Resist underlayer film-forming composition

Abstract

[Problem] The purpose of the present invention is to provide a resist underlayer film-forming composition that can further improve properties of a resist underlayer film, such as curing properties, heat resistance, etching resistance, planarization properties and embedding properties. [Solution] Provided is a resist underlayer film-forming composition comprising a novolac resin and a solvent, in which the novolac resin has a unit structure A having at least two amino groups, and the unit structure A is a bivalent group derived from a compound having a condensed ring structure and further has a monovalent organic group C1 or an organic group C2 that caps at least one end of the novolac resin.

Description

Resist underlayer film-forming composition

[0001] The present invention relates to a resist underlayer film-forming composition suitable for lithography in semiconductor substrate processing, a resist underlayer film obtained from the resist underlayer film-forming composition, a method for forming a resist pattern using the resist underlayer film-forming composition, and a method for manufacturing a semiconductor device using the composition.

[0002] In recent years, the semiconductor manufacturing process has progressed rapidly, and accordingly, there is a strong demand for higher quality and improved properties of resist underlayer films. For example, Patent Document 1 reports that a polymer containing a divalent group of a specific heteroaromatic ring containing an indole skeleton as part of its structure and an aryl-substituted divalent group such as an aryl-substituted methylene group as a structural unit can be used as a material that achieves both film density and etching resistance. However, although the planarization properties are mentioned, no demonstration has been provided.

[0003] Furthermore, Patent Document 2 reports that a polymer obtained by reacting an indole derivative with a mixture of specific types of aromatic aldehyde compounds can simultaneously ensure the solubility (applicability) of the polymer and the etching resistance and heat resistance of a hard mask layer using the polymer.

[0004] Furthermore, Patent Document 3 reports that a hard mask-forming composition containing a resin having a specific diarylaminobenzyl alcohol derivative as a partial structure can provide an organic film having high etching resistance and excellent solvent resistance and heat resistance. Furthermore, Patent Document 4 reports that a resist underlayer film-forming composition containing a 2-arylindole derivative / analog structure and a polymer having an aryl-substituted methylene group as a unit structure can form a good resist pattern shape without causing intermixing between the upper layer of the resist underlayer film and the layer coated thereon.

[0005] Furthermore, Patent Document 5 reports that a resist underlayer film-forming composition containing a compound having a specific bis(polycyclic aryl)fluorene derivative / analog structure as a structural unit provides a resist underlayer film material having high etching resistance, high heat resistance, and high solubility (coatability).

[0006] Japanese Patent Application Publication No. 2016-151024 Japanese Patent Application Publication No. 2020-105513 Japanese Patent Application Publication No. 2021-81686 International Publication Pamphlet WO2013-146670 International Publication Pamphlet WO2018-198960

[0007] However, with the rapid advancement of semiconductor manufacturing processes, there is a strong demand for higher quality and improved properties of resist underlayer films. Etching resistance is a particularly important property for organic films, and heat resistance is also required because deposition is performed on the resist underlayer film in some processes. Furthermore, in order to improve the quality and properties of resist underlayer films, various other properties are required in addition to etching resistance and heat resistance, such as curability and pattern embedding ability. Taking these properties into consideration, there is still room for improvement.

[0008] The present invention solves the above-mentioned problems. That is, the present invention includes the following. A first aspect of the present invention is a resist underlayer film-forming composition containing a novolac resin and a solvent, wherein the novolac resin has a unit structure A having at least two amino groups, the unit structure A being a divalent group derived from a compound having a fused ring structure, and further having a monovalent organic group C1 or organic group C2 that caps at least one end of the novolac resin, and the organic group C1 is represented by the following formula (1): (In formula (1), * represents a bond by which the organic group C1 is bonded to at least one terminal of the novolak resin, and Ar ６ represents an aryl group having 6 to 40 carbon atoms; R ６１represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can be bonded. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. R ６２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. ６４ , R ６５ each independently represents a hydrogen atom, a phenyl group which may be substituted with a hydroxy group, or a naphthyl group which may be substituted with a hydroxy group, R ６４ , R ６５ represents a phenyl group or a naphthyl group, R ６４ or R ６５ and an aryl group Ar ６ A new ring can be formed with m via a single bond or a methylene group. ４ represents 0 or 1, m ３ is m ４ When m is 0, it is an integer from 0 to (3+2n), and m ３ is m ４ When represents 1, it is an integer of 0 to (2+2n), and n is an aryl group Ar ６ indicates the degree of condensation of the benzene rings, and m ５ represents 0 or 1.) and the organic group C2 is represented by the following formula (2): In formula (2), * represents a bond that bonds the organic group C2 to at least one terminal of the novolak resin, and Ar ７ represents an aryl group having 6 to 40 carbon atoms; R ７１represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can be bonded. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. R ７２ represents a hydrogen atom, a methyl group, or a phenyl group. ６ is an integer from 0 to (3+2n), and n is an aryl group Ar ７ In a second aspect of the present invention, the unit structure A is a unit structure A1 or a unit structure A2, and the unit structure A1 is represented by the following formula (3): (In formula (3), * indicates a bond, and Ar ４ represents a benzene ring, Ar ３ and Ar ５ each independently represents a benzene ring or a fused ring formed of two or three benzene rings, R1 and R2 each represent a five-membered ring containing one nitrogen atom, and Ar ３ and R1, R1 and Ar ４ , Ar ４ and R2, R2 and Ar ５ are condensed to form Ar ３ , R1, Ar ４ , R2 and Ar ５ together form a fused polycyclic ring, R ４１ and R ４２ is Ar ４ The above substituents may be the same or different, and the substituents may be bonded to each other by a single bond or condensed. ３１ and R ５１ are Ar ３ Above and Ar ５ are the same or different substituents as above, and R ３１ , R ４１ , R４２ or R ５１ each represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can bond. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. n3 and n6 represent R ３１ and R ５１ n4 and n5 each independently represent an integer of 0 to 4, and R ４１ and R ４２ and n4+n5 is an integer of 0 to 4. The unit structure A2 includes a bis(azaaryl fused ring) structural unit represented by the following formula (4) or formula (4-2): In formula (4) and formula (4-2), * represents a bond, L represents a linking group that bonds to a carbon atom constituting a nitrogen-containing ring of the azaaryl fused ring and further bonds to another structure of the novolak resin, -(CR ４ R ５ ) m １ -, -R ６ -, -(Ar)m ２ -, -CH ２ -(Ar)m ２ -CH ２ - and -(cyclo-R)-, R ４ and R ５ are the same or different and each independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10, R ６represents a cycloalkylene group having 3 to 6 carbon atoms, Ar represents an arylene group having 6 to 30 carbon atoms which may be bonded to each other via a single bond, m ２ represents an integer of 1 to 3; cyclo-R represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring which may form a condensed ring with one or two benzene rings or naphthalene rings; Q represents a linking group bonding to a carbon atom constituting a nitrogen-containing ring of the condensed azaaryl ring; and is selected from the group consisting of —O—, —S—, and —SO ２ -, -CO-, -CONH-, -COO-, -NH-, -(CR ４ R ５ ) m １ -, -R ６ -, -(Ar)m ２ -, -CH ２ -(Ar)m ２ -CH ２ - and -(cyclo-R)-, R ４ and R ５ are the same or different and each independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10, R ６ represents a cycloalkylene group having 3 to 6 carbon atoms, Ar represents an arylene group having 6 to 30 carbon atoms which may be bonded to each other via a single bond, m ２ represents an integer of 1 to 3, cyclo-R represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring which may form a condensed ring with one or two benzene rings or naphthalene rings, and R １１ and R ２１ are the same or different and each independently represent: (i) a hydrogen atom or a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms; R １２ and R ２２are substituents on carbon atoms constituting the azaaryl fused ring, and are the same or different and each independently represent: (iv) a hydroxy group, a nitro group, a cyano group, a carboxyl group, a trifluoromethyl group, or a halogen atom; (v) an aryloxy group having 6 to 15 carbon atoms, an arylalkoxycarbonyl group having 8 to 15 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, or an aryl group having 6 to 30 carbon atoms; or (vi) an acyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an arylalkoxy group having 7 to 15 carbon atoms, an alkoxycarbonyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms; n1 and n2 are the same or different and each independently represent a substituent R １２ and R ２２ Ar represents the number of １ and Ar ２ are the same or different and each independently represent a benzene ring or a fused ring composed of two or three benzene rings.) A third aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, wherein the organic group C1 represented by formula (1) is a monovalent group derived from a hydroxy-containing aromatic methylol compound represented by the following formula (5): (In formula (5), Ar ６ , R ６１ , R ６２ , R ６４ , R ６５ , m ３ , m ４ and m ５ is the same as defined in formula (1), and R ６３represents a hydrogen atom or a methyl group.) A fourth aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, wherein the organic group C1 represented by formula (1) is a monovalent group derived from 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, or 2,6-di-tert-butyl-4-hydroxymethylphenol. A fifth aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, wherein the organic group C2 represented by formula (2) is a monovalent group derived from an aromatic vinyl compound represented by the following formula (6): (In formula (6), Ar ７ , R ７１ , R ７２ and m ６ is defined as in formula (2).) A sixth aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, wherein the organic group C2 represented by formula (2) is a monovalent group derived from styrene, 2-vinylnaphthalene, 4-tert-butylstyrene, or 4-tert-butoxystyrene. A seventh aspect of the present invention relates to the resist underlayer film-forming composition according to the second aspect, wherein the unit structure A1 represented by formula (3) is a divalent group derived from a compound having an indolocarbazole structure. A eighth aspect of the present invention relates to the resist underlayer film-forming composition according to the seventh aspect, wherein the aromatic group substituting the hydrogen atom on the fused ring of the compound having an indolocarbazole structure is a phenyl group. A ninth aspect of the present invention relates to the resist underlayer film-forming composition according to the second aspect, wherein all or some of the hydrogen atoms of the hydroxy group, amino group, or alkylamino group in the novolak resin are substituted with an alkynyl group having 2 to 10 carbon atoms. A tenth aspect of the present invention relates to the resist underlayer film-forming composition according to the second aspect, wherein the novolak resin further contains another unit structure, and the other unit structure is a divalent group derived from a monomer represented by any one of the following formulas (10-1) to (10-36) and / or a divalent group derived from a monomer represented by any one of the following formulas (10-37) to (10-69), and one end of the unit structure may be bonded to a bond of the organic group C1 or the organic group C2: (In formulas (10-1) to (10-36), * represents a bond, and H of OH may be replaced by a phenyl group or an alkynyl group having 2 to 10 carbon atoms.) (In formulas (10-37) to (10-69), * indicates a bond, and R ９２represents a hydrogen atom, a phenyl group, or an alkynyl group having 2 to 10 carbon atoms.) An eleventh aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, wherein the solvent has a boiling point of 160°C or higher. A twelfth aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, further comprising a crosslinking agent. A thirteenth aspect of the present invention relates to the resist underlayer film-forming composition according to the twelfth aspect, wherein the crosslinking agent is an aminoplast crosslinking agent or a phenoplast crosslinking agent. A fourteenth aspect of the present invention relates to the resist underlayer film-forming composition according to the first aspect, further comprising a surfactant. A fifteenth 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. A sixteenth aspect of the present invention relates to a resist underlayer film that is a baked product of a coating film comprising the composition according to any one of the first to fifteenth aspects. A 17th aspect of the present invention relates to a method for forming a resist pattern used in semiconductor manufacturing, comprising the step of applying the resist underlayer film-forming composition according to any one of the first to fifteenth aspects onto a semiconductor substrate and baking the composition to form a resist underlayer film. An 18th aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the steps 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 fifteenth aspects; forming a resist film on the resist underlayer film; forming a resist pattern on the resist film; etching the resist underlayer film using the resist pattern; and processing a semiconductor substrate using the patterned resist underlayer film. A 19th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 18th aspect, wherein a resist pattern is formed on the resist film by irradiation with light or an electron beam and development. A 20th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 18th aspect, wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film.A 21st aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the steps 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 fifteenth aspects; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film; etching the hard mask using the resist pattern; etching the resist underlayer film using the patterned hard mask; and processing a semiconductor substrate using the patterned resist underlayer film. A 22nd aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 21st aspect, in which the hard mask is formed by coating a composition containing an inorganic substance or vapor deposition of a composition containing an inorganic substance. A 23rd aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 21st aspect, in which a resist pattern is formed on the resist film by irradiation with light or an electron beam and development. A 24th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 21st aspect, in which the patterning of the resist film is performed by a nanoimprint method or a self-assembled film. A 25th aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the steps 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 fifteenth aspects; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film; etching the hard mask using the resist pattern; etching the resist underlayer film using the patterned hard mask; removing the hard mask; and processing a semiconductor substrate using the patterned resist underlayer film. A 26th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 25th 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. A 27th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 25th aspect, wherein a resist pattern is formed on the resist film by irradiating with light or an electron beam and developing.A 28th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 25th aspect, wherein the patterning of the resist film is performed by a nanoimprint method or a self-assembled film. A 29th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 25th aspect, wherein the removal of the hard mask is performed by etching or an alkaline chemical solution. A 30th aspect of the present invention relates to a method for manufacturing a semiconductor device, comprising the steps 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 fifteenth aspects; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film; etching the hard mask using the resist pattern; etching the resist underlayer film using the patterned hard mask; removing the hard mask; forming a vapor-deposited film (spacer) on the resist underlayer film after hard mask removal; processing the vapor-deposited film (spacer) by etching; removing the patterned resist underlayer film to leave the patterned vapor-deposited film (spacer); and processing a semiconductor substrate using the patterned vapor-deposited film (spacer). A 31st aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 30th aspect, wherein the hard mask is formed by coating a composition containing an inorganic substance or vapor-depositing a composition containing an inorganic substance. A 32nd aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 30th aspect, wherein a resist pattern is formed on the resist film by irradiation with light or an electron beam and development. A 33rd aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 30th aspect, wherein the pattern formation of the resist film is performed by a nanoimprint method or a self-assembled film. A 34th aspect of the present invention relates to the method for manufacturing a semiconductor device according to the 30th aspect, wherein the hard mask is removed by either etching or an alkaline chemical solution.

[0009] Novolak resins containing a fused ring amine structure and a terminal crosslinking group structure in the skeleton have good heat resistance, so when used in a resist underlayer film-forming composition, they produce a small amount of sublimation during high-temperature baking, have very high in-plane film uniformity, and exhibit high etching resistance. Furthermore, even without a crosslinking group, the polymer itself contains a crosslinking agent, providing sufficient curability. Furthermore, the curing temperature is high, providing sufficient reflowability, and thus providing good embeddability.

[0010] The resist underlayer film-forming composition of the present invention is characterized by comprising a novolak resin having a unit structure of a divalent group having at least two amino groups and having a monovalent organic group C1 or C2 that caps an end, and a solvent. Furthermore, the composition may optionally contain a crosslinker, an acid generator, or a surfactant. Each component will be described in detail below.

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

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

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

[0014] In this specification, the terms unit structure A, unit structure A', and unit structure B, which will be described later, are used as unit structures constituting a "novolac resin." Unit structure A is unit structure A1 or unit structure A2, which will be described later. Unit structure A' may be a divalent group having an aromatic ring other than unit structure A1 or unit structure A2, which will be described later. Unit structure B is a unit structure derived from a compound having a functional group that enables covalent bonding with the aromatic ring of unit structure A or unit structure A'. Unit structure D is a unit structure equivalent in bonding mode to composite unit structure A-B (or composite unit structure A'-B), which will be described later, and is a unit structure derived from a compound having an aromatic ring and a functional group that enables covalent bonding with the aromatic ring of unit structure A or unit structure A'. Because the bonding mode is the same, unit structure D can be replaced with composite unit structure A-B (or composite unit structure A'-B). In addition, in this specification, there is a C moiety that caps at least one end of the novolac resin. C moiety is a monovalent organic group C1 or organic group C2.

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

[0016] "Aromatic ring" (aromatic group, aryl group, arylene group) The term "aromatic ring" refers to a concept that encompasses aromatic hydrocarbon rings, aromatic heterocycles, and residues thereof [sometimes referred to as "aromatic groups," "aryl groups" (in the case of monovalent groups), or "arylene groups" (in the case of divalent groups)], and encompasses not only monocyclic (aromatic monocycles) but also polycyclic (aromatic polycycles). In the case of polycycles, at least one monocycle is an aromatic monocycle, but the remaining monocycles that form a condensed ring with the aromatic monocycle may be monocyclic heterocycles (heteromonocycles) or monocyclic alicyclic hydrocarbons (alicyclic monocycles).

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

[0018] The aromatic ring (for example, a benzene ring, a naphthalene ring, etc.) may have an optional substituent, and such substituents include a halogen atom, a saturated or unsaturated linear, branched, or cyclic hydrocarbon group (-R) (the hydrocarbon chain may be interrupted one or more times by an oxygen atom, and includes an alkyl group, an alkenyl group, an alkynyl group, a propargyl group, etc.), an alkoxy group or an aryloxy group (-OR, where R represents the hydrocarbon group -R), an alkylamino group [-NHR or -NR ２ (two R's may be the same or different), where R's represent the hydrocarbon group -R], a hydroxy group, an amino group (-NH ２ ), carboxyl group, cyano group, nitro group, ester group (-CO ２ R or -OCOR, where R represents the hydrocarbon group -R), an amide group [-NHCOR, -CONHR, -NRCOR (two Rs may be the same or different) or -CONR ２ (two R's may be the same or different), where R's represent the hydrocarbon group -R], a sulfonyl group (-SO ２ R, where R represents the hydrocarbon group —R), a sulfonic acid group (—SO ３ H), sulfide group (-SR, where R represents the hydrocarbon group -R), thiol group (-SH), organic group containing an ether bond [R １１ -O-R １１ (R １１ each independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or a phenyl group, a naphthyl group, an anthranyl group, or a pyrenyl group; a residue of an ether compound represented by the formula (I); an organic group having an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group; and an aryl group.

[0019] Furthermore, organic groups having one or more condensed rings of aromatic rings (such as benzene, naphthalene, anthracene, and pyrene) and one or more aliphatic or heterocyclic rings are also included. Examples of the aliphatic rings 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. The organic group may also have a structure in which two or more aromatic rings are linked by a divalent linking group such as an alkylene group.

[0020] "Heterocycle" The term "heterocycle" encompasses both aliphatic heterocycles and aromatic heterocycles, and is a concept that encompasses not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic). In the case of a polycyclic, at least one monocyclic ring is a heteromonocyclic ring, but the remaining monocyclic rings may be aromatic hydrocarbon monocyclic or alicyclic monocyclic. For the aromatic heterocycle, the examples of the "aromatic ring" above can be referred to. As with the aromatic ring of the "aromatic ring", it may have a substituent.

[0021] "Non-aromatic ring" (aliphatic ring) A "non-aromatic monocycle" refers to a monocyclic hydrocarbon that does not belong to the aromatic group, and is typically a monocycle of an alicyclic compound. It may also be called an aliphatic monocycle (which may include an aliphatic heteromonocycle, or may contain an unsaturated bond as long as it does not belong to the aromatic compound). As with the aromatic ring of the "aromatic ring", it may have a substituent.

[0022] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0023] "Non-aromatic polycyclic rings" refer to polycyclic hydrocarbons that are not aromatic, and are typically polycyclic alicyclic compounds. They may also be called aliphatic polycyclic rings (which may include aliphatic heterocyclic rings (where at least one of the monocyclic rings constituting the polycyclic ring is an aliphatic heterocyclic ring), or may contain unsaturated bonds as long as they do not belong to the aromatic compound category). They include non-aromatic bicyclic rings, non-aromatic tricyclic rings, and non-aromatic tetracyclic rings.

[0024] "Non-aromatic bicycle" refers to a fused ring composed of two monocyclic hydrocarbons that are not aromatic, typically two fused rings of an alicyclic compound. In this specification, it is also referred to as an aliphatic bicycle (which may include an aliphatic heterobicycle, and may contain unsaturated bonds as long as it does not belong to the aromatic compound). Examples of non-aromatic bicycles include bicyclopentane, bicyclooctane, and bicycloheptene.

[0025] A "non-aromatic tricyclic ring" refers to a fused ring composed of three monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of three alicyclic compounds (each of which may be a heterocyclic ring or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tricyclic rings include tricyclooctane, tricyclononane, and tricyclodecane.

[0026] The term "non-aromatic tetracyclic ring" refers to a fused ring composed of four monocyclic hydrocarbons that are not aromatic, and is typically a fused ring of four alicyclic compounds (each of which may be a heterocyclic ring or may contain an unsaturated bond as long as it is not an aromatic compound). Examples of non-aromatic tetracyclic rings include hexadecahydropyrene.

[0027] The term "carbon atoms constituting a ring (moiety)" refers to the carbon atoms constituting a hydrocarbon ring (which may be an aromatic ring, an aliphatic ring, or a heterocyclic ring) in an unsubstituted state.

[0028] The term "azaaryl fused ring" generally refers to a fused ring of an azaaryl group (nitrogen-containing aromatic heterocycle) and another aromatic ring. In the present invention, the nitrogen-containing aromatic heterocycle that is the azaaryl group is particularly a pyrrole ring. Furthermore, the term "bis(azaaryl fused ring) compound" refers to a compound containing a structural unit having two azaaryl fused rings, and in the present invention, particularly refers to a novolak resin containing unit structures of the formulas (4) and (4-2) described below.

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

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

[0031] <Resist Underlayer Film Forming Composition> The resist underlayer film forming composition of one embodiment of the present invention contains a specific novolak resin and a solvent, and may further contain a crosslinking agent and an acid, and may further contain additives such as an acid generator and a surfactant, as needed.

[0032] <Novolac Resin> The specific novolac resin contained in the resist underlayer film-forming composition of one embodiment of the present invention has a unit structure A having at least two amino groups, and the unit structure A is a divalent group derived from a compound having a fused ring structure. In the resist underlayer film-forming composition of the present invention, the unit structure A includes a novolac resin having unit structure A1 or unit structure A2. Furthermore, as long as the effects of the present invention are not impaired, the resist underlayer film-forming composition of the present invention can also include a novolac resin in which the unit structure A is a divalent group having an aromatic ring other than unit structure A1 or unit structure A2.

[0033] <Unit Structure A1> The unit structure A1 is represented by the following formula (3). In formula (3), Ar ４represents a benzene ring, Ar ３ and Ar ５ each independently represents a benzene ring or a fused ring formed of two or three benzene rings, R1 and R2 each represent a five-membered ring containing one nitrogen atom, and Ar ３ and R1, R1 and Ar ４ , Ar ４ and R2, R2 and Ar ５ are condensed to form Ar ３ , R1, Ar ４ , R2 and Ar ５ together form a fused polycyclic ring, R ４１ and R ４２ is Ar ４ The above substituents may be the same or different, and the substituents may be bonded to each other by a single bond or condensed. ３１ and R ５１ are Ar ３ Above and Ar ５ are the same or different substituents as above, and R ３１ , R ４１ , R ４２ or R ５１ each represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can bond. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. n3 and n6 represent R ３１ and R ５１ n4 and n5 each independently represent an integer of 0 to 4, and R ４１ and R ４２ and n4+n5 represents the number of substituents, each independently being an integer of 0 to 2, and n4+n5 is an integer of 0 to 4. Unless otherwise specified, hereinafter in this specification, * or ** indicates a bond.

[0034] The unit structure A1 is preferably a divalent group having at least two secondary amino groups, and the group is preferably a divalent group derived from a compound having a fused ring structure and having an aromatic group substituting a hydrogen atom on the fused ring.

[0035] Also, Ar ３ , Ar 4 and Ar ５ In the case where R1 and R2 are each a benzene ring, and R1 and R2 are each a five-membered ring hydrocarbon containing one nitrogen atom, the unit structure A1 represented by formula (3) can represent a divalent group derived from a compound having an indolocarbazole structure. ３１ , R ４１ , R ４２ or R ５１ Examples of the alkyl group include a phenyl group, a naphthyl group, an anthryl group, and a pyrene group, and the phenyl group is preferably used.

[0036] Examples of the compound having the unit structure A1 are shown below.

[0037]

[0038] <Unit Structure A2> The unit structure A2 includes one or more bis(azaaryl fused ring) structural units represented by the following formula (4) or formula (4-2), i.e., structural units in which two azaaryl fused rings, preferably two indole rings (for example, 2-phenylindole, which may have a substituent), are bonded via a linking group. In formula (4), the bond indicated by * extends from the linking group L. In formula (4-2), * indicates a bond, and Ar １ and Ar ２ It extends from.

[0039] In formula (4), L is a divalent linking group (excluding a single bond) that bonds to any carbon atom constituting each azaaryl fused ring and also bonds to other structures of the novolak resin. In formula (4-2), Q is a divalent linking group (excluding a single bond) that bonds to any carbon atom constituting each azaaryl fused ring. In formulas (4) and (4-2), Ar １ and Ar ２ , i.e., in the azaaryl fused ring However, it is preferably bonded to a carbon atom constituting the pyrrole ring moiety in the azaaryl fused ring.

[0040] Preferred linking groups L include -(CR ４ R ５ ) m １ -, -R ６ -, -(Ar)m ２ -, -CH ２ -(Ar)m ２ -CH ２ -, and -(cyclo-R)-. Preferred linking groups Q are -O-, -S-, and -SO ２ -, -CO-, -CONH-, -COO-, -NH-, -(CR ４ R ５ ) m １ -, -R ６ -, -(Ar)m ２ -, -CH ２ -(Ar)m ２ -CH ２ -, and -(cyclo-R)-. ４ and R ５ are the same or different and each independently represent a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10. ６ represents a cycloalkylene group having 3 to 6 carbon atoms, Ar represents an arylene group having 6 to 30 carbon atoms which may be bonded to each other via a single bond; m ２represents an integer of 1 to 3. Examples of Ar include a divalent benzene ring, naphthalene ring, anthracene ring, pyrene ring, biphenyl ring, and terphenyl ring. cyclo-R represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring, preferably a 6- to 8-membered ring, which may form a condensed ring with one or two benzene rings or naphthalene rings. The two bonds in cyclo-R refer to bonds extending from carbon atoms (preferably the same carbon atom, excluding carbon atoms belonging to an optionally contained condensed benzene ring or condensed naphthalene ring) constituting the ring of the alicyclic hydrocarbon group. The alicyclic hydrocarbon group may be a divalent monocyclic hydrocarbon group derived from cyclohexane, cyclopentane, or the like, or a divalent polycyclic hydrocarbon group derived from dicyclopentadiene, or the like. Examples of alicyclic hydrocarbon groups forming a fused ring with a benzene ring or a naphthalene ring include divalent hydrocarbon groups derived from tetralin, 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, indane, fluorene, benzocyclobutene, benzofluorene, dibenzofluorene, and acenaphthene. However, when the alicyclic hydrocarbon group is a five-membered ring, i.e., a divalent hydrocarbon group derived from cyclopentane, the number of benzene rings or naphthalene rings forming the fused ring is preferably 0 to 2.

[0041] In one embodiment of the present invention, when L in formula (4) or Q in formula (4-2) is a fluorene ring, R １１ and R ２１ At least a part of these is preferably an alkynyl group as described below.

[0042] Ar １ and Ar ２ are the same or different and each independently represent a benzene ring or a fused ring composed of two or three benzene rings, and form a fused ring (azaaryl fused ring) with the pyrrole ring moiety in formula (4) or formula (4-2). Examples of fused rings composed of two or three benzene rings include a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of substituted rings include biphenyl (a benzene ring substituted with a phenyl group) and terphenyl (a benzene ring substituted with a biphenyl group). Ar１ and Ar ２ is preferably a benzene ring.

[0043] R １１ and R ２１ is a substituent on the nitrogen atom of the azaaryl fused ring, i.e., a substituent on the nitrogen atom of the pyrrole ring moiety. １１ and R ２１ are the same or different and each independently represent: (i) a hydrogen atom or a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched or cyclic alkoxymethyl group having 2 to 20 carbon atoms (e.g., a methoxymethyl group); a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) above do not include oxygen-atom-containing substituents (e.g., a hydroxy group, an alkoxy group, an aryloxy group, a carboxyl group, a carbonyl group), sulfur-atom-containing substituents (e.g., a sulfonic acid group, a sulfide-containing group, a sulfonyl-containing group), nitrogen-atom-containing substituents (e.g., an amino group, a substituted amino group (e.g., a mono- or di-substituted amino group such as a monoalkylamine or a dialkylamine), an amido group, a nitro group, a cyano group), an aryl group (preferably an aryl group having 6 to 15 carbon atoms, e.g., or a halogen atom, or in the case of (iii), the hydrocarbon chain portion may be further interrupted by an oxygen atom-containing substituent (-O-, -C(O)-, -C(O)O-, -OC(O)-, etc.), a sulfur atom-containing substituent (-S-, etc.), a nitrogen atom-containing substituent (-N(R)C(O)-, -C(O)N(R)-, -OC(O)N(R)-, -N(R)C(O)O-, -N(R)C(O)N(R)-, -NR-, etc.), or an arylene group (phenylene group, etc.). Here, in the substituents used to interrupt the hydrocarbon chain, each R is independently the same or different and represents a hydrocarbon group having 1 to 30 carbon atoms.

[0044] Also, R １１ and R ２１ At least a portion of the groups may be substituted with an alkynyl group having 2 to 10 carbon atoms.

[0045] R １２ and R２２ are the same or different and each independently represent an optional substituent on a carbon atom constituting the azaaryl fused ring, and are not limited to a carbon atom constituting the pyrrole ring moiety, and are not limited to a carbon atom constituting the pyrrole ring moiety and a carbon atom constituting the azaaryl fused ring. １ , Ar ２ It may be a carbon atom constituting an aromatic ring portion. １２ and R ２２ are the same or different and each independently represent: (iv) a hydroxy group, a nitro group, a cyano group, a carboxyl group, a trifluoromethyl group, or a halogen atom; (v) an aryloxy group having 6 to 15 carbon atoms, an arylalkoxycarbonyl group having 8 to 15 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, or an aryl group having 6 to 30 carbon atoms; or (vi) an acyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an arylalkoxy group having 7 to 15 carbon atoms, an alkoxycarbonyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms;

[0046] However, the (v) and (vi) may be further substituted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, an aryl group, or a halogen atom, as in the (ii) and (iii) above; or the (vi) may have a hydrocarbon chain portion further interrupted by an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, or an arylene group (such as a phenylene group), as in the (iii) above. １２ and R ２２ represents the number of substituents, and may be 0.

[0047] Some representative examples of bis(azaaryl fused ring) structural units are listed below. Note that the bond from the structural unit is omitted. Also, examples in which hydrogen atoms are bonded to the nitrogen atoms on the azaaryl fused ring (indole ring) are listed as representative examples, but at least some of them can be replaced with R defined in the above formula (4) or formula (4-2). １１ , R ２１In addition, R defined in the formula (4) or (4-2) may be substituted. １２ , R ２２ The group may optionally have a substituent defined as:

[0048]

[0049]

[0050] Furthermore, H of NH of the amine skeleton may be substituted with the following substituents.

[0051] <Other Unit Structures> As described above, the novolak resin of the present invention may contain, in addition to the unit structures described above, other unit structures, as long as the effects of the present invention are not impaired. For example, the novolak resin may have a unit structure A' that is a divalent group having an aromatic ring other than the unit structure A1 or the unit structure A2. One end of the unit structure may be bonded to a bond of the organic group C1 or the organic group C2.

[0052] Preferably, such aromatic rings have from 6 to 30, more preferably from 6 to 24 carbon atoms.

[0053] Preferably, such aromatic ring is one or more benzene rings, naphthalene rings, anthracene rings, or pyrene rings; or a condensed ring of a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring with a heterocycle or an aliphatic ring (such as a fluorene ring, a benzofluorene ring, a dibenzofluorene ring, an indole ring, or a carbazole ring).

[0054] The aromatic ring may have any substituent, and the substituent preferably contains a heteroatom. In addition, the aromatic ring may have two or more aromatic rings connected by a linking group, and the linking group preferably contains a heteroatom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom.

[0055] Preferably, the "aromatic ring" is an organic group having 6 to 30 or 6 to 24 carbon atoms containing at least one heteroatom selected from N, S and O on, within or between the rings.

[0056] Examples of heteroatoms contained on the ring include nitrogen atoms contained in amino groups (e.g., propargylamino groups) and cyano groups; oxygen atoms contained in oxygen-containing substituents such as formyl groups, hydroxy groups, carboxyl groups, and alkoxy groups (e.g., propargyloxy groups); and nitrogen atoms and oxygen atoms contained in oxygen-containing and nitrogen-containing substituents such as nitro groups. Examples of heteroatoms contained in the ring include oxygen atoms contained in xanthene and nitrogen atoms contained in carbazole.

[0057] Heteroatoms contained in the linking group of two or more aromatic rings include an -NH- bond, an -NHCO- bond, an -O- bond, a -COO- bond, a -CO- bond, an -S- bond, an -SS- bond, an -SO ２ Examples of the unit structure A include a nitrogen atom, an oxygen atom, and a sulfur atom contained in the - bond. Preferably, the unit structure A is a unit structure having an aromatic ring having the above-mentioned oxygen-containing substituent, a unit structure having two or more aromatic rings connected by -NH-, or a unit structure having one or more fused rings of one or more aromatic hydrocarbon rings and one or more heterocyclic rings.

[0058] Preferably, the unit structure A' includes a phenol unit structure and an amine unit structure. For example, the phenol unit structure is derived from a monomer represented by the following formulas (10-1) to (10-36), and the amine unit structure is derived from a monomer represented by the following formulas (10-37) to (10-69).

[0059] The exemplary structures described below are merely examples, and in compounds in which hydroxy groups can be substituted on aromatic rings, the number of hydroxy groups can be within a theoretically possible range without being limited to the specific exemplary structures, and also include compounds in which any theoretically possible substituents, as described below, are bonded to the aromatic ring.

[0060] (Examples of monomers having a phenol unit structure) (* indicates a bond.) Furthermore, H of OH in the monomer having the phenol unit structure may be replaced with a phenyl group or an alkynyl group having 2 to 10 carbon atoms.

[0061] (Examples of Monomers Having Amine Unit Structures) (* indicates a bond.) In addition, R ９２ represents a hydrogen atom, a phenyl group, or an alkynyl group having 2 to 10 carbon atoms.

[0062] <Organic Group C1> The novolak resin has its terminals capped with a monovalent organic group C1 or C2. The organic group C1 is represented by the following formula (1). In formula (1), * represents a bond that bonds the organic group C1 to at least one terminal of the novolak resin, and Ar ６ represents an aryl group having 6 to 40 carbon atoms; R ６１ represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can be bonded. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. R ６２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. ６４ , R ６５ each independently represents a hydrogen atom, a phenyl group which may be substituted with a hydroxy group, or a naphthyl group which may be substituted with a hydroxy group, R ６４ , R ６５ represents a phenyl group or a naphthyl group, R ６４ or R ６５ and an aryl group Ar ６A new ring can be formed with m via a single bond or a methylene group. ４ represents 0 or 1, m ３ is m ４ When m is 0, it is an integer from 0 to (3+2n), and m ３ is m ４ When represents 1, it is an integer of 0 to (2+2n), and n is an aryl group Ar ６ indicates the degree of condensation of the benzene rings, and m ５ represents 0 or 1. In this specification, the degree of condensation of a benzene ring refers to the number of benzene rings condensed to one benzene ring. For example, a monocyclic benzene ring has a condensation degree of 0, a naphthalene ring has a condensation degree of 1, and an anthracene ring has a condensation degree of 2.

[0063] The organic group C1 represented by formula (1) is a monovalent group derived from a compound represented by the following formula (5). In formula (5), Ar ６ , R ６１ , R ６２ , R ６４ , R ６５ , m ３ , m ４ and m ５ is the same as formula (1), and R ６３ represents a hydrogen atom or a methyl group.

[0064] Examples of the compound represented by formula (5) are as follows:

[0065] Of these, the organic group C1 is preferably a monovalent group derived from a hydroxy-containing aromatic methylol compound such as 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, or 2,6-di-tert-butyl-4-hydroxymethylphenol.

[0066] <Organic Group C2> The organic group C2 is represented by the following formula (2): In formula (2), * represents a bond by which the organic group C2 is bonded to at least one terminal of the novolak resin, and Ar ７ represents an aryl group having 6 to 40 carbon atoms; R ７１represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can be bonded. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. R ７２ represents a hydrogen atom, a methyl group, or a phenyl group. ６ is an integer from 0 to (3+2n), and n is an aryl group Ar ７ indicates the degree of condensation of the aromatic rings that make up the

[0067] The organic group C2 represented by formula (2) is a monovalent group derived from an aromatic vinyl compound represented by the following formula (6). In formula (6), Ar ７ , R ７１ , R ７２ and m ６ is the same as equation (2).

[0068] Examples of the aromatic vinyl compound represented by formula (6) are as follows:

[0069] Of these, the organic group C2 is preferably a monovalent group derived from an aromatic vinyl compound such as styrene, 2-vinylnaphthalene, 4-tert-butylstyrene, or 4-tert-butoxystyrene.

[0070] <Unit Structure B> The novolak resin of the present invention preferably contains a composite unit structure AB represented by the following formula (7) and a C moiety that caps at least one end of the composite unit structure AB. Here, the composite unit structure AB represented by formula (7) is described, but in addition to the unit structure AB, other unit structures, for example, the above-mentioned unit structure A', may also be contained. In formula (7), n represents the number of composite unit structures A-B, and unit structure A may be the unit structure A1 or A2, or may be another divalent group having an aromatic ring. C represents the organic group C1 or C2.

[0071] The unit structure B is one or more unit structures containing a linking carbon atom [see the above-mentioned term definition section] that bonds to an aromatic ring in the unit structure A, and includes a structure represented by the formula (B1), (B2), or (B3) described below. The unit structure B is linked to the carbon atom of the unit structure A by a covalent bond.

[0072] Furthermore, at least one composite unit structure A-B may be replaced with one or more unit structures D including structures represented by the formulae (D1), (D2), and (D3) described below as an equivalent unit structure thereto.

[0073] <Formula (B1)> In formula (B1), R and R′ each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, a heterocyclic ring having 3 to 30 carbon atoms which may have a substituent, or a linear, branched, or cyclic alkyl group having 10 or less carbon atoms which may have a substituent. In addition, the two bonds in formula (B1) can be covalently bonded to the aromatic ring in the unit structure A.

[0074] In the definitions of R and R' in formula (B1), the terms "aromatic ring" and "heterocycle" can be referred to in the <Definition of Terms> section above.

[0075] In the definition of R and R′ in formula (B1), examples of the “alkyl group” include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1- Ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group ethyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group cyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,Examples of such cyclopropyl groups include 3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, and 2-ethyl-3-methylcyclopropyl groups, as well as n-heptyl, n-octyl, n-nonyl, and n-decyl groups. Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, or pyrenyl.

[0076] Furthermore, the unit structure containing the structure represented by formula (B1) may contain, for example, a structure in which two or three identical or different structures of formula (B1) are bonded to a divalent or trivalent linking group to form a dimer or trimer structure, as shown in formula (B11) below in each structure of formula (B1). (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 (a chain hydrocarbon or a cyclic hydrocarbon (which may be aromatic or non-aromatic)).

[0077] Examples of such a linking group include a linking group having two or three aromatic rings. Specific examples of the divalent or trivalent linking group include the following divalent linking group (L1) exemplified in the above formula (B11): [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)).

[0078] Other examples include divalent or trivalent linking groups of the following formulae (L2) and (L3). [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.

[0079] Examples also include divalent linking groups such as those of the following formula (L4), which can form a covalent bond with the linking carbon atom by an addition reaction between an acetylide and a ketone.

[0080] When at least one of R and R′ in formula (B1) is an aromatic ring, the aromatic ring [see, for example, Ar in formula (B12) below] may additionally be bonded to another unit structure B.

[0081] In this case, as in the following formula (D1), when one bond of the linking carbon atom is bonded to a polymer terminal T (hydrogen atom; various functional groups such as a hydroxy group or an unsaturated aliphatic hydrocarbon group; a terminal unit structure A; a unit structure A in another polymer chain, etc.), it can also be substituted for at least one composite unit structure A-B as a unit structure D equivalent to the composite unit structure A-B. That is, the aromatic ring [Ar in formula (D1)] in formula (D1) may be bonded to another unit structure B, and the remaining bond from the linking carbon atom shown in formula (D1) may be bonded to the aromatic ring of unit structure A, thereby extending the polymer chain.

[0082] Some specific examples of the unit structure B containing the structure represented by formula (B1) are as follows. * basically indicates the bonding site with the unit structure A. Needless to say, the structure may contain the exemplified structure as a part of the whole.

[0083] <Formula (B2)> In formula (B2), Z ０ represents an aromatic ring residue or aliphatic ring residue having 6 to 30 carbon atoms, which may have a substituent, or an organic group in which two 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 bicyclohexyl.

[0084] J １ and J ２each independently represents a divalent organic group which may have a direct bond or a substituent. The divalent organic group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxy group, an aryl group (e.g., a phenyl group, a substituted phenyl group), or a halogen atom (e.g., fluorine) as a substituent. Examples of linear alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0085] Furthermore, the unit structure containing the structure represented by formula (B2) may contain a structure in which two or three structures represented by formula (B2), which are the same or different from one another, are bonded to a divalent or trivalent linking group to form a dimer or trimer structure, similar to formula (B1).

[0086] In addition, in the embodiment in which an aromatic ring is contained in formula (B2) [Z in formula (B2)] ０ ], and therefore, similarly to the above-mentioned formula (B1), the aromatic ring [for example, Z ０ Ａｒ The aromatic ring in the formula (B21) may be additionally bonded to another structural unit B [vertical bond in the formula (B21)]. [In formula (B21), Z ０ Ａｒ is an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent, or an organic group in which two aromatic rings or aliphatic rings are linked by a single bond, and which has at least one aromatic ring; Z ０ Ａｒ The bond extending downward from ０ Ａｒ extending from the aromatic ring in J １ and J ２ is defined as in formula (B2).

[0087] In this case, the following formula (D2): [In formula (D2), Z ０ Ａｒ , J １ and J ２is defined as in formula (B21), and T represents a polymer terminal. ], when one bond of the linking carbon atom is bonded to a polymer terminal T (hydrogen atom; various functional groups such as a hydroxy group or an unsaturated aliphatic hydrocarbon group, a terminal unit structure A, a unit structure A in another polymer chain, etc.), it can also be substituted for at least one composite unit structure A-B as one unit structure D equivalent to the composite unit structure A-B. That is, the aromatic ring in formula (D2) [Z in formula (D2) ０ Ａｒ The aromatic ring in the unit structure A is bonded to another unit structure B, and the remaining connecting carbon atom in formula (D2) is bonded to the aromatic ring in the unit structure A, thereby extending the polymer chain.

[0088] Some specific examples of unit structures containing the structure represented by formula (B2) are as follows. * indicates the bonding site with unit structure A. Needless to say, the unit structure may contain the exemplified structure as a part of the whole.

[0089] <Formula (B3)>

[0090] In formula (B3), Z is a monocyclic ring or a bicyclic, tricyclic, or tetracyclic fused ring having 4 to 25 carbon atoms, which may have a substituent. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the monocyclic ring or the bicyclic, tricyclic, or tetracyclic fused ring excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the monocyclic ring or fused ring is a heterocyclic ring.

[0091] The monocycle is a non-aromatic monocycle; at least one of the monocycles constituting the bicycle, tricycle, or tetracycle is a non-aromatic monocycle, and the remaining monocycles may be aromatic or non-aromatic monocycles.

[0092] The monocyclic or bicyclic, tricyclic, or tetracyclic fused ring may further form a fused ring with one or more aromatic rings to form a pentacyclic or higher fused ring, and the number of carbon atoms in the pentacyclic or higher fused ring is preferably 40 or less. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the pentacyclic or higher fused ring excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the pentacyclic or higher fused ring is a heterocyclic ring.

[0093] X and Y may be the same or different and each represent -CR ３ R ４ represents a - group, and R ３ and R ４ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0094] x and y represent the numbers X and Y, respectively, and each independently represents 0 or 1. is bonded to any carbon atom (referred to as "carbon atom 1") constituting the non-aromatic monocyclic ring of Z (when x = 1) or extends from carbon atom 1 (when x = 0), is bonded to any carbon atom (referred to as "carbon atom 2") constituting the non-aromatic monocycle of Z (when y = 1) or extends from carbon atom 2 (when y = 0), and carbon atom 1 and carbon atom 2 may be the same or different, and when different, they may belong to the same non-aromatic monocycle or different non-aromatic monocycles.

[0095] Furthermore, in formula (B3), optionally, linking carbon atoms other than carbon atom 1 and carbon atom 2 may be included.

[0096] When Z is a tricyclic or higher fused ring, the permutation positional relationship between one or two non-aromatic monocycles to which carbon atoms 1 and 2 in formula (B3) belong and the remaining monocycles in the fused ring is arbitrary, and when carbon atom 1 and carbon atom 2 belong to different non-aromatic monocycles (referred to as "non-aromatic monocycle 1" and "non-aromatic monocycle 2," respectively), the permutation positional relationship between non-aromatic monocycle 1 and non-aromatic monocycle 2 in the fused ring is also arbitrary.

[0097] In the unit structure containing the structure represented by formula (B3), similarly to formula (B1), two or three structures of formula (B3), which may be the same or different, may be bonded to a divalent or trivalent linking group to form a dimer or trimer structure.

[0098] Some specific examples of the organic group containing the structure represented by formula (B3) are as follows. The bonding site to the unit structure A is not particularly limited. Needless to say, the structure may contain the exemplified structure as a part of the whole.

[0099] Examples include those with more than two bonds (*), but these excess bonds can be used for bonding to aromatic rings in other polymer chains, crosslinking, etc.

[0100] When Z in formula (B3) contains an aromatic ring, the aromatic ring [for example, Ar in formula (B32) below] １ [See reference] may additionally be bonded to another unit structure B. In formula (B32), Z １ is at least one non-aromatic monocyclic ring, Ar １ is Z １ and Z and Ar represent at least one aromatic monocyclic ring forming a condensed ring with a non-aromatic monocyclic ring of the formula １ The group as a whole constitutes a bicyclic, tricyclic, tetracyclic, or pentacyclic fused ring, optionally having a substituent, having 8 to 25 carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the bicyclic, tricyclic, or tetracyclic fused ring, excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the bicyclic, tricyclic, or tetracyclic fused ring is a heterocyclic ring.

[0101] The bicyclic, tricyclic, tetracyclic, or pentacyclic organic group may further form a fused ring with one or more aromatic rings to form a hexacyclic or higher ring, and the hexacyclic or higher fused ring preferably has 40 or less carbon atoms. The number of carbon atoms referred to here means only the number of carbon atoms constituting the ring skeleton of the hexacyclic or higher fused ring excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring when the hexacyclic or higher fused ring is a heterocyclic ring.

[0102] In addition, Z in the cyclic organic group １ and one or more non-aromatic monocyclic rings belonging to the group １ The order and positional relationship of one or more aromatic monocyclic rings belonging to Z includes any order. １ two or more non-aromatic monocyclic rings belonging to Ar １ When there are two or more aromatic monocyclic rings belonging to Z １ and non-aromatic monocyclic rings belonging to Ar １ and aromatic monocyclic rings belonging to the formula (B1) may be arranged alternately to form a condensed ring. X, Y, x, and y are defined as in formula (B3).

[0103] In this case, the following formula (D3): [wherein, Z １ , Ar １ , X, Y, x, and y are the same as those defined in formula (B32), and T represents a polymer terminal. ], when one bond of the linking carbon atom is bonded to a polymer terminal T (hydrogen atom; various functional groups such as a hydroxy group or an unsaturated aliphatic hydrocarbon group, a terminal unit structure A, a unit structure A in another polymer chain, etc.), it can also be substituted for at least one composite unit structure A-B as one unit structure D equivalent to the composite unit structure A-B. That is, the aromatic ring in formula (D3) [Ar in formula (D3)] １ ] may be bonded to another unit structure B, and the remaining connecting carbon atom shown in formula (D3) may be bonded to the aromatic ring of unit structure A, thereby extending the polymer chain.

[0104] As a more specific structure of formula (D3), for example, in the following formula (D31), T in formula (D3) is a hydrogen atom which is a terminal group, and p and k which can be bonds are １ and k ２ Among them, p and k １ , or p and k ２ This can result in one unit structure D equivalent to the composite unit structure AB.

[0105] In addition, k １ Tok ２ It can also function as unit structure A.

[0106] In addition, the following formula (D32) shows an example where T in formula (D3) is a phenyl group. In this example, p and k, which can be bonds, １ , k ２ and m, p and k １ , p and k ２ , or p and m can result in a single unit structure D equivalent to the composite unit structure AB.

[0107] In addition, k １ Tok ２ , k １ and m or k ２ and m, it can also function as a unit structure A.

[0108] Some specific examples of the structural unit D of formula (D3) (a structural unit equivalent to the composite structural unit A-B) are as follows. * indicates the bonding site with structural unit A.

[0109] In the unit structure D, a bond extends from the aromatic ring in these structures to bond to the unit structure B, but in the specific examples below, such a bond is omitted. Needless to say, the unit structure may contain the exemplified structure as a part of the whole.

[0110] In the above specific examples, when there is no bond from the aromatic ring, it can be a specific example of a polymer terminal.

[0111] In the novolak resin of the present invention, all or part of the hydrogen atoms of the hydroxy, amino or alkylamino groups may be substituted with alkynyl groups having 2 to 10 carbon atoms.

[0112] <Production of Novolac Resin> The novolac resin having the structure represented by the above formula (7) can be prepared by a known method. For the composite unit structure A-B, for example, a ring-containing compound represented by H-A-H and OHC-B, O═C-B, RO-B-OR, RO-CH ２ -B-CH ２ It can be prepared by condensing an oxygen-containing compound represented by —OR, etc., where A and B are as defined above, and R represents a hydrogen atom, a halogen atom, or an alkyl group having about 1 to 3 carbon atoms.

[0113] The ring-containing compound and the oxygen-containing compound may each be used alone or in combination of two or more. In this condensation reaction, the oxygen-containing compound can be used in an amount of 0.1 to 10 moles, preferably 0.1 to 2 moles, per mole of the ring-containing compound.

[0114] The condensation reaction that produces the A-B moiety of the composite unit structure of the novolac resin and the addition reaction that produces the C moiety at the terminal of the novolac resin can proceed simultaneously. Examples of catalysts that can be used in these reactions include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid; and carboxylic acids such as formic acid and oxalic acid. The amount of catalyst used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass per 100 parts by mass of the ring-containing compound (or the total amount of ring-containing compounds when multiple types are used).

[0115] The above condensation reaction and addition reaction can be carried out without a solvent, but are usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrates and does not inhibit the reaction. Examples include ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, and dioxane. Furthermore, if the catalyst used is a liquid, such as formic acid, it can also serve as a solvent. The condensation reaction temperature is usually 40°C to 200°C, preferably 100°C to 180°C. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 50 hours, preferably 5 minutes to 24 hours.

[0116] The weight average molecular weight of the novolak resin according to one embodiment of the present invention is usually 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0117] The resist underlayer film-forming composition of one embodiment of the present invention contains a solvent. The solvent is not particularly limited as long as it can dissolve the specific novolak resin and other optional components that are added as needed.

[0118] Examples of the solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate,Isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate Examples of suitable solvents include methyl acetoacetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

[0119] Also, solvents with boiling points of 160°C or higher can be included in combination with solvents with boiling points below 160°C.

[0120] As such a high-boiling point solvent, for example, the following compounds described in WO 2018 / 131562 (A1) can be preferably used. [R in formula (i)] １ , R ２ and R ３ each represents a hydrogen atom, an oxygen atom, a sulfur atom, or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and may be the same or different from each other and may be bonded to each other to form a ring structure.

[0121] Alternatively, 1,6-diacetoxyhexane (boiling point 260 ° C.), tripropylene glycol monomethyl ether (boiling point 242 ° C.), and various other high-boiling solvents described in paragraph 0082 of JP-A-2021-84974 can be preferably used.

[0122] 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 242°C), γ-butyrolactone (boiling point 204°C), benzyl alcohol (boiling point 205°C), propylene carbonate (boiling point 242°C), tetraethylene glycol dimethyl ether (boiling point 275°C), 1,6-diacetoxyhexane (boiling point 260°C), dipropylene glycol (boiling point 230°C), 1, 3-butylene glycol diacetate (boiling point 232° C.) and various other high boiling point solvents described in paragraphs 0023 to 0031 of the publication can be preferably used.

[0123] <Acid and / or Salt Thereof and / or Acid Generator> The resist underlayer film forming composition of one embodiment of the present invention may contain an acid and / or a salt thereof and / or an acid generator.

[0124] Examples of acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid. Salts of the aforementioned acids can also be used. Suitable salts include, but are not limited to, ammonia derivative salts such as trimethylamine salts and triethylamine salts, pyridine derivative salts, and morpholine derivative salts. A single acid and / or its salt can be used, or two or more can be used in combination. The amount of the acid and / or its salt is typically 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 solids content.

[0125] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0126] Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0127] Photoacid generators generate acid when the resist is exposed to light. This allows the acidity of the underlayer film to be adjusted. This is one way to match the acidity of the underlayer film to that of the upper layer resist. Adjusting the acidity of the underlayer film also allows for adjustment of the pattern shape of the upper layer resist.

[0128] Examples of the photoacid generator contained in the resist underlayer film-forming composition of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. Examples of the onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0129] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. Examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0130] The acid generator may be used alone or in combination of two or more thereof. When an acid generator is used, the proportion thereof is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass, relative to 100 parts by mass of the solid content of the resist underlayer film-forming composition.

[0131] <Other Optional Components> The resist underlayer film-forming composition of one embodiment of the present invention may contain, in addition to the above, a crosslinking agent, a surfactant, a light absorber, a rheology adjuster, an adhesion aid, and the like, as needed.

[0132] <Crosslinking Agent> Typical crosslinking agents include aminoplast crosslinking agents and phenoplast crosslinking agents. As the crosslinking agent, a crosslinking agent with high heat resistance can be used. As a crosslinking agent with high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0133] Aminoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, and polymers thereof. Crosslinking agents having at least two crosslink-forming substituents are preferred, including compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and methoxymethylated thiourea. Condensates of these compounds can also be used.

[0134] Preferably, it is at least one selected from the group consisting of tetramethoxymethyl glycoluril and hexamethoxymethyl melamine. Specific examples are as follows:

[0135] Phenoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated aromatics, their polymers, and the like. Preferred crosslinking agents have at least two crosslink-forming substituents per molecule, such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Condensates of these compounds can also be used.

[0136] In addition to the above, other examples of such compounds include compounds having a partial structure of the following formula (11) and polymers or oligomers having a repeating unit of the following formula (12).

[0137] The above R １１ , R １２ , R １３ , and R １４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the above-mentioned examples of these alkyl groups can be used. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5-n1), and (n1+n2) is an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is an integer of 0 to (4-n3), and (n3+n4) is an integer of 1 to 4. Oligomers and polymers having a repeating unit structure number of 2 to 100, or 2 to 50, can be used.

[0138] Some specific examples are as follows:

[0139] The crosslinking agents, such as aminoplast crosslinking agents and phenoplast crosslinking agents, may be used alone or in combination of two or more. The aminoplast crosslinking agent can be produced by a method known per se or a method equivalent thereto, or a commercially available product may be used. The amount of the crosslinking agent, such as aminoplast crosslinking agent and phenoplast crosslinking agent, 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, based on the total solids content of the resist underlayer film-forming composition of the present invention.

[0140] <Surfactant> The resist underlayer film forming composition according to the present invention can contain a surfactant in order to prevent pinholes, striations, and the like from occurring and to further improve coatability against surface irregularities.

[0141] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate.

[0142] Examples of suitable surfactants include fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, and R-40 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), and Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0143] The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

[0144] <Light absorber> Examples of the light absorber include commercially available light absorbers described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as C.I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C.I. C.I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; C.I. Disperse Violet 43; C.I. Disperse Blue 96; C.I. Fluorescent Brightening Agent 112, 135, and 163; C.I. Solvent Orange 2 and 45; C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, and 49; C.I. Pigment Green 10; C.I. Pigment Brown 2, etc. can be suitably used. The light-absorbing agent is usually blended in an amount of 10% by mass or less, and preferably 5% by mass or less, based on the total solid content of the resist underlayer film-forming composition according to the present invention.

[0145] <Rheology Adjuster> Rheology adjusters are added primarily to improve the fluidity of the resist underlayer film-forming composition, thereby improving the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes, particularly during the baking process. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di(n-butyl) maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology adjusters are typically incorporated in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition of the present invention.

[0146] <Adhesion aid> An adhesion aid is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film-forming composition, and particularly to prevent peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; Examples of the adhesion aid include silanes such as silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion aids are blended in an amount of usually less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the resist underlayer film-forming composition of the present invention.

[0147] The resist underlayer film-forming composition according to the present invention has a solids content of 0.1 to 70% by mass, or 0.1 to 60% by mass. The solids content is the content of all components of the resist underlayer film-forming composition excluding the solvent. The solids content may contain a crosslinkable resin in an amount of 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass.

[0148] <Resist Underlayer Film> The resist underlayer film can be formed, for example, as follows using the resist underlayer film-forming composition according to the present invention.

[0149] Substrates used in the manufacture of semiconductor devices (e.g., silicon wafer substrates, silicon dioxide coated substrates (SiO ２ The resist underlayer film-forming composition according to one embodiment of the present invention is applied onto a substrate (e.g., a silicon nitride substrate (SiN substrate), a silicon oxynitride substrate (SiON substrate), a titanium nitride substrate (TiN substrate), a tungsten substrate (W substrate), a glass substrate, an ITO substrate, a polyimide substrate, or a substrate coated with a low dielectric constant material (low-k material)) by a suitable application method such as a spinner or coater, and then baked using a heating means such as a hot plate to form a resist underlayer film. Baking conditions are appropriately selected from a baking temperature of 80°C to 800°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 150°C to 400°C and the baking time is 0.5 to 2 minutes. Air may be used as the atmospheric gas during baking, or an inert gas such as nitrogen or argon can also be used. In one embodiment, it is particularly preferred that the oxygen concentration is 1% or less. Here, the thickness of the formed underlayer film is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of a quartz imprint mold (mold replica) can be produced.

[0150] Furthermore, an adhesion layer and / or a silicon-containing layer containing 99% by mass or less, or 50% by mass or less of Si can be formed by coating or vapor deposition on the resist underlayer film according to one embodiment of the present invention. For example, an adhesion layer as described in JP-A-2013-202982 or JP-A-5827180, a silicon-containing resist underlayer film (inorganic resist underlayer film)-forming composition as described in WO 2009 / 104552 (A1) can be formed by spin coating, or a Si-based inorganic material film can be formed by CVD or the like.

[0151] Furthermore, by applying the resist underlayer film-forming composition of one embodiment of the present invention to a semiconductor substrate having a portion with a step and a portion without a step (a so-called stepped substrate) and baking it, the step between the portion with a step and the portion without a step can be reduced.

[0152] <Method for manufacturing a semiconductor device> (i) A method for manufacturing a semiconductor device, which is one aspect of the present invention, includes: a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition, which is one aspect of the present invention; a step of forming a resist film on the resist underlayer film; a step of forming a resist pattern on the resist film by irradiating with light or an electron beam and developing; a step of etching and patterning the resist underlayer film using the resist pattern; and a step of processing a semiconductor substrate using the patterned resist underlayer film.

[0153] (ii) A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to one aspect of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film by irradiating with light or an electron beam and developing; etching and patterning the hard mask using the resist pattern; etching and patterning the resist underlayer film using the patterned hard mask; and processing a semiconductor substrate using the patterned resist underlayer film.

[0154] (iii) A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to one aspect of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film by irradiating with light or an electron beam and developing; etching and patterning the hard mask using the resist pattern; etching and patterning the resist underlayer film using the patterned hard mask; removing the hard mask; and processing a semiconductor substrate using the patterned resist underlayer film.

[0155] (iv) A method for producing a semiconductor device according to one embodiment of the present invention includes the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to one embodiment of the present invention; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film by irradiating with light or an electron beam and developing; etching and patterning the hard mask using the resist pattern; etching and patterning the resist underlayer film using the etched hard mask; removing the hard mask; forming a vapor-deposited film (spacer) on the resist underlayer film after removing the hard mask; processing the vapor-deposited film (spacer) by etching; removing the patterned resist underlayer film to leave the patterned vapor-deposited film (spacer); and processing a semiconductor substrate using the patterned vapor-deposited film (spacer). A semiconductor substrate can be processed using the production methods (i) to (iv) above.

[0156] The step of forming a resist underlayer film using the resist underlayer film forming composition of one embodiment of the present invention is as described above in the "resist underlayer film" section.

[0157] A hard mask such as a silicon-containing film may be formed as a second resist underlayer film on the resist underlayer film formed in the above steps, and a resist pattern may be formed thereon [(ii) to (iv) above].

[0158] The hard mask may be a coating film of a composition containing an inorganic substance, or a vapor-deposited film of a composition containing an inorganic substance formed by a vapor deposition method such as CVD or PVD, and may be a SiON film, a SiN film, or a SiO ２ An example is a membrane.

[0159] Furthermore, an anti-reflective coating (BARC) may be formed on this hard mask, or a resist shape correction film without anti-reflective properties may be formed.

[0160] In the step of forming the resist pattern, exposure is performed through a mask (reticle) for forming a predetermined pattern or by direct writing. Examples of exposure sources that can be used include g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, and electron beam. After exposure, post-exposure baking is performed as needed. The resist is then developed with a developer (e.g., a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), and then rinsed with a rinse solution or pure water to remove the used developer. Post-baking is then performed to dry the resist pattern and enhance adhesion to the underlayer.

[0161] The etching step performed after the formation of the resist pattern is performed by dry etching.

[0162] The resist film may be patterned by a nanoimprinting method or a self-assembled film method. In the nanoimprinting method, a resist composition is molded using a patterned mold that is transparent to irradiated light. In the self-assembled film method, a pattern is formed using a self-assembled film that naturally forms a regular structure on the nanometer order, such as a diblock polymer (e.g., polystyrene-polymethyl methacrylate).

[0163] In the nanoimprint method, before applying the curable composition that will form the resist film, a silicon-containing layer (hard mask layer) may be optionally formed on the resist underlayer film by coating or vapor deposition, and further an adhesion layer may be formed on the resist underlayer film or the silicon-containing layer (hard mask layer) by coating or vapor deposition, and the curable composition that will form the resist film may be applied on the adhesion layer.

[0164] The following gases are used for processing the hard mask (silicon-containing layer), resist underlayer film, and substrate: CF ４ , CHF ３ , C.H. ２ F ２ , C.H. ３ F, C ４ F ６ , C ４ F ８ , O ２ , N２ O, NO ２ , He, H ２ These gases may be used alone or in combination of two or more. Furthermore, these gases may be mixed with argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon, or nitrogen trifluoride.

[0165] In addition, wet etching may be performed to simplify the process and reduce damage to the processed substrate. This leads to suppression of fluctuations in processing dimensions and reduction of pattern roughness, making it possible to process the substrate with high yield. Therefore, in steps (ii) to (iv) above, the hard mask can be removed using either etching or an alkaline chemical solution. In particular, when an alkaline chemical solution is used, there are no restrictions on the components, but it is preferable that the alkaline component contains the following:

[0166] Examples of the alkaline component include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, and (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N , N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, 1,5-diazabicyclo[4.3.0]nonene-5, etc. Furthermore, particularly from the viewpoint of handling, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, and an inorganic base may be used in combination with the quaternary ammonium hydroxide. As the inorganic base, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, rubidium hydroxide, etc. are preferred, with potassium hydroxide being more preferred.

[0167] The present invention will be explained in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0168] [Synthesis of Polymers] Polymers used in resist underlayer films having structural formulae (S1) to (S9) and polymers used in comparative examples having structural formulae (S'1) to (S'5) were synthesized using Compound Group A, Compound Group B, Compound Group C, Catalyst Group D, Solvent Group E, and Reprecipitation Solvent Group F shown below.

[0169] (Compound groups A to C)

[0170]

[0171] (Catalyst Group D) Methanesulfonic acid: D1 3-mercaptopropionic acid: D2 Tetrabutylammonium iodide: D3

[0172] (Solvent group E) Propylene glycol monomethyl ether acetate (=PGMEA): E1 Propylene glycol monomethyl ether (=PGME): E2 1,4-dioxane: E3 Tetrahydrofuran: E4 Aqueous sodium hydroxide solution: E5

[0173] (Reprecipitation Solvent Group F) Methanol: F1

[0174] (Separation Solvent Group G) Butyl acetate / water: G1

[0175] Synthesis Example 1: 12.0 g of (A1), 5.2 g of (B1), 3.5 g of (C1), 5.5 g of (D1), 0.8 g of (D2), and 40.6 g of (E1) were placed in a flask. The mixture was then heated to 80°C under nitrogen and reacted for approximately 5 hours. After the reaction was stopped, the mixture was reprecipitated with (F1) and dried to obtain resin (S1). The weight average molecular weight Mw measured by GPC in terms of polystyrene was approximately 2,500. The resulting resin was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a solution of the target compound.

[0176] The weight-average molecular weight of the polymer is a result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions are as follows: Device: HLC-8320GPC manufactured by Tosoh Corporation GPC column: TSKgel Super-Multipore HZ-N (2 columns) Column temperature: 40°C Flow rate: 0.35 mL / min Eluent: THF Standard sample: polystyrene

[0177] Synthesis Examples 2 to 13 Polymers to be used for resist underlayer films were synthesized by changing Compound Group A, Compound Group B, Compound Group C, Catalyst Group D, Solvent Group E, and Reprecipitation Solvent Group F. The experimental procedures were the same as in Synthesis Example 1. Compounds were combined under the following conditions to obtain Example Polymers (S1) to (S8), Comparative Polymers (S'1) to (S'5), and solutions thereof.

[0178]

[0179]

[0180] Synthesis Example 14: 10.0 g of the resin (S5) after the reprecipitation treatment obtained in Synthesis Example 5, 10.4 g of (C4), 0.5 g of (D3), 26.4 g of (E3), and 8.8 g of (E4) were placed in a flask. The mixture was then heated to 55°C under nitrogen and allowed to react for approximately 24 hours. After the reaction was stopped, the separation operation was repeated using (G1), and the organic layer was concentrated, redissolved in PGMEA, reprecipitated using (F1), and dried to obtain resin (S9). The weight average molecular weight Mw measured by GPC in terms of polystyrene was approximately 2,800. The obtained resin was dissolved in PGMEA, and ion exchange was performed using a cation exchange resin and an anion exchange resin for 4 hours to obtain a solution of the target compound.

[0181] [Preparation of Resist Underlayer Film] Polymers (S1) to (S9), (S′1) to (S′5), crosslinking agent (CR1), acid generator (Ad1), solvents (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME)), and Megafac R-40 (R-40, manufactured by DIC Corporation) as a surfactant were mixed in the proportions shown in the table below, and the mixture was filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare resist underlayer film materials (Examples M1-M10, Comparative Examples M1-M5).

[0182]

[0183] [Resist Solvent Dissolution Test] The resist underlayer film materials of Examples M1-M10 and Comparative Examples M1-M5 were baked at 400°C for 60 seconds, and the concentration was adjusted to approximately 100 nm. Each of these films was coated onto a silicon wafer using an ACT-8 oven manufactured by Tokyo Electron Limited, and baked in air at the specified temperature for the specified time shown in the table to form a 100 nm resist underlayer film. The formed resist underlayer film was immersed in a general-purpose thinner, PGME / PGMEA (7 / 3), for 60 seconds to confirm its solvent resistance. A film thickness reduction of 1% or less after immersion in the thinner was evaluated as "good" (Table 3). Note that samples that did not exhibit solvent resistance under air-baking conditions (Comparative Examples M1 and M2) were not evaluated in the following tests because it was difficult to evaluate them as resist underlayer films.

[0184] [Measurement of Etching Rate] The etcher and etching gas used for the etching measurement were as follows: RIE-200NL (manufactured by Samco): CF ４　　 50 sccm RIE-200NL (manufactured by Samco): O ２ / N ２ 10sccm / 200sccm

[0185] The resist underlayer film materials of Examples M1 to M10 and Comparative Examples M3 to M5 were baked at 400°C for 60 seconds to adjust the concentration to about 100 nm, and each was applied to a silicon wafer using a spin coater and baked. ４ , O２ / N ２ The dry etching rate was measured using a gas. The dry etching rate ratio was defined as the dry etching rate ratio of (resist underlayer film) / (KrF resist), and compositions with a dry etching rate ratio of less than 0.8 were evaluated as "good" (Table 3).

[0186] [Measurement of Heat Resistance] The resist underlayer film materials of Examples M1-M10 and Comparative Examples M3-M5 were baked at 400°C for 60 seconds, and the concentration was adjusted to a thickness of approximately 100 nm. Each was then applied to a silicon wafer using a spin coater and baked. The resulting films were heated from room temperature (approximately 20°C) at a rate of 10°C per minute and subjected to thermogravimetric analysis in the atmosphere. Films with a weight loss of 5% or less at 400°C were evaluated as "good" (Table 3).

[0187] [Sublimation Measurement] The resist underlayer film materials of Examples M1-M10 and Comparative Examples M3-M5 were baked at 400°C for 60 seconds, and the concentration was adjusted to about 100 nm, and each was applied to a silicon wafer using a spin coater. This wafer was set in a sublimation measurement device integrated with a hot plate adjusted to 300°C, baked for 60 seconds, and the sublimation was collected and quantified using a QCM sensor. For measurement, the hot plate was heated to 300°C, and the pump flow rate was set to 0.24 m ３ The temperature was set to / s and the wafer was left for aging for the first 60 seconds. Immediately afterwards, the film-coated wafer was quickly placed on the hot plate through the slide opening (the test object was installed), and sublimation was collected from the 60-second point to the 120-second point (60 seconds). The QCM sensor used electrodes made of a compound containing silicon and aluminum, with a quartz crystal diameter (sensor diameter) of 14 mm, an electrode diameter on the quartz crystal surface of 5 mm, and a resonant frequency of 9 MHz. Compositions with less than 1500 ng of sublimation in 60 seconds were judged to be good (Table 3).

[0188] [Test for embedding ability into uneven substrate] As a coating test for uneven substrate, a 100 nm thick SiO ２The substrate was checked for whether the resist underlayer film had filled open areas (OPEN) where no pattern had been formed and trenches with a width of 50 nm. The resist underlayer film-forming compositions of Examples M1-M8 and Comparative Examples M3-M5 were applied to the substrates, and then baked at 400°C for 60 seconds to form resist underlayer films with a thickness of approximately 100 nm. The planarization of these substrates was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and cases where the substrates were filled without voids were considered to have good embeddability and were rated as "good" (Table 3).

[0189]

[0190] From the above, by using the polymer obtained by the present invention, not only does the polymer alone exhibit sufficient solvent resistance in the atmosphere, but it also exhibits sufficient etching resistance against F-based and O-based gases, which are commonly used etching gases. In addition, the high heat resistance can suppress the generation of sublimates, and the self-crosslinking groups contained in the polymer can increase the crosslinking initiation temperature, resulting in sufficient reflowability and good embedding properties for patterned substrates. From these perspectives, it is expected that the polymer will be applicable to a wide range of semiconductor devices.

[0191] The resist underlayer film material used in the multilayer lithography process of the present invention exhibits excellent etching resistance, has good planarization and embedding properties on microfabricated substrates, and can provide an excellent resist pattern. It also has solvent resistance even in the atmosphere, exhibits sufficient curing properties, and can function as an anti-reflective coating. Furthermore, the underlayer film material of the present invention has been found to have heat resistance sufficient to form a hard mask on top by vapor deposition.

Claims

1. A resist underlayer film-forming composition comprising a novolac resin and a solvent, wherein the novolac resin has a unit structure A having at least two amino groups, the unit structure A being a divalent group derived from a compound having a fused ring structure, and further having a monovalent organic group C1 or organic group C2 that caps at least one end of the novolac resin, and the organic group C1 is represented by the following formula (1): (In formula (1), * represents a bond by which the organic group C1 is bonded to at least one terminal of the novolak resin, and Ar ６ represents an aryl group having 6 to 40 carbon atoms; R ６１ represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can be bonded. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. R ６２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. ６４ , R ６５ each independently represents a hydrogen atom, a phenyl group which may be substituted with a hydroxy group, or a naphthyl group which may be substituted with a hydroxy group, R ６４ , R ６５ represents a phenyl group or a naphthyl group, R ６４ or R ６５ and an aryl group Ar ６ A new ring can be formed with m via a single bond or a methylene group. ４ represents 0 or 1, m ３ is m ４ When m is 0, it is an integer from 0 to (3+2n), and m ３ is m ４ When represents 1, it is an integer of 0 to (2+2n), and n is an aryl group Ar ６ indicates the degree of condensation of the benzene rings, and m ５ represents 0 or 1.) and the organic group C2 is represented by the following formula (2): In formula (2), * represents a bond that bonds the organic group C2 to at least one terminal of the novolak resin, and Ar ７ represents an aryl group having 6 to 40 carbon atoms; R ７１ represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can be bonded. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. R ７２ represents a hydrogen atom, a methyl group, or a phenyl group. ６ is an integer from 0 to (3+2n), and n is an aryl group Ar ７ (2) The resist underlayer film-forming composition according to claim 1, wherein the aromatic ring condensation degree is 1 or 2.

2. The unit structure A is a unit structure A1 or a unit structure A2, and the unit structure A1 is represented by the following formula (3): (In formula (3), * indicates a bond, and Ar ４ represents a benzene ring, Ar ３ and Ar ５ each independently represents a benzene ring or a fused ring formed of two or three benzene rings, R1 and R2 each represent a five-membered ring containing one nitrogen atom, and Ar ３ and R1, R1 and Ar ４ , Ar ４ and R2, R2 and Ar ５ are condensed to form Ar ３ , R1, Ar ４ , R2 and Ar ５ together form a fused polycyclic ring, R ４１ and R ４２ is Ar ４ The above substituents may be the same or different, and the substituents may be bonded to each other by a single bond or condensed. ３１ and R ５１ are Ar ３ Above and Ar ５ are the same or different substituents as above, and R ３１ , R ４１ , R ４２ or R ５１ each represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a hydroxyl group, a cyano group, a nitro group, an amino group, a carboxyl group, an acetyl group, a -Y-Z group, a halogen atom, or a monovalent group formed by combining these groups when they can bond. Y represents an amino group, an oxygen atom, a sulfur atom, a carbonyl group, or an ester group, and Z represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. However, when Y is an amino group, a hydrogen atom of the amino group may be substituted with Z. n3 and n6 represent R ３１ and R ５１ n4 and n5 each independently represent an integer of 0 to 4, and R ４１ and R ４２ and n4+n5 is an integer of 0 to 4. The resist underlayer film-forming composition according to claim 1, wherein the unit structure A2 includes a bis(azaaryl fused ring) structural unit represented by the following formula (4) or formula (4-2): In formula (4) and formula (4-2), * represents a bond, L represents a linking group that bonds to a carbon atom constituting a nitrogen-containing ring of an azaaryl fused ring and further bonds to another structure of the novolak resin, and -(CR ４ R ５ ) m １ -, -R ６ -, -(Ar)m ２ -, -CH ２ -(Ar)m ２ -CH ２ - and -(cyclo-R)-, R ４ and R ５ are the same or different and each independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10, R ６ represents a cycloalkylene group having 3 to 6 carbon atoms, Ar represents an arylene group having 6 to 30 carbon atoms which may be bonded to each other via a single bond, m ２ represents an integer of 1 to 3; cyclo-R represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring which may form a condensed ring with one or two benzene rings or naphthalene rings; Q represents a linking group bonding to a carbon atom constituting a nitrogen-containing ring of the condensed azaaryl ring; and is selected from the group consisting of —O—, —S—, and —SO ２ -, -CO-, -CONH-, -COO-, -NH-, -(CR ４ R ５ ) m １ -, -R ６ -, -(Ar)m ２ -, -CH ２ -(Ar)m ２ -CH ２ - and -(cyclo-R)-, R ４ and R ５ are the same or different and each independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an aryl group having 6 to 30 carbon atoms; m １ represents an integer of 1 to 10, R ６ represents a cycloalkylene group having 3 to 6 carbon atoms, Ar represents an arylene group having 6 to 30 carbon atoms which may be bonded to each other via a single bond, m ２ represents an integer of 1 to 3, cyclo-R represents a divalent alicyclic hydrocarbon group having a 5- to 8-membered ring which may form a condensed ring with one or two benzene rings or naphthalene rings, and R １１ and R ２１ are the same or different and each independently represent: (i) a hydrogen atom or a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms; R １２ and R ２２ are substituents on carbon atoms constituting the azaaryl fused ring, and are the same or different and each independently represent: (iv) a hydroxy group, a nitro group, a cyano group, a carboxyl group, a trifluoromethyl group, or a halogen atom; (v) an aryloxy group having 6 to 15 carbon atoms, an arylalkoxycarbonyl group having 8 to 15 carbon atoms, an aryloxycarbonyl group having 7 to 15 carbon atoms, or an aryl group having 6 to 30 carbon atoms; or (vi) an acyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an arylalkoxy group having 7 to 15 carbon atoms, an alkoxycarbonyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms; n1 and n2 are the same or different and each independently represent a substituent R １２ and R ２２ Ar represents the number of １ and Ar ２ are the same or different and each independently represent a benzene ring or a fused ring formed of 2 to 3 benzene rings.

3. The resist underlayer film forming composition according to claim 1, wherein the organic group C1 represented by formula (1) is a monovalent group derived from a hydroxy-containing aromatic methylol compound represented by the following formula (5): (In formula (5), Ar ６ , R ６１ , R ６２ , R ６４ , R ６５ , m ３ , m ４ and m ５ is the same as defined in formula (1), and R ６３ represents a hydrogen atom or a methyl group.) 4. The resist underlayer film forming composition according to claim 1, wherein the organic group C1 represented by formula (1) is a monovalent group derived from 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, or 2,6-di-tert-butyl-4-hydroxymethylphenol.

5. The resist underlayer film forming composition according to claim 1, wherein the organic group C2 represented by formula (2) is a monovalent group derived from an aromatic vinyl compound represented by the following formula (6): (In formula (6), Ar ７ , R ７１ , R ７２ and m ６ is the same as the definition in equation (2).

6. The resist underlayer film forming composition according to claim 1, wherein the organic group C2 represented by formula (2) is a monovalent group derived from styrene, 2-vinylnaphthalene, 4-tert-butylstyrene, or 4-tert-butoxystyrene.

7. The resist underlayer film forming composition according to claim 2, wherein the unit structure A1 represented by formula (3) is a divalent group derived from a compound having an indolocarbazole structure.

8. The resist underlayer film forming composition according to claim 7, wherein the aromatic group substituting the hydrogen atom on the fused ring of the compound having an indolocarbazole structure is a phenyl group.

9. The resist underlayer film forming composition according to claim 2, wherein all or part of the hydrogen atoms of the hydroxy groups, amino groups or alkylamino groups in the novolak resin are substituted with alkynyl groups having 2 to 10 carbon atoms.

10. The resist underlayer film forming composition according to claim 2, wherein the novolak resin further contains another unit structure, and the other unit structure is a divalent group derived from a monomer represented by any one of the following formulas (10-1) to (10-36) and / or a divalent group derived from a monomer represented by any one of the following formulas (10-37) to (10-69), and one end of the unit structure may be bonded to a bond of the organic group C1 or the organic group C2. (In formulas (10-1) to (10-36), * represents a bond, and H of OH may be replaced by a phenyl group or an alkynyl group having 2 to 10 carbon atoms.) (In formulas (10-37) to (10-69), * indicates a bond, and R ９２ represents a hydrogen atom, a phenyl group, or an alkynyl group having 2 to 10 carbon atoms.

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

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

13. The resist underlayer film forming composition according to claim 12, wherein the crosslinking agent is an aminoplast crosslinking agent or a phenoplast crosslinking agent.

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

15. The resist underlayer film forming composition according to claim 1, further comprising an acid and / or a salt thereof and / or an acid generator.

16. A resist underlayer film which is a baked product of a coating film made of the composition according to any one of claims 1 to 15.

17. A method for forming a resist pattern used in the manufacture of semiconductors, comprising the step of applying the resist underlayer film-forming composition according to any one of claims 1 to 15 onto a semiconductor substrate and baking the composition to form a resist underlayer film.

18. A method for manufacturing a semiconductor device, comprising: 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 15; a step of forming a resist film on the resist underlayer film; a step of 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.

19. The method for manufacturing a semiconductor device according to claim 18, wherein a resist pattern is formed on the resist film by irradiation with light or an electron beam and development.

20. The method for manufacturing a semiconductor device according to claim 18, wherein the patterning of the resist film is carried out by a nanoimprint method or a self-assembled film.

21. A method for manufacturing a semiconductor device, comprising: 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 15; a step of forming a hard mask on the resist underlayer film; a step of further forming a resist film on the hard mask; a step of forming a resist pattern 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.

22. The method for manufacturing a semiconductor device according to claim 21, 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.

23. 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.

24. The method for manufacturing a semiconductor device according to claim 21, wherein the patterning of the resist film is carried out by a nanoimprint method or a self-assembled film.

25. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 15; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film; etching the hard mask using the resist pattern; etching the resist underlayer film using the patterned hard mask; removing the hard mask; and processing a semiconductor substrate using the patterned resist underlayer film.

26. The method for manufacturing a semiconductor device according to claim 25, 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.

27. The method for manufacturing a semiconductor device according to claim 25, wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development.

28. The method for manufacturing a semiconductor device according to claim 25, wherein the patterning of the resist film is carried out by a nanoimprint method or a self-assembled film.

29. The method for manufacturing a semiconductor device according to claim 25, wherein the hard mask is removed by either etching or an alkaline chemical solution.

30. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 15; forming a hard mask on the resist underlayer film; further forming a resist film on the hard mask; forming a resist pattern on the resist film; etching the hard mask using the resist pattern; etching the resist underlayer film using the patterned hard mask; removing the hard mask; forming a vapor-deposited film (spacer) on the resist underlayer film after removing the hard mask; processing the vapor-deposited film (spacer) by etching; removing the patterned resist underlayer film to leave the patterned vapor-deposited film (spacer); and processing a semiconductor substrate using the patterned vapor-deposited film (spacer).

31. The method for manufacturing a semiconductor device according to claim 30, 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.

32. The method for manufacturing a semiconductor device according to claim 30, wherein a resist pattern is formed on the resist film by irradiation with light or electron beams and development.

33. The method for manufacturing a semiconductor device according to claim 30, wherein the patterning of the resist film is carried out by a nanoimprint method or a self-assembled film.

34. The method for manufacturing a semiconductor device according to claim 30, wherein the hard mask is removed by etching or an alkaline chemical solution.

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