (A-2e)> (In formula (A-2e), L represents a single bond or a divalent linking group between any two carbon atoms constituting each azaaryl condensed ring, R １１ and R ２１ Each of these independently represents a hydrogen atom or an aromatic ring residue, and R １２ and R ２２ Each of these independently represents a substituent, and n1 and n2 independently represent R １２ and R ２２ This represents the number of substituents, and may be 0. １ and Ar ２ Each of these is a benzene ring or a fused ring composed of two or three benzene rings, each independently forming a fused ring with the pyrrole ring portion in formula (A-2e).

[0090] Furthermore, in the unit structure (A-I), R in formula (A-2e) １１ and R ２１ R may be a substituent. １１ and R ２１ If R is a substituent or an aromatic group residue, １１ and R ２１For example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) are further substituted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, an aryl group, or a halo group, or (iii) may have its hydrocarbon chain further interrupted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, or an arylene group.

[0091] In formula (A-2e), L is a single bond or a divalent linking group. L may be bonded to any carbon atom constituting each azaaryl fused ring, Ar １ Ar ２ That is, in the azaaryl condensed ring and It may be bonded to aromatic carbon atoms that make up the ring, but it is preferable that it is bonded to carbon atoms that make up the pyrrole ring portion in the azaaryl condensed ring.

[0092] Preferred linking groups (L) include -O-, -S-, and -SO ２ -, -CO-, -CONH-, -COO-, -NH-, -(CR １０２ R １０３ )m １ -, - (Ar １０１ )m ２ -ien-CH ２ - (Ar １０１ )m ２ -CH ２ Selected from the group consisting of - and - (cyclo-R) -. １０２ and R １０３ Each of these independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １ represents integers from 1 to 10. And Ar １０１ Each of these represents an arylene group with 6 to 30 carbon atoms; m ２is an integer from 1 to 3, which is the number of aromatic rings that are bonded to each other by single bonds. "cyclo-R" represents a divalent alicyclic hydrocarbon group of 5 to 8 members, preferably 6 to 8 members, which may form a fused ring with one or two benzene rings or naphthalene rings.

[0093] <Formulas (A-3a) and (A-3b)> (In the formula, Ar ３１ and Ar ３２ Each of these independently represents a residue in an aromatic ring, or together with the carbon atoms bonded to them, they represent a residue in an aromatic ring. X represents -O, -S-, -NH-, -CH ２ -ien-CH ２ -CH ２ (This represents -, or -CH=CH-.)

[0094] Ar ３１ and Ar ３２ Examples of aromatic rings in the residues of the aromatic ring include the aromatic ring represented by the aforementioned formula (G1). ３１ and Ar ３２ Examples of aromatic rings formed by these elements together with the carbon atoms bonded to them include fluorene rings, benzofluorene rings, and dibenzofluorene rings.

[0095] 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 replaced by substituents. The same applies to the following skeletons.

[0096] Examples of skeletons represented by formula (A-2b-1) include the following:

[0097] Examples of skeletons represented by formula (A-2b-2) include the following:

[0098] Examples of skeletons represented by formula (A-2c-1) include the following:

[0099] Examples of skeletons represented by formula (A-2c-2) or formula (A-2c-3) include the following:

[0100] Examples of skeletons represented by formula (A-2c-4) include the following:

[0101] Examples of skeletons represented by formula (A-2d) include the following:

[0102] Examples of skeletons represented by formula (A-2e) include the following. Note that there may be overlap between specific examples of skeletons represented by formula (A-2d) and specific examples of skeletons represented by formula (A-2e).

[0103] Examples of skeletons represented by formula (A-3a) include the following:

[0104] Examples of skeletons represented by formula (A-3b) include the following:

[0105] Other examples of nitrogen-containing aromatic heterocyclic skeletons include the following:

[0106] Furthermore, the hydrogen atoms of NH in the aromatic ring skeleton, the hydrogen atoms of the hydroxyl group bonded to the aromatic ring in the aromatic ring skeleton, and the hydrogen atoms bonded to the aromatic ring in the aromatic ring skeleton may be replaced with substituents. Examples of such substituents include substituents (S) represented by the following formulas (S1) to (S7).

[0107] (In formulas (S1) to (S7), R ｓａ R represents a monovalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.ｓｂ Each of these independently represents a single bond or a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｃ Each of these independently represents a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｄ ａｌｋｙｎｙｌ Each of these independently represents an alkynyl group with 2 to 4 carbon atoms. ｓａ Each of these independently represents a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms. ｓｂ Each of these independently represents a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms. ｓａ and X ｓｂ Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or X ｓａ and X ｓｂ The carbon atom bonded to the hydroxyl group, together with the carbon atom, forms a carbonyl group. n represents an integer from 0 to 5. * represents a bond.

[0108] <R ｓａ > R ｓａ Examples of monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms and monovalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms. Monovalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms have one or more carbon-carbon multiple bonds. When a monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, or all be carbon-carbon triple bonds, or a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated.

[0109] <R ｓｂ , and R ｓｃ > R ｓｂ , and R ｓｃExamples of divalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms include alkylene groups having 1 to 10 carbon atoms and divalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms. Divalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms have one or more carbon-carbon multiple bonds. When a divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, or all be carbon-carbon triple bonds, or a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated. ｓｂ , and R ｓｃ Examples include the following groups: (* indicates a link.)

[0110] <R ｓｄ ａｌｋｙｎｙｌ > R ｓｄ ａｌｋｙｎｙｌ This represents an alkynyl group having 2 to 4 carbon atoms. Examples of alkynyl groups having 2 to 4 carbon atoms include the ethynyl group, the 1-propynyl group, and the propargyl group (2-propynyl group).

[0111] <Ar ｓａ > Ar ｓａ In this context, 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, perinaphthane, pyrene, fluorene, and biphenyl.

[0112] <Ar ｓｂ > Ar ｓｂ In this context, 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.

[0113] < X ｓａ and Xｓｂ > X ｓａ and X ｓｂ Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. Examples of monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms. Monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms are residues obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0114] Examples of substituents represented by formula (S1) include the following groups. (* indicates a link.)

[0115] Examples of substituents represented by formula (S2) include the following groups. (* indicates a link.)

[0116] Examples of substituents represented by formula (S3) include the following groups. (* indicates a link.)

[0117] Examples of substituents represented by formula (S4) include the following groups. (* indicates a link.)

[0118] Examples of substituents represented by formula (S5) include the following groups. (* indicates a link.)

[0119] Examples of substituents represented by formula (S6) include the following groups. (* indicates a link.)

[0120] Examples of substituents represented by formula (S7) include the following groups. (* indicates a link.)

[0121] Other substituents include, for example, the following groups: (* indicates a link.)

[0122] The unit structure (A-I) is preferably at least one selected from the following. Note that the positions of the two bonds shown in each unit structure described below are for convenience only and can extend from any possible carbon atom; their positions are not limited.

[0123] (Example of a unit structure composed of an aromatic amine skeleton) -NH- can also take the form of a structure in which the hydrogen atom on N is substituted.

[0124]

[0125] (Examples of unit structures composed of nitrogen-containing aromatic heterocyclic skeletons)

[0126] The unit structure (A) in the novolac resin may include unit structures other than unit structure (A-I). Examples of unit structures other than unit structure (A-I) include unit structure (A-II) containing a phenolic hydroxyl group.

[0127] <<<A-4: Unit Structure (A-II)>>> Unit structure (A) may include unit structure (A-II) containing a phenolic hydroxyl group. Unit structure (A-II) has a skeleton with an aromatic ring. Here, unit structure (A-II) is a sub-concept of unit structure (A) and does not refer to a substructure of unit structure (A). The aromatic ring skeleton in unit structure (A-II) will be described below.

[0128] <<<<A-4-1: Phenol Skeleton>>>> The phenol skeleton refers to a skeleton having an aromatic ring and a hydroxyl group bonded to the aromatic ring. The number of hydroxyl groups bonded to the aromatic ring of the phenol skeleton is not particularly limited; there may be one or more. If there are more, there may be 2 to 10 or 2 to 8. If there are more, the hydroxyl groups may be bonded to the same aromatic ring (e.g., a benzene ring) or to different aromatic rings. In the unit structure (A), the hydrogen atoms of the hydroxyl groups bonded to the aromatic ring may be replaced by substituents. Examples of substituents include the substituents described above (indole structure) and substituents (S) represented by formulas (S1) to (S7).

[0129] Examples of phenol skeletons include those represented by the following formula (A-4). The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the hydroxyl group may be replaced by substituents. The same applies to the following skeletons. (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent an integer between 1 and 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent an integer between 0 and 4. However, the sum of n3a and n3b ​​is 1 or greater, the sum of n7a and n7b is 1 or greater, and the sum of n8a and n8b is 1 or greater.)

[0130] Furthermore, examples of phenol skeletons include those represented by the following formulas (A-5a), (A-5b), (A-5c), or (A-5d). (In the formula, Ar ４１ Each of these independently represents a residue of an aromatic ring. k1 and k2 each independently represent an integer of 1 or 2. １ is -O-, -CO-, -S-, -SO ２ - Represents an alkylene group which may be substituted with a halogen atom. When k1 is 1, X ２１ These are single bonds, -O-, -CO-, -S-, -SO ２- Represents an alkylene group which may be substituted with a halogen atom. When k2 is 1, X ２２ These are single bonds, -O-, -CO-, -S-, -SO ２ - Represents an alkylene group which may be substituted with a halogen atom. When k1 is 2, X ２１ This represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. When k2 is 2, X ２２ This represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. １ This represents a trivalent saturated hydrocarbon group. ２ represents a tetravalent saturated hydrocarbon group. m1 and m2 each independently represent integers from 0 to 3, provided that the sum of m1 and m2 is 1 or greater. m3 to m5 each independently represent integers from 0 to 3, provided that the sum of m3 to m5 is 1 or greater. m6 to m8 each independently represent integers from 0 to 3, provided that the sum of m6 to m8 is 1 or greater. m9 to m12 each independently represent integers from 0 to 3, provided that the sum of m9 to m12 is 1 or greater.

[0131] Ar ４１ Examples of aromatic rings in the aromatic ring residues include aromatic rings represented by the following formula (G3). These aromatic rings may have substituents.

[0132] X １ , and X ２ Examples of the number of carbon atoms in the alkylene group, which may be substituted with halogen atoms, include 1 to 20. Examples of the structure of the alkylene group include linear, branched, and cyclic structures, as well as combinations of two or more of these. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0133] Y １ , and Y ２ Examples of the number of carbon atoms in a saturated hydrocarbon group include 1 to 20. Examples of the structure of a saturated hydrocarbon group include linear, branched, and cyclic structures, as well as combinations of two or more of these.

[0134] Furthermore, examples of phenol skeletons include those represented by the following formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d). (In formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), and (A-6d), Ar ５１ Each of the following independently represents a residue in an aromatic ring. Each of n11 independently represents an integer from 1 to 4. Each of the following independently represents either 0 or 1. When p is 1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond; when p is 0, there is no ether bond that forms a bridging structure between aromatic rings. L represents a single bond or a divalent linking group.

[0135] Ar ５１ Examples of aromatic rings in include those represented by the above formula (G1), with benzene rings and naphthalene rings being preferred. Examples of L include a divalent group obtained by removing two hydrogen atoms from the following structure.

[0136] n11, for example, can each independently represent either 1 or 2.

[0137] Furthermore, examples of phenol skeletons include those represented by the following formulas (A-7a), (A-7b), or (A-7c). (In formula (A-7a), formula (A-7b), and formula (A-7c), Ar ６１ Each of these independently represents a residue in an aromatic ring. n21 independently represents an integer from 1 to 4.

[0138] Ar ６１ Examples of aromatic rings in this formula include those represented by formula (G1) above, with benzene rings and naphthalene rings being preferred. n21 independently represents, for example, 1 or 2.

[0139] Furthermore, examples of phenol skeletons include 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). (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. In equation (A-8a-2), n32 and n33 independently represent integers from 0 to 4, provided that the sum of n32 and n33 is 1 or greater. In equation (A-8d), n32 and n33 independently represent integers from 0 to 4, provided that the sum of n32 and n33 is 1 or greater. In equation (A-8b), X １ X represents -O- or -NH-. In formula (A-8d), X ２ These are -O-, -S-, or -CH ２ It represents -. In equation (A-8e), X ３ is -S-, -CH ２ It represents - or -NH-. In formula (A-8f), X ４ represents -CO- or -O-, X ５ is, -CH ２ (Represents - or -O-.)

[0140] n31, for example, independently represents 1 or 2. n32 and n33, for example, independently represent 0, 1, or 2.

[0141] 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 group may be replaced by substituents. The same applies to the following skeletons.

[0142] Examples of skeletons represented by formula (A-5a) include the following:

[0143] Examples of skeletons represented by formula (A-5b) include the following:

[0144] Examples of skeletons represented by formula (A-5c) include the following:

[0145] Examples of skeletons represented by formula (A-5d) include the following:

[0146] Examples of skeletons represented by formula (A-6a) include the following:

[0147] Examples of skeletons represented by formula (A-6b-1) or formula (A-6b-2) include the following:

[0148] Examples of skeletons represented by formula (A-6c) include the following:

[0149] Examples of skeletons represented by formula (A-6d) include the following:

[0150] Examples of skeletons represented by formula (A-7a), formula (A-7b), or formula (A-7c) include the following:

[0151] Examples of skeletons represented by formula (A-8a-1) or formula (A-8a-2) include the following:

[0152] Examples of skeletons represented by formula (A-8b) include the following:

[0153] Examples of skeletons represented by formula (A-8c) include the following:

[0154] Examples of skeletons represented by formula (A-8d) include the following:

[0155] Examples of skeletons represented by formula (A-8e) include the following:

[0156] Examples of skeletons represented by equation (A-8f) include the following:

[0157] Examples of skeletons represented by formula (A-8g-1) or formula (A-8g-2) include the following:

[0158] Other skeletons of the phenol skeleton include, for example, the following:

[0159] Furthermore, the H of the hydroxyl group bonded to the aromatic ring in the phenol skeleton, and the hydrogen atom bonded to the aromatic ring in the phenol skeleton, may be replaced with substituents. Examples of such substituents include the substituents (S) represented by formulas (S1) to (S7) described above.

[0160] (Examples of unit structures composed of a phenol skeleton)

[0161] <<<B-1: Unit Structure (B)>>> A unit structure (B) has one or more carbon atoms. A unit structure (B) is one or more unit structures that include linked carbon atoms [see (I-1) above] bonded to the aromatic ring in unit structure (A), and includes, for example, structures represented by formulas (B1), (B2), or (B3) shown below. A unit structure (B) can link two unit structures (A) by covalent bonding with a unit structure (A).

[0162] <<<B-2: Unit Structure (B-I)>>> Unit structure (B) preferably includes unit structure (B-I). Unit structure (B-I) is derived from an aldehyde compound or an aldehyde equivalent. An aldehyde equivalent is an organic compound that enables covalent bonding with an aromatic ring and is a ketone group; an acetal group; a ketal group; a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, alkoxy group or halo group bonded to the α-carbon atom of an alkylaryl group; or an organic compound having a carbon-carbon unsaturated bond. Here, unit structure (B-I) is a sub-concept of unit structure (B) and does not refer to a substructure of unit structure (B). Unit structure (B-I) will be explained below.

[0163] <<<<<B-3: Formula (B1)>>>>> The unit structure (B-I) includes, for example, the structure represented by the following formula (B1). The unit structure (B-I) may also be the structure represented by the following formula (B1). In formula (B1), R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have substituents, a heterocycle having 3 to 30 carbon atoms which may have substituents, or a linear, branched, or cyclic alkyl group having 10 or fewer carbon atoms which may have substituents. R and R' may together with the carbon atoms they bond to to form a ring structure. * represents a bond.

[0164] Examples of substituents include hydroxyl groups, carboxyl groups, formyl groups, nitro groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, cyano groups, groups in which the H of a hydroxyl group is replaced by the above substituent (S), and halo groups.

[0165] Furthermore, the two bonds in formula (B1) can each be covalently bonded to the respective aromatic rings in the two unit structures (A).

[0166] In the definitions of R and R' in formula (B1), refer to (I-3) and (I-4) above for "aromatic ring" and "heterocyclic ring."

[0167] In the definitions of R and R' in formula (B1), the "alkyl group" can refer to alkyl groups similar to those described above (indole structure).

[0168] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenantrenyl, naphthalenyl, and pyrenyl. More preferably, R is a hydrogen atom and R' is naphthalenyl.

[0169] Examples of structures having a ring structure formed by R and R' together with the carbon atoms to which they are bonded include the structure represented by the following formula. (In the formula, each Ar independently represents a residue of an aromatic ring. The carbon atoms indicated by * are the carbon atoms bonded to R and R' in formula (B1).)

[0170] Examples of Ar aromatic rings include the aromatic ring represented by formula (G1).

[0171] The unit structure (B-I) containing the structure represented by formula (B1) is derived, for example, from aldehyde compounds and ketone compounds. Examples of aldehyde compounds include the compound represented by the following formula (B-1a). Examples of ketone compounds include the compound represented by the following formula (B-1b). (In formulas (B-1a) and (B-1b), R and R' are equivalent to R and R' in formula (B1), respectively, except that R is an atom other than a hydrogen atom. In formula (B-1b), R and R' may, together with the carbon atom to which they are bonded, form a ring structure.)

[0172] For example, when obtaining novolac resin, the carbonyl groups in formulas (B-1a) and (B-1b) are converted to *-C-* in formula (B1).

[0173] A few specific examples of unit structures (B-I) that include the structure represented by formula (B1) are given below. * basically indicates the bonding site with unit structure (A). Needless to say, it is also acceptable for the example structure to be included as part of the whole.

[0174]

[0175] <<<<<B-4: Formula (B2)>>>>> The unit structure (B-I) includes, for example, the structure represented by the following formula (B2). The unit structure (B-I) may also be the structure represented by the following formula (B2).

[0176] In formula (B2), Z ０ This represents an aromatic ring residue, an aliphatic ring residue, or an organic group consisting of two or more aromatic or aliphatic rings linked by a single bond, which may have substituents and have 6 to 30 carbon atoms. 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 bicyclohexyl.

[0177] Examples of substituents include hydroxyl groups, carboxyl groups, formyl groups, nitro groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, cyano groups, groups in which the H of a hydroxyl group is replaced by the above substituent (S), and halo groups.

[0178] J １ and J ２ Each of these independently represents a divalent organic group which may have direct bonds or substituents. Preferably, the divalent organic group is a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an aryl group (such as a phenyl group or a substituted phenyl group), or a halo group (for example, fluorine). Examples of linear alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0179] The unit structure (B-I) containing the structure represented by formula (B2) is derived, for example, from compounds having a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom, compounds having a hydroxyl group, alkoxy group, or halo group bonded to the α-carbon atom (such as the benzyl carbon atom) of an alkylaryl group, or compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0180] Examples of compounds having a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom include the compound represented by the following formula (B-2a). Examples of compounds having a hydroxyl group, alkoxy group, or halo group bonded to the α-carbon atom (benzyl carbon atom, etc.) of an alkylaryl group include the compound represented by the following formula (B-2b). Examples of compounds having two carbon-carbon double bonds include the compound represented by the following formula (B-2c) or (B-2d). (In formula (B-2a), formula (B-2b), and formula (B-2b), J １ J ２ , and Z ０ J in equation (B2) １ J ２ , and Z ０ These are synonymous. In equation (B-2a), X ａ , and X ｂ Each of these independently represents a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom. In formula (B-2b), Y ａ , and Y ｂ Each of these independently represents a hydroxyl group, alkoxy group, or halo group bonded to the α-carbon (benzyl carbon atom, etc.) of the alkylaryl group. In formula (B-2d), n represents an integer from 0 to 4.

[0181] For example, when obtaining novolac resin, X in formula (B-2a) ａ -J １ However, in formula (B2) *-J １ It is converted to J. ２ -X ｂ However, J in formula (B2) ２ -* is converted to. For example, when obtaining novolac resin, Y in formula (B-2b) ａ -J １ However, in formula (B2) *-J １ It is converted to J. ２ -Y ｂ However, J in formula (B2) ２ -It will be converted to *.

[0182] An example of formula (B-2a) is the following compound.

[0183] An example of formula (B-2b) is the following compound.

[0184] An example of formula (B-2c) is the following compound.

[0185] A few specific examples of unit structures containing the structure represented by formula (B2) are given below. * indicates the bonding site with unit structure (A). Needless to say, any unit structure may include the example structure as part of the whole.

[0186]

[0187] The unit structure (B-I) includes, for example, the structure represented by the following formula (B3). The unit structure (B-I) including the structure represented by formula (B3) is derived, for example, from compounds having a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom, compounds having a hydroxyl group, alkoxy group, or halo group bonded to the α-carbon atom (such as the benzyl carbon atom) of an alkylaryl group, or compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0188] <<<<B-5: Formula (B3)>>>> In formula (B3), Z is a monocyclic or dicyclic, tricyclic, or tetracyclic fused ring having 4 to 25 carbon atoms, which may have substituents. The number of carbon atoms referred to herein means only the number of carbon atoms constituting the ring skeleton of the monocyclic or dicyclic, tricyclic, or tetracyclic fused ring, excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring if the monocyclic or fused ring is a heterocyclic ring.

[0189] The monoring described above is a monoring whose number of π electrons does not satisfy 4n+2 (where n is a non-negative integer) (hereinafter sometimes referred to as a "non-Hückel monoring"); at least one of the monorings constituting the diring, triring, and tetraring described above is a monoring whose number of π electrons does not satisfy 4n+2 (where n is a non-negative integer), and the remaining monorings may be monorings whose number of π electrons satisfies 4n+2 (where n is a non-negative integer) or monorings whose number of π electrons does not satisfy 4n+2 (where n is a non-negative integer).

[0190] The monocyclic, or bicyclic, tricyclic, or tetracyclic fused ring, may further form fused rings with one or more aromatic rings to form a quintuple or higher fused ring, wherein the number of carbon atoms in the quintuple or higher fused ring is preferably 40 or less. The number of carbon atoms referred to herein means only the number of carbon atoms constituting the ring skeleton of the quintuple or higher fused ring, excluding substituents, and does not include the number of heteroatoms constituting the heterocycle when the quintuple or higher fused ring is a heterocycle.

[0191] X and Y are the same or different, -CR ３１ R ３２ - Represents the base, R ３１ and R ３２ Each of these terms may be the same or different, representing a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0192] x and y represent the numbers X and Y, respectively, and each can independently represent either 0 or 1.

[0193] In formula (B3) And in formula (B3) At least one of these is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon Z") (when x=1, y=1) or extends from carbon Z (when x=0, y=0).

[0194] For example, in formula (B3) It is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon atom 1") (when x=1) or extends from carbon atom 1 (when x=0),

[0195] In formula (B3) It is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon atom 2") (when y=1) or extends from carbon atom 2 (when y=0), and carbon atom 1 and carbon atom 2 may be the same or different. If they are different, they may belong to the same non-Hückel monoring or to different non-Hückel monorings.

[0196] Furthermore, formula (B3) may optionally include linked carbon atoms other than carbon atoms 1 and 2. Note that if Z is a tricyclic or multicyclic fused ring, the permutational positional relationship between carbon atoms 1 and 2 in formula (B3) and one or two non-Hückel monorings to which they belong and the remaining monoring is arbitrary. Similarly, if carbon atoms 1 and 2 belong to different non-Hückel monorings (referred to as "non-Hückel monoring 1" and "non-Hückel monoring 2," respectively), the permutational positional relationship between non-Hückel monoring 1 and non-Hückel monoring 2 in the fused ring is also arbitrary. Some specific examples of organic groups containing the structure represented by formula (B3) are given below. The bonding site to the unit structure (A) is not particularly limited. Needless to say, the structure may include the example structure as part of the whole.

[0197] Although examples with more than two bonding sites (*) are included, these surplus bonding sites can be used for bonding to aromatic rings in other polymer chains, crosslinking, etc., or they may be hydrogen bonds.

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] In formula (B3) below, And in formula (B3) We will now describe the case where only one of the atoms is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon atom Z") (when x=1, y=1) or extends from carbon atom Z (when x=0, y=0). As a more specific structure of equation (B3) in this case, for example, in the following equation (C31), p and k can be bonding hands. １ and k ２ Of these, p and k １ , or p and k ２ This can result in the unit structure (B-I) represented by formula (B3). The remaining bonds are connected to hydrogen atoms.

[0205] Furthermore, in the following equation (C32), p and k can be bonding points. １ , k ２ And of m, p and k １ p and k ２ Alternatively, p and m can form the unit structure (B-I) represented by formula (B3). The remaining bonds are bonded to hydrogen atoms.

[0206] A few more specific examples of formula (B3) corresponding to formula (C31) or formula (C32) are given below. * indicates the bonding site with the unit structure (A).

[0207] In equation (B3), bonds extend from the aromatic rings in these structures to other unit structures (for example, unit structure (A)), but these bonds are omitted in the specific examples below. Needless to say, any unit structure may include the example structure as part of the whole. Furthermore, in the above specific example, if there are no bonds from the aromatic ring, it can be considered a specific example of a polymer end.

[0208] The composite unit structure in the novolac resin may include unit structures other than unit structure (A) and unit structure (B).

[0209] The novolac resin is preferably a resin synthesized from reaction raw materials containing an amine compound and an aldehyde compound or aldehyde equivalent. Examples of amine compounds include compounds having a skeleton with an aromatic ring, wherein the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton. Examples of aldehyde compounds include the compound represented by formula (B-1a) described above. Examples of aldehyde equivalents include the compounds represented by formulas (B-1b), (B-2a), (B-2b), (B-2c), or (B-2d) described above.

[0210] Novolac resins having the structure represented by formula (AB) can be prepared by known methods. For example, ring-containing compounds represented by H-A-H and OHC-B, O=C-B, RO-B-OR, RO-CH ２ -B-CH ２ It can be prepared by condensing oxygen-containing compounds represented by -OR, etc. Here, A and B are the same as above. R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0211] The ring-containing compound and the oxygen-containing compound may be used individually, or two or more may be used in combination. In this condensation reaction, the oxygen-containing compound can be used in a ratio of 0.1 to 10 moles, preferably 0.1 to 2 moles, per mole of the ring-containing compound.

[0212] Examples of catalysts used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid; and carboxylic acids such as formic acid and oxalic acid. The amount of catalyst used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass, per 100 parts by mass of the cyclic compound (total of multiple types).

[0213] The condensation reaction can be carried out without a solvent, but it is usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit 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, and dimethylformamide. The condensation reaction temperature is usually 40°C to 200°C, preferably 100°C to 180°C. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 50 hours, preferably 5 minutes to 24 hours.

[0214] The weight-average molecular weight of the novolac resin according to one aspect of the present invention is typically 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0215] The resin (G) content in the resist underlayer film forming composition 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. Here, the film-forming component refers to the component obtained by removing the solvent component from the resist underlayer film forming composition.

[0216] The molar ratio of unit structure (A) to unit structure (B) in the novolac resin is preferably, for example, 30:70 to 70:30, more preferably 30:70 to 50:50, even more preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50. The molar ratio of unit structure (A) to unit structure (B) in the novolac resin can also be expressed as the molar ratio of compound (A) that is the raw material for unit structure (A) to compound (B) that is the raw material for unit structure (B). The molar ratio of compound (A) to compound (B) is preferably, for example, 30:70 to 70:30, more preferably 30:70 to 50:50, even more preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50. Here, compound (A) may be one type or two or more types. Similarly, compound (B) may be one type or two or more types.

[0217] The molar ratio of unit structure (A-I) in unit structure (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%. Furthermore, the molar ratio of unit structure (A-I) in unit structure (A) can also be expressed as the molar ratio of compound (A-I) that serves as the raw material for unit structure (A-I) in compound (A). The molar ratio of compound (A) to compound (I) 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%.

[0218] The molar ratio of unit structure (B-I) in unit structure (B) 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%. Furthermore, the molar ratio of unit structure (B-I) in unit structure (B) can also be expressed as the molar ratio of compound (B-I) that serves as the raw material for unit structure (B-I) in compound (B). The molar ratio of compound (B) to compound (I) in compound (B) 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%.

[0219] <Solvent> A composition for forming a resist underlayer film, which is one aspect of the present invention, contains a solvent.

[0220] The solvent is not particularly limited as long as it can dissolve the resin (G) and any other optional components that may be added as needed.

[0221] Examples of solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and Luene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyethyl acetate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate,Isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl 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, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxybutylacetate Examples of solvents include 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used individually or in combination of two or more.

[0222] Furthermore, solvents with a boiling point of 160°C or higher can be included in combination with solvents with a boiling point of less than 160°C.

[0223] As such high-boiling point solvents, for example, the following compounds described in International Publication No. 2018 / 131562 (A1) can be preferably used.

[0224] [R in equation (i)] １ , R ２ and R ３represents an alkyl group having 1 to 20 carbon atoms which may be interrupted by a hydrogen atom, an oxygen atom, a sulfur atom or an amide bond, may be the same or different from each other, and may be bonded to each other to form a ring structure.], or, 1,6-diacetoxyhexane (boiling point 260 ° C), tripropylene glycol monomethyl ether (boiling point 242 ° C), and other various high-boiling solvents described in paragraph 0082 of the said published gazette can be preferably used.

[0225] Or, dipropylene glycol monomethyl ether acetate (boiling point 213 ° C), diethylene glycol monoethyl ether acetate (boiling point 217 ° C), diethylene glycol monobutyl ether acetate (boiling point 247 ° C), dipropylene glycol dimethyl ether (boiling point 171 ° C), dipropylene glycol monomethyl ether (boiling point 187 ° C), dipropylene glycol monobutyl ether (boiling point 231 ° C), tripropylene glycol monomethyl ether (boiling point 242 ° C), γ-butyrolactone (boiling point 204 ° C), benzyl alcohol (boiling point 205 ° C), propylene carbonate (boiling point 242 ° C), tetraethylene glycol dimethyl ether (boiling point 275 ° C), 1,6-diacetoxyhexane (boiling point 260 ° C), dipropylene glycol (boiling point 230 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C), and other various high-boiling solvents described in paragraphs 0023 to 0031 of the said published gazette can be preferably used.

[0226] The composition for forming a resist underlayer film which is one aspect of the present invention can contain an acid and / or its salt and / or an acid generator.

[0227] Examples of the acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and the like.

[0228] As the salt, the salts of the aforementioned acids can also be used. Examples of the salt include, but are not limited to, ammonia derivative salts such as trimethylamine salt and triethylamine salt, pyridine derivative salts, morpholine derivative salts, etc., which can be preferably used.

[0229] Only one kind of the acid and / or its salt can be used, or two or more kinds can be used in combination. The blending amount is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, more preferably 0.01 to 5% by mass based on the total solid content.

[0230] Examples of the acid generator include thermal acid generators and photoacid generators.

[0231] Examples of the thermal acid generator include 2,4,4,6 - tetrabromocyclohexadienone, benzoin tosylate, 2 - nitrobenzyl tosylate, K - PURE [registered trademark] CXC - 1612, CXC - 1614, TAG - 2172, TAG - 2179, TAG - 2678, TAG2689, 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 sulfonic acid alkyl esters, etc.

[0232] The photoacid generator generates an acid upon exposure of the resist. Therefore, the acidity of the lower layer film can be adjusted. This is one method for adjusting the acidity of the lower layer film to match the acidity of the upper layer resist. Also, by adjusting the acidity of the lower layer film, the pattern shape of the resist formed on the upper layer can be adjusted.

[0233] Examples of the photoacid generator included in the composition for forming a resist lower layer film of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds, etc.

[0234] Examples of iodonium salt compounds include iodonium salt compounds such as 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, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0235] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0236] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0237] Only one type of acid generator may be used, or two or more types may be used in combination.

[0238] If an acid generator is used, the ratio is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass, per 100 parts by mass of solid content of the resist underlayer film forming composition.

[0239] A resist underlayer film forming composition according to one aspect of the present invention may optionally contain, in addition to the above, a crosslinking agent, a surfactant, a photoabsorbent, a rheology modifier, an adhesion aid, and the like.

[0240] Typical crosslinking agents include aminoplast crosslinking agents and phenoplast crosslinking agents.

[0241] As the crosslinking agent, a crosslinking agent with high heat resistance can be used. Preferably, a crosslinking agent with high heat resistance is a compound containing a crosslinking substituent having an aromatic ring (e.g., a benzene ring, a naphthalene ring) in its molecule.

[0242] Examples of aminoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluryl, urea, and polymers thereof. Preferably, the crosslinking agent has at least two crosslinking substituents and is a compound such as methoxymethylated glycoluryl, butoxymethylated glycoluryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensed products of these compounds can also be used.

[0243] Preferably, it is at least one selected from the group consisting of tetramethoxymethylglycoluryl and hexamethoxymethylmelamine.

[0244] Here are a few specific examples:

[0245]

[0246] Examples of phenoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated aromatics and polymers thereof. Preferably, the crosslinking agent has at least two crosslinking substituents in one molecule, and is a compound 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, or α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Condensates of these compounds can also be used.

[0247] Examples of such compounds include compounds having the substructure of formula (4) below, and polymers or oligomers having the repeating unit of formula (5) below.

[0248] The above R １１ , R １２ , R １３ , and R １４ n1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups described above can be used. n1 is an integer from 1 to 4, n2 is an integer from 1 to (5-n1), and (n1+n2) is an integer from 2 to 5. n3 is an integer from 1 to 4, n4 is from 0 to (4-n3), and (n3+n4) is an integer from 1 to 4. The oligomers and polymers can be used with a number of repeating unit structures ranging from 2 to 100, or from 2 to 50.

[0249] Here are a few specific examples:

[0250]

[0251]

[0252]

[0253]

[0254] Crosslinking agents such as aminoplast crosslinking agents and phenoplast crosslinking agents may be used individually or in combination of two or more. Aminoplast crosslinking agents can be manufactured by known methods or similar methods, or commercially available products may be used.

[0255] Furthermore, the amount of crosslinking agent used, such as aminoplast crosslinking agent or phenoplast crosslinking agent, varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but 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, relative to the total solid content of the resist underlayer film forming composition according to the present invention, 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.

[0256] The resist underlayer film forming composition according to the present invention does not produce pinholes or striations, and a surfactant may be added to further improve the coatability against surface unevenness.

[0257] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as F-Top EF301, EF303, EF352 (trade names, manufactured by Tocem Products Co., Ltd.), Megafac F171, F173, R-30, R-40 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430, FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0258] The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film-forming composition according to the present invention. These surfactants may be added alone or in combination of two or more.

[0259] Examples of light absorbers include commercially available light absorbers listed in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry), such as C.I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C.I. DisperseRed 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; C. I. DisperseViolet 43; C. I. DisperseBlue 96; C. I. Fluorescent Brightening Agent 112, 135 and 163; C. I. SolventOrange 2 and 45; C. I. SolventRed 1, 3, 8, 23, 24, 25, 27 and 49; C. I. PigmentGreen 10; C. I. Pigment Brown 2 and others can be suitably used. The above light absorber is usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solid content of the resist underlayer film forming composition according to the present invention.

[0260] Rheology modifiers are added primarily to improve the fluidity of the resist underlayer film formation composition, and particularly in the baking process, to improve the uniformity of the resist underlayer film thickness and the filling of holes by the resist underlayer film formation composition. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di(n-butyl) malate, diethyl malate, and dinonyl malate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in a proportion of less than 30% by mass relative to the total solid content of the resist underlayer film formation composition according to the present invention.

[0261] Adhesion aids are added primarily to improve the adhesion between the substrate or resist and the resist underlayer film forming composition, and especially to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; and vinyltrichlorosilane. Examples of adhesive aids include silanes such as ran, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesive aids are typically blended in a proportion of less than 5% by mass, preferably less than 2% by mass, relative to the total solid content of the resist underlayer film forming composition according to the present invention.

[0262] The solid content of the resist underlayer film forming composition according to 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 excluding the solvent. The solid content may contain a crosslinkable resin in a proportion of 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass.

[0263] [Resist Underlayer Film] The resist underlayer film can be formed, for example, as follows, using the resist underlayer film forming composition according to the present invention.

[0264] Substrates used in the manufacture of semiconductor devices (e.g., silicon wafer substrates, silicon dioxide coated substrates (SiO ２ A resist underlayer film forming composition according to one embodiment of the present invention is applied to a substrate (such as a glass substrate, silicon nitride substrate (SiN substrate), silicon oxide nitride substrate (SiON substrate), titanium nitride substrate (TiN substrate), tungsten substrate (W substrate), glass substrate, ITO substrate, polyimide substrate, and low dielectric constant material (low-k material) coated substrate, etc.) using an appropriate coating method such as a spinner or coater, and then fired using a heating means such as a hot plate to form a resist underlayer film. The firing conditions are appropriately 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 may be used as the atmospheric gas during firing, or an inert gas such as nitrogen or argon may be used. In one embodiment, it is particularly preferable that the oxygen concentration is 1% or less. The thickness of the underlying film formed here can be, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica (mold replica) of the quartz imprint mold can be fabricated.

[0265] Furthermore, according to one aspect of the present invention, an adhesion layer and / or a silicon-containing layer containing 99% by mass or less, or 50% by mass or less, of Si can be formed on the resist underlayer film by coating or vapor deposition. For example, in addition to the method of forming the adhesion layer described in Japanese Patent Application Publication No. 2013-202982 and Japanese Patent No. 5827180, or the silicon-containing resist underlayer film (inorganic resist underlayer film) formation composition described in International Publication No. 2009 / 104552 (A1) by spin coating, a Si-based inorganic material film can be formed by CVD or the like.

[0266] Furthermore, by applying a resist underlayer film forming composition, which is one aspect of the present invention, to a semiconductor substrate having stepped portions and portions without steps (a so-called stepped substrate) and firing it, the step difference between the stepped portions and the portions without steps can be reduced.

[0267] [Pattern Forming Method] The pattern forming method of the present invention includes at least the step of applying the resist underlayer film forming composition of the present invention onto a semiconductor substrate and firing it to form a resist underlayer film. The pattern forming method of the present invention may also include the following steps: - A step of forming a resist film on the resist underlayer film. - A step of irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern. and - A step of etching the resist underlayer film using the resist pattern as a mask.

[0268] [Method for Manufacturing a Semiconductor Device] (i) A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to one aspect of the present invention; forming a resist film on the resist underlayer film; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and processing the semiconductor substrate through the patterned resist underlayer film.

[0269] (ii) A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to one aspect of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing the semiconductor substrate through the patterned resist underlayer film.

[0270] (iii) Furthermore, a method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to one aspect of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing the semiconductor substrate through the patterned resist underlayer film.

[0271] (iv) A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to one aspect of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film (spacer) on the resist underlayer film after the hard mask has been removed; processing the vapor-deposited film (spacer) by etching; removing the patterned resist underlayer film and leaving the patterned vapor-deposited film (spacer); and processing the semiconductor substrate through the patterned vapor-deposited film (spacer).

[0272] The semiconductor substrate can be processed using the manufacturing methods described in (i) to (iv) above.

[0273] The step of forming a resist underlayer film using a resist underlayer film formation composition according to one aspect of the present invention is as described above in [Resist Underlayer Film].

[0274] A hard mask, such as a silicon-containing film, may be formed as a second resist underlayer on the resist underlayer formed by the above process, and a resist pattern may be formed thereon [as described in (ii) to (iv)].

[0275] The hard mask may be a coated film of inorganic material, or a vapor-deposited film of inorganic material formed by vapor deposition methods such as CVD or PVD, or a SiO film, SiN film, or SiO ２ A membrane can be used as an example.

[0276] Furthermore, an anti-reflective coating (BARC) may be formed on this hard mask, or a resist shape correction film that does not have anti-reflective properties may be formed.

[0277] In the process of forming the resist pattern, exposure is performed either through a mask (reticle) for forming a predetermined pattern or by direct drawing. For example, g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, and electron beams can be used as exposure sources. After exposure, post-exposure baking is performed as needed. Then, the resist is developed with a developer (e.g., 2.38% by mass aqueous solution of tetramethylammonium hydroxide, butyl acetate), and further rinsed with a rinse solution or pure water to remove the used developer. Finally, post-baking is performed to dry the resist pattern and improve its adhesion to the substrate.

[0278] The etching process performed after the formation of the resist pattern is carried out by dry etching.

[0279] Furthermore, the following gases are used for processing the hard mask (silicon-containing layer), resist underlayer film, and substrate: CF ４ CHF ３ ,CH ２ F ２ CH ３ F, C ４ F ６ , C ４ F ８ , O ２ , N ２ O, NO ２ , H ２He can be used. These gases may be used alone or in mixtures of two or more gases. Furthermore, these gases may be mixed with argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon, or nitrogen trifluoride.

[0280] The resist film may be patterned by a nanoimprint method or a self-assembled film method.

[0281] In nanoimprint lithography, the resist composition is formed using a patterned mold that is transparent to irradiated light. In contrast, self-assembled film lithography uses self-assembled films, such as diblock polymers (e.g., polystyrene-polymethyl methacrylate), which naturally form ordered structures on the nanometer scale, to create patterns.

[0282] In the nanoimprint method, before applying the curable composition that will become the resist film, a silicon-containing layer (hard mask layer) may be optionally formed on the resist underlayer by coating or vapor deposition, and an adhesion layer may be further formed on the resist underlayer or the silicon-containing layer (hard mask layer) by coating or vapor deposition, and the curable composition that will become the resist film may be applied on the adhesion layer.

[0283] Furthermore, wet etching may be performed to simplify the process steps and reduce damage to the processed substrate. This helps to suppress variations in processed dimensions and a reduction in pattern roughness, making it possible to process the substrate with a high yield. For this reason, in (iii) to (iv) above, the hard mask can be removed by either etching or an alkaline chemical solution. In particular, when using an alkaline chemical solution, there are no restrictions on the components, but it is preferable that the alkaline components include the following.

[0284] 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, and (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N Examples include 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, from the viewpoint of handling, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, and an inorganic base may be used in combination with a quaternary ammonium hydroxide. As inorganic bases, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and rubidium hydroxide are preferred, with potassium hydroxide being more preferred.

[0285] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0286] The weight-average molecular weight Mw of the polymers shown in Synthesis Examples 1 to 9 below was obtained by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: GPC column: TSKgel Super-MultiporeHZ-N (2 columns) Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 0.35 ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0287] For the synthesis of polymers used as the resist underlayer film, the polymers with structural formulas (S1) to (S9) were synthesized using the following compound groups A, B, C, D, and E.

[0288] ○Compound groups A to B

[0289] ○Catalyst group C, solvent group D, reprecipitation solvent group E Methanesulfonic acid: C1 Mercaptopropionic acid: C2 Propylene glycol monomethyl ether acetate (=PGMEA): D1 Propylene glycol monomethyl ether (=PGME): D2 N-methylpyrrolidone: D3 Methanol: E1

[0290] [Synthesis Example 1] 10.0 g of A1, 4.3 g of B1, 0.4 g of C1, and 34.3 g of D1 were placed in a flask. The mixture was then heated under nitrogen until reflux was achieved and reacted for 1.5 hours. After the reaction was stopped, the mixture was reprecipitated with E1 and dried to obtain resin (S1). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 2,500. The obtained resin was dissolved in cyclohexanone (=CYH) to obtain a solution of the target compound. Subsequently, ion exchange was carried out for 4 hours using cation exchange resin and anion exchange resin as needed.

[0291] [Synthesis Examples 2-9] 10.0 g of A1, 4.3 g of B1, 3.0 g of B5, 0.6 g of C1, and 34.8 g of D1 were placed in a flask. The mixture was then heated under nitrogen until reflux was achieved and reacted for 2.5 hours. After the reaction was stopped, the mixture was reprecipitated with E1 and dried to obtain resin (S2). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 1,500. The obtained resin was dissolved in CYH to obtain a solution of the target compound. Resins S3-S9 (Synthesis Examples 3-9) were synthesized using a similar procedure, but for the redissolution of the obtained resin, a solvent that the resin dissolves in was selected. Furthermore, for the subsequent ion exchange operation, cation exchange resin and anion exchange resin were used as needed, and ion exchange was carried out for 4 hours. The amount of compounds added as raw materials for each resin, the synthesis conditions, etc. are shown in Table 1.

[0292]

[0293] The structural formulas and weight-average molecular weights Mw of the obtained resins S1 to S9 are shown below.

[0294]

[0295] Preparation of resist underlayer film formation compositions Resins (S1) to (S9), solvents (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CYH)), and the surfactant Megafac R-40 (manufactured by DIC Corporation, H1) were mixed in the proportions shown in Table 2 below and filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare resist underlayer film formation compositions (M1 to M8, comparative M1). The values ​​shown in Table 2 represent the weight percentage of the surfactant when the weight of the resin is assumed to be 100 parts, and for the solvents, the values ​​represent the weight percentage of each solvent when the total volume is assumed to be 100% by weight, independently of the weight of the resin.

[0296] [Leaching Test in Resist Solvent (Air)] The resist underlayer compositions of Examples 1-8 and Comparative Example 1 were applied onto a silicon wafer using a spin coater and fired in air at the predetermined temperature and time shown in Table 3 to form a resist underlayer with a thickness of approximately 65 nm. The formed resist underlayer was immersed in a general-purpose thinner, a PGME / PGMEA mixed solution (mass ratio = 7 / 3), for 60 seconds, and after spin-drying, it was fired at 100°C for 30 seconds. The resistance to the solvent was confirmed by comparing the film thickness before and after thinner immersion. A reduction in film thickness of 1% or less before and after thinner immersion was judged as "○", and a reduction of more than 1% was judged as "×". The results are shown in Table 3.

[0297] [Measurement of Sublimation Volume] The sublimation volume was measured using the sublimation volume measuring apparatus described in International Publication No. 2007 / 111147. The resist underlayer film forming compositions prepared in Examples 1 to 8 and Comparative Example 1 were applied to silicon wafers and baked at 350°C for 60 seconds to adjust the film thickness to 65 nm. This adjusted resist underlayer film forming composition was applied to a 4-inch diameter silicon wafer substrate using a spin coater at 1500 rpm for 60 seconds. The coated silicon wafer substrate was set in the sublimation measuring apparatus, which has an integrated hot plate adjusted to 300°C, and baked for 60 seconds. The sublimated material was collected by a QCM (Quartz Crystal Microbalance) sensor, i.e., a quartz oscillator on which electrodes were formed. A QCM sensor utilizes the property that when sublimated material adheres to the surface (electrode) of a quartz crystal oscillator, the frequency of the quartz crystal oscillator changes (decreases) according to its mass, allowing for the measurement of minute changes in mass.

[0298] The detailed measurement procedure is as follows: The hot plate of the sublimation volume measuring device is heated to 300°C, and the pump flow rate is set to 1 m³. ３The device was set to / s and left undisturbed for the first 60 seconds to stabilize. Immediately thereafter, a silicon wafer substrate coated with the resist underlayer film formation composition was quickly placed onto the hot plate through the slide opening, and sublimation was collected from 60 seconds to 120 seconds (60 seconds) after the silicon wafer substrate was placed on the hot plate. The flow attachment (detection part) connecting the QCM sensor and the collection funnel of the sublimation quantity measuring device was used without a nozzle. Therefore, the airflow flows in without restriction from the flow path (diameter: 32 mm) to the chamber unit, which is 30 mm away from the sensor (quartz oscillator). The QCM sensor used a material mainly composed of silicon and aluminum (AlSi (Ti deposited on the surface)) as the electrode, with a quartz oscillator diameter (sensor diameter) of 14 mm, an electrode diameter on the surface of the quartz oscillator of 5 mm, and a resonant frequency of 9 MHz. For each measurement, the QCM sensor was connected via a serial cable that allows direct data transfer to a PC, and dedicated software was installed, enabling real-time measurement of the sublimation volume.

[0299] The obtained frequency changes were converted from the intrinsic values ​​of the quartz crystal oscillator used for measurement to grams, and the relationship between the amount of sublimation of one silicon wafer substrate coated with the resist underlayer film formation composition and the passage of time was clarified. Note that the first 60 seconds were left unattended for equipment stabilization (the silicon wafer substrate was not set), and the measurements from 60 seconds after the silicon wafer substrate was placed on the hot plate to 120 seconds represent the measured amount of sublimation of the wafer. Using the amount of sublimation of the resist underlayer film formation composition of Comparative Example 1, quantified from the sublimation amount measuring device, as a baseline, a value of "○" was used if the amount of sublimation was less than that of Comparative Example 1, and "×" if it was greater than or equal to that of Comparative Example 1. The results are shown in Table 3.

[0300]

[0301] Based on the above, it can be concluded that novolac resins having an indole structure in their side chains have an advantage over novolac resins without an indole structure in their lower sublimation rate. Furthermore, as described in this embodiment, since the amount of sublimation generated from the resin is small, similar effects can be obtained even when using crosslinking agents or acid generators.

Claims

1. A composition for forming a resist underlayer film, comprising a resin (G) having an indole structure in its side chain and a solvent, wherein the resin (G) is not a resin in which the indole structure is bonded to the carbon atom at position 9 of the fluorene ring via a carbon-carbon double bond.

2. The resist underlayer film forming composition according to claim 1, wherein the resin (G) has a composite unit structure, the composite unit structure comprises a unit structure (A) having an aromatic ring, and a unit structure (B) having one or more carbon atoms, and the resin (G) is a resin obtained by a reaction that generates a covalent bond between the carbon atoms constituting the aromatic ring of the unit structure (A) and the carbon atoms in the unit structure (B).

3. The resist underlayer film forming composition according to claim 2, wherein the unit structure (A) comprises a unit structure (A-I) containing at least a nitrogen atom, the unit structure (A-I) has a skeleton having an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

4. The resist underlayer film forming composition according to claim 2, wherein the unit structure (A) comprises a unit structure (A-II) containing a phenolic hydroxyl group, the unit structure (A-II) has a skeleton having an aromatic ring, and the skeleton is a phenol skeleton.

5. The resist underlayer film forming composition according to claim 1, wherein the indole structure is at least one of the following formulas (C-1), (C-2), (C-3), (C-4), (C-5), (C-6), and (C-7), and in the indole structure, at least one hydrogen atom may be replaced by a substituent. (In formulas (C-1) to (C-7), L １ R represents a single bond or an alkylene group with 1 to 3 carbon atoms. １ Ar represents a hydrogen atom, a phenyl group, or a naphthyl group. １ Ar represents a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or biphenyl ring. ２ and Ar ３ Each of these independently represents a benzene ring or a naphthalene ring, and * represents a bond.

6. The resist underlayer film forming composition according to claim 5, wherein the substituent in the indole structure, which may replace at least one hydrogen atom, is one or more groups selected from halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxy groups, hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, and ether-bond-containing groups.

7. The resist underlayer film forming composition according to claim 1, wherein the solvent comprises a solvent with a boiling point of 160°C or higher.

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

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

10. The resist underlayer film forming composition according to claim 9, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

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

12. A resist underlayer film on a semiconductor substrate, which is a cured product of a resist underlayer film forming composition according to any one of claims 1 to 11.

13. A method for forming a resist pattern used in semiconductor manufacturing, comprising the step of applying a resist underlayer film forming composition according to any one of claims 1 to 11 onto a semiconductor substrate and firing it to form a resist underlayer film.

14. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 11; forming a resist film on the resist underlayer film; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; and processing a semiconductor substrate through the patterned resist underlayer film.

15. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 11; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; and processing the semiconductor substrate through the patterned resist underlayer film.

16. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 11; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; and processing the semiconductor substrate through the patterned resist underlayer film.

17. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 11; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; etching the hard mask through the resist pattern to form a patterned hard mask; etching the resist underlayer film through the patterned hard mask to form a patterned resist underlayer film; removing the hard mask; forming a vapor-deposited film on the resist underlayer film after removal of the hard mask; processing the vapor-deposited film by etching; removing the patterned resist underlayer film to leave the patterned vapor-deposited film; and processing the semiconductor substrate through the patterned vapor-deposited film.

18. The method for manufacturing a semiconductor device according to claim 15, wherein the hard mask is formed by coating a composition containing an inorganic substance or by vapor deposition of an inorganic substance.

19. The method for manufacturing a semiconductor device according to claim 14, wherein the resist film is patterned by nanoimprint or self-assembled film.

20. The method for manufacturing a semiconductor device according to claim 16, wherein the hard mask is removed by etching or by an alkaline chemical solution.

Images