Composition for forming resist underlayer film

Abstract

The purpose of the present invention is to provide a composition for forming a resist underlayer film, which further improves the properties of the resist underlayer film, such as curability, heat resistance, etching resistance, planarization, embeddability, and the like. [Solution] A composition for forming a resist underlayer film, which is characterized by containing a novolac resin that contains a side chain having a structure represented by formula (D), and a solvent. In formula (D), Ar2 represents an aromatic ring. -O-Ar2 formula (D): The novolac resin contains a composite unit structure A-B represented by formula (AB), and the unit structure A contains a phenol unit structure and / or an amine unit structure. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resist underlayer film-forming composition, a resist underlayer film which is a fired product of a coating film formed from the composition, and a method for producing a semiconductor device using the composition. Background Art

[0002] In the manufacture of semiconductor devices, micro-machining is performed by photolithography. It is known that the photolithography has the following problem: when the resist layer on the substrate is exposed to ultraviolet lasers such as KrF excimer lasers and ArF excimer lasers, a resist pattern having a desired shape is not formed due to the influence of standing waves caused by the reflection of the ultraviolet laser on the substrate surface. In order to solve this problem, a resist lower layer film (anti-reflection film) is provided between the substrate and the resist layer. It is further known that various organic resins are used as compositions for forming the resist lower layer film.

[0003] In addition, in order to reduce the thin film of the resist layer required with the miniaturization of the resist pattern, it is also known to form at least two layers of resist underlayer films and use the resist underlayer films as a mask material. As materials for forming the above-mentioned at least two layers, organic resins (for example, acrylic resins, novolac resins, polyether resins, polyester resins), silicone resins (for example, organopolysiloxanes), and inorganic silicon compounds (for example, SiON, SiO2) can be cited. When dry etching is performed using the pattern formed by the above-mentioned organic resin layer as a mask, the pattern is required to have etching resistance to etching gases (for example, fluorocarbons, oxygen, etc.).

[0004] As a composition for forming such a resist underlayer film, for example, Patent Document 1 discloses a resist underlayer film-forming composition containing a polymer having a structural unit represented by the following formula (1) and a solvent.

[0005]

[0006] (Where X 1 represents a divalent organic group having 6 to 20 carbon atoms and having at least one aromatic ring which may be substituted with a halogenated group, a nitro group, an amino group or a hydroxyl group, 2 represents an organic group having 6 to 20 carbon atoms and having at least one aromatic ring which may be substituted with a halide group, a nitro group, an amino group or a hydroxyl group, or a methoxy group.

[0007] Patent document 2 discloses a composition for forming an anti-etching agent underlayer film, which comprises a polymer, wherein the polymer comprises multiple identical or different structural units having methoxymethyl groups and ROCH2- groups other than methoxymethyl groups (R is a monovalent organic group, a hydrogen atom or a mixture thereof), and a connecting group connecting the multiple structural units.

[0008] In addition, Patent Document 3 reports that a composition for forming an anti-etching underlayer film comprising an epoxy resin having a hydroxymethyl portion, a plurality of film materials capable of undergoing a cross-linking reaction with the epoxy resin, an acid catalyst and a solvent has good embedding properties and can provide a cross-linking agent for an anti-etching underlayer film that can be used in a photolithography process and has high dry etching resistance, heat resistance, etc.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: International Publication No. WO2014-171326

[0012] Patent Document 2: International Publication No. WO2021-172295

[0013] Patent Document 3: Japanese Patent Application Laid-Open No. 2020-148891 Summary of the invention

[0014] Problems to be solved by the invention

[0015] However, with the rapid progress of semiconductor manufacturing processes, there is a strong demand for higher quality and improved properties of resist underlayer films. Although properties such as curability, heat resistance, etching resistance, planarization, and embedding properties are required, these properties still have room for improvement.

[0016] Means for solving problems

[0017] The present invention solves the above-mentioned problems. That is, the present invention includes the following solutions.

[0018] A first aspect of the present invention relates to a resist underlayer film-forming composition, comprising: a novolac resin having a side chain having a structure represented by the following formula (D); and a solvent.

[0019] -O-Ar 2 Formula (D)

[0020] (Where Ar 2 It is an aromatic ring.)

[0021] A second aspect of the present invention relates to the resist underlayer film forming composition according to the first aspect, wherein the Ar 2 It is an aromatic ring having an aromatic hydrocarbon ring and / or an aromatic hetero ring.

[0022] A third aspect of the present invention relates to the resist underlayer film forming composition according to the second aspect, wherein the aromatic hydrocarbon ring is an aromatic hydrocarbon ring containing a benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene structure,

[0023] The aromatic heterocyclic ring is an aromatic heterocyclic ring containing an indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole or phenothiazine structure.

[0024] A fourth aspect of the present invention relates to the resist underlayer film forming composition according to the second aspect, wherein the aromatic hydrocarbon ring is benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene.

[0025] The aromatic heterocyclic ring is any one selected from the group consisting of indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole and phenothiazine.

[0026] A fifth aspect of the present invention relates to the resist underlayer film forming composition according to the first aspect, wherein the Ar 2 For the -CH2-OR 12 (Where R 12 The term "alkyl" refers to an aromatic ring substituted with a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and which may contain a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom.

[0027] A sixth aspect of the present invention relates to the resist underlayer film forming composition according to the fifth aspect, wherein the R 12 A hydrogen atom or a methyl group.

[0028] A seventh aspect of the present invention relates to the resist underlayer film forming composition according to the fifth aspect, wherein the aromatic hydrocarbon ring is an aromatic hydrocarbon ring containing a benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene structure,

[0029] The aromatic heterocyclic ring is an aromatic heterocyclic ring containing an indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole or phenothiazine structure.

[0030] An eighth aspect of the present invention relates to the resist underlayer film forming composition according to the fifth aspect, wherein the aromatic hydrocarbon ring is benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene.

[0031] The aromatic heterocyclic ring is any one selected from the group consisting of indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole and phenothiazine.

[0032] A ninth aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, wherein the novolac resin is a novolac resin having a repeating composite unit structure AB represented by the following formula (AB) and further having a structure of the above formula (D) in its side chain.

[0033]

[0034] (In the above formula (AB),

[0035] n represents the number of composite unit structures AB,

[0036] The unit structure A comprises a phenol unit structure and / or an amine unit structure,

[0037] Unit structure B represents one or more unit structures including the structure represented by the following formula (B1), formula (B2) or formula (B3),

[0038] * indicates a bond. )

[0039]

[0040] [In formula (B1),

[0041] R and R' each independently represent a hydrogen atom, an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent, a heterocyclic residue having 3 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent,

[0042] * indicates a bonding bond. ]

[0043] *——J 1 ——Z 0 ——J 2 ——* (B2)

[0044] [In formula (B2),

[0045] Z 0 represents an aromatic ring residue or an aliphatic ring residue having 6 to 30 carbon atoms which may have a substituent, or an organic group in which two aromatic ring residues or aliphatic ring residues are linked via a single bond,

[0046] J 1 and J 2 Each independently represents a divalent organic group which is directly bonded or may have a substituent,

[0047] * indicates a bonding bond. ]

[0048]

[0049] [In formula (B3),

[0050] Z is a monocyclic, bicyclic, tricyclic or tetracyclic condensed ring having 4 to 25 carbon atoms and optionally having a substituent, wherein the monocyclic ring is a non-aromatic monocyclic ring; at least one of the monocyclic rings constituting the bicyclic, tricyclic and tetracyclic rings is a non-aromatic monocyclic ring, and the remaining monocyclic rings may be either aromatic or non-aromatic. The monocyclic, bicyclic, tricyclic or tetracyclic condensed ring may further form a condensed ring with one or more aromatic rings to form a condensed ring of at least five rings,

[0051] X and Y are the same or different, indicating -CR 1 R 2 -Base, R 1 and R 2 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms,

[0052] x and y each represent the number of X and Y, and each independently represents 0 or 1.

[0053] *——X x is bonded to any carbon atom (referred to as "carbon atom 1") of the non-aromatic monocyclic ring constituting Z (when x=1), or extends from carbon atom 1 (when x=0),

[0054] Y y - is bonded to any carbon atom (referred to as "carbon atom 2") of the non-aromatic monocyclic ring constituting Z (when y=1), or extends from carbon atom 2 (when y=0),

[0055] The carbon atom 1 and the carbon atom 2 may be the same or different, and in different cases, may belong to the same non-aromatic monocyclic ring or different non-aromatic monocyclic rings.

[0056] * indicates a bonding bond. ]

[0057] The tenth aspect of the present invention relates to the composition for forming an anti-etching agent underlayer film as described in the ninth aspect, wherein the phenol unit structure is a chemical structure in which at least one hydroxyl group is bonded to an aromatic ring and has at least one aromatic ring selected from a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a fluorene ring, a benzofluorene ring or a dibenzofluorene ring, and the aromatic rings can be condensed with each other or bonded by a single bond, a straight chain, a branched chain or a cyclic alkyl group having 1 to 8 carbon atoms.

[0058] The 11th aspect of the present invention relates to the composition for forming an anti-etching underlayer film described in the 9th aspect, wherein the above-mentioned phenol unit structure contains a structure derived from at least one monomer selected from the following formulas 1 to 36 which may have a substituent, and the H of OH in formulas 1 to 36 may be substituted by the following substituent.

[0059]

[0060] Substituents

[0061] * indicates a bonding bond.

[0062] Substituents

[0063]

[0064] * indicates a bonding bond.

[0065] The 12th aspect of the present invention relates to the composition for forming an anti-etching agent underlayer film described in the 9th aspect, wherein the above-mentioned amine unit structure is a chemical structure having at least one heterocyclic ring selected from a pyrrole ring, an indole ring, and a carbazole ring, or is a unit structure in which any two or more aromatic rings of a benzene ring or a naphthalene ring are bonded to each other via a nitrogen atom, or the above-mentioned heterocyclic ring and the aromatic ring are condensed with each other, or the above-mentioned heterocyclic ring and the aromatic ring are bonded or condensed via a single bond, a quaternary carbon, or an aliphatic ring having 5 to 7 carbon atoms.

[0066] The 13th embodiment of the present invention relates to the composition for forming an anti-etching underlayer film described in the 9th embodiment, wherein the above-mentioned amine unit structure contains a structure derived from at least one monomer selected from the following formulas 37 to 75 which may have a substituent, and the H of NH in formulas 37 to 75 may be substituted by the following substituent.

[0067]

[0068] Substituents

[0069] * indicates a bonding bond.

[0070] Substituents

[0071]

[0072] * indicates a bonding bond.

[0073] A fourteenth aspect of the present invention is the resist underlayer film forming composition according to the first aspect, wherein the solvent has a boiling point of 160° C. or higher.

[0074] A fifteenth aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, further comprising a cross-linking agent.

[0075] A sixteenth aspect of the present invention is the resist underlayer film-forming composition according to the fifteenth aspect, wherein the crosslinking agent is an aminoplast crosslinking agent or a phenoplast crosslinking agent.

[0076] A seventeenth aspect of the present invention relates to the resist underlayer film forming composition according to the first aspect, further comprising a surfactant.

[0077] An eighteenth aspect of the present invention relates to the resist underlayer film forming composition according to the first aspect, further comprising an acid and / or a salt thereof and / or an acid generator.

[0078] A nineteenth aspect of the present invention relates to a resist underlayer film which is a fired product of a coating film formed from the composition according to any one of the first to eighteenth aspects.

[0079] A 20th aspect of the present invention relates to a method for forming a resist pattern for semiconductor manufacturing, comprising the step of applying the resist underlayer film forming composition according to any one of the first to eighteenth aspects onto a semiconductor substrate and firing the composition to form a resist underlayer film.

[0080] A 21st aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the following steps:

[0081] a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of the first to eighteenth aspects;

[0082] forming a resist film on the resist underlayer film;

[0083] forming a resist pattern on the resist film;

[0084] a step of etching the resist underlayer film using the resist pattern; and

[0085] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0086] A 22nd aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 21st aspect, wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development.

[0087] A 23rd aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 21st aspect, wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

[0088] A 24th aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the following steps:

[0089] a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of the first to eighteenth aspects;

[0090] forming a hard mask on the resist underlayer film;

[0091] A step of further forming a resist film on the hard mask;

[0092] forming a resist pattern on the resist film;

[0093] a step of etching the hard mask using the resist pattern;

[0094] a step of etching the resist underlayer film using the patterned hard mask; and

[0095] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0096] A 25th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 24th aspect, wherein the hard mask is formed by coating or vapor deposition of an inorganic substance.

[0097] A 26th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 24th aspect, wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development.

[0098] A 27th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 24th aspect, wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

[0099] A 28th aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the following steps:

[0100] a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of the first to eighteenth aspects;

[0101] forming a hard mask on the resist underlayer film;

[0102] A step of further forming a resist film on the hard mask;

[0103] forming a resist pattern on the resist film;

[0104] a step of etching the hard mask using the resist pattern;

[0105] A step of etching the resist underlayer film using the patterned hard mask;

[0106] A process of removing the hard mask; and

[0107] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0108] A 29th aspect of the present invention is directed to the method for manufacturing a semiconductor device according to the 28th aspect, wherein the hard mask is formed by coating a composition containing an inorganic substance or vapor deposition of a composition containing an inorganic substance.

[0109] A 30th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 28th aspect, wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development.

[0110] A 31st aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 28th aspect, wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

[0111] A 32nd aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 28th aspect, wherein the hard mask is removed by either etching or an alkaline chemical solution.

[0112] A thirty-third aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the following steps:

[0113] a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of the first to eighteenth aspects;

[0114] forming a hard mask on the resist underlayer film;

[0115] A step of further forming a resist film on the hard mask;

[0116] forming a resist pattern on the resist film;

[0117] a step of etching the hard mask using the resist pattern;

[0118] A step of etching the resist underlayer film using the patterned hard mask;

[0119] A step of removing the hard mask;

[0120] A step of forming a vapor-deposited film (spacer) on the resist underlayer film after the hard mask is removed;

[0121] A step of processing the vapor deposited film (spacer) by etching;

[0122] a step of removing the patterned resist underlayer film to leave the patterned vapor-deposited film (spacer); and

[0123] A step of processing a semiconductor substrate using the patterned vapor-deposited film (spacer).

[0124] A 34th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 33rd aspect, wherein the hard mask is formed by coating a composition containing an inorganic substance or vapor deposition of a composition containing an inorganic substance.

[0125] A 35th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 33rd aspect, wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development.

[0126] A 36th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 33rd aspect, wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

[0127] A 37th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 33rd aspect, wherein the hard mask is removed by either etching or an alkaline chemical solution.

[0128] Effects of the Invention

[0129] The present application has a novolac resin with a hydroxymethyl ether side chain, compared with a novolac resin without a hydroxymethyl ether side chain, even if it does not include a crosslinking agent, a curing catalyst and only a polymer also shows self-crosslinking, so it can also show sufficient curability even under a nitrogen atmosphere. Therefore, sufficient curability can be obtained even under an atmospheric atmosphere as used in the past and a nitrogen atmosphere. Therefore, it can be widely used in a variety of semiconductor manufacturing processes. In addition, due to its high heat resistance, it is also good to coat silicon wafers even when sintered at high temperatures, and its etching resistance is also high. Further, it is also good to coat well to a vapor deposition substrate with various height differences, so that flatness and embedding are also good. By changing the skeleton of the novolac resin and the skeleton that is hydroxymethylated, it can be adjusted to the appropriate optical constants for suppressing reflection during exposure. DETAILED DESCRIPTION

[0130] The resist underlayer film-forming composition of the present invention is a resist underlayer film-forming composition characterized by comprising a novolac resin having a hydroxymethyl ether structure in a side chain and a solvent, and optionally comprising a crosslinking agent, an acid generator or a surfactant.

[0131] Hereinafter, the details of each component will be described.

[0132] <Definition of terms>

[0133] In this specification, the definitions of main terms related to the novolac resin as one embodiment of the present invention are described below. Unless otherwise specified, the definitions of the following terms apply to the novolac resin.

[0134] "Novolac resin"

[0135] The term "novolak resin" is used in a broad sense to include not only phenol / formaldehyde resins (so-called novolac-type phenolic resins) and aniline / formaldehyde resins (so-called novolac-type aniline resins) in a narrow sense, but also a polymer formed by covalent bond formation (substitution reaction, addition reaction, condensation reaction, or addition condensation reaction, etc.) between an organic compound having a functional group capable of covalently bonding to an aromatic ring [for example, an aldehyde group, a ketone group, an acetal group, a ketal group, a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon, a hydroxyl group, an alkoxy group or a halide group bonded to an α-position carbon atom (benzyl carbon atom, etc.) of an alkylaryl group; a carbon-carbon unsaturated bond of divinylbenzene, dicyclopentadiene, etc.] and an aromatic ring in a compound having an aromatic ring (preferably having a substituent containing a heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. on the aromatic ring) in the presence of an acid catalyst or under reaction conditions equivalent thereto.

[0136] Therefore, the novolac resin referred to in the present application specification is formed by connecting a plurality of compounds having aromatic rings to form a polymer by forming a covalent bond with an aromatic ring in a compound having an aromatic ring via a connecting carbon atom through an organic compound containing a carbon atom derived from the above-mentioned functional group (sometimes referred to as a "connecting carbon atom").

[0137] In this specification, the terms unit structure A, unit structure B, and unit structure C are used as unit structures constituting the "phenolic varnish 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 can be covalently bonded to the aromatic ring of unit structure A. Unit structure C is a unit structure having an equivalent bonding method to composite unit structure AB, and is a unit structure derived from a compound having an aromatic ring and having a functional group that can be covalently bonded to the aromatic ring of unit structure A. Since the bonding method is the same, unit structure C can replace composite unit structure AB.

[0138] "Residue"

[0139] The so-called "residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or a heteroatom (nitrogen atom, oxygen atom, sulfur atom, etc.) is replaced with a bonding bond, and can be a monovalent group or a polyvalent group. For example, if one hydrogen atom is replaced with one bonding bond, it becomes a monovalent organic group, and if two hydrogen atoms are replaced with bonding bonds, it becomes a divalent organic group.

[0140] "Aromatic ring" (aromatic group, aryl group, arylene group)

[0141] The term "aromatic ring" is a concept including aromatic hydrocarbon rings, aromatic heterocycles, and residues thereof [sometimes referred to as "aromatic groups", "aryl groups" (in the case of monovalent groups) or "arylene groups" (in the case of divalent groups)], and includes not only monocyclic types (aromatic monocyclic rings) but also polycyclic types (aromatic polycyclic rings). In the case of polycyclic types, at least one monocyclic ring is an aromatic monocyclic ring, and the remaining monocyclic rings forming a condensed ring with the aromatic monocyclic ring may be monocyclic heterocyclic rings (heteromonocyclic rings) or monocyclic alicyclic hydrocarbons (alicyclic monocyclic rings).

[0142] Examples of the aromatic ring include benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, benzo[9,10]phenanthrene, benzanthracene, pyrene, Fluorene, biphenyl, coronene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, coronene, dibenzo[g,p] Aromatic hydrocarbon rings such as acenaphthene, dihydroacenaphthene, tetracene, pentacene, and cyclooctatetraene, more typically benzene, naphthalene, anthracene, phenanthrene, pyrene, and the like; furan, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, purine, quinoline, isoquinoline, chromene, thianthrene, phenothiazine, phenanthrene, phenanthracene ... Aromatic heterocycles such as oxazine, xanthene, acridine, phenazine, carbazole, and indolocarbazole are typically indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, and phenothiazine. More typically, indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole, and phenothiazine can be mentioned, but the present invention is not limited to these.

[0143] The aromatic ring (e.g., benzene ring, naphthalene ring, etc.) may optionally have a substituent, and examples of such a substituent include a halogen atom, a saturated or unsaturated straight chain, branched chain or cyclic hydrocarbon group (-R) (which may be interrupted once or more by an oxygen atom in the middle of the hydrocarbon chain. It includes alkyl, alkenyl, alkynyl, propargyl, etc.), an alkoxy or aryloxy group (-OR, where R represents the above hydrocarbon group -R), an alkylamino group [-NHR or -NR2 (the two Rs may be the same or different), where R represents the above hydrocarbon group -R], a hydroxyl group, an amino group (-NH2), a carboxyl group , cyano group, nitro group, ester group (-CO2R or -OCOR, where R represents the above hydrocarbon group -R), amide group [-NHCOR, -CONHR, -NRCOR (the two Rs may be the same or different) or -CONR2 (the two Rs may be the same or different), where R represents the above hydrocarbon group -R], sulfonyl group (-SO2R, where R represents the above hydrocarbon group -R), sulfonic acid group (-SO3H), sulfide group (-SR, where R represents the above hydrocarbon group -R), thiol group (-SH), organic group containing ether bond [R11 -OR 11 (R 11 Each independently represents an alkyl group having 1 to 6 carbon atoms such as methyl and ethyl, phenyl, naphthyl, anthracenyl, and pyrenyl. ) is a residue of an ether compound represented by; for example, an organic group containing an ether bond including a methoxy group, an ethoxy group, and a phenoxy group], and a substituent such as an aryl group.

[0144] Furthermore, organic groups having a condensed ring formed by one or more aromatic rings (benzene, naphthalene, anthracene, pyrene, etc.) and one or more aliphatic rings or heterocyclic rings are also included. Further, examples of the aliphatic rings here include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene, and examples of the heterocyclic rings include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0145] The organic group may be an organic group having a structure in which two or more aromatic rings are connected via a divalent connecting group such as an alkylene group.

[0146] "Heterocyclic"

[0147] "Heterocycle" is a concept that includes both aliphatic heterocycles and aromatic heterocycles, and includes not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic). In the case of a polycyclic, at least one monocyclic ring is a heteromonocyclic ring, and the remaining monocyclic rings may be aromatic hydrocarbon monocyclic rings or alicyclic monocyclic rings. As aromatic heterocycles, the examples of the above-mentioned "aromatic ring" can be referred to. As with the aromatic ring of the above-mentioned "aromatic ring", it may have a substituent.

[0148] "Non-aromatic ring" (aliphatic ring)

[0149] The so-called "non-aromatic monocyclic ring" is a monocyclic hydrocarbon that is not aromatic, typically a monocyclic ring of an alicyclic compound. It can be called an aliphatic monocyclic ring (it can include an aliphatic heteromonocyclic ring, and it can include an unsaturated bond as long as it is not an aromatic compound). Like the aromatic ring of the above-mentioned "aromatic ring", it can have a substituent.

[0150] Examples of the non-aromatic monocyclic ring (aliphatic ring, aliphatic monocyclic ring) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0151] The so-called "non-aromatic polycyclic" is a polycyclic hydrocarbon that is not aromatic, typically a polycyclic alicyclic compound. It can be called an aliphatic polycyclic [which may include an aliphatic heteropolycyclic (at least one of the monocyclics constituting the polycyclic is an aliphatic heterocyclic), and may include an unsaturated bond as long as it is not an aromatic compound]. It includes a non-aromatic bicyclic, a non-aromatic tricyclic, and a non-aromatic tetracyclic.

[0152] The so-called "non-aromatic bicyclic ring" is a condensed ring composed of two monocyclic hydrocarbons that are not aromatic, and is typically a condensed ring of two alicyclic compounds. In this specification, it is sometimes referred to as an aliphatic bicyclic ring (which may include an aliphatic heterobicyclic ring and may include an unsaturated bond as long as it is not an aromatic compound). Examples of the non-aromatic bicyclic ring include dicyclopentane, dicyclooctane, and dicycloheptene.

[0153] The so-called "non-aromatic tricyclic ring" is a condensed ring composed of three monocyclic hydrocarbons that are not aromatic, and is typically a condensed ring of three alicyclic compounds (each of which may be a heterocyclic ring and may contain an unsaturated bond as long as it is not an aromatic compound). Examples of the non-aromatic tricyclic ring include tricyclooctane, tricyclononane, and tricyclodecane.

[0154] The so-called "non-aromatic tetracyclic ring" is a condensed ring composed of four monocyclic hydrocarbons that are not aromatic, and is typically a condensed ring of four alicyclic compounds (each of which may be a heterocyclic ring and may contain an unsaturated bond as long as it is not an aromatic compound). Examples of the non-aromatic tetracyclic ring include hexahydropyrene and the like.

[0155] The "carbon atoms constituting the ring (part)" refers to the carbon atoms constituting the hydrocarbon ring (which may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring) in a state without a substituent.

[0156] The term "hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0157] In the chemical structural formula representing the unit structure of the phenolic varnish resin in the present application specification, a bond (indicated by *) is sometimes recorded for convenience. Unless otherwise specified, such a bond can adopt any bonding position in the unit structure that can be bonded, and the bonding position in the unit structure is not limited at all.

[0158] <Resist underlayer film forming composition>

[0159] A resist underlayer film-forming composition according to one embodiment of the present invention contains a specific novolac resin and a solvent.

[0160] <Novolac resin>

[0161] The novolac resin includes a composite unit structure AB represented by the following formula (AB).

[0162]

[0163] In formula (AB), n represents the number of composite unit structures AB, unit structure A is a divalent organic group containing a phenol unit structure and / or an amine unit structure, and unit structure B has the following structure.

[0164] <Unit structure A>

[0165] The unit structure A is a structural unit having an aromatic ring. Such an aromatic ring preferably has 6 to 30 carbon atoms, more preferably 6 to 24 carbon atoms.

[0166] Such an aromatic ring is preferably one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings; or a condensed ring of a benzene ring, naphthalene ring, anthracene ring, pyrene ring and a heterocyclic ring or an aliphatic ring.

[0167] The aromatic ring may optionally have a substituent, preferably containing a heteroatom in the substituent. In addition, the aromatic ring may be connected to two or more aromatic rings via a linker, preferably containing a heteroatom in the linker. As the heteroatom, for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc. may be mentioned.

[0168] The "aromatic ring" is preferably an organic group having 6 to 30, or 6 to 24 carbon atoms, containing at least one hetero atom selected from a nitrogen atom, a sulfur atom and an oxygen atom on, within or between the rings.

[0169] As heteroatoms contained in the ring, for example, nitrogen atoms contained in amino (for example, propargylamino) and cyano groups; oxygen atoms contained in formyl, hydroxyl, carboxyl, alkoxy (for example, propargyloxy) groups as oxygen-containing substituents, nitrogen atoms and oxygen atoms contained in nitro groups as oxygen-containing substituents and nitrogen-containing substituents. As heteroatoms contained in the ring, for example, oxygen atoms contained in xanthene and nitrogen atoms contained in carbazole can be mentioned. As heteroatoms contained in the linking group of two or more aromatic rings, nitrogen atoms, oxygen atoms, and sulfur atoms contained in -NH- bonds, -NHCO- bonds, -O- bonds, -COO- bonds, -CO- bonds, -S- bonds, -SS- bonds, and -SO2- bonds can be mentioned.

[0170] The unit structure A is preferably a unit structure having the above-mentioned aromatic ring having an oxygen-containing substituent, a unit structure having two or more aromatic rings connected by -NH-, or a unit structure having a condensed ring formed by one or more aromatic hydrocarbon rings and one or more heterocyclic rings.

[0171] It is preferred that the unit structure A contains a phenol unit structure and / or an amine unit structure.

[0172] The so-called phenol unit structure is a chemical structure in which at least one hydroxyl group is bonded to an aromatic ring and has at least one aromatic ring selected from a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a fluorene ring, a benzofluorene ring and a dibenzofluorene ring, and is a unit structure in which the above aromatic rings can be condensed with each other or bonded by a single bond, a straight chain, a branched chain or a cyclic alkyl group having 1 to 8 carbon atoms.

[0173] The so-called amine unit structure is a chemical structure having at least one heterocyclic ring selected from a pyrrole ring, an indole ring, and a carbazole ring, or a unit structure in which any two or more aromatic rings of a benzene ring or a naphthalene ring are bonded to each other via a nitrogen atom, or the above heterocyclic ring and the aromatic ring are condensed to each other, or the above heterocyclic ring and the aromatic ring are bonded or condensed via a single bond, a quaternary carbon, or an aliphatic ring having 5 to 7 carbon atoms.

[0174] Examples of such a monomer having a phenol unit structure and a monomer having an amine unit structure are as follows.

[0175] It should be noted that the following exemplified structure is an example, and the number of hydroxyl groups in the compound that can be substituted with hydroxyl groups on the aromatic ring is not limited to the specific exemplified structure, and can be substituted within a theoretically achievable range. In addition, it also includes substances in which any substituent that can be theoretically bonded to the aromatic ring is bonded.

[0176] (Examples of Monomers Having a Phenol Unit Structure)

[0177]

[0178] (Examples of Monomers Having an Amine Unit Structure)

[0179]

[0180] Furthermore, the H of NH of the monomer having an amine unit structure and the H of OH of the monomer having a phenol unit structure may be substituted with the substituents described below.

[0181] Substituents

[0182]

[0183] * indicates a bonding bond.

[0184] Substituents

[0185]

[0186] * indicates a bonding bond.

[0187] In addition, the unit structure A is preferably at least one selected from the following: It should be noted that the positions of the two bonds shown in each unit structure described below are only shown for convenience and can extend from any possible carbon atom, and the positions are not limited.

[0188] (Examples of unit structures derived from heterocycles)

[0189]

[0190] (Examples of unit structures derived from aromatic hydrocarbons having oxygen-containing substituents)

[0191]

[0192]

[0193] (Example of a unit structure derived from an aromatic hydrocarbon linked via -NH-)

[0194] -NH- can also have a structure in which a hydrogen atom on N is substituted.

[0195]

[0196] <Unit structure B>

[0197] Unit structure B is one or more unit structures including a connecting carbon atom (refer to the above term definition section) bonded to the aromatic ring in unit structure A, including the structure represented by formula (B1), formula (B2) or formula (B3) described below. Unit structure B can connect two unit structures A by covalently bonding to the carbon atom on the aromatic ring of unit structure A.

[0198] Furthermore, at least one composite unit structure AB may be replaced by one or more unit structures C including structures represented by formula (C1), formula (C2) and formula (C3) described later, which are one unit structure equivalent thereto.

[0199] <Formula (B1)>

[0200]

[0201] In formula (B1),

[0202] R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent.

[0203] Furthermore, the two bonds of formula (B1) may be covalently bonded to the aromatic ring in unit structure A.

[0204] In the definitions of R and R' in formula (B1), regarding "aromatic ring" and "heterocycle", refer to the above-mentioned <Definition of Terms>.

[0205] In the definitions of R and R' in formula (B1), examples of "alkyl" include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2 -methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl- n-Butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2 ,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, n-heptyl, n-octyl, n-nonyl, n-decyl.

[0206] Preferably, R and R' are each independently phenyl, naphthyl, anthracenyl, phenanthryl, naphthacene or pyrene.

[0207] In addition, in the unit structure including the structure shown in formula (B1), for example, two or three structures of the above formula (B1) that are identical or different from each other are combined with a divalent or trivalent linking group to form a dimer or trimer structure. In this case, as shown in the following formula (B11) in each structure of the above formula (B1), one of the two bonds is combined with the above linking group.

[0208]

[0209] As such a linking group, for example, a linking group having two or three aromatic rings (corresponding to unit structure A) can be cited. As specific examples of divalent or trivalent linking groups, in addition to the following divalent linking group (L1) exemplified in the above formula (B11), divalent or trivalent linking groups of the following formula (L2) and formula (L3) can also be cited.

[0210]

[0211] [X 1 represents a single bond, a methylene group, an oxygen atom, a sulfur atom, -N(R 1 )-, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (including chain hydrocarbons and cyclic hydrocarbons (which may be aromatic or non-aromatic)).]

[0212]

[0213] [X 2 represents a methylene group, an oxygen atom, -N(R 2 )-, R 2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 20 carbon atoms.]

[0214]

[0215] Another example is a divalent linking group such as the following formula (L4) which can form a covalent bond to a carbon atom by an addition reaction of an acetylide with a ketone.

[0216]

[0217] When at least one of R and R′ in formula (B1) is an aromatic ring, the aromatic ring may be additionally bonded to another unit structure B [for example, see Ar in formula (B12) below].

[0218]

[0219] In this case, when a bond connecting a carbon atom is bonded to a polymer terminal T (hydrogen atom; various functional groups such as a hydroxyl group and an unsaturated aliphatic hydrocarbon group, a terminal unit structure A, a unit structure A in another polymer chain, etc.) as shown in the following formula (C1), at least one composite unit structure AB may be replaced as a unit structure C equivalent to the composite unit structure AB. That is, the polymer chain may be extended by bonding to another unit structure B through the above-mentioned aromatic ring [Ar in formula (C1)] in formula (C1), and bonding to the aromatic ring of the unit structure A by utilizing the bond from the remaining connecting carbon atom shown in formula (C1).

[0220]

[0221] Some specific examples of the unit structure B including the structure represented by formula (B1) are given below. * Basically represents a bonding site with the unit structure A. Of course, a structure including the exemplified structure as a part of the whole may be used.

[0222]

[0223] <Formula (B2)>

[0224] *——J 1 ——Z 0 ——j 2 ——* (B2)

[0225] In formula (B2),

[0226] Z 0 It represents an aromatic ring residue or aliphatic ring residue having 6 to 30 carbon atoms which may have a substituent, or an organic group in which two aromatic or aliphatic rings are linked by a single bond. Examples of the organic group in which two aromatic or aliphatic rings are linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and dicyclohexyl.

[0227] J 1 and J 2 Each independently represents a divalent organic group which is directly bonded or may have a substituent. The divalent organic group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an aryl group (phenyl, substituted phenyl, etc.) or a halogenated group (e.g., fluorine) as a substituent. Examples of the linear alkylene group include methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0228] In addition, in the unit structure including the structure represented by formula (B2), similarly to the above formula (B1), it may include two or three structures of the above formula (B2) which are the same or different from each other and are bonded to a divalent or trivalent linking group to form a dimer or trimer structure.

[0229] It should be noted that since the formula (B2) includes a scheme in which an aromatic ring is contained [Z in the formula (B2) 0 ], so as in the above formula (B1), the aromatic ring [for example, Z in the following formula (B21) 0 Ar The aromatic ring in formula (B21)] may be additionally bonded to other unit structures B [vertical bonding bonds in formula (B21)].

[0230]

[0231] [In formula (B21),

[0232] Z 0 Ar is an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent, or an organic group having at least one aromatic ring in which two aromatic rings or aliphatic rings are connected by a single bond, wherein Z 0 Ar The bond extending downward from Z 0 Ar The aromatic rings in the

[0233] J 1 and J 2 Same as the definition of formula (B2).]

[0234] In this case, when a bond connecting a carbon atom is bonded to a polymer terminal T (hydrogen atom; various functional groups such as a hydroxyl group and an unsaturated aliphatic hydrocarbon group, terminal unit structure A, unit structure A in other polymer chains, etc.) as shown in the following formula (C2), at least one composite unit structure AB may be replaced as a unit structure C equivalent to the composite unit structure AB. That is, the aromatic ring in formula (C2) [Z in formula (C2)] 0 Ar The aromatic ring in the formula (C2) is bonded to the other unit structure B, and is bonded to the aromatic ring of the unit structure A via the bond from the remaining connecting carbon atom shown in the formula (C2) to extend the polymer chain.

[0235]

[0236] [In formula (C2),

[0237] Z 0 Ar , J1 and J 2 Same as the definition of formula (B21),

[0238] T represents the polymer terminus.]

[0239] Some specific examples of the unit structure including the structure represented by formula (B2) are as follows: * represents a bonding site with the unit structure A. Of course, the unit structure may include the exemplified structure in part of the whole.

[0240]

[0241] <Formula (B3)>

[0242]

[0243] In formula (B3),

[0244] Z is a monocyclic ring or a bicyclic, tricyclic or tetracyclic condensed ring having 4 to 25 carbon atoms which may have a substituent. Furthermore, the number of carbon atoms here refers to the number of carbon atoms constituting the ring skeleton of the monocyclic ring or the bicyclic, tricyclic or tetracyclic condensed ring excluding the substituent, and does not include the number of heteroatoms constituting the heterocyclic ring when the monocyclic or condensed ring is a heterocyclic ring.

[0245] The monocyclic ring is a non-aromatic monocyclic ring; at least one of the monocyclic rings constituting the bicyclic, tricyclic and tetracyclic rings is a non-aromatic monocyclic ring, and the remaining monocyclic rings may be either an aromatic monocyclic ring or a non-aromatic monocyclic ring.

[0246] The above-mentioned monocyclic, bicyclic, tricyclic or tetracyclic condensed ring may further form a condensed ring with one or more aromatic rings to form a pentacyclic or higher condensed ring, and the number of carbon atoms in the pentacyclic or higher condensed ring is preferably 40 or less. The number of carbon atoms here refers to the number of carbon atoms constituting the ring skeleton of the above-mentioned pentacyclic or higher condensed ring excluding substituents, and does not include the number of heteroatoms constituting the heterocycle when the above-mentioned pentacyclic or higher condensed ring is a heterocycle.

[0247] X and Y are the same or different, indicating -CR 3 R 4 -Base, R 3 and R 4 Each of them is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0248] x and y each represent the number of X and Y, and each independently represents 0 or 1.

[0249] *-X xis bonded to any carbon atom (referred to as "carbon atom 1") of the non-aromatic monocyclic ring constituting Z (in the case of x=1) or extends from carbon atom 1 (in the case of x=0),

[0250] Y y -* is bonded to any carbon atom (referred to as "carbon atom 2") of the above-mentioned non-aromatic monocyclic ring constituting Z (when y=1) or extends from carbon atom 2 (when y=0), and carbon atom 1 and carbon atom 2 may be the same or different, and in different cases, may belong to the same non-aromatic monocyclic ring or different non-aromatic monocyclic rings.

[0251] Furthermore, in formula (B3), a connecting carbon atom other than carbon atom 1 and carbon atom 2 may also be optionally included.

[0252] It should be noted that, when Z is a condensed ring of tricyclic or higher type, the serial positional relationship in the condensed ring formed by one or two non-aromatic monocyclic rings to which carbon atoms 1 and 2 in formula (B3) respectively belong and the remaining monocyclic ring is arbitrary. When carbon atom 1 and carbon atom 2 belong to different non-aromatic monocyclic rings (referred to as "non-aromatic monocyclic ring 1" and "non-aromatic monocyclic ring 2", respectively), the serial positional relationship between the non-aromatic monocyclic ring 1 and the non-aromatic monocyclic ring 2 in the condensed ring is also arbitrary.

[0253] In the unit structure including the structure represented by formula (B3), similarly to the above formula (B1), two or three structures of the above formula (B3) which are the same or different from each other may be bonded to a divalent or trivalent linking group to form a dimer or trimer structure.

[0254] Some specific examples of the organic group including the structure represented by formula (B3) are as follows: The bonding site with the unit structure A is not particularly limited. Of course, a structure including the exemplified structure in part of the whole may be used.

[0255] It should be noted that this also includes examples where the number of bonds (*) exceeds 2, and the remaining bonds can be used for bonding with aromatic rings in other polymer chains, crosslinking, and the like.

[0256]

[0257] It should be noted that, when Z in formula (B3) contains an aromatic ring, the aromatic ring [for example, referring to Ar in formula (B32) below] 1 ] can be additionally combined with other unit structures B.

[0258]

[0259] In formula (B32),

[0260] Z 1 represents at least one non-aromatic monocyclic ring, Ar 1 Represents Z 1 The non-aromatic monocyclic ring of the present invention forms at least one aromatic monocyclic ring condensed with the non-aromatic monocyclic ring of the present invention, as Z and Ar 1 As a whole, it constitutes a bicyclic, tricyclic, tetracyclic or pentacyclic condensed ring which may have a substituent and has a carbon number of 8 to 25. Furthermore, the number of carbon atoms here refers to the number of carbon atoms constituting the ring skeleton of the bicyclic, tricyclic or tetracyclic condensed ring excluding the substituent, and does not include the number of heteroatoms constituting the heterocyclic ring when the bicyclic, tricyclic or tetracyclic condensed ring is a heterocyclic ring.

[0261] The above-mentioned bicyclic, tricyclic, tetracyclic or pentacyclic organic group may further form a condensed ring with one or more aromatic rings to become a hexacyclic or higher ring. The number of carbon atoms in the hexacyclic or higher ring condensed ring is preferably 40 or less. The number of carbon atoms here refers to the number of carbon atoms constituting the ring skeleton of the above-mentioned pentacyclic or higher ring condensed ring excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the above-mentioned hexacyclic or higher ring condensed ring is a heterocyclic ring.

[0262] In addition, among the cyclic organic groups, Z 1 One or more non-aromatic monocyclic rings and Ar 1 The sequential position relationship of one or more aromatic monocyclic rings of Z includes any sequential position relationship. 1 There are two or more non-aromatic monocyclic rings belonging to Ar 1 When there are two or more aromatic monocyclic rings, Z 1 The non-aromatic monocyclic ring and the Ar 1 The aromatic monocyclic rings may be arranged alternately to form a condensed ring.

[0263] In addition, X, Y, x, and y have the same definitions as in formula (B3).

[0264] In this case, when a bond connecting a carbon atom is bonded to a polymer terminal T (hydrogen atom; various functional groups such as a hydroxyl group and an unsaturated aliphatic hydrocarbon group, terminal unit structure A, unit structure A in other polymer chains, etc.) as shown in the following formula (C3), at least one composite unit structure AB may be replaced as a unit structure C equivalent to the composite unit structure AB. That is, the aromatic ring in formula (C3) [Ar in formula (C3)] 1 ] is combined with other unit structures B, and is combined with the aromatic ring of unit structure A by utilizing the bond from the remaining connecting carbon atom shown in formula (C3) to extend the polymer chain.

[0265]

[0266] [In formula (C3),

[0267] Z 1 ,Ar 1 , X, Y, x and y are the same as defined in formula (B32),

[0268] T represents the polymer terminus.]

[0269] As a more specific structure of formula (C3), for example, for the following formula (C31), T in formula (C3) is a hydrogen atom as a terminal group, and p and k1, or p and k2 among p, k1 and k2 that can become a bonding bond can form a unit structure C equivalent to the composite unit structure AB.

[0270] In addition, it is also possible to function as the unit structure A by k1 and k2.

[0271]

[0272] In addition, the following formula (C32) represents an example where T in formula (C3) is a phenyl group. In this example, among p, k1, k2, and m that can be a bonding bond, p and k1, p and k2, or p and m can form a unit structure C equivalent to the composite unit structure AB.

[0273] In addition, the unit structure A may be functioned by k1 and k2, k1 and m, or k2 and m.

[0274]

[0275] More specific examples of the unit structure C (one unit structure equivalent to the composite unit structure AB) of the formula (C3) are as follows: * represents a bonding site with the unit structure A.

[0276] In the unit structure C, the bond to the unit structure B extends separately from the aromatic ring in these structures, but in the specific examples below, such a bond is omitted. Of course, the unit structure may include the exemplified structure as a part of the whole.

[0277]

[0278] In addition, in the above-mentioned specific examples, when there is no bond derived from an aromatic ring, it can be a specific example of a polymer terminal.

[0279] <Side chain of novolac resin>

[0280] The novolac resin having the repeating composite unit structure AB represented by the above formula (AB) further has a structure represented by the following formula (D) in its side chain.

[0281] -O-Ar 2 Formula (D)

[0282] In the formula, Ar 2 For the "aromatic ring", see the above <Definition of Terms>.

[0283] Ar in formula (D) 2 An aromatic ring having an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring is preferred. For the "aromatic hydrocarbon ring" and "aromatic heterocyclic ring", see the above-mentioned <Definition of Terms>.

[0284] Preferably, the aromatic hydrocarbon ring is an aromatic hydrocarbon ring containing a benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene structure, more preferably benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene. The above-mentioned aromatic heterocyclic ring is an aromatic heterocyclic ring that may contain nitrogen, and may be an aromatic heterocyclic ring containing an indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole or phenothiazine structure.

[0285] Examples of the aromatic heterocycle that may contain nitrogen include pyrrole, indole, isoindole, phenylindole, imidazole, pyrazole, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, carbazole, indolocarbazole, furan, thiophene or phenothiazine, but preferably indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole or phenothiazine.

[0286] Ar 2 For the -CH2-OR 12 Aromatic rings of substituted aromatic hydrocarbon rings and / or aromatic heterocycles.

[0287] In the formula, R 12 It represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and which may contain a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom.

[0288] Preferably, the above R 12 A hydrogen atom or a methyl group.

[0289] The side chain having the structure of formula (D) may be directly bonded to the main chain of the unit structure B, or may be bonded to the aromatic ring as the side chain of the unit structure B. It is further preferred that the aromatic ring is an aromatic ring having an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring which may be substituted with a halogenated group, a hydroxyl group, a hydroxymethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched ether group having 1 to 6 carbon atoms.

[0290] For the meanings of “aromatic ring”, “aromatic hydrocarbon ring” and “aromatic heterocycle”, refer to the corresponding descriptions in the above <Definition of Terms>, respectively.

[0291] The structure of formula (D) may have a hydroxymethyl ether structure in part thereof. Therefore, in the following description, the structure represented by formula (D) may be simply referred to as a hydroxymethyl ether structure, but the entire structure represented by formula (D) is not necessarily a hydroxymethyl ether structure.

[0292] <Examples of Unit Structures of Novolac Resins>

[0293] Examples of the unit structure of the novolac resin having the structure of formula (D) of the present invention include the following: The bond (*) means a bond to the main chain of the novolac resin.

[0294]

[0295] In the above example, X has the following structure. When X is written across multiple aromatic rings, it means that X replaces a hydrogen atom of any carbon of the aromatic ring being crossed. The wavy line of Y indicates the bond to the side directly connected to the aromatic ring.

[0296]

[0297] Examples of the side chain having the structure of the formula (D) in the unit structure of the main chain of the novolac resin include the following: The bond (*) refers to the unit structure of the main chain of the novolac resin.

[0298]

[0299]

[0300]

[0301] In the above example, X has the following structure. When X is written across multiple aromatic rings, it means that X replaces a hydrogen atom of any carbon of the aromatic ring being crossed. The wavy line of Y indicates the bond to the side directly connected to the aromatic ring.

[0302]

[0303] <Manufacturing of novolac resin>

[0304] The phenolic varnish resin having a structure represented by formula (AB) can be prepared by a known method. For example, it can be prepared by condensing a ring-containing compound represented by HAH with an oxygen-containing compound represented by OHC-B, O=CB, RO-B-OR, RO-CH2-B-CH2-OR, etc. Here, in the formula, A and B have the same meanings as above. R represents a hydrogen atom, a halogen atom or an alkyl group having about 1 to 3 carbon atoms.

[0305] Furthermore, by adding a methylol reagent to the novolac resin, a methylol ether structure can also be introduced.

[0306] As an example of a production method, for example, a novolac resin containing a halogen atom is condensed with an -OH monomer having a side chain having a hydroxymethyl ether structure to produce a novolac resin having a hydroxymethyl ether structure in the side chain. However, if either the novolac resin or the hydroxymethyl reagent has a halogen atom and the other has a hydroxyl group, a novolac resin having a hydroxymethyl ether structure in the side chain can be produced.

[0307] It should be noted that in this reaction, the side reaction of the methylol reagent entering the nitrogen atom can occur to the extent that the effects of the invention are not impaired, and the novolac resin of the present invention does not exclude the inclusion of partial structures generated by these side reactions.

[0308] As particularly preferred hydroxymethyl reagents, the following examples can be cited, but are not limited to these. It should be noted that the F of the halogen atom in the following structure can be replaced by Cl, Br, I, and when it is replaced by -CH2-OH, the side chain has -O-Ar 2 In the case of the structure of -CH2-OH, the H atom of OH may be substituted with a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom.

[0309]

[0310]

[0311]

[0312]

[0313] The ring-containing compound and the oxygen-containing compound may be used alone or in combination of two or more. In the condensation reaction, the oxygen-containing compound may be used in a ratio of 0.1 to 10 mol, preferably 0.1 to 2 mol, based on 1 mol of the ring-containing compound.

[0314] As the catalyst used in the condensation reaction, inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid, and carboxylic acids such as formic acid and oxalic acid can be used. The amount of the catalyst used varies depending on the type of catalyst used, but is generally 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, relative to 100 parts by mass of the ring-containing compound (or the total amount thereof in the case of a plurality of types).

[0315] The condensation reaction can be carried out without a solvent, but is usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrate and does not impair the reaction. Examples thereof include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether ..., diethylene glycol dimethyl ether, diethylene glycol dimethyl The condensation reaction temperature is usually 40 to 200° C., preferably 100 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.

[0316] The weight average molecular weight of the novolac resin according to one embodiment of the present invention is usually 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0317] <Solvent>

[0318] The resist underlayer film forming composition which is one embodiment of the present invention contains a solvent.

[0319] The solvent is not particularly limited as long as it can dissolve the specific novolac resin and other optional components added as necessary.

[0320] Examples of the solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, -Ethoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 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, lactic acid Butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, pentyl formate, isoamyl formate, methyl acetate, ethyl acetate, pentyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate Ester, ethyl ethoxylate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 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, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

[0321] Furthermore, a solvent having a boiling point of 160° C. or higher and a solvent having a boiling point of less than 160° C. may be contained in combination.

[0322] As such a high boiling point solvent, for example, the following compounds described in International Publication No. 2018 / 131562 (A1) can be preferably used.

[0323]

[0324] [R in formula (i) 1 , R 2 and R 3 Each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom or an amide bond, and may be the same or different and may be bonded to each other to form a ring structure.]

[0325] Alternatively, 1,6-diacetoxyhexane (boiling point 260° C.) and tripropylene glycol monomethyl ether (boiling point 242° C.) described in JP-A-2021-84974, and various high boiling point solvents described in paragraph 0082 of the publication can be preferably used.

[0326] Alternatively, dipropylene glycol monomethyl ether acetate (boiling point 213°C), diethylene glycol monoethyl ether acetate (boiling point 217°C), diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol dimethyl ether (boiling point 171°C), dipropylene glycol monomethyl ether (boiling point 187°C), dipropylene glycol monobutyl ether (boiling point 231°C), tripropylene glycol monomethyl ether (boiling point 231°C), and dipropylene glycol monomethyl ether (boiling point 231°C) described in Japanese Patent Application Laid-Open No. 2019-20701 can be preferably used. The present invention relates to various high boiling point solvents as described in paragraphs 0023 to 0031 of the disclosure.

[0327] <Acid and / or its salt and / or acid generator>

[0328] The resist underlayer film-forming composition as one embodiment of the present invention may contain an acid and / or a salt thereof and / or an acid generator.

[0329] Examples of the acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthoic acid.

[0330] As the salt, the salt of the above acid can also be used. The salt is not limited, and ammonia derivative salts such as trimethylamine salt and triethylamine salt, pyridine derivative salt, morpholine derivative salt, etc. can be preferably used.

[0331] The acid and / or its salt may be used alone or in combination of two or more thereof. The amount thereof is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the total solid content.

[0332] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0333] Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0334] The photoacid generator generates acid when the resist is exposed. Therefore, the acidity of the lower film can be adjusted. This is a method for matching the acidity of the lower film with the acidity of the upper resist. In addition, by adjusting the acidity of the lower film, the pattern shape of the resist formed on the upper layer can be adjusted.

[0335] Examples of the photoacid generator contained in the resist underlayer film-forming composition of the present invention include: Salt compounds, sulfonimide compounds and disulfonyldiazomethane compounds, etc.

[0336] As Salt compounds, such as diphenyl iodide Hexafluorophosphate, diphenyl iodide Trifluoromethanesulfonate, diphenyl iodide Nonafluorobutane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Camphorsulfonate and bis(4-tert-butylphenyl)iodide Trifluoromethanesulfonate and other iodine Sulfonium salt compounds and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0337] Examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0338] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0339] The acid generator may be used alone or in combination of two or more.

[0340] When the acid generator is used, the ratio thereof is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass based on 100 parts by mass of the solid content of the resist underlayer film-forming composition.

[0341] <Other optional ingredients>

[0342] The resist underlayer film-forming composition as one embodiment of the present invention may contain a crosslinking agent, a surfactant, a light absorber, a rheology control agent, an adhesion promoter, a curing catalyst, and the like in addition to the above-mentioned components as necessary.

[0343] <Cross-linking agent>

[0344] As representative crosslinking agents, aminoplast crosslinking agents and phenoplast crosslinking agents can be exemplified.

[0345] As the crosslinking agent, a crosslinking agent with high heat resistance can be used. As the crosslinking agent with high heat resistance, a compound having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule and containing a crosslinking-forming substituent can be preferably used.

[0346] As aminoplast crosslinking agents, there can be mentioned highly alkylated, alkoxylated or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, polymers thereof, etc. Preferred crosslinking agents are those having at least two crosslinking-forming substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea or methoxymethylated thiourea. In addition, condensates of these compounds can also be used.

[0347] It is preferably at least one selected from tetramethoxymethyl glycoluril and hexamethoxymethylmelamine.

[0348] Some specific examples are as follows.

[0349]

[0350] Examples of the phenolic plastic crosslinking agent include highly alkylated, alkoxylated or alkoxyalkylated aromatic compounds, and polymers thereof. Preferred crosslinking agents are those having at least two crosslinking substituents in one molecule, such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Condensates of these compounds may also be used.

[0351] Examples of such a compound include, in addition to the above, a compound having a partial structure of the following formula (4) and a polymer or oligomer having a repeating unit of the following formula (5).

[0352]

[0353] The above R 11 , R 12 , R 13 and R 14 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups exemplified above can be used. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5-n1), and (n1+n2) represents an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is 0 to (4-n3), and (n3+n4) represents an integer of 1 to 4. The oligomer and polymer can be used in a range of 2 to 100 or 2 to 50 repeating unit structures.

[0354] Some specific examples are as follows.

[0355]

[0356]

[0357] Aminoplast crosslinking agents, phenoplast crosslinking agents and other crosslinking agents may be used alone or in combination of two or more. The aminoplast crosslinking agent may be produced by a known method or a method based thereon, or a commercially available product may be used.

[0358] The amount of crosslinking agents such as aminoplast crosslinking agents and phenolic plastic crosslinking agents used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 mass % or more, 0.01 mass % or more, 0.05 mass % or more, 0.5 mass % or more, or 1.0 mass % or more, and 80 mass % or less, 50 mass % or less, 40 mass % or less, 20 mass % or less, or 10 mass % or less, relative to the total solid content of the resist underlayer film forming composition according to the present invention.

[0359] <Surfactant>

[0360] The resist underlayer film-forming composition according to the present invention may contain a surfactant in order to prevent pinholes, streaks, and the like from being generated and to further improve coating properties on uneven surfaces.

[0361] Examples of the surfactant include 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; and nonionic surfactants,

[0362] EF301, EF303, EF352 (manufactured by PT-EPT, trade name), EF303, EF352 171. F173, R-30, R-40 (made by Dainippon Co., Ltd., trade name), Fururo FC430, FC43 1 (Sumitomo Solar Co., Ltd., trade name), ASUNALA AG710, SAMULANO S-382, SC101, S Fluorine-based surfactants such as C102, SC103, SC104, SC105, SC106 (trade name manufactured by Asahi Glass Co., Ltd.),

[0363] Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0364] The amount of these surfactants blended 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.

[0365] <Other additives>

[0366] As the light absorber, for example, commercially available light absorbers described in "Industrial Colorant Technology and Market" (published by CMC) and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry) can be suitably used, for example, CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; CI Disperse Orange 1, 5, 13, CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI Disperse Violet 43; CI Disperse Blue 96; CI Fluorescent Brighteners 112, 135, and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27, and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The light absorber is usually blended in a ratio of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film-forming composition of the present invention.

[0367] The rheology modifier is mainly added for the purpose of improving the fluidity of the resist underlayer film-forming composition, especially in the baking process, to improve the film thickness uniformity of the resist underlayer film and to improve the filling property of the resist underlayer film-forming composition into the inside of the hole. As specific examples, phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, octyldecyl adipate, maleic acid derivatives such as di(n-butyl) maleate, diethyl maleate, dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, or stearic acid derivatives such as n-butyl stearate and glyceryl stearate can be cited. These rheology control agents are usually blended in a ratio of less than 30 mass % based on the total solid content of the resist underlayer film-forming composition according to the present invention.

[0368] The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film-forming composition, and particularly for the purpose of preventing 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; silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole. Heterocyclic compounds such as azole, ureaazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion promoters are usually mixed in a ratio 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 of the present invention.

[0369] The curing catalyst is effective for curing the film, and specific examples thereof include sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium maleate, triphenylsulfonium trifluoroacetate, triphenylsulfonium hydrochloride, and triphenylsulfonium acetate, but the present invention is not limited to these.

[0370] The solid content of the resist underlayer film forming composition of the present invention is 0.1 to 70 mass % or 0.1 to 60 mass %. The solid content is the content ratio of all components excluding the solvent from the resist underlayer film forming composition. The crosslinkable resin may be contained in the solid content at a ratio of 1 to 99.9 mass %, or 50 to 99.9 mass %, or 50 to 95 mass %, or 50 to 90 mass %.

[0371] <Resist underlayer film>

[0372] The resist underlayer film can be formed, for example, in the following manner using the resist underlayer film-forming composition according to the present invention.

[0373] On a substrate used in the manufacture of semiconductor devices (for example, a silicon wafer substrate, a silicon dioxide-coated substrate (SiO2 substrate), a silicon nitride substrate (SiN substrate), a silicon oxide nitride substrate (SiON substrate), a titanium nitride substrate (TiN substrate), a tungsten substrate (W substrate), a glass substrate, an ITO substrate, a polyimide substrate, and a low dielectric constant material (low-k material) coated substrate, etc.), a composition for forming an anti-etching underlayer film as one embodiment of the present invention is applied by a suitable coating method such as a spin coater or a coater, and then fired using a heating means such as a hot plate to form an anti-etching underlayer film. As conditions for firing, a firing temperature of 80°C to 800°C and a firing time of 0.3 to 60 minutes are appropriately selected. Preferably, the firing temperature is 150°C to 400°C and the firing time is 0.5 to 2 minutes. As an atmospheric gas during firing, air can be used, or an inert gas such as nitrogen or argon can be used. In one embodiment, it is particularly preferred that the oxygen concentration is 1% or less. Here, the thickness of the formed lower layer film is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm. In addition, if a quartz substrate is used as the substrate, a replica of the quartz imprint mold (mold replica) can be produced.

[0374] In addition, it is also possible to form a close-fitting layer and / or a layer containing silicon containing less than 99% by mass or less than 50% by mass of Si by coating or vapor deposition on the resist underlayer film as one embodiment of the present invention. For example, in addition to the close-fitting layer described in Japanese Unexamined Patent Publication No. 2013-202982, Japanese Patent No. 5827180, and the resist underlayer film (inorganic resist underlayer film) containing silicon described in International Publication No. 2009 / 104552 (A1) by spin coating, it is also possible to form an inorganic material film of Si system by CVD method etc.

[0375] In addition, by coating the anti-etching agent underlayer film forming composition as one embodiment of the present invention on a semiconductor substrate having a portion with a height difference and a portion without a height difference (so-called height difference substrate) and firing it, the height difference between the portion with a height difference and the portion without a height difference can be reduced.

[0376] <Method for manufacturing semiconductor device>

[0377] (i)

[0378] A method for manufacturing a semiconductor device as one embodiment of the present invention includes the following steps:

[0379] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as one embodiment of the present invention;

[0380] a step of forming a resist film on the resist underlayer film;

[0381] A step of forming a resist pattern on a resist film by irradiating the resist film with light or an electron beam and developing the resist film;

[0382] A step of etching the resist underlayer film using the resist pattern to perform patterning; and

[0383] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0384] (ii)

[0385] In addition, a method for manufacturing a semiconductor device as one embodiment of the present invention includes the following steps:

[0386] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as one embodiment of the present invention;

[0387] A step of forming a hard mask on the resist underlayer film;

[0388] A step of further forming a resist film on the hard mask;

[0389] A step of forming a resist pattern on a resist film by irradiating the resist film with light or an electron beam and developing the resist film;

[0390] A process of etching the hard mask using the resist pattern to perform patterning;

[0391] A step of etching the resist underlayer film using the patterned hard mask to perform patterning; and

[0392] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0393] (iii)

[0394] In addition, a method for manufacturing a semiconductor device as one embodiment of the present invention includes the following steps:

[0395] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as one embodiment of the present invention;

[0396] A step of forming a hard mask on the resist underlayer film;

[0397] A step of further forming a resist film on the hard mask;

[0398] A step of forming a resist pattern on a resist film by irradiating the resist film with light or an electron beam and developing the resist film;

[0399] A process of etching the hard mask using the resist pattern to perform patterning;

[0400] A step of etching the resist underlayer film using the patterned hard mask to perform patterning;

[0401] A process of removing the hard mask; and

[0402] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0403] (iv)

[0404] In addition, a method for manufacturing a semiconductor device as one embodiment of the present invention includes the following steps:

[0405] A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition as one embodiment of the present invention;

[0406] A step of forming a hard mask on the resist underlayer film;

[0407] A step of further forming a resist film on the hard mask;

[0408] A step of forming a resist pattern on a resist film by irradiating the resist film with light or an electron beam and developing the resist film;

[0409] A process of etching the hard mask using the resist pattern to perform patterning;

[0410] A step of etching the resist underlayer film using the etched hard mask to perform patterning;

[0411] A step of removing the hard mask;

[0412] A step of forming a vapor-deposited film (spacer) on the resist underlayer film after the hard mask is removed;

[0413] A step of processing the vapor deposited film (spacer) by etching;

[0414] A step of removing the patterned resist underlayer film to leave the patterned vapor-deposited film (spacer); and

[0415] A step of processing a semiconductor substrate using the patterned vapor-deposited film (spacer).

[0416] The semiconductor substrate can be processed using the manufacturing methods (i) to (iv) above.

[0417] The step of forming a resist underlayer film using the resist underlayer film-forming composition which is one embodiment of the present invention is as described in the above-mentioned section "Resist underlayer film".

[0418] On the resist underlayer film formed by the above steps, a hard mask such as a film containing silicon may be formed as a second resist underlayer film, and a resist pattern [the above (ii) to (iv)] may be formed thereon.

[0419] The hard mask may be a coating film of a composition containing an inorganic substance, or a vapor-deposited film of an inorganic substance formed by a vapor deposition method such as CVD or PVD, and examples thereof include a SiON film, a SiN film, or a SiO 2 film.

[0420] Furthermore, an anti-reflection film (BARC) may be formed on the hard mask, or a resist shape correction film having no anti-reflection capability may be formed.

[0421] In the above-mentioned process of forming the resist pattern, exposure is carried out by being used to form a mask (photomask) of a prescribed pattern or by directly describing. In the exposure source, for example, g-rays, i-rays, KrF excimer lasers, ArF excimer lasers, EUV, electron beams can be used. After exposure, post-exposure heating (Post Exposure Bake) is carried out as required. Then, development is carried out by a developer (for example, 2.38% by mass tetramethylammonium hydroxide aqueous solution), and further rinsed with rinse solution or pure water, and the developer used is removed. Then, post-baking is carried out for the drying of the resist pattern and the adhesion with substrate of improvement.

[0422] The etching step performed after the resist pattern is formed is performed by dry etching.

[0423] The resist film can be patterned by a nanoimprint method or a self-assembled film method.

[0424] For the nanoimprint method, the resist composition is molded using a mold (mold) that is transparent and patterned relative to the irradiated light. In addition, for the self-assembled film method, a self-assembled film of a regular structure of nanometer level is naturally formed using diblock polymers (polystyrene-polymethyl methacrylate, etc.) and the like to carry out patterning.

[0425] In the nanoimprint method, before applying the curable composition that becomes the resist film, a layer containing silicon (hard mask layer) can be optionally formed on the resist underlayer film by coating or vapor deposition, and further a bonding layer can be formed on the resist underlayer film or on the layer containing silicon (hard mask layer) by coating or vapor deposition, and the curable composition that becomes the resist film is applied on the bonding layer.

[0426] It should be noted that the following gases can be used in the processing of the hard mask (layer containing silicon) / resist lower film / substrate, namely, CF4, CHF3, CH2F2, CH3F, C4F6, C4F8, O2, N2O, NO2, He, H2. These gases can be used alone or in combination of two or more gases. Furthermore, argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon or nitrogen trifluoride can be mixed with these gases for use.

[0427] It should be noted that wet etching is sometimes performed for the purpose of simplifying the process steps and reducing damage to the processed substrate. This suppresses the change in processing dimensions and the reduction in pattern roughness, and enables the substrate to be processed with a good yield. Therefore, in the above (ii) to (iv), the hard mask can also be removed by either etching or alkaline liquid. In particular, when using an alkaline liquid, there is no limitation on the components, but the following are preferably included as alkaline components.

[0428] Examples of the alkaline component include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N -methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinol, cyclohexylamine, 1,5-diazabicyclo[4,3,0]nonene-5, etc. In addition, from the viewpoint of handling, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, and an inorganic base can be used in combination with a quaternary ammonium hydroxide. As the inorganic base, an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, and rubidium hydroxide is preferred, and potassium hydroxide is more preferred.

[0429] Example

[0430] (1) Synthesis of polymers

[0431] The following compound group A, compound group B, compound group C, catalyst group D, solvent group E, and reprecipitation solvent group F were used to synthesize the structures (S1) to (S20) as comparative examples and the structures (S'1) to (S'25) as polymers used as resist underlayer films.

[0432] Compound Groups A to C

[0433]

[0434] Catalyst group D, solvent group E, reprecipitation solvent group F, separation solvent group G

[0435] Methanesulfonic acid: D1

[0436] Potassium carbonate: D2

[0437] Propylene glycol monomethyl ether acetate (=PGMEA): E1

[0438] N-Methylpyrrolidone: E2

[0439] Methanol: F1

[0440] Methanol / water: F2

[0441] [Synthesis example 1]

[0442] 100.0 g of diphenylamine (A1), 73.4 g of 4-fluorobenzaldehyde (B1), 2.8 g of methanesulfonic acid and 749.9 g of PGMEA were added to a flask. Then, it was heated under nitrogen until reflux and reacted for about 4 hours. After the reaction stopped, it was reprecipitated with methanol / water and the resin was taken out. It was dried to obtain a resin (S1). The weight average molecular weight Mw measured by GPC in terms of polystyrene was about 4,200. The obtained resin was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target compound solution.

[0443]

[0444] [Synthesis Example 21]

[0445] 10.0 g of the reprecipitated resin (S1), 3.27 g of 2,6-dihydroxymethyl-4-methylphenol (C1), 2.4 g of potassium carbonate, and 36.6 g of N-methylpyrrolidone were added to a flask. Then, it was heated to 120°C under nitrogen and reacted for about 14 hours. After the reaction stopped, the potassium carbonate was removed by filtration, neutralized with 1N-HCl NMP solution, reprecipitated with methanol / water, and the resin was taken out. It was dried to obtain a resin (S'1). The weight average molecular weight Mw measured by GPC in terms of polystyrene was about 5,600. The obtained resin was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain the target compound solution.

[0446]

[0447] [Table 1]

[0448]

[0449]

[0450]

[0451]

[0452] Preparation of resist underlayer film

[0453] Polymers (S1) to (S20) and (S'1) to (S'25), crosslinking agents (CL1 to CL2), acid generators (Ad1 to Ad2), solvents (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CYH)), and Megaphak R-40 (manufactured by DIC Corporation, G1) as a surfactant were mixed in the proportions shown in the following table, and filtered using a 0.1 μm polytetrafluoroethylene microfilter to prepare resist underlayer film materials (M1 to M26, comparison M1 to comparison M21).

[0454]

[0455] [Table 2]

[0456]

[0457]

[0458] [Dissolution test in resist solvent]

[0459] The resist lower film materials of Comparative Examples 1-20 and Examples 1-26 were coated on a silicon wafer using a spin coater, and the prescribed temperature / prescribed time recorded in the table was fired under the atmosphere to form a resist lower film with a film thickness of about 150nm. The formed resist lower film was immersed in PGME / PGMEA=7 / 3 as a general diluent for 60 seconds, and the resistance to solvents was confirmed. The reduction rate of the film thickness before and after the diluent immersion was judged to be 0 (Table 1). In addition, the above-mentioned lower film material was coated on a silicon wafer using ACT-8 made by Tokyo Elektronik Co., Ltd., and the prescribed temperature / prescribed time recorded in the table was fired under nitrogen to form a 75nm resist lower film. As described above, it was immersed in PGME / PGMEA=7 / 3 for 60 seconds to confirm the resistance to solvents. The case where the reduction rate of the film thickness before and after the diluent immersion is less than the comparative example is judged as 0 (Table 1). The reduction rate of the film thickness is indicated in (). It should be noted that the samples (Comparative Examples 1-20) with large dissolution into the resist solvent when fired in the atmosphere as a general firing condition cannot be used as a resist lower film. Therefore, they are excluded from the comparative examples in subsequent evaluations. As an alternative comparative example, a general resist lower film (Comparative Example 21) containing a crosslinking agent and a curing catalyst is prepared and set as a comparative example in subsequent evaluations.

[0460] [Table 3]

[0461] (Table 1)

[0462]

[0463]

[0464] [Measurement of etching rate]

[0465] The resist lower film materials of Comparative Example 21 and Examples 1-26 were each coated on a silicon wafer using a spin coater. The prescribed temperature / prescribed time recorded in the table was fired on a hot plate to form a 75nm resist lower film. The dry etching rate was measured using O2 / N2 gas or CF4 gas as etching gas (Table 2). The dry etching rate ratio recorded in () is the dry etching rate ratio of (resist lower film) / (phenol novolac resin film). The situation where the etching rate is slow relative to the comparative example is judged as 0, and the situation where it is fast is judged as ×.

[0466] The etcher and etching gas used in the etching measurement were as follows.

[0467] RIE-200NL (manufactured by SAMU): CF4 50sccm

[0468] RIE-200NL (manufactured by SAMU): O2 / N2 10sccm / 200sccm

[0469] [Measurement of optical constants]

[0470] The solutions of the resist underlayer film-forming compositions prepared in Comparative Example 21 and Examples 1-26 were applied to silicon wafers using a spin coater. The resist underlayer films were fired at the specified temperature / prescribed time described in the table on a hot plate to form a 50nm resist underlayer film. The refractive index (n value) and optical absorption coefficient (also referred to as k value, attenuation coefficient) of these resist underlayer films at a wavelength of 193nm were measured using a spectroscopic ellipsometer (Table 2).

[0471] [Applicability Evaluation]

[0472] The resist lower film materials of Comparative Example 21 and Examples 1-26 were coated on a silicon wafer using ACT-8 manufactured by Tokyo Elektronik Co., Ltd., and fired at the specified temperature / specified time described in the table under the atmosphere to form a 75nm resist lower film. Then, an optical microscope was used to observe the film surface (wafer center and edge) to confirm whether there was a problem with the coating. The so-called "problem" here refers to the occurrence of shrinkage cracks (crawling) and pinholes on the film surface, and the formation of concave-convex (Table 2) that is not usually observed on the coating surface. The situation where there is no problem with the coating is judged as 0.

[0473] [Table 4]

[0474] (Table 2)

[0475]

[0476] [Coating and Coverage Test on Height Difference Substrates]

[0477] As a coating / coating test to a high-low substrate, SiO2, SiN, and TiN substrates with a film thickness of 200nm were used. After the resist lower film forming composition modulated in Comparative Example 21 and Examples 1-26 was applied to the substrate, the prescribed temperature / prescribed time recorded in the table was fired to form a resist lower film of about 150nm. In the case of a high-low substrate, the coating of the resist lower film sometimes differs or deteriorates depending on the substrate species. Therefore, it was confirmed by visual inspection whether the high-low substrate with various vapor-deposited films can be coated without unevenness. The situation where it can be coated without unevenness is judged as 0.

[0478] In addition, the same device was used to compare the coating thickness of the dense area and the area without pattern (open area). The flattening property was evaluated by measuring the film thickness difference between the groove area (pattern part) and the open area (no pattern part) of the height difference substrate (the coating height difference between the groove area and the open area is called bias). Here, the so-called flattening property refers to the film thickness difference (Iso-dense bias) of the coated material existing on the upper part of the part with pattern (groove area (pattern part)) and the part without pattern (open area (no pattern part)). The case where the deviation is improved relative to the comparative example is judged as ○ (Table 3).

[0479] [Table 5]

[0480] (Table 3)

[0481]

[0482]

[0483] [Test of embedding properties into uneven substrates]

[0484] As a coating / covering test on a high-low substrate, SiO2, SiN, and TiN substrates with a film thickness of 200 nm were used. The resist underlayer film-forming composition prepared in Comparative Example 21 and the following Examples was applied to the substrate and then fired at the specified temperature / prescribed time described in the table to form a resist underlayer film of about 150 nm.

[0485] In addition, using a scanning electron microscope (S-4800) manufactured by Hitachi HiTech Nologis, the embedding property of the groove region (dense pattern region) with a groove width of 50 nm and a pitch of 100 nm present in the above substrate was evaluated. The embedding property was judged to be 0 when the resist lower film could be filled to the bottom of the groove (Table 4).

[0486] [Table 6]

[0487] (Table 4)

[0488]

[0489]

[0490] As mentioned above, the material of the embodiment is different from the previous material, and even if it does not contain a cross-linking agent or a curing catalyst, it also shows curability in the atmosphere and in nitrogen, so it can be judged to have self-cross-linking property. Of course, it can also be used by containing a cross-linking agent and a curing catalyst as in the past. These materials have high heat resistance, so they also show good coating properties to silicon wafers when fired at high temperatures. In addition, this material can freely change the optical constants by changing the polymer type skeleton, and can suppress reflection during exposure, so a good resist pattern can be formed. In addition, it also shows good etching resistance compared with the comparative example to fluorine or oxygen gas as the main etching gas. Further, it also shows good coating properties on the vapor-deposited film with various height differences, and the embedding property and flattening property to the fine height difference substrate are also good. Therefore, it is expected to become a material that can be widely used in a variety of semiconductor manufacturing processes.

Claims

1. A resist underlayer film-forming composition, characterized in that: The invention comprises: a novolac resin having a side chain having a structure of the following formula (D), and a solvent, -O-Ar 2 Formula (D) In the formula, Ar 2 It is an aromatic ring.

2. The resist underlayer film-forming composition according to claim 1, wherein the Ar 2 It is an aromatic ring having an aromatic hydrocarbon ring and / or an aromatic hetero ring.

3. The resist underlayer film-forming composition according to claim 2, wherein the aromatic hydrocarbon ring is an aromatic hydrocarbon ring containing a benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene structure, The aromatic heterocycle is an aromatic heterocycle containing an indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole or phenothiazine structure.

4. The resist underlayer film-forming composition according to claim 2, wherein the aromatic hydrocarbon ring is benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene, The aromatic heterocyclic ring is any one selected from indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole and phenothiazine.

5. The resist underlayer film-forming composition according to claim 1, wherein the Ar 2 For the -CH2-OR 12 Aromatic ring of substituted aromatic hydrocarbon ring and / or aromatic heterocyclic ring, -CH2-OR 12 In, R 12 It represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms and which may contain a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom.

6. The resist underlayer film-forming composition according to claim 5, wherein R 12 A hydrogen atom or a methyl group.

7. The resist underlayer film-forming composition according to claim 5, wherein the aromatic hydrocarbon ring is an aromatic hydrocarbon ring containing a benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene structure. The aromatic heterocycle is an aromatic heterocycle containing an indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole or phenothiazine structure.

8. The resist underlayer film-forming composition according to claim 5, wherein the aromatic hydrocarbon ring is benzene, naphthalene, anthracene, pyrene, phenanthrene, fluorene, benzofluorene or dibenzofluorene, The aromatic heterocyclic ring is any one selected from indole, phenylindole, carbazole, indolocarbazole, furan, thiophene, pyrrole and phenothiazine.

9. The resist underlayer film-forming composition according to claim 1, wherein the novolac resin is a novolac resin having a repeating composite unit structure AB represented by the following formula (AB) and further having a structure of the formula (D) in its side chain, In the formula (AB), n represents the number of composite unit structures AB, The unit structure A comprises a phenol unit structure and / or an amine unit structure, Unit structure B represents one or more unit structures including the structure represented by the following formula (B1), formula (B2) or formula (B3), * indicates a bond; In formula (B1), R and R' each independently represent a hydrogen atom, an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent, a heterocyclic residue having 3 to 30 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent, * indicates a bond; *-J 1 -Z 0 -J 2 -* (B2) In formula (B2), Z 0 represents an aromatic ring residue or an aliphatic ring residue having 6 to 30 carbon atoms which may have a substituent, or an organic group in which two aromatic ring residues or aliphatic ring residues are linked via a single bond, J 1 and J 2 Each independently represents a divalent organic group which is directly bonded or may have a substituent, * indicates a bond; In formula (B3), Z is a monocyclic, bicyclic, tricyclic or tetracyclic condensed ring having 4 to 25 carbon atoms and optionally having a substituent, wherein the monocyclic ring is a non-aromatic monocyclic ring; at least one of the monocyclic rings constituting the bicyclic, tricyclic and tetracyclic rings is a non-aromatic monocyclic ring, and the remaining monocyclic rings may be either aromatic or non-aromatic, and the monocyclic, bicyclic, tricyclic or tetracyclic condensed ring may further form a condensed ring with one or more aromatic rings to form a condensed ring of at least five rings, X and Y are the same or different, indicating -CR 1 R 2 -Base, R 1 and R 2 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, x and y each represent the number of X and Y, and each independently represents 0 or 1. *-X x In the case of x=1, it is bonded to carbon atom 1, and in the case of x=0, it extends from carbon atom 1, wherein carbon atom 1 is any carbon atom of the non-aromatic monocyclic ring constituting Z. Y y -* is bound to carbon atom 2 when y=1, and extends from carbon atom 2 when y=0, wherein carbon atom 2 is any carbon atom of the non-aromatic monocyclic ring constituting Z, The carbon atom 1 and the carbon atom 2 may be the same or different, and in different cases, may belong to the same non-aromatic monocyclic ring or to different non-aromatic monocyclic rings. * indicates a bonding bond.

10. The composition for forming a resist underlayer film according to claim 9, wherein the phenol unit structure is a chemical structure in which at least one hydroxyl group is bonded to an aromatic ring and has at least one aromatic ring selected from a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a fluorene ring, a benzofluorene ring and a dibenzofluorene ring, and the aromatic rings are condensed with each other or bonded via a single bond or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

11. The resist underlayer film-forming composition according to claim 9, wherein the phenol unit structure contains a structure derived from at least one monomer selected from the following formulas 1 to 36 which may have a substituent, and H of OH in formulas 1 to 36 may be substituted by the following substituent; Substituents * indicates a bond, Substituents * indicates a bonding bond.

12. The resist underlayer film forming composition according to claim 9, wherein the amine unit structure is a chemical structure having at least one heterocyclic ring selected from a pyrrole ring, an indole ring, and a carbazole ring, or a unit structure in which any two or more aromatic rings of a benzene ring or a naphthalene ring are bonded to each other via a nitrogen atom, or the heterocyclic ring and the aromatic ring are condensed to each other, or the heterocyclic ring and the aromatic ring are bonded or condensed via a single bond, a quaternary carbon, or an aliphatic ring having 5 to 7 carbon atoms.

13. The resist underlayer film-forming composition according to claim 9, wherein the amine unit structure contains a structure derived from at least one monomer selected from the following formulae 37 to 75 which may have a substituent, and the H of NH in formulae 37 to 75 may be substituted with the following substituent, Substituents * indicates a bond, a substituent * indicates a bonding bond. 14 . The resist underlayer film-forming composition according to claim 1 , wherein the solvent has a boiling point of 160° C. or higher. 15 . The resist underlayer film-forming composition according to claim 1 , further comprising a cross-linking agent. 16 . The resist underlayer film-forming composition according to claim 15 , wherein the crosslinking agent is an aminoplast crosslinking agent or a phenoplast crosslinking agent. 17 . The resist underlayer film-forming composition according to claim 1 , further comprising a surfactant. 18 . The resist underlayer film-forming composition according to claim 1 , further comprising an acid and / or a salt thereof and / or an acid generator. 19 . A resist underlayer film, which is a fired product of a coating film formed from the composition according to claim 1 . 20 . A method for forming a resist pattern for semiconductor manufacturing, comprising the step of applying the resist underlayer film-forming composition according to claim 1 onto a semiconductor substrate and firing the composition to form a resist underlayer film.

21. A method for manufacturing a semiconductor device, comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 18; forming a resist film on the resist underlayer film; forming a resist pattern on the resist film; a step of etching the resist underlayer film using the resist pattern; and A step of processing a semiconductor substrate using the patterned resist underlayer film. 22 . The method for manufacturing a semiconductor device according to claim 21 , wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development. 23 . The method for manufacturing a semiconductor device according to claim 21 , wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

24. A method for manufacturing a semiconductor device, comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 18; forming a hard mask on the resist underlayer film; A step of further forming a resist film on the hard mask; forming a resist pattern on the resist film; a step of etching the hard mask using the resist pattern; a step of etching the resist underlayer film using the patterned hard mask; and A step of processing a semiconductor substrate using the patterned resist underlayer film. 25 . The method for manufacturing a semiconductor device according to claim 24 , wherein the hard mask is formed by coating or evaporating an inorganic material. 26 . The method for manufacturing a semiconductor device according to claim 24 , wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development. 27 . The method for manufacturing a semiconductor device according to claim 24 , wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

28. A method for manufacturing a semiconductor device, comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 18; forming a hard mask on the resist underlayer film; A step of further forming a resist film on the hard mask; forming a resist pattern on the resist film; a step of etching the hard mask using the resist pattern; A step of etching the resist underlayer film using the patterned hard mask; A process of removing the hard mask; and A step of processing a semiconductor substrate using the patterned resist underlayer film. 29 . The method for manufacturing a semiconductor device according to claim 28 , wherein the hard mask is formed by coating a composition containing an inorganic substance or by vapor deposition of a composition containing an inorganic substance. 30 . The method for manufacturing a semiconductor device according to claim 28 , wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development. 31 . The method for manufacturing a semiconductor device according to claim 28 , wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

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

33. A method for manufacturing a semiconductor device, comprising the following steps: A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 18; forming a hard mask on the resist underlayer film; A step of further forming a resist film on the hard mask; forming a resist pattern on the resist film; a step of etching the hard mask using the resist pattern; A step of etching the resist underlayer film using the patterned hard mask; A step of removing the hard mask; A step of forming a vapor-deposited film, i.e., a spacer, on the resist underlayer film after the hard mask is removed; A step of processing the vapor deposited film, i.e., the spacer, by etching; a step of removing the patterned resist underlayer film to leave the patterned vapor-deposited film, i.e., the spacer; and A step of processing a semiconductor substrate using the patterned vapor deposited film, ie, spacers. 34 . The method for manufacturing a semiconductor device according to claim 33 , wherein the hard mask is formed by coating a composition containing an inorganic substance or by vapor deposition of a composition containing an inorganic substance. 35 . The method for manufacturing a semiconductor device according to claim 33 , wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development. 36 . The method for manufacturing a semiconductor device according to claim 33 , wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.

37. The method for manufacturing a semiconductor device according to claim 33, wherein the hard mask is removed by either etching or an alkaline chemical solution.

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