Resist underlayer film forming composition

Abstract

Provided is a composition for forming a resist underlayer film that is insoluble in resist solvents, has good optical constants, and allows the etching rate to be adjusted suitably, wherein the composition has an excellent ability to fill and flatten stepped substrates. A composition for forming a resist underlayer film, the composition including: (A) a crosslinkable compound represented by formula (I) and (D) a solvent. [In the formula, n is an integer of 2-6, the n-number of Z each independently are monovalent organic groups including a mono-, di-, tri-, tetra-, penta-, or hexaformylaryl group, the n-number of A each independently represent -OCH2CH(OH)CH2O- or (BB), and T is an n-valent hydrocarbon group and / or repeating unit of a polymer optionally having at least one group selected from the group consisting of a hydroxy group, an epoxy group, an acyl group, an acetyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azide group, a thiol group, a sulfo group, and an allyl group and optionally interrupted by a carbonyl group and / or an oxygen atom.]

Description

[Technical field]

[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 producing a patterned substrate using the resist underlayer film-forming composition, and a method for producing a semiconductor device. [Background technology]

[0002] Conventionally, in the manufacture of semiconductor devices, microfabrication by lithography using a photoresist composition has been performed. The microfabrication is a processing method in which a thin film of a photoresist composition is formed on a substrate to be processed such as a silicon wafer, and the thin film is irradiated with active light such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developed, and the substrate to be processed such as a silicon wafer is etched using the obtained photoresist pattern as a protective film. In recent years, the integration density of semiconductor devices has increased, and the wavelength of the active light used has been shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). In addition, for the purpose of further microfabrication, lithography techniques using extreme ultraviolet light (EUV, 13.5 nm) or electron beam (EB) as active light have also been developed.

[0003] In the lithography process, when a resist layer on a substrate is exposed to an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser, a problem is known in which a resist pattern having a desired shape cannot be formed due to the influence of standing waves caused by the reflection of the ultraviolet laser on the substrate surface. To solve this problem, a resist underlayer film (anti-reflective film) is provided between the substrate and the resist layer.

[0004] In order to suppress mixing with the resist laminated on top of such a photoresist, the resist underlayer film formed between the photoresist and the substrate to be processed is generally formed as a thermosetting crosslinked film that does not mix with the resist by being applied to the substrate and then undergoing a baking process.

[0005] It is known that various resins are used as compositions for forming resist underlayer films. For example, Patent Document 1 and Patent Document 2 disclose photoresist underlayer film forming materials containing resins having repeating units obtained by novolakizing a compound having a bisphenol group. In addition, Patent Document 3 discloses a spin-coatable anti-reflective coating composition containing a polymer having three or more condensed aromatic rings in the main chain of the polymer.

[0006] However, when there are steps on the underlying substrate to be processed, or when densely patterned areas and areas without patterns exist on the same wafer, it is necessary to flatten the film surface with an underlayer film. A resin suitable for such a purpose has been proposed (Patent Document 4).

[0007] On the other hand, in order to form such a thermosetting film, a resist underlayer film-forming composition contains a crosslinking compound (crosslinking agent) and a catalyst (crosslinking catalyst) for promoting a crosslinking reaction in addition to a polymer resin as a main component. Regarding the problem of flattening the film surface by the underlayer film, the study of these components has not been sufficient. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2006-259249 A [Patent Document 2] JP 2007-316282 A [Patent Document 3] Special Publication No. 2010-528334 [Patent Document 4] WO 2014 / 024836 A1 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a composition for forming a resist underlayer film that is insoluble in a resist solvent, has good optical constants, and allows the etching rate to be appropriately adjusted, and that has excellent filling properties and planarization properties for substrates with irregularities. [Means for solving the problem]

[0010] The present invention encompasses the following: [1] (A) a crosslinkable compound represented by the following formula (I), and (D) Solvent A resist underlayer film forming composition comprising the compound. [ka] [In the formula, n is an integer of 2 to 6, n Z's each independently represent a monovalent organic group containing a mono-, di-, tri-, tetra-, penta-, or hexaformylaryl group; n A's each independently represent -OCH2CH(OH)CH2O-, or [ka] represents T may have at least one group selected from the group consisting of a hydroxy group, an epoxy group, an acyl group, an acetyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, and an allyl group, and is an n-valent hydrocarbon group which may be interrupted by a carbonyl group and / or an oxygen atom, and / or a repeating unit of a polymer. [2] The resist underlayer film forming composition according to [1], wherein the crosslinkable compound (A) further contains a self-crosslinking group. [3] The resist underlayer film forming composition according to [1], further comprising a film material (B) capable of crosslinking reaction with the crosslinkable compound (A). [4] The resist underlayer film forming composition according to [3], wherein the crosslinkable film material (B) includes at least one selected from the group consisting of a resin containing an aliphatic ring, a novolak resin, a polyether resin, a polyester resin, an acrylic resin, a methacrylic resin, and a compound different from the crosslinkable compound (A). [5] The novolak resin is represented by the following formula (1a), formula (1b), and formula (1c): [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring. 3 The group represented by and two R 4 may be different from each other, two k's each independently represent 0 or 1, m0 represents an integer of 3 to 500, n0, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent the following formula (2): [ka] (Wherein, two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are defined as in formula (1b), and two Q 1each independently represents a structural unit represented by the formula (2). The resist underlayer film forming composition according to [4], wherein the composition is represented by any one or two or more of the repeating structural units represented by the following formula: [6] A compound different from the crosslinkable compound (A) is [ka] (in formula (2), each of the two Ar represents an aryl group having at least one hydroxy group as a substituent, and Q represents a divalent linking group having at least one benzene ring or naphthalene ring, a methylene group, or a single bond), [7] The resist underlayer film forming composition according to any one of [1] to [6], further comprising an acid catalyst (C). [8] A resist underlayer film, which is a cured product of a coating film comprising the resist underlayer film forming composition according to any one of [1] to [7]. [9] A method for producing a patterned substrate, comprising the steps of: applying the resist underlayer film forming composition according to any one of [1] to [7] onto a semiconductor substrate and curing the composition to form a resist underlayer film; applying a resist onto the resist underlayer film and baking the resist to form a resist film; exposing the resist underlayer film and the semiconductor substrate coated with the resist to light; and developing and patterning the resist film after exposure.

[10] The method for producing a patterned substrate according to [9], wherein the curing is carried out by baking.

[11] The method for producing a patterned substrate according to [9], wherein after baking, the curing is carried out by irradiating with ultraviolet light.

[12] 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 [1] to [7], forming a resist film thereon, forming a resist pattern by irradiating with light or an electron beam and developing, etching the underlayer film using the resist pattern, and processing a semiconductor substrate with the patterned underlayer film. Effect of the Invention

[0011] The resist underlayer film forming composition according to the present invention has a higher curing end temperature than that of conventional products, so that the resin can be kept flowing for a long time. Therefore, when the resist underlayer film forming composition according to the present invention is applied to a fine pattern of a substrate, the fluidity of the composition is maintained for a certain period of time until three-dimensionalization by crosslinking progresses. As a result, the resist underlayer film forming composition according to the present invention can fill the fine pattern of the stepped substrate without gaps. The resist underlayer film formed by applying the resist underlayer film forming composition according to the present invention to the stepped substrate and baking it can further suppress the film thickness difference (Iso-dense bias) between the patterned portion (dense area (patterned portion)) and the patterned portion (open area (no pattern)) of the coating formed thereon. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] [Resist underlayer film forming composition] The resist underlayer film forming composition according to the present invention comprises (A) a crosslinkable compound represented by the following formula (I), and (D) Solvent Includes.

[0013] Optionally, the resist underlayer film forming composition according to the present invention comprises: (B) a membrane material capable of crosslinking with the crosslinkable compound (A), and / or (C) Acid catalyst It may further include.

[0014] Furthermore, the resist underlayer film forming composition according to the present invention may contain additives such as an acid generator and a surfactant, if necessary.

[0015] [(A) Crosslinkable compound] The crosslinkable compound (A) used in the present invention is represented by the following formula (I). [ka] [In the formula, n is an integer of 2 to 6, n Z's each independently represent a monovalent organic group containing a mono-, di-, tri-, tetra-, penta-, or hexaformylaryl group; n A's each independently represent -OCH2CH(OH)CH2O-, or [ka] represents T may have at least one group selected from the group consisting of a hydroxy group, an epoxy group, an acyl group, an acetyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, and an allyl group, and is an n-valent hydrocarbon group which may be interrupted by a carbonyl group and / or an oxygen atom, and / or a repeating unit of a polymer. Z may have an ester bond at the terminal of the bond to A.

[0016] The formyl group refers to a group represented by -CHO. The aryl group includes a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, pyrenyl group, etc., and is preferably a C6-C 18 Aryl groups, more preferably C6-C 14 Aryl groups, more preferably C6-C 10 An aryl group, most preferably a C6 aryl group.

[0017] Substituents include halogen atoms, hydroxy groups, nitro groups, amino groups, glycidyl groups, C1-C 10 Alkyl groups, C1-C10 Alkoxy groups, C4-C 40 Examples include an aryl group, a C1-C6 acyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylthio group, and a C1-C6 carboxyl group. The substitution positions of the formyl group and the above-mentioned substituents in the aryl group are not particularly limited.

[0018] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0019] C1-C 10Examples 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, a cyclopentyl ... n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 1-ethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3- Ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples of such cyclopropyl groups include 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

[0020] C1-C 10 Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 5-methyl-n-pentyloxy group, a 6-methyl-n-pentyloxy group, a 7-methyl-n-pentyloxy group, a 8-methyl-n-pentyloxy group, a 9-methyl-n-pentyloxy group, a 10-methyl-n-pentyloxy group, a 11-methyl-n-butoxy group, a 22-methyl-n-butoxy group, a 23-methyl-n-pentyloxy group, a 24-methyl-n-pentyloxy group, a 25-methyl-n-pentyloxy group, a 26-methyl-n-pentyloxy group, a 27-methyl-n-pentyloxy group, a 28-methyl-n-pentyloxy group, a 29-methyl-n-pentyloxy group, a 30-methyl-n-pentyloxy group, a 31-methyl-n-pentyloxy group, a 32-methyl-n-pentyloxy group, a 33-methyl-n-pentyloxy group, a 34-methyl-n-pentyloxy group, a 35-methyl-n-pentyloxy group, a 36 Examples of the alkoxy group include pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy. The alkoxy group is preferably a C1-C9 alkoxy group, more preferably a C1-C6 alkoxy group, and even more preferably a C1-C3 alkoxy group.

[0021] C4-C 40 Examples of the aryl group include a phenyl group, a naphthyl group, a tolyl group, a benzyl group, a trityl group, a styryl group, a furyl group, a thienyl group, and a pyridyl group.

[0022] The C1-C6 acyl group, the C1-C6 alkoxycarbonyl group, the C1-C6 alkylthio group, and the C1-C6 carboxyl group refer to groups represented by RCO-, ROCO-, RS-, and RCOO-, respectively, when the alkyl group is R.

[0023] A hydrocarbon group refers to a group formed by removing n hydrogen atoms from a hydrocarbon compound. The hydrocarbon compounds referred to in the present invention include aromatic hydrocarbon compounds which may be interrupted by aliphatic hydrocarbon groups, aliphatic hydrocarbon compounds which may be interrupted by aromatic rings, and the like, which may contain heteroatoms such as N, O, and S. The number of carbon atoms is preferably 12 or more, more preferably 16 or more, and is preferably 72 or less, more preferably 60 or less.

[0024] Examples of T when n is 2 include alkylene groups, arylene groups, alkylene groups interrupted by arylene groups (e.g., alkylene groups interrupted by phenylene or alkoxyphenylene groups), arylene groups interrupted by alkylene groups (e.g., allylphenylene groups interrupted by propylene groups), arylene groups substituted with alkyl groups (e.g., biphenylene groups substituted with methyl groups), arylene groups interrupted by oxygen atoms (e.g., naphthylene groups interrupted by oxygen atoms), arylene groups interrupted by alkylene groups and substituted with alkyl groups (e.g., tolylene groups and naphthylene groups interrupted by methylene groups), etc. When n is 2, T may be a repeating unit of the polymer represented by the above examples.

[0025] The crosslinkable compound (A) may contain a self-crosslinking group. The self-crosslinking group means that when the crosslinkable compound (A) is a polymerizable compound, even if it becomes a polymer, it contains a group (self-crosslinking group) that can crosslink with itself (without containing a crosslinking agent). Specific examples of the self-crosslinking group include a hydroxyl group and an aldehyde group.

[0026] Specific examples of the crosslinkable compound represented by formula (I) used in the present invention are as follows. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0027] The content of the crosslinkable compound (A) in the resist underlayer film forming composition according to the present invention is usually 0.01 mass% or more, preferably 0.1 mass% or more, and more preferably 1.0 mass% or more, based on the total solid content, and is usually 100 mass% or less, preferably 99 mass% or less, and more preferably 98 mass% or less.

[0028] The compound (A) represented by the above formula (I) in which n is 2 can be obtained by reacting a compound having two hydroxy groups represented by the following formula (101) with a glycidyl ether compound represented by the following formula (102). [ka] [ka] [In the formula, Z and T are as defined above.]

[0029] The crosslinkable compound (A) represented by the above formula (I) can be obtained by reacting a compound having two glycidyl ether groups represented by the following formula (103) with a hydroxy compound represented by the following formula (104). [ka] [ka] [In the formula, Z and T are as defined above.]

[0030] The compounds represented by the above formulae (102) and (103) can also be replaced with compounds represented by the following formulae (105) and (106), respectively. [ka] [ka] [In the formula, Z and T are as defined above.]

[0031] Either reaction may be carried out in a suitable solvent and in the presence of a suitable catalyst. Such a solvent is not particularly limited as long as it can uniformly dissolve the compound having a hydroxy group represented by the above formula (101) and the glycidyl ether compound represented by the formula (102), the compound having a glycidyl ether group represented by the formula (103) and the hydroxy compound represented by the formula (104), the compound represented by the formula (101) and the compound represented by the formula (105), or the compound represented by the formula (106) and the compound represented by the formula (104), and does not inhibit the reaction or induce a side reaction.

[0032] For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclohexanone, Examples of the solvent include butanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred.

[0033] Examples of the catalyst include quaternary ammonium salts such as tetrabutylammonium bromide, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, and phosphine compounds such as triphenylphosphine. Ethyltriphenylphosphonium bromide is preferred.

[0034] In order to prevent unreacted acid, catalyst, inactivated catalyst, etc. from remaining in the reaction system, a cation exchange resin or anion exchange resin for catalysts can be used.

[0035] [(B) Membrane material capable of crosslinking with crosslinkable compound (A)] The membrane material optionally used in the present invention can be used without any particular limitation as long as it is a material capable of undergoing a crosslinking reaction with the crosslinkable compound (A). The membrane material may be a polymer, an oligomer, or a low molecular weight compound having a molecular weight of 1,000 or less. Examples of crosslinking groups present in the membrane material include, but are not limited to, hydroxyl groups, carboxyl groups, amino groups, and alkoxy groups.

[0036] (a) Examples of the film material capable of undergoing a crosslinking reaction include alicyclic epoxy polymers having a repeating structural unit represented by the following formula (1), as disclosed in WO 2011 / 021555 A1. [ka] (T represents a repeating unit structure having an aliphatic ring in the main chain of the polymer, and E represents an epoxy group or an organic group having an epoxy group.)

[0037] E is a substituent on the aliphatic ring, and may be either an epoxy group directly bonded to the aliphatic group, or an organic group having an epoxy group (for example, a glycidyl group) bonded to the aliphatic group. The aliphatic ring is, for example, one in which 4 to 10 carbon atoms are linked in a ring, and particularly one in which 6 carbon atoms are linked in a ring. The aliphatic ring may have other substituents in addition to the substituent E (epoxy group or organic group having an epoxy group). Such substituents include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, and an amino group. The alicyclic epoxy polymer represented by the above formula (1) has a weight average molecular weight of 600 to 1,000,000, and preferably 1,000 to 200,000. The number of repeating units of the alicyclic epoxy polymer (A) represented by the above formula (1) is 2 to 3,000, or 3 to 600.

[0038] For example, the following polymers are exemplified. [ka]

[0039] (b) Examples of the membrane material capable of a crosslinking reaction include those represented by the following formulae (1a), (1b) and (1c): [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring. 3 The group represented by and two R4 may be different from each other, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, n, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent the following formula (2): [ka] (Wherein, two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are defined as in formula (1b), and two Q 1 each independently represents a structural unit represented by the formula (2). Examples of the repeating structural units include polymers having one or more of the repeating structural units represented by the following formula:

[0040] Preferably, the R 3 The aromatic hydrocarbon group represented by is a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.

[0041] (c) Examples of the membrane material capable of crosslinking include those having the following formula (1): [ka] (In formula (1), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted by a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; and R4 and R5 may form a ring together with the carbon atom to which they are attached; and n1 and n2 each represent an integer of 1 to 3.

[0042] Preferably, in the formula (1), R1, R2, R3, and R5 each represent a hydrogen atom, and R4 is a polymer containing a unit structure representing a phenyl group or a naphthyl group. Preferably, in the formula (1), R1, R2, and R3 each represent a hydrogen atom, and R4 and R5 together with the carbon atom to which they are attached form a fluorene ring, wherein the carbon atom is the 9-position carbon atom of the fluorene ring formed, and the polymer includes a unit structure.

[0043] Preferably, the compound represented by the following formula (2) and / or formula (3): [ka] (In formula (2) and formula (3), R1, R2, R6, R7, and R8 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted by a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; and R4 and R5 may form a ring together with the carbon atom to which they are attached; n1 and n2 are each an integer from 1 to 3; and n3 to n5 are each an integer of 1 to 4.

[0044] Preferably, in the formula (2) and / or formula (3), R1, R2, R3, R5, R6, R7, and R8 each represent a hydrogen atom, and R4 is a polymer containing a unit structure representing a phenyl group or a naphthyl group.

[0045] (d) Examples of the membrane material capable of a crosslinking reaction include polymers containing a unit structure formed from a reaction product of a fused heterocyclic compound and a bicyclic compound, as disclosed in WO 2013 / 005797 A1.

[0046] The fused heterocyclic compound is preferably a carbazole compound or a substituted carbazole compound. Preferably, the bicyclo ring compound is dicyclopentadiene, substituted dicyclopentadiene, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3,8-diene, or substituted tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3,8-diene.

[0047] The above polymer is preferably a polymer containing a unit structure represented by the following formula (1), a unit structure represented by the following formula (2), a unit structure represented by the following formula (3), or a combination thereof. [ka] (In the formula, R 1 ~R 14 are substituents of a hydrogen atom, each independently being a halogen group, a nitro group, an amino group, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms which may be substituted by such a group; Ar is an aromatic ring group having 6 to 40 carbon atoms; 10 , n 13 , n 14 and n 15 are integers from 0 to 3, and n3, n4, n7, n8, n 11 and n 12 are each an integer from 0 to 4.) Preferably, in the above formula (3), Ar is a phenyl group or a naphthyl group.

[0048] (e) Examples of the crosslinkable membrane material include those having the formula (1): [ka] (In formula (1), A is a hydroxy-substituted phenylene group derived from polyhydroxybenzene, and B is a monovalent fused aromatic hydrocarbon ring group in which 2 to 4 benzene rings are fused.)

[0049] Preferably, A is a hydroxy-substituted phenylene group derived from a benzenediol or benzenetriol. Preferably, A is a hydroxy-substituted phenylene group derived from catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, or phloroglucinol. Preferably, the fused aromatic hydrocarbon ring group of B is a naphthalene ring group, an anthracene ring group, or a pyrene ring group. Preferably, the fused aromatic hydrocarbon ring group of B has a halogen group, a hydroxyl group, a nitro group, an amino group, a carboxyl group, a carboxylate group, a nitrile group, or a combination thereof as a substituent.

[0050] (f) Examples of the membrane material capable of crosslinking include those having the following formula (1): [ka] (In formula (1), Ar 1 , and Ar 2 represents a benzene ring or a naphthalene ring, and R 1 and R 2 are each a substituent for a hydrogen atom on these rings and are selected from the group consisting of a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, and the aryl group each represent an organic group which may contain an ether bond, a ketone bond, or an ester bond; R 3is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, and the aryl group represent an organic group which may contain an ether bond, a ketone bond, or an ester bond; R 4 is selected from the group consisting of an aryl group and a heterocyclic group having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group; R 5 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R 4 and R 5 may form a ring together with the carbon atom to which they are attached. n1 and n2 are each an integer of 0 to 3.

[0051] Preferably, R in the above formula (1) 5 is a hydrogen atom, and R 4 is an optionally substituted phenyl group, naphthyl group, anthryl group, or pyrenyl group. Preferably, R in the above formula (1) 3 is a hydrogen atom or a phenyl group. Preferably, in the unit structure (A), Ar 1 and Ar 2 contains a unit structure (a1) one of which is a benzene ring and the other is a naphthalene ring. Preferably, in the unit structure (A), Ar 1 and Ar 2 Both of these contain a unit structure (a2) which is a benzene ring. A copolymer containing the unit structure (a1) and the unit structure (a2) is preferred.

[0052] Preferably, the unit structure (A) of formula (1) and the unit structure (B) of the following formula (2): [ka] (In formula (2), R 6 is selected from the group consisting of aryl groups and heterocyclic groups having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group; R 7 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R 6 and R 7 may form a ring together with the carbon atom to which they are attached. A copolymer containing the unit structure (a1) and the unit structure (B) is preferred.

[0053] (g) Examples of the membrane material capable of crosslinking include those having the following formula (1): [ka] (In formula (1), R 1 , R 2 , and R 3 are substituents of hydrogen atoms in the ring, each independently being a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond.4 R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond. 5 is a hydrogen atom, or a halogen atom, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms which may be substituted with a hydroxyl group, or a heterocyclic group; R 6 is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, or a hydroxyl group, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, or R 5 and R 6 may form a ring together with the carbon atom to which they are attached. Ring A and ring B each represent a benzene ring, a naphthalene ring, or an anthracene ring. n1, n2, and n3 each represent an integer of 0 or more up to the maximum number that can be substituted on the ring.

[0054] Preferably, ring A and ring B are both benzene rings, n1, n2, and n3 are 0, and R 4 is a hydrogen atom. Preferably, R 5 is a hydrogen atom, or a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, a phenyl group which may be substituted with a hydroxyl group, a naphthyl group, an anthryl group, or a pyrenyl group; R 6 is a hydrogen atom.

[0055] (h) Examples of the membrane material capable of crosslinking include those represented by the following formulae (1a), (1b) and (1c): [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring. 3 The group represented by and two R 4 may be different from each other, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, n, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent the following formula (2): [ka] (Wherein, two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are defined as in formula (1b), and two Q 1 each independently represents a structural unit represented by the formula (2). It represents a structural unit represented by the formula: Examples of the repeating structural units include polymers having one or more of the repeating structural units represented by the following formula:

[0056] Preferably, the R 3 The aromatic hydrocarbon group represented by is a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.

[0057] (i) Examples of the membrane material capable of crosslinking include those having the following formula (1): [ka] (In formula (1), R 1 ~R 4 Each independently represents a hydrogen atom or a methyl group. 1 represents a divalent organic group containing at least one arylene group which may be substituted with an alkyl group, an amino group, or a hydroxyl group.

[0058] Preferably, in formula (1), X 1 The arylene group in the definition is a phenylene group, a biphenylene group, a terphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a pyrenylene group, or a carbazolylene group.

[0059] Preferably, in formula (1), X 1 is expressed as equation (2): [ka] [In formula (2), A 1 represents a phenylene group or a naphthylene group. 2 is a phenylene group, a naphthylene group, or a group of formula (3): [ka] (In formula (3), A 3 and A 4 each independently represents a phenylene group or a naphthylene group. The dotted line represents a bond. ) represents an organic group. The dotted line represents a bond. ] is an organic group represented by the formula:

[0060] (j) Examples of the film material capable of a crosslinking reaction include novolak resins obtained by reacting an aromatic compound (A) with an aldehyde (B) having a formyl group bonded to a secondary or tertiary carbon atom of an alkyl group having 2 to 26 carbon atoms, as disclosed in WO 2017 / 069063 A1.

[0061] Preferably, the novolac resin has the following formula (1): [ka] (In formula (1), A represents a divalent group derived from an aromatic compound having 6 to 40 carbon atoms, and b 1 represents an alkyl group having 1 to 16 carbon atoms; 2 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0062] Preferably, A is a divalent radical derived from an aromatic compound containing an amino group, a hydroxyl group, or both. Preferably, A is a divalent group derived from an aromatic compound, including an arylamine compound, a phenolic compound, or both. Preferably, A is a divalent group derived from aniline, diphenylamine, phenylnaphthylamine, hydroxydiphenylamine, carbazole, phenol, N,N'-diphenylethylenediamine, N,N'-diphenyl-1,4-phenylenediamine, or a polynuclear phenol. Preferably, the polynuclear phenol is dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 2,2'-biphenol, or 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane.

[0063] Preferably, the novolac resin is represented by the following formula (2): [ka] (In formula (2), a 1 and a 2 represents an optionally substituted benzene ring or naphthalene ring, R 1 represents a secondary amino group or a tertiary amino group, a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, an arylene group, or a divalent group to which any of these groups are optionally bonded. 3 represents an alkyl group having 1 to 16 carbon atoms; 4 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0064] (k) Examples of the crosslinkable membrane material include those represented by the following formula (1a) and / or formula (1b): [ka] [In formula (1a) and (1b), two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group or a heterocyclic group which may have a substituent; R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 each represents a phenyl group, they may be bonded to each other to form a fluorene ring, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, p represents an integer of 3 to 500, X represents a benzene ring, and the two -C(CH3)2- groups bonded to the benzene ring are in a meta or para position relationship. Examples of the polymer include a polymer having a repeating structural unit represented by the following formula:

[0065] Preferably, the polymer is the polymerization reaction product of at least one bisphenol compound and at least one aromatic aldehyde or aromatic ketone. Preferably, the R 3 The aromatic hydrocarbon group represented by is a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.

[0066] (l) Examples of cross-linkable membrane materials include poly(epoxide) resins having an epoxy functionality of greater than 2.0 and less than 10, such as those disclosed in JP-A-11-511194.

[0067] Preferably, the poly(epoxide) resin is selected from the group consisting of bisphenol A-epichlorohydrin resin products, epoxy novolacs, o-cresol epoxy novolacs, polyglycidyl ethers, polyglycidyl amines, cycloaliphatic epoxides, and polyglycidyl esters. Preferably, the poly(epoxide) resin has an epoxy functionality greater than 3.5.

[0068] (m) Examples of the crosslinkable film material or novolac film material include compounds represented by the following formula (1) and novolac film materials as disclosed in WO 2018 / 198960 A1. [ka] [In formula (1), [ka] represents a single bond or a double bond, X 1 is -N(R 1 )- or -CH(R 1 )-, X 2 is -N(R 2 )- or -CH(R 2 )-, X 3 -N=, -CH=, -N(R 3)- or -CH(R 3 )-, X 4 -N=, -CH=, -N(R 4 )- or -CH(R 4 )-, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, wherein the alkyl group and the aryl group may be substituted by a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group or a hydroxy group and may be interrupted by an oxygen atom or a sulfur atom, R 5 , R 6 , R 9 and R 10 are the same or different and each represents a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1.

[0069] Preferably, R in formula (1) 1 , R 2 , R 3 or R 4is a hydroxy group or a C1 to C20 linear, branched or cyclic alkyl group which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom or a sulfur atom.

[0070] Preferably, the compound contains one or more units of one or more of repeating units a, b, c, d, e, f, g, h, and i represented by the following formula (2). [ka] [ka] Formula (2) [In formula (2), [ka] represents a single bond or a double bond, X 1 is -N(R 1 )-, -CH(R 1 )-, -N< or -CH<; X 2 is -N(R 2 )-, -CH(R 2 )-, -N< or -CH<; X 3 -N=, -CH=, -N(R 3 )-, -CH(R 3 )-, -N< or -CH<; X 4 -N=, -CH=, -N(R 4 )-, -CH(R 4 )-, -N< or -CH<; R 1 , R 2 , R 3 and R 4are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, wherein the alkyl group and the aryl group may be substituted by a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group or a hydroxy group and may be interrupted by an oxygen atom or a sulfur atom, R 5 , R 6 , R 9 and R 10 are the same or different and each represents a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1; B 1 and B 2 are the same or different and each represents a group derived from an aromatic compound selected from the group consisting of a C1-20 linear, branched or cyclic alkyl group optionally interrupted by a hydrogen atom, an oxygen atom or a sulfur atom, a C6-40 aryl group and a C6-40 heterocyclic group; B 1 and B 2 may form a ring together with the carbon atom to which they are bonded, and a hydrogen atom of the group derived from the aromatic compound may be substituted with a C1-20 alkyl group, a phenyl group, a condensed ring group, a heterocyclic group, a hydroxy group, an amino group, an ether group, an alkoxy group, a cyano group, a nitro group, or a carboxyl group.]

[0071] Preferably, the compound contains one or more units of one or more of repeating units j, k, l, m, r, s, t, u, v, and w represented by the following formula (3). [ka] [ka] Formula (3) [In formula (3), [ka] represents a single bond or a double bond, X 1 represents -N< or -CH<; X 2 represents -N< or -CH<; X 3 -N=, -CH=, -N(R 3 )- or -CH(R 3 )-, X 4 -N=, -CH=, -N(R 4 )- or -CH(R 4 )-, R 3 and R 4 are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, wherein the alkyl group and the aryl group may be substituted by a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group or a hydroxy group and may be interrupted by an oxygen atom or a sulfur atom, R 5 , R 6 , R 9 and R 10are the same or different and each represents a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1; p and q are integers from 0 to 20, When the p methylene groups and the q methylene groups are two or more, they may be interrupted by an oxygen atom or a sulfur atom. B 3 represents a direct bond, or a group derived from a C6-40 aromatic compound which may be substituted with a C1-20 alkyl group, a phenyl group, a fused ring group, a heterocyclic group, a hydroxy group, an amino group, an ether group, an alkoxy group, a cyano group, a nitro group, or a carboxyl group.]

[0072] Preferably, R in formula (1) 1 , R 2 , R 3 or R 4 is a hydroxy group or a C1 to C20 linear, branched or cyclic alkyl group which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom or a sulfur atom.

[0073] (n) Examples of crosslinkable membrane materials include epoxy adducts formed by reacting an epoxy group-containing compound having at least two epoxy groups with an epoxy adduct-forming compound having one epoxy addition reactive group, as disclosed in WO 2017 / 002653 A1. Such epoxy adducts can be exemplified by the following:

[0074] [ka] [ka]

[0075] [ka]

[0076] [ka]

[0077] (In the formula, a, b, c, and d are each 0 or 1, and a+b+c+d=1.)

[0078] (o) Examples of the crosslinkable membrane material include those of the formula (1):

[0079] [ka] (In the formula, A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, and X1 represents a compound represented by formula (2), formula (3), formula (4), or formula (5):

[0080] [ka] (wherein R1 and R2 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms, and R1 and R2 may be bonded to each other to form a ring having 3 to 6 carbon atoms; R3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms), and Q represents formula (6) or formula (7): [ka] (wherein Q1 represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the phenylene group, naphthylene group, and anthrylene group are each optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; n1 and n2 each represent the number 0 or 1; and X2 represents formula (2), formula (3), or formula (5)).

[0081] Preferably, the structure represented by formula (1) is represented by formula (12): [ka] (In the formula, R1, R2, and Q have the same meanings as defined above.) Or, equation (13): [ka] (wherein, X1 is as defined above, Y is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, or an alkylthio group having 1 to 6 carbon atoms, m is an integer of 0 to 4, and when m is 2 to 4, the Ys may be the same or different.) This is the structure represented by the following formula:

[0082] (p) Examples of the crosslinkable membrane material include those represented by formula (1) or (2): [ka] In the formula, R1 and R2 each represent a hydrogen atom, a methyl group, an ethyl group, or a halogen atom; A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group; Q represents a compound represented by formula (3) or formula (4): [ka] [In the formula, Q1 represents an alkylene group having 1 to 15 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the phenylene group, naphthylene group, and an anthrylene group are each optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; n1 and n2 each represent the number 0 or 1; X1 represents a group represented by formula (5), (6), or formula (7): [ka] (wherein R3 and R4 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms, and R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R5 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms).) represents.} represents.

[0083] Preferably, the polymer has the formula (12): [ka] (wherein Q has the same meaning as defined above).

[0084] Preferably, the polymer has formula (13) and formula (14): [ka] [Wherein, Q2 is represented by formula (15), formula (16) or formula (17): [ka] (In the formula, Y, m, R3, R4 and R5 are as defined above), and Q3 represents the formula (18): [ka] (In the formula, Q4 represents an alkylene group having 1 to 15 carbon atoms, and n3 and n4 each represent the number 0 or 1.) is a polymer having a repeating unit structure represented by the following formula.

[0085] (q) Examples of the membrane material capable of a crosslinking reaction include those represented by the following formulae (1), (2), and (3): [ka] (In the above formula, X represents a hydrogen atom or an aromatic fused ring; Y represents an aromatic fused ring, and X and Y may be bonded to each other to form a fused ring; R1, R2, R3, R4, R5, R 10 , R 11 and R 12 each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, R6, R7, and R8 each represent a hydrogen atom or a linear or cyclic alkyl group having 1 to 10 carbon atoms; R9 represents a linear or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms; R7 and R8 may be bonded to each other to form a ring; M and Q each represent a direct bond or a linking group; and n represents an integer of 0 or 1.) or a combination of such polymers, in which, when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) are 0.3≦a≦0.95, 0.005≦b≦0.7, and 0≦c≦0.45, respectively.

[0086] Preferably, the polymer contains unit structures represented by formula (1) and formula (2), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1) and the ratio of the number (b) of unit structures represented by formula (2) satisfy 0.305≦a+b≦1, 0.3≦a≦0.95, and 0.005≦b≦0.7. Preferably, the polymer contains unit structures represented by formula (1) and formula (3), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1) and the ratio of the number (c) of unit structures represented by formula (3) satisfy 0.35≦a+c≦1, 0.3≦a≦0.95, and 0.05≦c≦0.7. Preferably, the polymer contains unit structures represented by formula (1), formula (2), and formula (3), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) are 0.355≦a+b+c≦1, 0.3≦a≦0.9, 0.005≦b≦0.65, and 0.05≦c≦0.65. Preferably, the unit structure represented by formula (1) is a unit structure consisting of vinylnaphthalene, acenaphthylene, vinylanthracene, vinylcarbazole, or a derivative thereof. be.

[0087] (r) Examples of the membrane material capable of crosslinking reaction include those having the following formula (2): [ka] (In the formula (2), each of the two Ar's represents an aryl group, the aryl group has at least one hydroxyl group as a substituent, and Q represents a divalent linking group having at least one benzene ring or naphthalene ring, a methylene group, or a single bond.) The molecular weight of the compound is, for example, 150 to 600.

[0088] In formula (2), examples of the aryl group represented by Ar include phenyl, biphenylyl, naphthyl, anthryl, and phenanthryl. In addition, when Q represents a divalent linking group having at least one benzene ring or naphthalene ring, examples of the divalent linking group include a divalent group in which at least one of the two hydrogen atoms of a methylene group is replaced with a phenyl group, a biphenylyl group, or a naphthyl group, a divalent aromatic group selected from the group consisting of a phenylene group, a biphenylylene group, and a naphthylene group, and a divalent group having the divalent aromatic group and a methylene group, an ether group (-O- group), or a sulfide group (-S- group). Examples of the monomer include compounds represented by the following formulas (2-1) to (2-6). [ka] (In formula (2-6), m represents an integer of 0 to 3.)

[0089] (s) Examples of the film material capable of a crosslinking reaction include a film material having a structure in which one fullerene molecule is reacted with a compound represented by the following formula (1): [ka] (In the formula, each R independently represents an alkyl group having 1 to 10 carbon atoms.) Examples of the fullerene derivative include a fullerene derivative having one to six molecules of a malonic acid diester represented by the following formula:

[0090] (t) Examples of the membrane material capable of a crosslinking reaction include polyfunctional (meth)acrylate compounds having a molecular weight of 300 to 10,000, which are in a liquid state at room temperature and atmospheric pressure, as disclosed in WO 2011 / 132640 A1.

[0091] Preferably, the compound has 2 to 20 (meth)acrylate groups in the molecule. Preferably, the compound has a molecular weight of 300 to 2,300.

[0092] Such compounds can be exemplified below.

[0093] [ka]

[0094] [ka]

[0095] (u) Examples of the membrane material capable of a crosslinking reaction include compound (E) containing partial structure (I) and partial structure (II) as disclosed in WO 2017 / 154921 A1, in which the partial structure (II) contains a hydroxy group generated by a reaction between an epoxy group and a proton-generating compound, the partial structure (I) is at least one partial structure selected from the group consisting of partial structures represented by the following formulas (1-1) to (1-5), or a partial structure consisting of a combination of a partial structure represented by formula (1-6) and a partial structure represented by formula (1-7) or formula (1-8), and the partial structure (II) is a partial structure represented by the following formula (2-1) or formula (2-2). [ka] (In the formula, R 1 , R 1a , R 3 , R 5 , R 5a , and R 6a each represents a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group consisting of a combination thereof; R 2 , R 2a , R 4 , and R 6each represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R 2 , R 2a , R 4 , R 6 represents a monovalent group, R 1 , R 1a , R 3 , R 5a , and R 6a represents a divalent group, R 5 represents a trivalent group, R 7 , R 8 , R 9 , R 10 and R 11 each represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, n represents the number of repeating units from 1 to 10, and the dotted lines represent chemical bonds with adjacent atoms.

[0096] Preferably, compound (E) contains an epoxy group and a hydroxy group in a molar ratio of 0≦(epoxy group) / (hydroxy group)≦0.5, and contains partial structure (II) in a molar ratio of 0.01≦(partial structure (II)) / (partial structure (I)+partial structure (II))≦0.8. Preferably, compound (E) is a compound containing at least one partial structure (I) and at least one partial structure (II). Preferably, the above R 5a , and R 6a each represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, or a divalent group consisting of a combination thereof. Preferably, compound (E) contains 1 to 1000 of each of partial structures (I) and (II).

[0097] (v) Examples of the crosslinkable membrane material include compounds containing at least one photodegradable nitrogen-containing structure and / or photodegradable sulfur-containing structure and a hydrocarbon structure, as disclosed in WO 2018 / 030198 A1.

[0098] Preferably, the compound is a compound having at least one photodegradable nitrogen-containing structure and / or at least one photodegradable sulfur-containing structure in the molecule. Preferably, the above compound is a compound in which a photodegradable nitrogen-containing structure and / or a photodegradable sulfur-containing structure and a hydrocarbon structure are present in the same molecule, or a combination of compounds in which such structures are present in different molecules. Preferably, the hydrocarbon structure is a saturated or unsaturated group having 1 to 40 carbon atoms, and is a linear, branched or cyclic hydrocarbon group. Preferably, the photodecomposable nitrogen-containing structure is a structure that generates a reactive nitrogen-containing functional group or a reactive carbon functional group upon irradiation with ultraviolet light, or a structure that contains a reactive nitrogen-containing functional group or a reactive carbon-containing functional group generated by irradiation with ultraviolet light. Preferably, the photodecomposable nitrogen-containing structure is a photodecomposable nitrogen-containing structure which may contain a sulfur atom, and the structure is an azide structure, a tetraazole structure, a triazole structure, an imidazole structure, a pyrazole structure, an azole structure, a diazo structure, or a structure containing a combination thereof. Preferably, the photodecomposable sulfur-containing structure is a structure which generates an organic sulfur radical or a carbon radical upon irradiation with ultraviolet light, or a structure which contains an organic sulfur radical or a carbon radical generated upon irradiation with ultraviolet light. Preferably, the photodecomposable sulfur-containing structure is a photodecomposable sulfur-containing structure which may contain a nitrogen atom, and the structure is a trisulfide structure, a disulfide structure, a sulfide structure, a thioketone structure, a thiophene structure, a thiol structure, or a structure containing a combination thereof.

[0099] Preferred are the following compounds: [ka] [ka]

[0100] (w) Examples of the membrane material capable of undergoing a crosslinking reaction include compounds represented by the following formula (1), as disclosed in WO 2019 / 013293 A1. [ka] (In formula (1), R 1 are each independently a divalent group having 1 to 30 carbon atoms, R 2 ~R 7 each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group or a hydroxyl group; R 5 At least one of m is a hydroxyl group or a thiol group; 2 , m 3 and m 6 are each independently an integer of 0 to 9, 4 and m 7 are each independently an integer of 0 to 8, 5 is an integer from 1 to 9, n is an integer from 0 to 4, and p 2 ~p 7 are each independently an integer of 0 to 2.

[0101] Preferred are the following compounds: [ka]

[0102] (x) Examples of the membrane material capable of a crosslinking reaction include compounds represented by the following general formula (1), as disclosed in JP-A-2016-216367. [ka] (In the formula, n1 and n2 each independently represent 0 or 1, W is a single bond or any of the structures represented by the following formula (2), R1 is any of the structures represented by the following general formula (3), and m1 and m2 each independently represent an integer of 0 to 7, with the proviso that m1+m2 is 1 or more and 14 or less.) [ka] (In the formula, l represents an integer of 0 to 3, and R a ~R f each independently represents a hydrogen atom, an optionally fluorinated alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R a and R b may be bonded to form a cyclic compound.) [ka] (In the formula, * represents a bonding site to an aromatic ring, and Q1 represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, anthracenyl group, or pyrenyl group. When Q1 represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, a methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group.)

[0103] Preferably, the compound represented by the general formula (1) is a compound represented by the following general formula (4). [ka] (In the formula, m3 and m4 represent 1 or 2, and W and R1 are the same as defined above.)

[0104] Preferably, the W is either a single bond or a structure represented by the following formula (5). [ka] (In the formula, l is the same as above.)

[0105] Preferably, the compound represented by the general formula (1) has two or more Q1 in the molecule, and the Q1 includes one or more types of structures represented by the following general formula (6) and one or more types of structures represented by the following general formula (7). [ka] (wherein ** represents the bond site to the carbonyl group, R h represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms; R h The methylene group constituting the formula may be substituted with an oxygen atom or a carbonyl group. [ka] (wherein ** represents the bond site to the carbonyl group, R i represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms; R j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7. However, n3+n4 is 0 or more and 7 or less. n5 represents 0 to 2.

[0106] (y) Examples of the membrane material capable of crosslinking reaction include compounds represented by the following general formula (1A), as disclosed in JP 2017-119670 A. [ka] (In the formula, R is a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO2- group, R1 is a group represented by the following general formula (1B), and m1 and m2 are integers satisfying 1≦m1≦5, 1≦m2≦5, and 2≦m1+m2≦8.) [ka] (In the formula, X 1 is a group represented by the following general formula (1C), and X is a group represented by the following general formula (1D). [ka] (In the formula, (X) represents the bonding site with X.) [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (1E), and n5 is 0, 1, or 2. [ka] (In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group.

[0107] Preferably, the molecular weight of the compound is 2,500 or less.

[0108] Preferred are the compounds represented by the following general formula (2A) and the compounds represented by the following general formula (3A). [ka] (In the formula, R is a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO2- group, R2 is a group represented by the following general formula (2B), and m3 and m4 are integers satisfying 1≦m3≦5, 1≦m4≦5, and 2≦m3+m4≦8.) [ka] (In the formula, X 11 is a group represented by the following general formula (2C), and X' is a group represented by the following general formula (2D). [ka] (In the formula, (X') represents the bonding site with the X'.) [ka] (In the formula, n3 is 0 or 1, n4 is 1 or 2, and X 4 is a group represented by the following general formula (2E), and n6 is 0, 1, or 2. [ka] (In the formula, R 11 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. [ka] (In the formula, R 101 , R 102 , R 103 , R 104 are each independently a hydroxyl group, m100 is 1, 2, or 3, R 100 represents a hydrogen atom or a hydroxyl group when m100 is 1, a single bond or a group represented by the following general formula (3B) when m100 is 2, and a group represented by the following general formula (3C) when m100 is 3, in which the hydrogen atom on the aromatic ring may be substituted with a methyl group or a methoxy group. m101 is 0 or 1, m102 is 1 or 2, m103 is 0 or 1, m104 is 1 or 2, and m105 is 0 or 1. When m101 is 0, n101 and n102 are integers that satisfy 0≦n101≦3, 0≦n102≦3, and 1≦n101+n102≦4, and when m101 is 1, n101, n102, n103, and n104 are integers that satisfy 0≦n101≦2, 0≦n102≦2, 0≦n103≦2, 0≦n104≦2, and 2≦n101+n102+n103+n104≦8. [ka] (In the formula, * indicates a bond position, and R 106 , R 107is a hydrogen atom or an organic group having 1 to 24 carbon atoms and not containing an ester bond, and R 106 and R 107 may be bonded to form a cyclic structure. [ka] (In the formula, * indicates a bond position, and R 108 is a hydrogen atom or an organic group having 1 to 15 carbon atoms.

[0109] (z) Examples of polyether membrane materials include polymers represented by the following general formula (1), as disclosed in WO2012 / 050064: The following formula (1): [ka] (wherein Ar1 represents an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms), [ka] (In formula (2), Ar2, Ar3, and Ar4 each represent an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms, and T represents a carbonyl group or a sulfonyl group), or a polymer containing a unit structure represented by formula (1) and a unit structure represented by formula (2).

[0110] The crosslinkable membrane material (B) is preferably (B1) a membrane material containing an aliphatic ring (e.g., (a)(m) above); (B2) Novolak film materials (e.g., (b)(c)(d)(e)(f)(g)(h)(i)(j)(k)(l) above), (B3) polyether membrane materials (e.g. (z) above); (B4) polyester film materials (e.g. (o) and (p) above); (B5) a compound different from the crosslinkable compound (A) (e.g., the above (m), (n), (r), (s), (t), (u), (v), (w), (x), and (y)), (B6) Membrane materials containing aromatic fused rings (e.g., (q) above), (B7) Acrylic resin, and (B8) Methacrylic resin The compound includes at least one selected from the group consisting of:

[0111] When the resist underlayer film forming composition of the present invention contains a crosslinkable film material (B) (film material or polymer), the content of the crosslinkable film material (B) is usually 1 to 99.9 mass%, preferably 50 to 99.9 mass%, more preferably 50 to 95 mass%, and even more preferably 50 to 90 mass%, based on the total solid content.

[0112] [(C) Acid catalyst] The acid catalyst optionally contained in the resist underlayer film forming composition according to the present invention is not particularly limited as long as it is a catalyst capable of promoting the reaction between the above-mentioned crosslinking compound (A) and the film material (B) capable of crosslinking reaction.

[0113] Examples of the acid catalyst include pyridinium p-toluenesulfonate, pyridinium p-hydroxybenzenesulfonate, pyridinium trifluoromethanesulfonate, p-toluenesulfonic acid, p-hydroxybenzenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, chlorobenzenesulfonic acid, 4-methylphenolsulfonate, benzenesulfonic acid, naphthalenesulfonic acid, citric acid, benzoic acid, and other sulfonic acid compounds and carboxylic acid compounds, as well as K-PURE (registered trademark) TAG2689, TAG2690, TAG2678, and CXC-1614 (all manufactured by King Industries), which are quaternary ammonium salts of trifluoromethanesulfonic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other thermal acid generators such as organic sulfonic acid alkyl esters. These acid catalysts may be contained alone or in combination of two or more. Among the acid catalysts, pyridinium p-hydroxybenzenesulfonate is preferred.

[0114] The acid catalyst may be a photoacid generator. Preferred photoacid generators include onium salt-based photoacid generators such as bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate and triphenylsulfonium trifluoromethanesulfonate, halogen-containing compound-based photoacid generators such as phenyl-bis(trichloromethyl)-s-triazine, and sulfonic acid-based photoacid generators such as benzoin tosylate and N-hydroxysuccinimide trifluoromethanesulfonate. Preferred examples include sulfonic acid-based photoacid generators such as TPS-Tf, DTBPI-PFBS, TPS-CS, and TPS-PFBS (manufactured by Toyo Gosei Co., Ltd.). The photoacid generator is present in an amount of 0.2 to 10% by mass, preferably 0.4 to 5% by mass, based on the total solid content.

[0115] In order to prevent unreacted acid, catalyst, inactivated catalyst, etc. from remaining in the reaction system, a catalyst ion exchange resin can be used. For example, a sulfonic acid type strong acid ion exchange resin can be used as the catalyst ion exchange resin.

[0116] When the resist underlayer film forming composition according to the present invention contains an acid catalyst, the acid catalyst is contained in an amount of, for example, 1% by mass to 30% by mass, preferably 5% by mass to 15% by mass, based on the content of the crosslinking agent.

[0117] (D) Solvent In the resist underlayer film forming composition according to the present invention, the solvent for dissolving the above-mentioned crosslinking compound (A), as well as the optional crosslinkable film material (B), the acid catalyst (C), and other components is not particularly limited as long as it is a solvent that can dissolve these components uniformly.

[0118] For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclohexanone, Butanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

[0119] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. It is advantageous to use the solvent used for preparing the crosslinkable compound (A) or the crosslinkable membrane material (B) as a solvent, which contributes to the effective use of resources.

[0120] These solvents may be mixed with high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate.

[0121] The amount of the solvent is selected so that the solid content of the resist underlayer film-forming composition according to the present invention is preferably 0.1 to 70 mass %, more preferably 0.1 to 60 mass %, where the solid content refers to the content ratio of all components excluding the solvent in the resist underlayer film-forming composition.

[0122] [Other ingredients] In addition to the above, a surfactant, a rheology control agent, an adhesion aid, a light absorbing agent, and the like can be added to the resist underlayer film forming composition according to the present invention, if necessary.

[0123] The resist underlayer film forming composition of the present invention may contain a surfactant as an optional component to improve the coating property on the semiconductor substrate. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; F-TOP (registered trademark) EF301, EF303, and EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Megafac (registered trademark) F171, F173, R-30, R-30N, R-40, and R-40-LM (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); , DIC Corporation), Fluorad FC430, FC431 (all manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.), and other fluorine-based surfactants, and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more. The blending amount of these surfactants is usually 2.0 mass % or less, 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.

[0124] The rheology control agent is mainly added to improve the flowability of the resist underlayer film forming composition, and to improve the film thickness uniformity of the resist underlayer film and the filling ability of the resist underlayer film forming composition into the hole, especially in 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-normal butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyl decyl adipate, maleic acid derivatives such as di-normal 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 normal butyl stearate and glyceryl stearate.These rheology control agents are usually blended at a ratio of less than 30% by mass based on the total solid content of the resist underlayer film forming composition.

[0125] The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film forming composition, and in particular to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; and the like. Examples of the adhesive auxiliary 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 auxiliary agents are usually blended in an amount of less than 5 mass%, preferably less than 2 mass%, based on the total solid content of the resist underlayer film-forming composition for lithography.

[0126] Examples of the light absorbing agent include commercially available light absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthesis Chemistry), such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI Disperse Violet 43; CI Disperse Blue 96; and CI Fluorescent Brightening Agent. Suitable examples of the light absorbing agent that can be used include CI Solvent Orange 2 and 45, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pigment Green 10, and CI Pigment Brown 2. The light absorbing agent is typically 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.

[0127] In addition, the resist underlayer film forming composition according to the present invention can contain a crosslinking agent other than the crosslinking compound represented by formula (I). Examples of such crosslinking agents include melamine-based, substituted urea-based, and polymers thereof. A crosslinking agent having at least two crosslink-forming substituents is preferable, and is a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds can also be used. Among these, methoxymethylated glycoluril is preferred.

[0128] The crosslinking agent other than the crosslinkable compound represented by formula (I) is a compound represented by the following formula (2-1) or (2-2) (hereinafter referred to as "crosslinking agent (B)").

[0129] [ka]

[0130] In the above formula (2-1) and the above formula (2-2), Q 1 is a single bond or m 12 is a 0.05-valent organic group, R 12 and R 15 are each independently an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; R 13 and R 16 are each independently a hydrogen atom or a methyl group; R 14 and R 17 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. 12 is an integer from 1 to 3, and n 13 is an integer from 2 to 5, and n 14 is an integer from 0 to 3, and n 15 are integers from 0 to 3, and 3≦(n 12 +n 13 +n 14 +n 15 )≦6. 16 is an integer from 1 to 3, and n 17 is an integer from 1 to 4, and n 18 is an integer from 0 to 3, and n 19 are integers from 0 to 3, and these are 2≦(n 16 +n 17 +n 18 +n 19 )≦5. 12 is an integer between 2 and 10.

[0131] For more information, see Q 1 is a single bond or a group selected from a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic group having 6 to 40 carbon atoms, or a combination thereof;12 Here, examples of the chain hydrocarbon group include the alkyl group described below, and examples of the aromatic group include the aryl group described below.

[0132] Examples of the alkyl group having 2 to 10 carbon atoms include 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, a cyclo Pentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl ethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3- Ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples of the cyclopropyl group include a 3-trimethylcyclopropyl group, a 1-ethyl-2-methylcyclopropyl group, a 2-ethyl-1-methylcyclopropyl group, a 2-ethyl-2-methylcyclopropyl group, and a 2-ethyl-3-methylcyclopropyl group.

[0133] Moreover, examples of the alkyl group having 1 to 10 carbon atoms include the above alkyl groups having 2 to 10 carbon atoms and further include a methyl group.

[0134] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 5-methyl-n-butoxy group, a 6-methyl-n-butoxy group, a 7-methyl-n-butoxy group, a 8-methyl-n-butoxy group, a 9-methyl-n-butoxy group, a 10-methyl-n-butoxy group, a 11-methyl-n-propoxy group, a 12-methyl-n-propoxy group, a 22-methyl-n-propoxy group, a 12-methyl-n-butoxy group, a 13-methyl-n-butoxy group, a 14-methyl-n-butoxy group, a 15-methyl-n-butoxy group, a 16-methyl-n-butoxy group, a 17-methyl-n-butoxy group, a 18-methyl-n-butoxy group, a 25-methyl-n-butoxy group, a 26-methyl-n-butoxy group, a 27-methyl-n-butoxy group, a 28-methyl-n-butoxy group, a 29-methyl-n-butoxy group, a 30-methyl-n-butoxy group, a 31-methyl-n-butoxy group, a Examples of such groups include aryl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.

[0135] Examples of the aryl group having 6 to 40 carbon atoms include a phenyl group, a naphthyl group, and anthryl group.

[0136] Specific examples of the crosslinking agent (B) include compounds represented by the following formulae (3-1) to (3-40), but are not limited to these.

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] In the resist underlayer film forming composition of the present embodiment, these crosslinking agents (B) may be used alone or in combination of two or more kinds.

[0143] In this embodiment, the crosslinking agent (B) can be appropriately synthesized by applying a known method, and the synthesis method is not particularly limited. For example, it can be obtained by reacting a compound represented by the following formula (2'-1) or the following formula (2'-2) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. Note that a crosslinking agent (B) in which 1 mole of a compound represented by the following formula (2'-1) or the following formula (2'-2) is substituted with 1 mole of a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms is called a mono-substitution product, a crosslinking agent (B) in which 2 moles are substituted in the same manner is called a di-substitution product, a crosslinking agent (B) in which 3 moles are substituted in the same manner is called a tri-substitution product, and a crosslinking agent (B) in which 4 moles are substituted in the same manner is called a tetra-substitution product.

[0144] [ka]

[0145] In the above formula (2'-1) or (2'-2), Q 1’ is a single bond or m 12’ That is, Q is an organic group having a valence of 1. 1’ is a single bond or a group selected from a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic group having 6 to 40 carbon atoms, or a combination thereof; 12’ Here, examples of the chain hydrocarbon group include the above-mentioned alkyl groups, and examples of the aromatic group include the above-mentioned aryl groups.

[0146] Also, R 12’ , R 13’ , R 15’ and R 16’ are each independently a hydrogen atom or a methyl group; R 14’ and R 17’ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. 12’ is an integer from 1 to 3, and n 13’ is an integer from 2 to 5, and n 14’ is an integer from 0 to 3, and n 15’ are integers from 0 to 3, and 3≦(n 12’ +n 13’ +n 14’ +n 15’ )≦6. 16’ is an integer from 1 to 3, and n 17’ is an integer from 1 to 4, and n 18’ is an integer from 0 to 3, and n 19’ are integers from 0 to 3, and these are 2≦(n 16’ +n 17’ +n 18’ +n 19’ )≦5. 12’ is an integer between 2 and 10.

[0147] Specific examples of the compound represented by formula (2'-1) or (2'-2) include compounds represented by formulas (4-1) to (4-27) below, but are not limited to these.

[0148] [ka]

[0149] [ka]

[0150] Specifically, the crosslinking agent (B) can be obtained by reacting a compound represented by the above formula (2'-1) or (2'-2) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms in the presence of an acid catalyst.

[0151] The resist underlayer film-forming composition according to the present invention can be prepared by uniformly mixing the above-mentioned components by a conventional method. The prepared resist underlayer film-forming composition is preferably used after filtering using a filter having a pore size of, for example, 0.2 μm or 0.1 μm and / or a filter having a pore size of 0.01 μm.

[0152] [Method for manufacturing patterned substrate] The method for producing a patterned substrate using the resist underlayer film forming composition according to the present invention includes the steps of applying the resist underlayer film forming composition onto a semiconductor substrate and curing it to form a resist underlayer film, applying a resist onto the resist underlayer film and baking it to form a resist film, exposing the resist underlayer film and the semiconductor substrate covered with the resist, and developing and patterning the resist film after exposure. Each step will be described below in order.

[0153] Examples of the semiconductor substrate to which the resist underlayer film forming composition according to the present invention is applied include silicon substrates, germanium substrates, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, and spin coating (spin-on glass: SOG). Examples of the inorganic film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0154] Onto such a semiconductor substrate, the resist underlayer film forming composition according to the present invention is applied by an appropriate application method such as a spinner, a coater, etc. Thereafter, the applied film is cured to form the resist underlayer film according to the present invention, which is a cured product of the applied film. The means for curing the coating film include baking the coating film using a heating means such as a hot plate, and photo-curing the coating film by irradiating it with light (for example, ultraviolet light). The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 120°C to 350°C, the baking time is 0.5 to 30 minutes, more preferably, the baking temperature is 150°C to 300°C, the baking time is 0.8 to 10 minutes, and most preferably, the baking temperature is 200°C to 260°C, and the baking time is 0.8 to 3 minutes. The thickness of the resist underlayer film formed is, for example, 0.001 μm to 10 μm, preferably 0.002 μm to 1 μm, more preferably 0.005 μm to 0.5 μm, and most preferably 0.02 to 0.3 μm. If the baking temperature is lower than the above range, crosslinking may be insufficient, and the resist underlayer film formed may not be resistant to a resist solvent or an aqueous hydrogen peroxide solution. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may be decomposed by heat. When the coating film is cured only by baking, the resist underlayer film according to the present invention is a baked product of the coating film.

[0155] Instead of curing the coating film only by baking, the coating film may be heat-treated at a relatively low temperature (e.g., 10 to 80° C. lower than the above-mentioned bake temperature) and then photocured to complete the curing. Alternatively, the coating film may be heat-treated at the above-mentioned bake temperature for a shorter period of time and then photocured to complete the curing. For the photocuring treatment, ultraviolet light is preferably used. The irradiation energy is usually 100 to 1,000 mJ / cm. 2 It is. By appropriately combining thermal curing and photocuring, the planarization properties of the resist underlayer film can be further improved.

[0156] Next, a resist pattern is formed on the resist underlayer film. The resist pattern can be formed by a general method, that is, by applying a photoresist solution onto the resist underlayer film (after forming one or several layers of coating material as necessary), pre-baking (if necessary), irradiating (exposure) with light or electron beams through a predetermined mask, and post-exposure baking (abbreviated as PEB (Post Exposure Bake)) (if necessary, developing, rinsing, and drying). The resist used in the present invention is a photoresist or an electron beam resist. The photoresist solution used to form the resist pattern is not particularly limited as long as it is sensitive to the light used for exposure, and a positive photoresist can be used. Chemically amplified photoresists consisting of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low molecular compound that decomposes in an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and photoresists consisting of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate and an acid-soluble binder, and photoacid generator are examples of photoresists that can be used to form the resist pattern. Examples of such photoresists include chemically amplified photoresists consisting of a low molecular weight compound and a photoacid generator that decomposes to increase the alkaline dissolution rate of the photoresist, and DNQ-novolac type non-chemically amplified photoresists that utilize the difference in the alkaline dissolution rate between exposed and unexposed areas. Examples of such photoresists include PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), TDUR-P3435LP and THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Instead of the positive photoresist, a negative photoresist can also be used.

[0157] In addition, examples of the electron beam resist applied to the upper part of the resist underlayer film in the present invention include a composition consisting of a resin containing a Si-Si bond in the main chain and an aromatic ring at the end and an acid generator that generates an acid when irradiated with an electron beam, or a composition consisting of poly(p-hydroxystyrene) in which a hydroxyl group is substituted with an organic group containing N-carboxyamine and an acid generator that generates an acid when irradiated with an electron beam. In the latter electron beam resist composition, the acid generated from the acid generator by irradiation with an electron beam reacts with the N-carboxyaminooxy group in the polymer side chain, and the polymer side chain decomposes into a hydroxyl group, exhibits alkali solubility, and dissolves in an alkaline developer to form a resist pattern. Acid generators that generate acid upon irradiation with an electron beam include halogenated organic compounds such as 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, and 2-chloro-6-(trichloromethyl)pyridine; onium salts such as triphenylsulfonium salts and diphenyliodonium salts; and sulfonic acid esters such as nitrobenzyl tosylate and dinitrobenzyl tosylate.

[0158] The exposure is carried out through a mask (reticle) for forming a predetermined pattern, and for example, i-rays, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used. An alkaline developer is used for the development, and the development temperature is appropriately selected from 5°C to 50°C and the development time is appropriately selected from 10 seconds to 300 seconds. Examples of the alkaline developer include alkaline aqueous solutions such as aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine. Furthermore, a surfactant or the like can be added to these developers. A method can also be used in which development is carried out with an organic solvent such as butyl acetate instead of an alkaline developer, and the part of the photoresist where the alkaline dissolution rate is not improved is developed.

[0159] Next, the resist underlayer film is dry-etched using the formed resist pattern as a mask, whereby if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed.

[0160] Furthermore, a desired pattern is formed by wet etching using an aqueous hydrogen peroxide solution with the resist underlayer film after dry etching (if a resist pattern remains on the resist underlayer film, the resist pattern is also used) as a mask. Examples of chemicals for wet etching include basic hydrogen peroxide aqueous solution obtained by mixing an organic amine such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, or triethanolamine with hydrogen peroxide to make the pH basic, and acidic hydrogen peroxide aqueous solution obtained by mixing an inorganic acid such as hydrochloric acid or sulfuric acid with hydrogen peroxide. Other chemicals that can make the pH basic, such as urea mixed with hydrogen peroxide and heated to cause thermal decomposition of urea to generate ammonia and finally make the pH basic, can also be used as chemicals for wet etching. The temperature at which the basic hydrogen peroxide aqueous solution and the acidic hydrogen peroxide aqueous solution are used is preferably 25°C to 90°C, more preferably 40°C to 80°C. The wet etching time is preferably 0.5 to 30 minutes, and more preferably 1 to 20 minutes.

[0161] As described above, a semiconductor device can be manufactured through the steps of forming a resist underlayer film on a semiconductor substrate from a resist underlayer film forming composition, forming a resist film thereon, forming a resist pattern by irradiating with light or an electron beam and developing, etching the underlayer film with the resist pattern, and processing a semiconductor substrate with the patterned underlayer film. EXAMPLES

[0162] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these.

[0163] The chemical structures (examples) and abbreviations of the raw materials used in the synthesis examples are as follows: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the above formula, m represents an integer of 0 to 3). [ka] [ka] [ka]

[0164] The weight average molecular weight of the resin (polymer) obtained in the following synthesis examples is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). For the measurement, a GPC device manufactured by Tosoh Corporation was used, and the measurement conditions are as follows. GPC column: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko K.K.) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 1.0ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0165] [Synthesis Example 1] In a 100 mL two-neck flask, 12.17 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 15.00 g of HP-6000 (DIC Corporation), 0.60 g of ethyltriphenylphosphonium bromide (Hokko Chemical Industry Co., Ltd.), and 27.76 g of propylene glycol monomethyl ether (hereinafter abbreviated as PGME in this specification) were placed. The mixture was then heated to 140°C and refluxed and stirred for about 17.5 hours. After the reaction was completed, 27.8 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 27.8 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the solution, and the solution was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-1) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 660. [ka]

[0166] [Synthesis Example 2] In a 100 mL two-neck flask, 15.36 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 15.00 g of YX-4000 (Mitsubishi Chemical Co., Ltd.), 0.75 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 31.1 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 17.5 hours. After the reaction was completed, 31.1 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 31.1 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-2) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 590. [ka]

[0167] [Synthesis Example 3] In a 100 mL two-neck flask, 17.55 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 15.00 g of HP-4700 (DIC Corporation), 0.86 g of ethyltriphenylphosphonium bromide (Hokko Chemical Industry Co., Ltd.), and 33.4 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 17.5 hours. After the reaction was completed, 33.4 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 33.4 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-3) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,100. [ka]

[0168] [Synthesis Example 4] In a 100 mL two-neck flask, 13.50 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 9.30 g of GT-401 (butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone, Daicel Corporation), 0.66 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 22.8 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 17.5 hours. After the reaction was completed, 20.6 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 20.6 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-4) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,200. [ka]

[0169] [Synthesis Example 5] In a 100 mL two-neck flask, 12.19 g of 2-hydroxy-1-naphthaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.00 g of 9,9-bis(4-glycidyloxyphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.60 g of ethyltriphenylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 27.8 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 13 hours. After the reaction was completed, 27.8 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 27.8 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-5) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 610. [ka]

[0170] [Synthesis Example 6] In a 100 mL two-neck flask, 13.33 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 15.00 g of RE810-NM (Nippon Kayaku Co., Ltd.), 0.65 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 28.9 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 13 hours. After the reaction was completed, 29.0 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 29.0 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-6) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 780. [ka]

[0171] [Synthesis Example 7] In a 100 mL two-neck flask, 8.16 g of terephthalaldehyde acid (Tokyo Chemical Industry Co., Ltd.), 8.00 g of HP-4700 (DIC Corporation), 0.46 g of ethyltriphenylphosphonium bromide (Hokko Chemical Industry Co., Ltd.), and 38.7 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 14 hours. After the reaction was completed, 16.6 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 16.6 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-7) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,450. [ka]

[0172] [Synthesis Example 8] In a 100 mL two-neck flask, 4.59 g of 4-hydroxy-isophthalaldehyde (Tokyo Chemical Industry Co., Ltd.), 4.50 g of HP-4700 (DIC Corporation), 0.26 g of ethyltriphenylphosphonium bromide (Hokko Chemical Industry Co., Ltd.), and 9.34 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 14 hours. After the reaction was completed, 9.3 g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 9.3 g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-8) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,500. [ka]

[0173] [Synthesis Example 9] A polymer was obtained by the method described in Synthesis Example 10 of Japanese Patent No. 6191831. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,000. The obtained polymer was dissolved in propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA in this specification), and an anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and a cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Co., Ltd.) were added, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a compound solution (1-9) was obtained.

[0174] [Synthesis Example 10] 72.46g of PGME, 26.00g of RE810-NM (manufactured by Nippon Kayaku Co., Ltd.), 20.81g of BPA-CA (manufactured by Konishi Chemical Co., Ltd.), 2.18g of ethyltriphenylphosphonium bromide, and 0.32g of hydroquinone were added to a 100mL two-neck flask, and the mixture was reacted at 140°C for 24 hours to obtain a solution containing a reaction product. After diluting to a 20% by mass solution with PGME, 147.90g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 147.90g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added, and the mixture was stirred at 60°C for 4 hours, filtered, and the resin was separated to obtain a solution of a compound having the structure of formula (1-10). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 18,000. [ka]

[0175] [Synthesis Example 11] In a 100mL two-neck flask, 4.37g of acrylic acid (Tokyo Chemical Industry Co., Ltd.), 10.00g of HP-4700 (DIC Corporation), 0.56g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), 0.03g of hydroquinone (Tokyo Chemical Industry Co., Ltd.), and 34.91g of PGME were placed. The mixture was then heated to 100°C and refluxed and stirred for about 21 hours. After the reaction was completed, 15.0g of anion exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 15.0g of cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-11) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,400. [ka]

[0176] [Example 1] To 3.34 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.05 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.60 g of the solution of the compound having the structure of formula (1-1) obtained in Synthesis Example 1 (solid content 24.2 mass %), 0.73 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 5.35 g of PGMEA, and 1.63 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0177] [Example 2] To 1.63 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.05 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.62 g of the solution of the compound having the structure of formula (1-2) obtained in Synthesis Example 2 (solid content 23.6 mass %), 0.73 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 5.35 g of PGMEA, and 1.61 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0178] [Example 3] To 1.63 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.05 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.57 g of the solution of the compound having the structure of formula (1-3) obtained in Synthesis Example 3 (solid content 25.9 mass %), 0.73 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 5.35 g of PGMEA, and 1.67 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0179] [Example 4] To 1.63 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.05 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.68 g of the solution of the compound having the structure of formula (1-4) obtained in Synthesis Example 4 (solid content 21.5 mass %), 0.73 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 5.35 g of PGMEA, and 1.55 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0180] [Example 5] To 1.63 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.05 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.54 g of the solution of the compound having the structure of formula (1-5) obtained in Synthesis Example 5 (solid content 27.1 mass %), 0.73 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 5.35 g of PGMEA, and 1.69 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0181] [Example 6] To 1.63 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.05 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.63 g of the solution of the compound having the structure of formula (1-6) obtained in Synthesis Example 6 (solid content 23.4 mass %), 0.73 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 5.35 g of PGMEA, and 1.61 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0182] [Example 7] To 3.02 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.09 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.06 g of the solution of the compound having the structure of formula (1-7) obtained in Synthesis Example 7 (solid content 25.5 mass %), 1.35 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.46 g of PGMEA, and 2.02 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0183] [Example 8] To 3.02 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content 29.9 mass%), 0.09 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.64 g of the solution of the compound having the structure of formula (1-8) obtained in Synthesis Example 8 (solid content 16.5 mass %), 1.35 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 0.56 g of PGMEA, 0.06 g of PGME, and 8.28 g of cyclohexanone were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0184] [Example 9] 0.10 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.73 g of the solution of the compound having the structure of formula (1-1) obtained in Synthesis Example 1 (solid content was 24.2 mass %), 1.57 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of PGMEA, and 3.50 g of PGME were added to 4.15 g of the solution of the compound having the structure of formula (1-11) obtained in Synthesis Example 11 (solid content was 25.3 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0185] [Example 10] 0.10 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.63 g of the solution of the compound having the structure of formula (1-3) obtained in Synthesis Example 3 (solid content was 25.9 mass %), 1.57 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of PGMEA, and 3.61 g of PGME were added to 4.15 g of the solution of the compound having the structure of formula (1-11) obtained in Synthesis Example 11 (solid content was 25.3 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0186] [Example 11] 0.10 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.73 g of the solution of the compound having the structure of formula (1-1) obtained in Synthesis Example 1 (solid content was 24.2 mass %), 1.57 g of PGME containing 2 mass % of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 6.74 g of PGMEA, and 1.20 g of PGME were added to 3.66 g of PGMEA containing NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Company, Inc.) (solid content was 28.7 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0187] [Example 12] 0.10 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.62 g of the solution of the compound having the structure of formula (1-3) obtained in Synthesis Example 3 (solid content was 25.9 mass %), 1.57 g of PGME containing 2 mass % of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 6.74 g of PGMEA, and 1.31 g of PGME were added to 3.66 g of PGMEA containing NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Company, Inc.) (solid content was 28.7 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0188] [Example 13] 0.10 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.73 g of the solution of the compound having the structure of formula (1-1) obtained in Synthesis Example 1 (solid content was 24.2 mass %), 1.57 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of PGMEA, and 2.43 g of PGME were added to 5.22 g of the solution of the compound having the structure of formula (1-10) obtained in Synthesis Example 10 (solid content was 20.1 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0189] [Example 14] To 5.22 g of the solution of the compound having the structure of formula (1-10) obtained in Synthesis Example 10 (solid content was 20.1 mass%), 0.10 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.62 g of the solution of the compound having the structure of formula (1-3) obtained in Synthesis Example 3 (solid content was 25.9 mass%), 1.57 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of PGMEA, and 2.54 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0190] [Comparative Example 1] To 3.02 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content: 29.9 mass%), 0.09 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.27 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 1.35 g of PGME containing 2 mass % of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.46 g of PGMEA, and 2.81 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0191] [Comparative Example 2] To 3.02 g of the compound solution (1-9) obtained in Synthesis Example 9 (solid content: 29.9 mass%), 0.09 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.27 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.35 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 7.46 g of PGMEA, and 2.81 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0192] [Comparative Example 3] 0.10 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.42 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.57 g of PGME containing 2 mass % of pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of PGMEA, and 4.18 g of PGME were added to 4.15 g of the solution of the compound having the structure of formula (1-11) obtained in Synthesis Example 11 (solid content: 25.3 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0193] [Comparative Example 4] 0.10 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.42 g of PL-LI (manufactured by Midori Chemical Industry Co., Ltd.), 1.57 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 6.74 g of PGMEA, and 2.51 g of PGME were added and dissolved in 3.66 g of PGMEA containing NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Company, Inc.) (solid content: 28.7 mass %), and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0194] [Comparative Example 5] To 5.22 g of the solution of the compound having the structure of formula (1-10) obtained in Synthesis Example 10 (solid content: 20.1 mass%), 0.10 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.42 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.57 g of PGME containing 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.95 g of PGMEA, and 3.74 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0195] (Elution test in resist solvent) The solutions of the resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-14 were each applied onto a silicon wafer using a spin coater, and baked on a hot plate at 300°C for 60 seconds to form resist underlayer films (film thickness 0.20 μm). These resist underlayer films were immersed in each of the solvents used for resists, namely ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. These resist underlayer films were insoluble in any of these solvents.

[0196] (Check the curing end temperature) The solutions of the resist underlayer film forming compositions prepared in Comparative Example 1-2 and Example 1-8 were each applied onto a silicon wafer using a spin coater and baked on a hot plate at an arbitrary temperature for 60 seconds to form a resist underlayer film (film thickness 0.20 μm). The temperature at which these resist underlayer films did not dissolve in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (=curing end temperature) was confirmed. The method was the same as the dissolution test into the resist solvent. The results are shown in Table 1.

[0197] [Table 1]

[0198] The curing end temperature is higher in Example 1-8 than in Comparative Example 1-2. It is understood that the crosslinking agent used in the examples has high fluidity and cures slowly compared to the case where a conventional crosslinking agent is used.

[0199] (Optical constant measurement) The solutions of the resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-14 were each applied onto a silicon wafer using a spin coater. The resist underlayer film (film thickness 0.05 μm) was formed by baking on a hot plate at 300° C. for 60 seconds. The refractive index (n value) and optical absorption coefficient (k value, also called extinction coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer. The results are shown in Table 2.

[0200] [Table 2]

[0201] By changing the type of epoxy compound or aldehyde compound, the optical constants of the crosslinking agent can be changed significantly. Comparing Examples 1-8 using these crosslinking agents with Comparative Examples 1-2 using conventional crosslinking agents, it is possible to change the optical constants of materials with the same composition ratio by changing the type of crosslinking agent. This tendency is the same for Comparative Example 3 and Examples 9-10, Comparative Example 4 and Examples 11-12, and Comparative Example 5 and Examples 13-14, and the reflectance can be suppressed by selecting an appropriate crosslinking agent.

[0202] [Dry etching rate measurement] The etcher and etching gas used in the measurement of the dry etching rate were as follows: RIE-10NR (Samco): CF4 The solutions of the resist underlayer film forming compositions prepared in Comparative Example 1-5 and Examples 1-14 were each applied onto a silicon wafer using a spin coater. The resist underlayer film (film thickness 0.20 μm) was formed by baking on a hot plate at 300° C. for 60 seconds. The dry etching rates were measured using CF4 gas as the etching gas, and the dry etching rate ratios of Comparative Example 1-5 and Examples 1-14 were obtained. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film) / (KrF photoresist). The results are shown in Table 3.

[0203] [Table 3]

[0204] By changing the type of epoxy compound or aldehyde compound, the etching rate of the crosslinking agent can be changed significantly. Comparing Examples 1-8 using these crosslinking agents with Comparative Examples 1-2 using conventional crosslinking agents, the etching rate of materials with the same composition ratio can be changed by changing the type of crosslinking agent. This tendency is the same for Comparative Example 3 and Examples 9-10, Comparative Example 4 and Examples 11-12, and Comparative Example 5 and Examples 13-14, and processability can be improved by selecting an appropriate crosslinking agent.

[0205] (Embeddability evaluation) The embeddability was confirmed in a dense pattern area with a SiO2 substrate having a thickness of 200 nm, a trench width of 50 nm, and a pitch of 100 nm. The resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-14 were applied onto the above substrate, and then baked at 300°C for 60 seconds or at 260°C for 60 seconds to form a resist underlayer film of about 200 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the presence or absence of filling of the resist underlayer film forming composition into the inside of the pattern was confirmed. The results are shown in Table 4. When the resist underlayer film was formed without gaps into the inside of the pattern, the embeddability was evaluated as good ("○"), and when it was not embedded into the inside of the pattern or holes or gaps existed inside the pattern, the embeddability was evaluated as poor ("×").

[0206] [Table 4]

[0207] Example 1-14 exhibits embeddability equivalent to that of Comparative Example 1-5, which used a conventional crosslinking agent.

[0208] (Coating test for stepped substrate) As a coating test for a stepped substrate, a comparison was made between the coating thickness of an 800 nm trench area (TRENCH) and an open area (OPEN) where no pattern was formed on a 200 nm thick SiO2 substrate. The resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-14 were applied to the above substrate, and then baked at 300°C for 60 seconds to form a resist underlayer film of about 200 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference (the coating step between the trench area and the open area, which is called the bias) between the trench area (patterned part) and the open area (no pattern part) of the stepped substrate. The results are shown in Table 5. Here, planarization means that the film thickness difference (Iso-TRENCH bias) of the coating material present on the upper part of the part where the pattern exists (TRENCH (patterned part)) and the part where the pattern does not exist (open area (no pattern)) is small. Examples in which an improvement of 10 nm or more was confirmed compared to the comparative example were rated as ◯, and examples in which an improvement of 30 nm or more was confirmed compared to the comparative example were rated as ⊚.

[0209] [Table 5]

[0210] Comparing Comparative Example 2 with Examples 1-8, Comparative Example 3 with Examples 9-10, Comparative Example 4 with Examples 11-12, and Comparative Example 5 with Examples 13-14, it was confirmed that the Examples had a significant improvement in planarization properties. These results are believed to be due to the fact that the curing end temperature of the crosslinking agent used in the Examples was higher than the curing end temperature when a conventional crosslinking agent was used, making it possible to maintain a long flow time for the resin.

[0211] The crosslinking agent according to the present invention can also be used as a polymer having a self-crosslinking group.

[0212] [Synthesis Example 12] In a 100 mL two-neck flask, 7.91 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 9.50 g of NC-7300L (Nippon Kayaku Co., Ltd.), 0.39 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 41.5 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 14 hours. After the reaction was completed, 17.8 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 17.8 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-12) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 750. [ka]

[0213] [Synthesis Example 13] In a 100 mL two-neck flask, 6.86 g of 4-hydroxy-3-methoxybenzaldehyde (Tokyo Chemical Industry Co., Ltd.), 9.50 g of HP-4700 (DIC Corporation), 0.38 g of ethyltriphenylphosphonium bromide (Hokko Chemical Industry Co., Ltd.), and 39.1 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 14 hours. After the reaction was completed, 16.7 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 16.7 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Corporation) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-13) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 750. [ka]

[0214] [Synthesis Example 14] In a 100 mL two-neck flask, 7.16 g of 4-hydroxy-3-methoxybenzaldehyde (Tokyo Chemical Industry Co., Ltd.), 9.00 g of JER-1031S (Mitsubishi Chemical Co., Ltd.), 0.40 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 38.6 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 14 hours. After the reaction was completed, 16.6 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 16.6 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-14) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,000. [ka]

[0215] [Synthesis Example 15] In a 100 mL two-neck flask, 7.21 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 8.00 g of JER-1031S (Mitsubishi Chemical Co., Ltd.), 0.35 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 36.3 g of PGME were placed. The mixture was then heated to 140°C and refluxed and stirred for about 14 hours. After the reaction was completed, 15.6 g of anion exchange resin (product name: Dowex (registered trademark) 550A, Muromachi Technos Co., Ltd.) and 15.6 g of cation exchange resin (product name: Amberlite (registered trademark) 15JWET, Organo Co., Ltd.) were added to the solution, and the mixture was subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-15) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,000. [ka]

[0216] [Synthesis Example 16] Into a 100 mL two-neck flask were placed 3.19 g of 2-hydroxy-1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 3.08 g of 9-anthracenecarboxylic acid, 10.00 g of HP-4700 (DIC Corporation), 0.52 g of ethyltriphenylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.), and 39.2 g of PGME. The mixture was then heated to 140°C and stirred under reflux for approximately 14 hours. After completion of the reaction, the solution was added with an anion exchange resin ( 16.8 g of Dowex (registered trademark) 550A (Muromachi Technos Co., Ltd.) and 16.8 g of cation exchange resin (registered trademark Amberlite 15JWET (Organo Co., Ltd.) were added and subjected to ion exchange treatment at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-16) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,700. [ka]

[0217] [Example 15] 0.05 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.22 g of PGME containing 5 mass % pyridinium p-hydroxybenzenesulfonate, 1.88 g of PGMEA, and 2.34 g of PGME were added to 2.50 g of the solution of the compound having the structure of formula (1-12) obtained in Synthesis Example 12 (solid content: 21.9 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0218] [Example 16] 0.08 g of PGMEA containing 1 mass % surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.31 g of PGME containing 5 mass % pyridinium p-hydroxybenzenesulfonate, 2.68 g of PGMEA, and 4.03 g of PGME were added to 2.90 g of the solution of the compound having the structure of formula (1-13) obtained in Synthesis Example 13 (solid content: 27.0 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0219] [Example 17] 0.05 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.47 g of 5 mass % of pyridinium p-hydroxybenzenesulfonate containing PGME, 1.91 g of PGMEA, and 2.92 g of PGME were added to 1.66 g of the solution of the compound having the structure of formula (1-15) obtained in Synthesis Example 15 (solid content: 28.1 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0220] [Example 18] 0.06 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.22 g of PGME containing 5 mass % of pyridinium p-hydroxybenzenesulfonate, 2.53 g of PGMEA, and 1.88 g of PGME were added to 2.31 g of the solution of the compound having the structure of formula (1-16) obtained in Synthesis Example 16 (solid content: 23.7 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0221] [Example 19] To 1.86 g of the solution of the compound having the structure of formula (1-14) obtained in Synthesis Example 14 (solid content: 25.0 mass%), 0.05 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.47 g of propylene glycol monomethyl ether containing 5% of TPS-Tf (photoacid generator, manufactured by Toyo Gosei Co., Ltd.), 1.91 g of PGMEA, and 2.72 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0222] [Example 20] 0.05 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.47 g of propylene glycol monomethyl ether containing 5% of TPS-Tf (photoacid generator, manufactured by Toyo Gosei Co., Ltd.), 1.79 g of PGMEA, and 1.34 g of PGME were added to 1.66 g of the solution of the compound having the structure of formula (1-15) obtained in Synthesis Example 15 (solid content: 28.1 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0223] [Comparative Example 6] 0.04 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 1.79 g of PGMEA, and 1.34 g of PGME were added to and dissolved in 1.82 g of the solution of the compound having the structure of formula (1-12) obtained in Synthesis Example 12 (solid content: 21.9 mass %), and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0224] [Comparative Example 7] 0.07 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 4.72 g of PGMEA, and 2.72 g of PGME were added to and dissolved in 2.49 g of a solution (solid content: 28.1 mass %) of the compound having the structure of formula (1-15) obtained in Synthesis Example 15, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0225] (Thermosetting test) The resist underlayer film compositions prepared in Examples 15 to 18 and Comparative Examples 6 and 7 were each applied onto a silicon wafer using a spin coater. The composition was heated on a hot plate at 280°C for 60 seconds to form a resist underlayer film having a thickness of 200 nm. The resist underlayer film was immersed in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate for 1 minute, spin-dried, and then baked at 100°C for 60 seconds. The film thickness was measured to calculate the remaining film ratio, and the solvent strippability was evaluated. The results are shown in Table 6. In Examples 15 to 18, the crosslinking reaction caused by the acid generated by heat gave resistance to the solvent, resulting in a film remaining rate of 100%. In contrast, in Comparative Examples 6 and 7, no acid was generated by heat, and no crosslinking reaction occurred, so resistance to the solvent was not obtained, resulting in a film remaining rate of 0%.

[0226] [Table 6]

[0227] (Photocuring test) The resist underlayer film compositions prepared in Examples 19 and 20 and Comparative Example 7 were each applied onto a silicon wafer using a spin coater. The resist underlayer film was heated on a hot plate at 170°C for 60 seconds to form a resist underlayer film having a thickness of 150 nm. This resist underlayer film was then exposed to 500 mJ / cm 2 of ultraviolet light using a UV irradiation unit (wavelength 172 nm) manufactured by Ushio Inc. 2 After irradiating the film with ultraviolet light, it was heated on a hot plate at 160°C for 60 seconds. The film obtained was immersed in a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate in a ratio of 7:3 for 1 minute, spin-dried, and baked at 100°C for 60 seconds. The film thickness was measured to calculate the remaining film ratio, and the solvent peelability by light irradiation (ultraviolet light irradiation) was evaluated. The results are shown in Table 7. In Examples 19 and 20, the curing reaction occurred due to the effect of the acid generated by light, which provided resistance to the solvent, and the film remaining rate was 100%. In contrast, in Comparative Example 7, there was no acid generated by light, so the curing reaction did not occur, and therefore resistance to the solvent was not obtained, and the film remaining rate was 0%.

[0228] [Table 7]

[0229] (Coating test for stepped substrate) As a coating test for a stepped substrate, a comparison was made between the coating thickness of an 800 nm trench area (TRENCH) and an open area (OPEN) where no pattern was formed on a 200 nm thick SiO2 substrate. The resist underlayer film forming compositions prepared in Examples 15-18 were applied to the substrate, and then baked at 240°C for 60 seconds to form a resist underlayer film of about 200 nm. In addition, the resist underlayer film compositions prepared in Examples 19 and 20 were applied to the substrate using a spin coater, and then heated on a hot plate at 170°C for 60 seconds to form a resist underlayer film of 150 nm in thickness. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference (the coating step between the trench area and the open area, which is called the bias) between the trench area (patterned area) and the open area (no patterned area) of the stepped substrate. Here, planarization means that the difference in film thickness (Iso-TRENCH bias) of the coating applied on the upper portion of the portion where a pattern is present (TRENCH (pattern portion)) and the portion where no pattern is present (open area (non-pattern portion)) is small. The results are shown in Table 8. Note that examples where the difference in film thickness (Iso-TRENCH bias) of the coating was 100 nm or more were rated as ×, 100 nm or less as ○, 50 nm or less as ◎, and 20 nm or less as ◎◎ were rated.

[0230] [Table 8]

[0231] In Examples 15 to 18, the crosslinking initiation temperature of the crosslinking group present in the polymer is high, and the crosslinking reaction starts after sufficient reflow at high temperature, so a good planarizing film can be obtained. In Examples 19 and 20, the crosslinking reaction does not occur at 170°C, so sufficient reflowability is obtained at this stage, and sufficient planarization is obtained on a stepped substrate. Furthermore, a good planarizing film can be obtained by curing with light.

[0232] [Synthesis Example 17] In a two-neck flask, 40.0 g of EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), 20.3 g of 9-anthracene carboxylic acid, and 13.7 g of benzoic acid were dissolved in 302.0 g of propylene glycol monomethyl ether, and then 1.5 g of benzyl triethylammonium was added and refluxed for 24 hours to cause a reaction. 11 g of cation exchange resin (product name: Dowex [registered trademark] 550A, Muromachi Technos Co., Ltd.) and 11 g of anion exchange resin (product name: Urban Light [registered trademark] 15JWET, Organo Co., Ltd.) were added to the obtained solution and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a compound 2 solution was obtained. The weight average molecular weight Mw of the obtained compound measured by GPC in terms of polystyrene was 4,100.

[0233] [ka]

[0234] [Example 21] 0.05 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.20 g of PGME containing 5 mass % of pyridinium p-hydroxybenzenesulfonate, 0.05 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 1.88 g of PGMEA, and 2.53 g of PGME were added to 2.19 g of the resin solution obtained in Synthesis Example 12 (solid content: 21.9 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0235] [Example 22] 0.07 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.29 g of PGME containing 5 mass % of pyridinium p-hydroxybenzenesulfonate, 0.07 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 2.68 g of PGMEA, and 4.24 g of PGME were added to 2.64 g of the resin solution obtained in Synthesis Example 13 (solid content: 27.0 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0236] [Example 23] To 1.93 g of the resin solution obtained in Synthesis Example 3 (solid content: 25.9% by mass), 0.05 g of PGMEA containing 1% by mass of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.20 g of PGME containing 5% by mass of pyridinium p-hydroxybenzenesulfonate, 0.05 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 1.88 g of PGMEA, and 2.89 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0237] [Example 24] 0.05 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.21 g of PGME containing 5 mass % of pyridinium p-hydroxybenzenesulfonate, 0.03 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 1.88 g of PGMEA, and 2.81 g of PGME were added to 2.02 g of the resin solution obtained in Synthesis Example 3 (solid content: 25.9 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0238] [Example 25] 0.05 g of PGMEA containing 1 mass % of a surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.21 g of PGME containing 5 mass % of pyridinium p-hydroxybenzenesulfonate, 0.03 g of tetramethoxymethylglycoluril, 1.88 g of PGMEA, and 2.81 g of PGME were added to 2.02 g of the resin solution obtained in Synthesis Example 3 (solid content: 25.9 mass %) and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[0239] [Comparative Example 8] 0.2 g of tetramethoxymethyl glycoluril, 0.2 g of propylene glycol monomethyl ether containing 5% pyridinium p-toluenesulfonate, 0.08 g of propylene glycol monomethyl ether acetate containing 1% of a surfactant (manufactured by DIC Corporation, product name: Megafac [product name] R-40, fluorine-based surfactant), 2.1 g of propylene glycol monomethyl ether, and 2.6 g of propylene glycol monomethyl ether acetate were mixed with 4.9 g of the resin solution obtained in Synthesis Example 17 (solid content: 16.0%). The mixture was then filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0240] (Thermosetting test) The resist underlayer film compositions prepared in Examples 21 to 25 and Comparative Example 8 were each applied onto a silicon wafer using a spin coater. The composition was heated on a hot plate at 240°C for 60 seconds to form a resist underlayer film having a thickness of 200 nm. The solvent strippability was evaluated by immersing the baked coating film in a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (7:3) for 1 minute, spin drying, baking at 100°C for 60 seconds, and measuring the film thickness to calculate the remaining film ratio (Table 9). In Examples 21 to 25 and Comparative Example 8, a crosslinking reaction occurred due to acid generated by heat, which provided resistance to solvents and resulted in a film remaining rate of 100%.

[0241] [Table 9]

[0242] [Dry etching rate measurement] The etcher and etching gas used in the measurement of the dry etching rate were as follows: RIE-10NR (Samco): CF4 The solutions of the resist underlayer film forming compositions prepared in Examples 21-25 and Comparative Example 8 were each applied onto a silicon wafer using a spin coater. The resist underlayer film (film thickness 0.20 μm) was formed by baking on a hot plate at 240° C. for 60 seconds or at 215° C. for 60 seconds. The dry etching rate was measured using CF4 gas as the etching gas, and the dry etching rate ratio of Examples 21-25 and Comparative Example 8 was obtained. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film) / (Comparative Example 8) (Table 10). As can be seen from Examples 21 to 37, by further adding a crosslinking agent to a compound having a crosslinking group, the etching rate is lowered compared to a system in which a crosslinking agent is added to a compound not having a crosslinking group, as in Comparative Example 8, and it is possible to improve processability.

[0243] [Table 10] [Industrial Applicability]

[0244] According to the present invention, it is possible to provide a resist underlayer film-forming composition that has excellent embedding properties and planarization properties for uneven substrates; a resist underlayer film that is formed by applying and baking the composition, is insoluble in a resist solvent, has good optical constants, and allows the etching rate to be appropriately adjusted; and a method for manufacturing a patterned substrate and a method for manufacturing a semiconductor device utilizing the same.

Claims

1. (A) a crosslinkable compound represented by the following formula (I): (C) an acid catalyst, and (D) Solvent A resist underlayer film forming composition comprising the compound. 【Chemistry 138】 [In the formula, n is an integer from 2 to 6, n Z's each independently represent a monovalent organic group containing a mono-, di-, tri-, tetra-, penta-, or hexaformylaryl group; Each of the n A's independently represents -OCH ２ CH(OH)CH ２ O-, or 【Chemistry 139】 represents T is an n-valent hydrocarbon group and / or a repeating unit of a polymer. The n-valent hydrocarbon group may have at least one group selected from the group consisting of a hydroxy group, an epoxy group, an acyl group, an acetyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, and an allyl group. The n-valent hydrocarbon group may be interrupted by a carbonyl group and / or an oxygen atom. The n-valent hydrocarbon group has at least one group selected from the group consisting of a hydroxy group, an epoxy group, an acyl group, an acetyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, and an allyl group, and may be interrupted by a carbonyl group and / or an oxygen atom.

2. 2. The resist underlayer film forming composition according to claim 1, wherein the crosslinkable compound (A) further contains a self-crosslinking group, and the self-crosslinking group is a hydroxy group or an aldehyde group.

3. The resist underlayer film forming composition according to claim 1 , further comprising a film material (B) capable of crosslinking reaction with the crosslinkable compound (A).

4. 4. The resist underlayer film forming composition according to claim 3, wherein the crosslinkable film material (B) comprises at least one selected from the group consisting of a resin containing an aliphatic ring, a novolak resin, a polyether resin, a polyester resin, an acrylic resin, a methacrylic resin, and a compound different from the crosslinkable compound (A).

5. The novolak resin is represented by the following formula (1a), formula (1b), and formula (1c): 【Chemistry 140】 [Wherein, two R １ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; ２ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R ３ represents an aromatic hydrocarbon group which may have a substituent; R ４ represents a hydrogen atom, a phenyl group, or a naphthyl group, and R ３ and R ４ When each of R represents a phenyl group, they may be bonded to each other to form a fluorene ring. ３ and two R ４ The atoms or groups represented by may be different from each other, two k's each independently represent 0 or 1, m ０ represents an integer from 3 to 500; ０ , n １ and n ２ represents an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Qs each independently represent the following formula (2): 【Chemistry 141】 (Wherein, two R １ , two R ２ , two R ３ , two R ４ , two k, n １ , n ２ and X are defined as in formula (1b), and two Q １ each independently represents a structural unit represented by the formula (2). The resist underlayer film forming composition according to claim 4 , wherein the repeating structural unit is one or more of the repeating structural units represented by the formula:

6. A compound different from the crosslinkable compound (A) is 【Chemistry 142】 (In formula (2), each of the two Ar's represents an aryl group having at least one hydroxyl group as a substituent, and Q represents a divalent linking group having at least one benzene ring or naphthalene ring, a methylene group, or a single bond.) The resist underlayer film forming composition according to claim 4,

7. The resist underlayer film forming composition according to any one of claims 1 to 6, further comprising a crosslinking agent other than the crosslinkable compound represented by the above formula (I).

8. A resist underlayer film, which is a cured product of a coating film comprising the resist underlayer film forming composition according to any one of claims 1 to 7.

9. A method for manufacturing a patterned substrate, comprising the steps of: applying a resist underlayer film forming composition according to any one of claims 1 to 7 onto a semiconductor substrate and curing it to form a resist underlayer film; applying a resist onto the resist underlayer film and baking it to form a resist film; exposing the resist underlayer film and the semiconductor substrate coated with the resist; and developing and patterning the resist film after exposure.

10. A method for producing a patterned substrate as described in claim 9, further comprising baking to effect said hardening.

11. A method for producing a patterned substrate as described in claim 9, wherein after baking, the curing is carried out by irradiating with ultraviolet light.

12. A method for producing a patterned substrate as described in claim 11, further comprising baking after the ultraviolet irradiation.

13. 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 described in any one of claims 1 to 7, forming a resist film thereon, forming a resist pattern by irradiating with light or an electron beam and developing, etching the underlayer film with the resist pattern, and processing a semiconductor substrate with the patterned underlayer film.

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