Resist underlayer film forming composition

Abstract

A novel resist underlayer film formation composition is provided. [Solution] A resist underlayer film forming composition comprising a polymer (X) having a plurality of identical or different structural units having a methoxymethyl group and a ROCH2- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group that links the plurality of structural units, and a solvent.

Description

[Technical Field]

[0001] The present invention relates to a resist underlayer forming composition, a resist underlayer film which is a fired product of a coated film made from the composition, and a method for manufacturing a semiconductor device using the composition. [Background technology]

[0002] Microfabrication is performed using lithography processes in the manufacturing of semiconductor devices. In these lithography processes, when the resist layer on a substrate is exposed with an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser, a problem is known to occur where the resist pattern with the desired shape cannot be formed due to the influence of standing waves generated by the reflection of the ultraviolet laser from the substrate surface. To solve this problem, a resist underlayer film (anti-reflective film) is used between the substrate and the resist layer. It is known that novolac resin is used as the composition for forming the resist underlayer film.

[0003] Furthermore, in order to thin the resist layer as required by the miniaturization of resist patterns, a lithography process is known in which at least two resist underlayer films are formed and these resist underlayer films are used as mask materials. Examples of materials for forming the at least two layers include organic resins (e.g., acrylic resins, novolac resins), silicon resins (e.g., organopolysiloxanes), and inorganic silicon compounds (e.g., SiON, SiO2). When dry etching using the pattern formed from the organic resin layer as a mask, it is necessary that the pattern has etching resistance to etching gases (e.g., fluorocarbons).

[0004] As a composition for forming such a resist underlayer film, for example, Patent Document 1 describes the following formula (1):

[0005] [ka]

[0006] (In the formula, X 1 X represents a divalent organic group having 6 to 20 carbon atoms and having at least one aromatic ring which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group. 2 (This represents an organic group having 6 to 20 carbon atoms, or a methoxy group, having at least one aromatic ring which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group.) A resist underlayer film forming composition is disclosed, comprising a polymer having a structural unit represented by and a solvent. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] WO2014 / 171326A1 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, conventional resist underlayer film forming compositions still fall short of requirements such as improved solubility in PGME and PGMEA, solvents commonly used in the semiconductor industry; reduced amount of sublimation contaminating equipment; improved planarity of coatings on stepped substrates; and increased hardness of the resulting resist underlayer film. Furthermore, it is important to maintain or improve properties such as avoiding the use of harmful chemicals in resin preparation, not eluting into resist solvents, obtaining desired optical constants, and being able to follow irregular patterns that arise as the pattern width narrows. [Means for solving the problem]

[0009] This invention solves the above problems. In other words, this invention encompasses the following: [1] A resist underlayer film forming composition comprising a polymer (X) having a plurality of identical or different structural units having a methoxymethyl group and a ROCH2- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group that links the plurality of structural units, and a solvent. [2] R may be substituted with a phenyl group, a naphthyl group or an anthracenyl group, and may be interrupted by an oxygen atom or a carbonyl group, a saturated or unsaturated linear or branched C2-C chain 20 Aliphatic hydrocarbon group, C3-C 20 A resist underlayer film forming composition according to [1], comprising an alicyclic hydrocarbon group, a hydrogen atom, or a mixture thereof. [3] The resist underlayer forming composition according to [1] or [2], wherein the linking group comprises an alkylene group, an ether group, or a carbonyl group. [4] A resist underlayer forming composition according to any one of [1] to [3], wherein the structural unit comprises an aromatic ring, heterocycle, or fused ring which may have a phenolic hydroxyl group and which may have a substituted or unsubstituted amino group. [5] A resist underlayer forming composition according to any one of [1] to [4], further comprising a polymer (X) and a crosslinkable film material (Y). [6] A resist underlayer film forming composition according to any one of [1] to [5], further comprising a crosslinking agent. [7] A resist underlayer forming composition according to any one of [1] to [6], further comprising an acid and / or an acid generator. [8] A resist underlayer film forming composition according to any one of [1] to [7], further comprising a surfactant. [9] The resist underlayer film forming composition according to any one of [1] to [8], wherein the solvent comprises a solvent having a boiling point of 160°C or higher. A resist underlayer film characterized by being a fired product of a coating film comprising the composition described in any one of the items [1] to [9].

[11] A step of forming a resist underlayer film on a semiconductor substrate using the composition described in any one of [1] to [9], A step of forming a resist film on the formed resist underlayer film, A process of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it. A step of etching and patterning the resist underlayer film through the formed resist pattern, and Process of processing a semiconductor substrate via a patterned resist underlayer film. A method for manufacturing a semiconductor device containing [a specific component].

[12] A step of forming a resist underlayer film on a semiconductor substrate using the composition described in any one of [1] to [9], A step of forming a hard mask on the formed resist underlayer film, A step of forming a resist film on the formed hard mask, A process of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it. A step of etching and patterning the hard mask through the formed resist pattern, and A step of etching and patterning the resist underlayer film through a patterned hard mask, and Process of processing a semiconductor substrate via a patterned resist underlayer film. A method for manufacturing a semiconductor device containing [a specific component].

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

[11] or

[12] , wherein the step of forming a resist underlayer film is performed by nanoimprint

[11] or

[12] . [Effects of the Invention]

[0010] According to the present invention, a novel resist underlayer forming composition is provided that eliminates the need to use harmful chemicals in the preparation of the resin, meets the requirements for improved solubility in PGME and PGMEA, reduction of the amount of sublimation contaminating the equipment, improved coating planarity on stepped substrates, and increased hardness of the resulting resist underlayer film, while maintaining other desirable properties. [Modes for carrying out the invention]

[0011] The resist underlayer film forming composition according to the present invention comprises a polymer (X) containing a plurality of identical or different structural units having a methoxymethyl group and a ROCH2- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group that links the plurality of structural units, and a solvent.

[0012] [Polymer (X)] The polymer (X) comprises a plurality of identical or different structural units having a methoxymethyl group and a ROCH2- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group that connects the plurality of structural units.

[0013] The monovalent organic group R may preferably be substituted with a phenyl group, a naphthyl group, or an anthracenyl group, and may be interrupted by an oxygen atom or a carbonyl group, forming a saturated or unsaturated linear or branched C2-C chain. 20 Aliphatic hydrocarbon group, C3-C 20 This refers to alicyclic hydrocarbon groups, or mixtures thereof. "Mixture" means that the multiple ROCH2- groups present within a single structural unit may be different, and that the ROCH2- groups in each of two or more structural units may be different.

[0014] Typical saturated aliphatic hydrocarbon groups include linear or branched alkyl groups having 2 to 20 carbon atoms, such as ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl Examples include ethyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, and 1-methoxy-2-propyl group.

[0015] Cyclic alkyl groups can also be used. For example, cyclic alkyl groups having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, and 1,2-dimethyl-cyclobutyl group. Examples include tyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group.

[0016] Typical unsaturated aliphatic hydrocarbon groups include alkenyl groups having 2 to 20 carbon atoms, such as ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, and 1-methyl-2 -Butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hex Cenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl Examples include propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0017] The saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group, and cyclic alkyl group may be interrupted once or twice or more by an oxygen atom and / or a carbonyl group. Particularly preferred are the -CH2CH2CH2CH3 group and the -CH(CH3)CH2OCH3 group.

[0018] Polymer (X) can be synthesized by polymerizing a compound having a methoxymethyl group and possibly a phenolic hydroxyl group, a compound that reacts with a methoxymethyl group to give a ROCH2- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and optionally a compound containing a functional group that acts as a linking group (e.g., aldehyde, ketone, ROCH2-Ar-CH2OR (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof)) in the presence of an acid catalyst (e.g., a sulfonic acid compound).

[0019] Examples of compounds that have a methoxymethyl group and may also have a phenolic hydroxyl group, which can be used in the synthesis of polymer (X), include 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl.

[0020] As a compound that reacts with a methoxymethyl group used in the synthesis of polymer (X) to give a ROCH2- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), an organic compound having a non-phenolic hydroxyl group in the molecule is preferred. Even if the molecule does not have a non-phenolic hydroxyl group, it may be an organic compound having a functional group that can be chemically converted into a non-phenolic hydroxyl group, such as an alkoxy group (-OR), an aldehyde group (-CHO), a carboxyl group (-COOH), an ester group (-COOR), or a ketone group (-COR). There may be one non-phenolic hydroxyl group, or a functional group that can be chemically converted into a non-phenolic hydroxyl group, in the molecule, or two or more. The organic compound can be an aliphatic hydrocarbon (preferably with 10 or fewer carbon atoms), an alicyclic hydrocarbon (preferably with 20 or fewer carbon atoms), or an aromatic hydrocarbon (for example, having at least one hydroxyl group in which the α-carbon is aliphatic). Examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, aliphatic alcohols (e.g., n-butanol), compounds represented by Ar-CH2OH (where Ar is, for example, benzene, naphthalene, anthracene, pyrene, fluorene, or m-terphenyl), aldehydes, ketones, and methylol compounds. Dioxane is not a compound that provides a ROCH2- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and is also harmful to the human body, so it is preferable not to use it.

[0021] Examples of organic compounds having an aldehyde group include aliphatic aldehydes such as formaldehyde, paraformaldehyde, butyraldehyde, and crotonaldehyde, and aromatic aldehydes such as furfural, pyridinecarboxaldehyde, benzaldehyde, naphthylaldehyde, anthrylaldehyde, phenanthrylaldehyde, salicylaldehyde, phenylacetaldehyde, biphenylaldehyde, 3-phenylpropionaldehyde, tolylaldehyde, (N,N-dimethylamino)benzaldehyde, acetoxybenzaldehyde, 1-pyrenecarboxaldehyde, and anisaldehyde.

[0022] Examples of organic compounds having the aforementioned ketone group include diaryl ketones such as diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, ditolyl ketone, 9-fluorenone, anthraquinone, and acenaphthaquinone, and spiroketones such as 11H-benzo[b]fluoren-11-one, 9H-tribenzo[a,f,l]triindene-9,14,15-trione, and indeno[1,2-b]fluoren-6,12-dione.

[0023] The structural units of the polymer (X) obtained in this manner preferably include aromatic rings, heterocycles, or fused rings, which may have phenolic hydroxyl groups and may have substituted or unsubstituted amino groups. Furthermore, the linking groups that connect the multiple structural units preferably include alkylene groups, ether groups, or carbonyl groups.

[0024] The compounds used in the synthesis of polymer (X) are not limited to one compound, but may be used in combination of two or more compounds. Therefore, the multiple structural units having a methoxymethyl group and a ROCH2- group other than the methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof) may be the same or different.

[0025] The weight-average molecular weight of the polymer (X) contained in the resist underlayer film-forming composition of the present invention is not particularly limited. It can be, for example, 1,000 or more, 2,000 or more, 500,000 or less, or 100,000 or less, on a standard polystyrene basis.

[0026] [solvent] The resist underlayer film forming composition of the present invention can be prepared by dissolving each of the above components in a suitable solvent and is used in a homogeneous solution state.

[0027] Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0028] Furthermore, high-boiling point solvents with a boiling point of 180°C or higher can also be used. Specific examples of high-boiling point organic solvents include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, triethylene Glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples include 6 - hexanediol diacetate, triethylene glycol diacetate, γ - butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, and the like.

[0029] These solvents can be used alone or in combination of two or more. The proportion of the solid content excluding the organic solvent from the composition is, for example, 0.5% to 30% by mass, preferably 0.8% to 15% by mass.

[0030] Also, the following compounds described in WO2018 / 131562A1 can also be used. [Chemical formula] (In formula (i), R 1 , R 2 and R 3 each represent an alkyl group having 1 to 20 carbon atoms which may be interrupted by a hydrogen atom, an oxygen atom, a sulfur atom or an amide bond, may be the same or different from each other, and may be bonded to each other to form a ring structure.)

[0031] Examples of alkyl groups having 1 to 20 carbon atoms include linear or branched alkyl groups that may or may not have substituents, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, cyclohexyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, p-tert-butylcyclohexyl group, n-decyl group, n-dodecylnonyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. Preferably, it is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0032] Examples of alkyl groups having 1 to 20 carbon atoms interrupted by an oxygen atom, a sulfur atom, or an amide bond include those containing the structural units -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. -O-, -S-, -NHCO-, or -CONH- may be present in one or more units within the alkyl group. Specific examples of alkyl groups having 1 to 20 carbon atoms interrupted by -O-, -S-, -NHCO-, or -CONH- units include methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, and butylaminocarbonyl groups. The group is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, or octadecyl group, each of which is substituted with a methoxy group, ethoxy group, propoxy group, butoxy group, methylthio group, ethylthio group, propylthio group, butylthio group, methylcarbonylamino group, ethylcarbonylamino group, methylaminocarbonyl group, ethylaminocarbonyl group, etc. Preferably, it is a methoxy group, ethoxy group, methylthio group, or ethylthio group, and more preferably, it is a methoxy group or ethoxy group.

[0033] Because these solvents have relatively high boiling points, they are also effective in imparting high embedding and high planarity properties to resist underlayer film forming compositions.

[0034] The following are specific examples of preferred compounds represented by formula (i). [ka]

[0035] Among the above, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and The following formula: [ka] Compounds represented by formula (i) are preferred, and particularly preferred compounds represented by formula (i) are 3-methoxy-N,N-dimethylpropionamide and N,N-dimethylisobutylamide.

[0036] These solvents can be used individually or in combination of two or more. Among these solvents, those with a boiling point of 160°C or higher are preferred, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide, 2,5-dimethylhexane-1,6-diyldiacetate (DAH; cas, 89182-68-3), and 1,6-diacetoxyhexane (cas, 6222-17-9) are particularly preferred. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutylamide are especially preferred.

[0037] [Optional ingredients] The resist underlayer film forming composition of the present invention may further contain at least one of the following as optional components: a crosslinking agent, an acid and / or an acid generator, a thermal acid generator, and a surfactant.

[0038] (Crosslinking agent) The resist underlayer film forming composition of the present invention may further contain a crosslinking agent. Preferably, the crosslinking agent is a crosslinkable compound having at least two crosslinking substituents. Examples include melamine compounds, substituted urea compounds, and phenolic compounds or polymers thereof, having crosslinking substituents such as methylol groups and methoxymethyl groups. Specifically, examples include compounds such as methoxymethylated glycoluryl, butoxymethylated glycoluryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, and butoxymethylated benzoguanamine. Examples include tetramethoxymethylglycoluryl, tetrabutoxymethylglycoluryl, and hexamethoxymethylmelamine. Furthermore, substituted urea compounds include compounds such as methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. Examples include tetramethoxymethylurea and tetrabutoxymethylurea. Condensed forms of these compounds can also be used. Examples of phenolic compounds include tetrahydroxymethylbiphenol, tetramethoxymethylbiphenol, tetrahydroxymethylbisphenol, tetramethoxymethylbisphenol, and compounds represented by the following formula. [ka] [ka]

[0039] As the crosslinking agent, a compound having at least two epoxy groups can also be used. Examples of such compounds include tris(2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and Daicel Corporation's Epolleed® GT-401, GT-403, GT-301, and GT-30 2. Celoxide® 2021, 3000, 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, 807, 152, 154, 180S75, 871, 872 manufactured by Mitsubishi Chemical Corporation, EPPN201, EPPN202, EPPN102, EPPN103S, EPPN104S, EPPN1020, EPPN1025, EPPN1027 manufactured by Nippon Kayaku Co., Ltd., and Denacol® EX-25 manufactured by Nagase ChemteX Corporation. 2. Examples include EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321, CY175, CY177, CY179, CY182, CY184, CY192 from BASF Japan Ltd., and Epiclon 200, 400, 7015, 835LV, and 850CRP from DIC Corporation. As the compound having at least two epoxy groups, an epoxy resin having an amino group can also be used. Examples of such epoxy resins include YH-434 and YH-434L (manufactured by Shin-Nippon Chemical Epoxy Manufacturing Co., Ltd.).

[0040] The crosslinking agent may also be a compound having at least two blocked isocyanate groups. Examples of such compounds include Takenate® B-830 and B-870N manufactured by Mitsui Chemicals, Inc., and Vestanat® B1358 / 100 manufactured by Evonik Degussa.

[0041] The crosslinking agent may also be a compound having at least two vinyl ether groups. Examples of such compounds include bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, tri(ethylene glycol) divinyl ether, divinyl adipate ester, diethylene glycol divinyl ether, 1,2,4-tris(4-vinyloxybutyl) trimellitate, 1,3,5-tris(4-vinyloxybutyl) trimellitate, bis(4-(vinyloxy)butyl) terephthalate, bis(4-(vinyloxy)butyl) isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, and cyclohexanedimethanol divinyl ether.

[0042] Furthermore, a crosslinking agent with high heat resistance can be used as the crosslinking agent. Preferably, a crosslinking agent with high heat resistance is a compound containing a crosslinking substituent having an aromatic ring (e.g., a benzene ring, a naphthalene ring) in its molecule.

[0043] Examples of this compound include compounds having the substructure of formula (4) below, or polymers or oligomers having the repeating unit of formula (5) below. [ka] The above R 11 , R 12 , R 13 , and R 14 n is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups described above can be used. n1 is an integer from 1 to 4, n2 is an integer from 1 to (5-n1), and (n1+n2) is an integer from 2 to 5. n3 is an integer from 1 to 4, n4 is from 0 to (4-n3), and (n3+n4) is an integer from 1 to 4. The oligomers and polymers can be used with a number of repeating unit structures ranging from 2 to 100, or from 2 to 50.

[0044] Examples of compounds, polymers, and oligomers of formulas (4) and (5) are given below. [ka] [ka] [ka]

[0045] The above compounds can be obtained as products of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, compound (4-23) can be obtained from Honshu Chemical Industry Co., Ltd. under the trade name TMOM-BP, compound (4-24) can be obtained from Asahi Organic Chemicals Co., Ltd. under the trade name TM-BIP-A, and compound (4-28) can be obtained from Finechem Co., Ltd. under the trade name PGME-BIP-A. The amount of crosslinking agent added varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more relative to the total solids, and is 80% by mass or less, 50% by mass or less, 40% by mass or less, 20% by mass or less, or 10% by mass or less. These crosslinking agents may undergo crosslinking reactions by self-condensation, but if crosslinkable substituents are present in the polymer of the present invention, they can undergo crosslinking reactions with those crosslinkable substituents.

[0046] You may add one of these crosslinking agents, or you may add two or more in combination.

[0047] (Acids and / or acid generators) The resist underlayer film forming composition according to the present invention may contain an acid and / or an acid generator.

[0048] Examples of acids include carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, pyridinium phenolsulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid, as well as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Only one type of acid may be used, or two or more types may be used in combination. The amount added is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass, relative to the total solid content.

[0049] Examples of acid generators include thermal acid generators and photoacid generators. Examples of thermal acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE® CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG-2689, TAG-2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), as well as quaternary ammonium salts of trifluoroacetic acid, alkyl organic sulfonates, and the like.

[0050] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0051] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0052] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0053] Only one type of acid generator may be used, or two or more types may be used in combination. When an acid generator is used, the ratio is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass, per 100 parts by mass of the solid content of the resist underlayer film forming composition.

[0054] (Surfactants) The resist underlayer film forming composition of the present invention may further contain a surfactant. 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 monosodium Nonionic surfactants such as thearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters; F-Top® EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Megafac® F171, F173, R-30, R-30-N, R-40, R-4 Examples of fluorine-based surfactants include 0-LM (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard® AG710, Surflon® S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). One of these surfactants may be added, or two or more may be added in combination. The content ratio of the surfactant is, for example, 0.01% to 5% by mass relative to the solid content of the resist underlayer film forming composition of the present invention excluding the solvent described later.

[0055] [Membrane material (Y)] The polymer (X) according to the present invention can also be used as a crosslinking agent for the film material (Y). That is, the resist underlayer film-forming composition according to the present invention further comprises a film material (Y) that can crosslink with the polymer (X). The film material (Y) can be said to be a film material that can crosslink with the polymer (X).

[0056] The membrane material (Y) used optionally in the present invention can be used without particular limitations as long as it is a material capable of crosslinking with the polymer (X) described above. The membrane material may be a polymer, an oligomer, or a low molecular weight compound with 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.

[0057] (a) Examples of crosslinkable film materials include alicyclic epoxy polymers having repeating structural units represented by the following formula (1), as disclosed in WO 2011 / 021555 A1. [ka] (T represents a repeating unit structure with an aliphatic ring in the polymer's main chain, and E represents an epoxy group or an organic group containing an epoxy group.)

[0058] E is a substituent on the aliphatic ring, and either the epoxy group is directly bonded to the aliphatic group, or an organic group having an epoxy group (e.g., a glycidyl group) is bonded to the aliphatic group. The aliphatic ring is, for example, a ring in which 4 to 10 carbon atoms are linked cyclically, and in particular a ring in which 6 carbon atoms are linked cyclically. The aliphatic ring may have substituents other than substituent E (an epoxy group or an organic group having an epoxy group). Examples of such substituents include alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, halogen atoms, nitro groups, and amino groups. The alicyclic epoxy polymer represented by formula (1) above has a weight-average molecular weight of 600 to 1,000,000, preferably 1,000 to 200,000. The number of repeating units of the alicyclic epoxy polymer (A) represented by formula (1) above is 2 to 3,000, or 3 to 600.

[0059] For example, the following polymers are given as examples. [ka]

[0060] (b) Examples of crosslinkable film materials include those described in WO 2014 / 024836 A1, such as those of formula (1a), formula (1b), and formula (1c): [ka] [In the formula, two R 1 Each of these 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, and the two R 2 Each of these 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 R represents an aromatic hydrocarbon group which may have substituents, 4 R represents a hydrogen atom, a phenyl group, or a naphthyl group, and is bonded to the same carbon atom. 3 and R 4 When each of them represents a phenyl group, they may bond to each other to form a fluorene ring, and in formula (1b) the two R 3 The group represented by and the two R 4 The atoms or groups represented by may be different from each other, the two ks each independently represent 0 or 1, m represents an integer from 3 to 500, n, n1 and n2 represent integers from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or a heteroatom, and the two Qs each independently represent the following equation (2): [ka] (In the formula, two R 1 , two R 2 , two R 3 , two R 4 The two k, n1, n2 and X are equivalent to equation (1b), and the two Q 1 Each of these independently represents a structural unit represented by formula (2) above. Examples include polymers having one or more of the repeating structural units represented by .

[0061] Preferably, the R 3 The aromatic hydrocarbon group represented is a phenyl group, naphthyl group, anthryl group, or pyrenyl group.

[0062] (c) Examples of crosslinkable film materials include those disclosed in WO 2010 / 147155 A1, such as 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, alkenyl group, or 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, alkenyl group, or 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 with a halogen group, a nitro group, an amino group, or a hydroxyl group. R5 represents a C1-C10 alkyl group, a C6-C40 aryl group, or a heterocyclic group, which may be substituted with a hydrogen atom, a halogen group, a nitro group, an amino group, or a hydroxyl group, and R4 and R5 may form a ring together with the carbon atom to which they are bonded. Examples include polymers containing a unit structure represented by n1 and n2, where n1 and n2 are integers from 1 to 3.

[0063] Preferably, the polymer contains a unit structure in formula (1) in which R1, R2, R3, and R5 each represent a hydrogen atom, and R4 represents a phenyl group or a naphthyl group. Preferably, the polymer according to claim 1, wherein in formula (1), R1, R2, and R3 each represent a hydrogen atom, and R4 and R5, together with the carbon atoms to which they are bonded, form a fluorene ring, and the unit structure includes a carbon atom at position 9 of the formed fluorene ring.

[0064] Preferably, the following formula (2) and / or formula (3): [ka] (In equations (2) and (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, alkenyl group, or 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, alkenyl group, or 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 with a halogen group, a nitro group, an amino group, or a hydroxyl group. R5 represents a C1-C10 alkyl group, a C6-C40 aryl group, or a heterocyclic group, which may be substituted with a hydrogen atom, a halogen group, a nitro group, an amino group, or a hydroxyl group, and R4 and R5 may form a ring together with the carbon atom to which they are bonded. n1 and n2 are integers from 1 to 3, n3 to n5 are integers from 1 to 4. The polymer contains a unit structure represented by ( ).

[0065] Preferably, the polymer contains a unit structure in formula (2) and / or formula (3) in which R1, R2, R3, R5, R6, R7, and R8 each represent a hydrogen atom, and R4 represents a phenyl group or a naphthyl group.

[0066] (d) Examples of crosslinkable membrane materials include polymers containing a unit structure consisting of a reaction product of a condensed heterocyclic compound and a bicyclocyclic compound, as disclosed in WO 2013 / 005797 A1.

[0067] Preferably, the condensed heterocyclic compound is a carbazole compound or a substituted carbazole compound. Preferably, the above bicyclocyclic 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 It is dodeca-3,8-diene.

[0068] Preferably, the polymer is a polymer comprising a unit structure represented by formula (1), a unit structure represented by formula (2), a unit structure represented by formula (3), or a combination thereof. [ka] (In the formula, R 1 ~R 14 is a substituent on the hydrogen atom, each independently being a halogen group, a nitro group, an amino group, or 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 with these groups, and Ar is an aromatic ring group having 6 to 40 carbon atoms, n1, n2, n5, n6, n9, n 10 , n 13 , n 14 and n 15 Each of these is an integer from 0 to 3, such as n3, n4, n7, n8, n 11 and n 12 (Each of these is an integer between 0 and 4.) Preferably, in formula (3) above, Ar is a phenyl group or a naphthyl group.

[0069] (e) Examples of crosslinkable film materials include those disclosed in WO 2012 / 176767 A1, such as formula (1): [ka] Examples of polymers include those containing the unit structure of (in formula (1), where A is a hydroxyl group-substituted phenylene group derived from polyhydroxybenzene, and B is a monovalent condensed aromatic hydrocarbon ring group formed by the condensation of 2 to 4 benzene rings).

[0070] Preferably, A is a hydroxyl group-substituted phenylene group derived from a benzenediol or benzenetriol. Preferably, A is a hydroxyl group-substituted phenylene group derived from catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, or phloroglucinol. Preferably, the condensed aromatic hydrocarbon ring group of B is a naphthalene ring group, an anthracene ring group, or a pyrene ring group. Preferably, the condensed aromatic hydrocarbon ring group of B has a halogen group, hydroxyl group, nitro group, amino group, carboxyl group, carboxylic acid ester group, nitrile group, or a combination thereof as a substituent.

[0071] (f) Examples of crosslinkable film materials include those disclosed in WO 2013 / 047516 A1, such as the following formula (1): [ka] (In formula (1), Ar 1 , and Ar 2 Each represents either a benzene ring or a naphthalene ring, and R 1 and R 2 Each of these is a substituent on a hydrogen atom on these rings, selected from the group consisting of halogen groups, nitro groups, amino groups, hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, alkenyl group and aryl group represent organic groups which may contain ether bonds, ketone bonds or ester bonds. R 3 This 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, alkenyl group and aryl group represent an organic group which may contain an ether bond, a ketone bond or an ester bond. R 4 This 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 organic groups which may be substituted with halogen groups, nitro groups, amino groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, formyl groups, carboxyl groups, or hydroxyl groups. R 5R 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 These may form a ring together with the carbon atoms to which they are bonded. n1 and n2 are integers from 0 to 3. Examples include polymers containing a unit structure (A) represented by ).

[0072] Preferably, R in formula (1) above 5 is a hydrogen atom, and R 4 The group may be a phenyl group, naphthyl group, anthryl group, or pyrenyl group, which may be substituted. Preferably, R in formula (1) above 3 This is either a hydrogen atom or a phenyl group. Preferably, in the above unit structure (A), Ar 1 and Ar 2 This includes a unit structure (a1) in which one is a benzene ring and the other is a naphthalene ring. Preferably, in the above unit structure (A), Ar 1 and Ar 2 Both contain a unit structure (a2) which is a benzene ring. Preferably, it is a copolymer containing unit structure (a1) and unit structure (a2).

[0073] Preferably, a unit structure (A) of formula (1) and a unit structure (B) of the following formula (2): [ka] (In formula (2), R 6 R 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 organic groups which may be substituted with halogen groups, nitro groups, amino groups, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, formyl groups, carboxyl groups, or hydroxyl groups.7 R 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 These may form a ring together with the carbon atoms to which they are bonded. ) This is a copolymer containing these elements. Preferably, it is a copolymer containing unit structure (a1) and unit structure (B).

[0074] (g) Examples of crosslinkable film materials include those disclosed in WO 2013 / 146670 A1, such as the following formula (1): [ka] (In formula (1), R 1 , R 2 , and R 3 R is a substituent on the hydrogen atom of the ring, and each can independently be a halogen group, a nitro group, an amino group, a hydroxyl group, a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C6 to C40 aryl group, or a combination thereof, which may include an ether bond, a ketone bond, or an ester bond. 4 R may contain 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 include an ether bond, a ketone bond, or an ester bond. 5 R is a hydrogen atom, or a halogen group, nitro group, amino group, formyl group, carboxyl group, alkyl carboxylate group, phenyl group, alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms which may be substituted with a hydroxyl group, and R 6 is a C1 to C10 alkyl group, a C6 to C40 aryl group, or a heterocyclic group, which may be substituted with a hydrogen atom, a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, an alkyl carboxylate group, or a hydroxyl group, or R5 and R 6 These may form a ring together with the carbon atoms to which they are bonded. Rings A and B represent a benzene ring, a naphthalene ring, or an anthracene ring, respectively. n1, n2, and n3 are integers greater than or equal to 0 and up to the maximum number that can be substituted in the ring. Examples of polymers having a unit structure represented by ) are shown.

[0075] Preferably, both ring A and ring B are benzene rings, n1, n2, and n3 are 0, and R 4 That is a hydrogen atom. Preferably, R 5 R is a hydrogen atom, or a phenyl group, naphthyl group, anthryl group, or pyrenyl group which may be substituted with a halogen group, a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, an alkyl carboxylate group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group, and 6 That is a hydrogen atom.

[0076] (h) Examples of crosslinkable film materials include those described in WO 2014 / 129582 A1, such as those with the following formulas (1a), (1b), and (1c): [ka] [In the formula, two R 1 Each of these 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, and the two R 2 Each of these 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 R represents an aromatic hydrocarbon group which may have substituents, 4 R represents a hydrogen atom, a phenyl group, or a naphthyl group, and is bonded to the same carbon atom. 3 and R 4 When each of them represents a phenyl group, they may bond to each other to form a fluorene ring, and in formula (1b) the two R 3 The group represented by and the two R4 The atoms or groups represented by may be different from each other, the two ks each independently represent 0 or 1, m represents an integer from 3 to 500, n, n1 and n2 represent integers from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or a heteroatom, and the two Qs each independently represent the following equation (2): [ka] (In the formula, two R 1 , two R 2 , two R 3 , two R 4 The two k, n1, n2 and X are equivalent to equation (1b), and the two Q 1 Each of these independently represents a structural unit represented by formula (2) above. This represents a structural unit. Examples include polymers having one or more of the repeating structural units represented by .

[0077] Preferably, the R 3 The aromatic hydrocarbon group represented is a phenyl group, naphthyl group, anthryl group, or pyrenyl group.

[0078] (i) Examples of crosslinkable film materials include those disclosed in WO 2016 / 072316 A1, such as the following formula (1): [ka] (In formula (1), R 1 ~R 4 Each of these independently represents either a hydrogen atom or a methyl group. 1 This 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. Examples include polymers containing a unit structure represented by ).

[0079] Preferably, in formula (1), X 1The 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.

[0080] Preferably, in formula (1), X 1 is formula (2):

Chemical formula

Chemical formula

[0081] (j) As the film material capable of undergoing a crosslinking reaction, there can be mentioned novolak resins obtained by the reaction of an aromatic compound (A) with an aldehyde (B) having a formyl group bonded to a secondary carbon atom or a tertiary carbon atom of an alkyl group having 2 to 26 carbon atoms, as disclosed in WO 2017 / 069063 A1.

[0082] Preferably, the novolak resin has the following formula (1):

Chemical formula

[0083] Preferably, A is a divalent group 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 containing an arylamine compound, a phenol 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.

[0084] Preferably, the novolak resin has the following formula (2):

Chemical formula

[0085] (k) As the film material capable of undergoing a crosslinking reaction, there are the following formula (1a) and / or formula (1b) as disclosed in WO 2017 / 199768 A1:

Chemical formula

[0086] Preferably, the polymer is a polymerization 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 is a phenyl group, naphthyl group, anthryl group, or pyrenyl group.

[0087] (l) Examples of crosslinkable film materials include poly(epoxide) resins having an epoxy functional value greater than 2.0 and less than 10, as disclosed in Japanese Patent Application Publication No. 11-511194.

[0088] 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, polyglycidylamines, alicyclic epoxides, and polyglycidyl esters. Preferably, the poly(epoxide) resin has an epoxy functional value greater than 3.5.

[0089] (m) Examples of crosslinkable membrane materials or novolac membrane materials include compounds represented by the following formula (1) and novolac membrane 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 )- represents, X 2 is -N(R 2 )- or -CH(R 2 )- represents, X 3 -N=, -CH=, -N(R 3 )- or -CH(R 3 )- represents, X 4 -N=, -CH=, -N(R 4 )- or -CH(R 4 )- represents, R 1 , R 2 , R 3 and R 4 These are identical or different, each representing 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, and the alkyl and aryl groups may be substituted with a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or a hydroxyl group, and may be interrupted by an oxygen atom or a sulfur atom. R 5 , R 6 , R 9and R 10 These are identical or different, and each represents a hydrogen atom, a hydroxyl 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. 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 amino group, nitro group, cyano group, hydroxyl group, glycidyl group, and carboxyl group. R 7 and R 8 They are identical or different, each representing either a benzene ring or a naphthalene ring. n and o are either 0 or 1.

[0090] Preferably, R in formula (1) 1 , R 2 , R 3 or R 4 However, it is a C1-20 linear, branched, or cyclic alkyl group that may be substituted with a hydroxyl group and may be interrupted by an oxygen atom or a sulfur atom.

[0091] Preferably, the compound contains one or more of the repeating units a, b, c, d, e, f, g, h, 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< represents, X 2 is -N(R 2 )-,-CH(R 2 )-, -N< or -CH< represents, X 3 -N=, -CH=, -N(R 3 )-,-CH(R 3 )-, -N< or -CH< represents, X 4 -N=, -CH=, -N(R 4 )-,-CH(R 4 )-, -N< or -CH< represents, R 1 , R 2 , R 3 and R 4 These are identical or different, each representing 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, and the alkyl and aryl groups may be substituted with a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or a hydroxyl group, and may be interrupted by an oxygen atom or a sulfur atom. R 5 , R 6 , R 9 and R 10 These are identical or different, and each represents a hydrogen atom, a hydroxyl 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. 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 amino group, nitro group, cyano group, hydroxyl group, glycidyl group, and carboxyl group. R 7 and R 8 They are identical or different, each representing either a benzene ring or a naphthalene ring. n and o are either 0 or 1. B 1 and B 2 B represents a group derived from an aromatic compound selected from the group consisting of a linear, branched, or cyclic alkyl group of C1-20 or a C6-40 aryl group and a C6-40 heterocyclic group, which may be the same or different and may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom. 1 and B 2 These may form a ring together with the carbon atoms to which they are bonded, and the hydrogen atoms of the groups derived from the aromatic compound may be substituted with C1-20 alkyl groups, phenyl groups, fused ring groups, heterocyclic groups, hydroxyl groups, amino groups, ether groups, alkoxy groups, cyano groups, nitro groups, or carboxyl groups.

[0092] Preferably, the compound contains one or more of the 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 This represents -N< or -CH<, X 2 This represents -N< or -CH<, X 3 -N=, -CH=, -N(R 3 )- or -CH(R 3 )- represents, X 4 -N=, -CH=, -N(R 4 )- or -CH(R 4 )- represents, R 3 and R 4These are identical or different, each representing 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, and the alkyl and aryl groups may be substituted with a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or a hydroxyl group, and may be interrupted by an oxygen atom or a sulfur atom. R 5 , R 6 , R 9 and R 10 These are identical or different, and each represents a hydrogen atom, a hydroxyl 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. 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 amino group, nitro group, cyano group, hydroxyl group, glycidyl group, and carboxyl group. R 7 and R 8 They are identical or different, each representing either a benzene ring or a naphthalene ring. n and o are either 0 or 1. p and q are integers between 0 and 20. If there are two or more methylene groups, the p and q methylene groups may be interrupted by oxygen or sulfur atoms. B 3 [This represents a group derived from a C6-40 aromatic compound that is directly bonded or substituted with a C1-20 alkyl group, phenyl group, fused ring group, heterocyclic group, hydroxyl group, amino group, ether group, alkoxy group, cyano group, nitro group, or carboxyl group.]

[0093] Preferably, R in formula (1) 1 , R 2 , R 3 or R 4is a C1-20 linear, branched or cyclic alkyl group which may be substituted with a hydroxy group or a hydroxy group and may be interrupted by an oxygen atom or a sulfur atom.

[0094] (n) As the film material capable of undergoing a crosslinking reaction, there may be mentioned an epoxy adduct formed by the reaction of an epoxy group-containing compound having at least two epoxy groups and an epoxy adduct-forming compound having one epoxy addition-reactive group, as disclosed in WO 2017 / 002653 A1. Such an epoxy adduct can be exemplified as follows.

[0095]

Chemical formula

Chemical formula

[0096]

Chemical formula

[0097]

Chemical formula

[0098] (In the formula, a, b, c, and d are each 0 or 1, and a + b + c + d = 1.)

[0099] (o) As the film material capable of undergoing a crosslinking reaction, there may be mentioned those as disclosed in WO 2005 / 098542 A1, of the formula (1):

[0100]

Chemical formula

[0101] [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 alkyl groups 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, and 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 alkyl groups 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 is formula (6) or formula (7): [ka] Examples of polymers having a structure represented by the formula (wherein Q1 represents an alkylene group, phenylene group, naphthylene group, or anthrylene group having 1 to 10 carbon atoms, and the phenylene group, naphthylene group, and anthrylene group may each 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 n1 and n2 each represent the number 0 or 1, and X2 represents formula (2), formula (3), or formula (5)).

[0102] Preferably, the structure represented by formula (1) is formula (12): [ka] (In the formula, R1, R2, and Q have the same meanings as defined above.) or, formula (13): [Chemical formula] (wherein, X1 represents the same meaning as defined above, Y represents 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 represents an integer from 0 to 4, and when m is from 2 to 4, the Ys may be the same or different) It is a structure represented by the following.

[0103] (p) As the film material capable of undergoing a crosslinking reaction, as disclosed in WO 2006 / 115074 A1, formula (1) or formula (2): [Chemical formula] (wherein, 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, and Q is formula (3) or formula (4): [Chemical formula] [wherein, 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 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 a number of 0 or 1, and X1 is formula (5), (6) or formula (7): [Chemical formula] (In the formula, 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 alkyl groups 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. Also, 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 alkyl groups 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.) A polymer having a repeating unit structure represented by} is an example.

[0104] Preferably, the polymer is of formula (12): [ka] It is a polymer having a repeating unit structure represented by the formula (wherein Q is the same as above).

[0105] Preferably, the polymer is of formula (13) and formula (14): [ka] [In the formulas, Q2 is formula (15), formula (16), or formula (17): [ka] (In the formula, Y, m, R3, R4, and R5 are the same as above.) and Q3 is formula (18): [ka] (In the formula, Q4 represents an alkylene group having 1 to 15 carbon atoms, and n3 and n4 represent the number 0 or 1, respectively.) This is a polymer having a repeating unit structure represented by ].

[0106] (q) Examples of crosslinkable membrane materials include those described in WO 2008 / 069047 A1, such as formulas (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 of these 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 chain or cyclic alkyl group having 1 to 10 carbon atoms. R9 represents a chain or cyclic alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, and also, R7 and R8 may be bonded to each other to form a ring. M and Q represent direct bonds or linking groups, respectively. n represents an integer of 0 or 1.) A polymer comprising a polymer or a combination thereof containing at least one unit structure selected from the group consisting of unit structures represented by ), wherein when the total number of all unit structures constituting the polymer is set to 1.0, the ratio of the number of unit structures represented by formula (1) (a), the ratio of the number of unit structures represented by formula (2) (b), and the ratio of the number of unit structures represented by formula (3) (c) is 0.3 ≤ a ≤ 0.95, 0.005 ≤ b ≤ 0.7, and 0 ≤ c ≤ 0.45.

[0107] 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 set to 1.0, the ratio of the number of unit structures represented by formula (1) (a) and the ratio of the number of unit structures represented by formula (2) (b) are 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 set to 1.0, the ratio of the number of unit structures represented by formula (1) (a) and the ratio of the number of unit structures represented by formula (3) (c) are 0.35 ≤ a + c ≤ 1, 0.3 ≤ a ≤ 0.95, and 0.05 ≤ c ≤ 0.7. Preferably, the polymer contains unit structures represented by formulas (1), (2), and (3), and when the total number of all unit structures constituting the polymer is set to 1.0, the ratio of the number of unit structures represented by formula (1) (a), the ratio of the number of unit structures represented by formula (2) (b), and the ratio of the number of unit structures represented by formula (3) (c) is such that 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.

[0108] (r) Examples of crosslinkable film materials include those disclosed in WO 2018 / 203464 A1, such as those described in formula (2): [ka] Examples of compounds represented by formula (2) (wherein the two Ars each represent an aryl group, the 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) include compounds whose molecular weight is, for example, 150 to 600.

[0109] In formula (2), examples of the aryl group represented by Ar include a phenyl group, a biphenylyl group, a naphthyl group, anthryl group, and a phenanthryl group. Furthermore, when Q represents a divalent linking group having at least one benzene ring or naphthalene ring, examples of such divalent linking groups include a divalent group in which at least one of the two hydrogen atoms of a methylene group is substituted 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 such a divalent aromatic group with a methylene group, an ether group (-O- group), or a sulfide group (-S- group). Examples of such monomers include compounds represented by the following formulas (2-1) to (2-6). [ka] (In equation (2-6), m represents an integer between 0 and 3.)

[0110] (s) Examples of crosslinkable membrane materials include those disclosed in WO 2011 / 108365 A1 and WO 2016 / 143436 A1, where the following formula (1) is used for one molecule of fullerene: [ka] (In the formula, R independently represents an alkyl group having 1 to 10 carbon atoms.) Examples include fullerene derivatives to which one to six molecules of malonic acid diester represented by [the formula shown] are added.

[0111] (t) Examples of crosslinkable membrane materials include polyfunctional (meth)acrylate compounds with molecular weights of 300 to 10,000 that are in a liquid state at room temperature and atmospheric pressure, as disclosed in WO 2011 / 132640 A1.

[0112] Preferably, the compound is a compound having 2 to 20 (meth)acrylate groups in its molecule. Preferably, the molecular weight of the compound is 300 to 2,300.

[0113] Examples of such compounds are given below.

[0114] [ka]

[0115] [ka]

[0116] (u) Examples of crosslinkable membrane materials include compounds (E) such as those disclosed in WO 2017 / 154921 A1, which include a substructure (I) and a substructure (II), wherein the substructure (II) includes a hydroxyl group produced by the reaction of an epoxy group with a proton-generating compound, and the substructure (I) is at least one substructure selected from the group consisting of substructures represented by the following formulas (1-1) to (1-5), or a substructure consisting of a combination of a substructure represented by formula (1-6) and a substructure represented by formula (1-7) or formula (1-8), and the substructure (II) is a substructure 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 of these 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. 2 , R 2a , R 4 , and R 6Each of these 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. 2 , R 2a , R 4 , R 6 R is a monovalent group. 1 , R 1a , R 3 , R 5a , and R 6a R is a divalent group. 5 R indicates a trivalent group, 7 , R 8 , R 9 , R 10 and R 11 Each of the following 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 line indicates a chemical bond with an adjacent atom.

[0117] Preferably, compound (E) contains epoxy groups and hydroxyl groups in a molar ratio of 0 ≤ (epoxy groups) / (hydroxyl groups) ≤ 0.5, and substructure (II) in a molar ratio of 0.01 ≤ (substructure (II)) / (substructure (I) + substructure (II)) ≤ 0.8. Preferably, compound (E) is a compound comprising at least one substructure (I) and at least one substructure (II). Preferably, the above R 5a , and R 6a These are divalent groups consisting of an alkylene group with 1 to 10 carbon atoms, an arylene group with 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, or a combination thereof. Preferably, compound (E) contains substructure (I) and substructure (II) in a ratio of 1 to 1000 units each.

[0118] (v) Examples of crosslinkable membrane materials include compounds comprising at least one photodegradable nitrogen-containing structure and / or a photodegradable sulfur-containing structure and a hydrocarbon structure, as disclosed in WO 2018 / 030198 A1.

[0119] Preferably, the above compound is a compound having one or more photodegradable nitrogen-containing structures and / or photodegradable sulfur-containing structures within its 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 exist within the same molecule, or a combination of compounds in which these structures exist in molecules with different properties. 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 photodegradable nitrogen-containing structure is a structure that generates a reactive nitrogen-containing functional group or a reactive carbon-containing functional group upon ultraviolet irradiation, or a structure that includes a reactive nitrogen-containing functional group or a reactive carbon-containing functional group generated upon ultraviolet irradiation. Preferably, the photodegradable nitrogen-containing structure is a photodegradable nitrogen-containing structure that may contain a sulfur atom, and the structure includes an azide structure, a tetraazole structure, a triazole structure, an imidazole structure, a pyrazole structure, an azole structure, a diazo structure, or a combination thereof. Preferably, the photodegradable sulfur-containing structure is a structure that generates an organic sulfur radical or a carbon radical upon ultraviolet irradiation, or a structure that contains an organic sulfur radical or a carbon radical generated upon ultraviolet irradiation. Preferably, the photodegradable sulfur-containing structure is a photodegradable sulfur-containing structure that may contain a nitrogen atom, and the structure includes a trisulfide structure, a disulfide structure, a sulfide structure, a thioketone structure, a thiophene structure, a thiol structure, or a combination thereof.

[0120] Preferably, the following compounds: [ka] [ka]

[0121] (w) Examples of crosslinkable membrane materials include compounds represented by the following formula (1), as disclosed in WO 2019 / 013293 A1. [ka] (In formula (1), R 1 Each of these is an independent divalent group with 1 to 30 carbon atoms, and R 2 ~R 7 Each of these is independently 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 them is a hydroxyl group or a thiol group, 2 , m 3 and m 6 Each of these is an independent integer from 0 to 9, and m 4 and m 7 Each of these is an independent integer from 0 to 8, and m 5 n is an integer from 1 to 9, n is an integer from 0 to 4, and p 2 ~p 7 (Each of these is an independent integer between 0 and 2.)

[0122] Preferably, the following compounds: [ka]

[0123] (x) Examples of crosslinkable film materials include compounds represented by the following general formula (1), as disclosed in Japanese Patent Application Publication No. 2016-216367. [ka] (In the formula, n1 and n2 each independently represent 0 or 1, W is either a single bond or a structure shown in formula (2) below, R1 is one of the structures shown in general formula (3) below, and m1 and m2 each independently represent integers from 0 to 7, where m1 + m2 is between 1 and 14.) [ka] (In the formula, l represents an integer from 0 to 3, R a ~R f Each of these independently represents a hydrogen atom or a fluorine-substituted alkyl group, phenyl group, or phenylethyl group having 1 to 10 carbon atoms, and R a and R b (They may combine 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, naphthyl, anthracenyl, or pyrenyl group. When Q1 represents a linear, branched saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, the methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group.)

[0124] Preferably, the compound represented by general formula (1) is the compound represented by general formula (4) below. [ka] (In the formula, m3 and m4 represent 1 or 2, and W and R1 are as described above.)

[0125] Preferably, 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.)

[0126] Preferably, the compound represented by the general formula (1) has two or more Q1 molecules, and the Q1 molecules include one or more of the structures represented by the general formula (6) and the general formula (7). [ka] (In the formula, ** represents the bonding site to the carbonyl group, R h R represents a linear, branched, saturated, or unsaturated hydrocarbon group having 1 to 30 carbon atoms. h The methylene group constituting the compound may be substituted with an oxygen atom or a carbonyl group. [ka] (In the formula, ** represents the bonding site to the carbonyl group, R i R represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms. j n represents a linear or branched hydrocarbon group with 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group with 1 to 10 carbon atoms, or an alkanoyloxy group with 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, each an integer from 0 to 7. However, n3 + n4 is between 0 and 7. n5 represents 0 to 2.

[0127] (y) Examples of crosslinkable film materials include compounds represented by the following general formula (1A), as disclosed in Japanese Patent Application Publication No. 2017-119670. [ka] (In the formula, R is a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, an -SO- group, or an -SO2- group; R1 is the group represented by the general formula (1B) below; and m1 and m2 are integers satisfying 1 ≤ m1 ≤ 5, 1 ≤ m2 ≤ 5, and 2 ≤ m1 + m2 ≤ 8.) [ka] (In the formula, X 1 (where X is the group represented by the following general formula (1C), and X is the group represented by the following general formula (1D).) [ka] (In the formula, (X) indicates the point of connection with X.) [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, where n1 is 0 or 1, n2 is 1 or 2, and X 3 (This is the group represented by the following general formula (1E), where n5 is 0, 1, or 2.) [ka] (In the formula, R 10 (wherein 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.)

[0128] Preferably, the molecular weight of the compound is 2,500 or less.

[0129] Preferably, the compounds are those 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, an -SO- group, or an -SO2- group; R2 is the group represented by the general formula (2B) below; and m3 and m4 are integers satisfying 1 ≤ m3 ≤ 5, 1 ≤ m4 ≤ 5, and 2 ≤ m3 + m4 ≤ 8.) [ka] (In the formula, X 11 X' is the group represented by the following general formula (2C), and X' is the group represented by the following general formula (2D). [ka] (In the formula, (X') indicates the point of connection with X'.) [ka] (In the formula, n3 is 0 or 1, n4 is 1 or 2, X 4 (This is the group represented by the following general formula (2E), where n6 is 0, 1, or 2.) [ka] (In the formula, R 11 (wherein 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 Each is independently a hydroxyl group, m100 is 1, 2, or 3, and R 100 When m100 is 1, it is a hydrogen atom or a hydroxyl group; when m100 is 2, it is a single bond or a group represented by the following general formula (3B); and when m100 is 3, it is a group represented by the following general formula (3C), and the hydrogen atom on the aromatic ring in the formula 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. If m101 is 0, then n101 and n102 are integers satisfying 0≦n101≦3, 0≦n102≦3, and 1≦n101+n102≦4. If m101 is 1, then n101, n102, n103, and n104 are integers satisfying 0≦n101≦2, 0≦n102≦2, 0≦n103≦2, 0≦n104≦2, and 2≦n101+n102+n103+n104≦8. [ka] (In the formula, * indicates the bond position, R 106 , R 107R is an organic group that does not contain a hydrogen atom or an ester bond with 1 to 24 carbon atoms. 106 and R 107 They may combine to form a cyclic structure. [ka] (In the formula, * indicates the bond position, R 108 (This refers to a hydrogen atom or an organic group with 1 to 15 carbon atoms.)

[0130] (z) Examples of polyether film materials include polymers represented by the following general formula (1), as disclosed in WO2012 / 050064. Formula (1): [ka] (In formula (1), Ar1 represents an organic group containing an arylene group or heterocyclic group having 6 to 50 carbon atoms.) The unit structure is represented by the following formula (2): [ka] A polymer comprising a unit structure represented by formula (1) and a combination of the unit structures represented by formula (2), where Ar2, Ar3, and Ar4 each represent organic groups containing an arylene group or heterocyclic group having 6 to 50 carbon atoms, and T represents a carbonyl group or a sulfonyl group.

[0131] The above crosslinkable film material (Y) is preferably, (Y1) A membrane material containing an aliphatic ring (e.g., (a)(m) above), (Y2) Novolac film material (e.g., the above (b)(c)(d)(e)(f)(g)(h)(i)(j)(k)(l)), (Y3) Polyether film material (e.g., (z) above), (Y4) Polyester membrane material (e.g., (o)(p) above), (Y5) A compound different from the crosslinkable compound (A) (for example, the above (m)(n)(r)(s)(t)(u)(v)(w)(x)(y)), (Y6) A film material containing an aromatic condensed ring (e.g., (q) above), (Y7) Acrylic resin, and (Y8) Methacrylic resin It includes at least one selected from the group consisting of the following.

[0132] When the resist underlayer film-forming composition according to the present invention contains a crosslinkable film material (Y) (film material or polymer), the content of the crosslinkable film material (Y) is usually 1 to 99.9% by mass, preferably 50 to 99.9% by mass, more preferably 50 to 95% by mass, and even more preferably 50 to 90% by mass, relative to the total solid content.

[0133] The resist underlayer film forming composition of the present invention may further contain absorbents, rheology modifiers, adhesion aids, and the like. Rheology modifiers are effective in improving the fluidity of the underlayer film forming composition. Adhesion aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

[0134] (Photo-absorbing agent) Examples of light absorbers include commercially available light absorbers listed in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry), such as CIDisperse 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; CIDisperse Orange 1,5,13,25,29,30,31,44,57,72 and 73; CIDisperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199 and 210; CIDisperse Violet 43; CIDisperse Blue 96; and CIFluorescent Brightening Agent. 112, 135 and 163; CISolvent Orange 2 and 45; CISolvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CIPigment Green 10; CIPigment Brown 2, etc., can be suitably used. The above light absorbers are usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solid content of the resist underlayer film forming composition.

[0135] (Rheological modifier) Rheology modifiers are primarily added to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the uniformity of the resist underlayer film thickness and enhance the filling of holes by the resist underlayer film-forming composition. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as din-normal butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as din-normal butyl malate, diethyl malate, and dinonyl malate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in a proportion of less than 30% by mass relative to the total solid content of the resist underlayer film-forming composition.

[0136] (Adhesion aid) Adhesion aids are added primarily to improve the adhesion between the substrate or resist and the resist underlayer film-forming composition, and especially to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; and methyloltric Examples of adhesive aids include silanes such as lorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesive aids are usually blended in a proportion of less than 5% by mass, preferably less than 2% by mass, relative to the total solid content of the resist underlayer film forming composition.

[0137] The solid content of the resist underlayer film forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the proportion of all components in the resist underlayer film forming composition excluding the solvent. The proportion of the polymer in the solid content is preferably in the order of 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

[0138] One way to evaluate whether a resist underlayer film-forming composition is in a uniform solution state is to observe its passability through a specific microfilter. The resist underlayer film-forming composition according to the present invention passes through a microfilter with a pore size of 0.1 μm and exhibits a uniform solution state.

[0139] Examples of microfilter materials include fluororesins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, but PTFE (polytetrafluoroethylene) is preferred.

[0140] [Underlying resist film] The resist underlayer can be formed using the resist underlayer forming composition according to the present invention as follows. The resist underlayer film forming composition of the present invention is applied to a substrate used in the manufacture of semiconductor devices (e.g., silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low-k material coated substrates, etc.) by an appropriate coating method such as a spinner or coater, and then fired using a heating means such as a hot plate to form a resist underlayer film. The firing conditions are appropriately selected from a firing temperature of 80°C to 600°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 350°C and the firing time is 0.5 to 2 minutes. Air may be used as the atmospheric gas during firing, or an inert gas such as nitrogen or argon may be used. The thickness of the underlayer film formed is, for example, 10 to 1000 nm, or 20 to 500 nm, or 30 to 400 nm, or 50 to 300 nm. Furthermore, by using a quartz substrate, it is possible to create a replica (mold replica) of the quartz imprint mold.

[0141] Furthermore, an adhesion layer and / or a silicone layer containing 99% by mass or less, or 50% by mass or less, of Si can be formed on the resist underlayer film according to the present invention by coating or vapor deposition. For example, in addition to the method of forming the adhesion layer described in Japanese Patent Application Publication No. 2013-202982 and Japanese Patent No. 5827180, and the silicon-containing resist underlayer film (inorganic resist underlayer film) forming composition described in WO2009 / 104552A1 by spin coating, a Si-based inorganic material film can be formed by CVD or the like.

[0142] Furthermore, by applying the resist underlayer forming composition according to the present invention onto a semiconductor substrate having a stepped portion and a non-stepped portion (a so-called stepped substrate) and firing it, a resist underlayer can be formed in which the step difference between the stepped portion and the non-stepped portion is in the range of 3 to 70 nm.

[0143] [Manufacturing method for semiconductor devices] The method for manufacturing a semiconductor device according to the present invention is: A step of forming a resist underlayer film using the resist underlayer film forming composition according to the present invention, A step of forming a resist film on the formed resist underlayer film, A process of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it. A step of etching and patterning the resist underlayer film through the formed resist pattern, and Process of processing a semiconductor substrate via a patterned resist underlayer film. Includes.

[0144] Furthermore, the method for manufacturing a semiconductor device according to the present invention is A step of forming a resist underlayer film using the resist underlayer film forming composition according to the present invention, A step of forming a hard mask on the formed resist underlayer film, A step of forming a resist film on the formed hard mask, A process of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it. A step of etching and patterning the hard mask through the formed resist pattern, and A step of etching and patterning the resist underlayer film through a patterned hard mask, and Process of processing a semiconductor substrate via a patterned resist underlayer film. Includes.

[0145] The process of forming a resist underlayer film using the resist underlayer film forming composition according to the present invention is as described above.

[0146] An organopolysiloxane film may be formed as a second resist underlayer on the resist underlayer formed by the above process, and a resist pattern may be formed on it. This second resist underlayer may be a SiON film or SiN film formed by a vapor deposition method such as CVD or PVD. Furthermore, an anti-reflective coating (BARC) may be formed as a third resist underlayer on this second resist underlayer, and this third resist underlayer may be a resist shape correction film that does not have anti-reflective properties.

[0147] In the process of forming the resist pattern, exposure is performed either through a mask (reticle) for forming a predetermined pattern or by direct drawing. For example, g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, or electron beam can be used as the exposure source. After exposure, post-exposure baking is performed as needed. Then, the resist is developed with a developer (e.g., a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), and further rinsed with a rinse solution or pure water to remove the used developer. Finally, post-baking is performed to dry the resist pattern and improve its adhesion to the substrate.

[0148] The etching process performed after the formation of the resist pattern is carried out by dry etching. Examples of etching gases used for dry etching include CHF3, CF4, and C2F6 for the second resist underlayer film (organopolysiloxane film), O2, N2O, and NO2 for the first resist underlayer film formed from the resist underlayer film forming composition of the present invention, and CHF3, CF4, and C2F6 for surfaces having steps, recesses, and / or protrusions. Furthermore, argon, nitrogen, or carbon dioxide can be mixed with these gases and used.

[0149] [Formation of a resist underlayer by nanoimprint lithography] The process of forming the resist underlayer film described above can also be carried out by nanoimprint lithography. This method is as follows: A step of applying a curable composition onto the formed resist underlayer film, A step of bringing the curable composition into contact with the mold, A step of irradiating the curable composition with light or an electron beam to form a cured film, and A step of separating the cured film from the mold, Includes.

[0150] In the release process of optical nanoimprint technology, adhesion between the resist composition and the substrate is crucial. If the adhesion between the resist composition and the substrate is poor, when the mold is pulled apart during the release process, some of the photocured product obtained by curing the resist composition may peel off while remaining attached to the mold, resulting in pattern peeling defects. As a technique to improve the adhesion between the resist composition and the substrate, a technique has been proposed to form an adhesion layer between the resist composition and the substrate, which is a layer that adheres the resist composition and the substrate together.

[0151] Furthermore, highly etching-resistant layers are sometimes used for pattern formation in nanoimprinting. Organic materials and silicone materials are commonly used as materials for highly etching-resistant layers. In addition, adhesion layers and silicon-containing silicone layers can be formed on the nanoimprint resist underlayer film by coating or vapor deposition. If these adhesion layers and silicon-containing silicone layers are hydrophobic and exhibit a high pure water contact angle, it is expected that the adhesion between the films will be improved and peeling will be less likely if the underlayer film is also hydrophobic and exhibits a high pure water contact angle. Conversely, if the adhesion layers and silicone layers are hydrophilic and exhibit a low pure water contact angle, it is expected that the adhesion between the films will be improved and peeling will be less likely if the underlayer film is also hydrophilic and exhibits a low pure water contact angle.

[0152] Furthermore, depending on the properties of the adhesion film, silicone layer, and underlying film, elements such as He, H2, N2, and air can be used.

[0153] The polymer (X) according to the present invention exhibits a desired pure water contact angle not only during low-temperature firing but also during high-temperature firing, and maintains the desired pure water contact angle even when mixed with a crosslinking agent, acid catalyst, and surfactant as a material. This makes it possible to improve adhesion to the upper film and is expected to exhibit good permeability to gases such as He, H2, N2, and air. Furthermore, the polymer (X) according to the present invention exhibits good planarization properties, and by changing the molecular framework, the optical constants and etching rate can be adjusted to suit the process.

[0154] (Curable composition) The photoresist formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. Examples include positive photoresists consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator. Examples include APEX-E (Chypre Corporation), PAR710 (Sumitomo Chemical Co., Ltd.), and SEPR430 (Shin-Etsu Chemical Co., Ltd.). Furthermore, examples include fluorine-containing polymer-based photoresists, such as those described in Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), and Proc.SPIE, Vol.3999, 365-374 (2000).

[0155] (Step of applying the curable composition) This step involves applying a curable composition onto a resist underlayer film formed by the resist underlayer film manufacturing method according to the present invention. Methods for applying the curable composition include, for example, inkjet coating, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scanning. Inkjet coating is suitable for applying the curable composition as droplets, while spin coating is suitable for coating the curable composition. In this step, an adhesion layer and / or a silicone layer containing 99% by mass or less, or 50% by mass or less, of Si can also be formed on the resist underlayer film by coating or vapor deposition, and the curable composition can be applied thereon.

[0156] (Step of bringing the curable composition into contact with the mold) In this process, the curable composition is brought into contact with the mold. For example, by bringing a liquid curable composition into contact with a mold having a prototype pattern for transferring the pattern shape, a liquid film is formed in which the curable composition fills the depressions of the fine pattern on the surface of the mold.

[0157] Considering the process of irradiating with light or electron beams, which will be described later, it is recommended to use a mold made of a light-transmitting material as the base material. Specifically, the mold base material is preferably a light-transmitting resin such as glass, quartz, PMMA, or polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocurable film, or a metal film. Quartz is more preferably used as the mold base material because it has a small coefficient of thermal expansion and low pattern distortion.

[0158] The fine patterns on the surface of the mold preferably have a pattern height of 4 nm or more and 200 nm or less. A certain pattern height is necessary to improve the processing accuracy of the substrate, but a lower pattern height results in less force being used to separate the mold from the cured film in the process of separating the cured film and the mold described later, and also reduces the number of defects remaining on the mask side due to the resist pattern being torn off. Considering these factors, it is recommended to select and adopt a pattern height with an appropriate balance. Furthermore, the elastic deformation of the resist pattern due to the impact when peeling off the mold may cause adjacent resist patterns to come into contact, resulting in adhesion or damage to the resist patterns. This can sometimes be avoided by keeping the pattern height approximately twice the pattern width (aspect ratio of 2 or less).

[0159] To improve the release properties between the curable composition and the mold surface, the mold may be pre-treated. One method of surface treatment is to apply a release agent to the mold surface to form a release agent layer. Examples of release agents include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. Preferably, fluorine-based and hydrocarbon-based release agents are used. A commercially available product is, for example, Optool® DSX manufactured by Daikin Industries, Ltd. One type of release agent may be used alone, or two or more types may be used in combination.

[0160] In this process, the pressure applied to the curable composition when bringing the mold into contact with the curable composition is not particularly limited. A pressure of 0 MPa or higher and 100 MPa or lower is recommended. Preferably, the pressure is 0 MPa or higher and 50 MPa or lower, 30 MPa or lower, or 20 MPa or lower.

[0161] If the press-spreading of droplets of the curable composition is progressing in the preceding step (the step of applying the curable composition), the spreading of the curable composition in this step will be completed quickly. As a result, the time during which the mold and the curable composition are in contact can be shortened. The contact time is not particularly limited, but is preferably 0.1 seconds or more, 600 seconds or less, 3 seconds or less, or 1 second or less. If the contact time is too short, the spreading and filling will be insufficient, and defects called unfilled defects may occur.

[0162] This process can be carried out under any of the following conditions: under an atmospheric atmosphere, under a reduced pressure atmosphere, or under an inert gas atmosphere. Preferably, it is carried out under a pressure of 0.0001 atmospheres or more and 10 atmospheres or less. To prevent the influence of oxygen and moisture on the curing reaction, it is recommended to carry out the process under a reduced pressure atmosphere or an inert gas atmosphere. Specific examples of inert gases that can be used to create an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, CFCs, HCFCs, HFCs, or mixtures thereof.

[0163] This process may be carried out in an atmosphere containing a condensable gas (hereinafter referred to as a "condensable gas atmosphere"). In this specification, a condensable gas is a gas that, when filled together with the curable composition into the recesses of the fine pattern formed on the mold and into the gaps between the mold and the substrate, condenses and liquefies due to the capillary pressure generated during filling. The condensable gas exists as a gas in the atmosphere before the curable composition and the mold come into contact in this process. When this process is carried out in a condensable gas atmosphere, the gas filling the recesses of the fine pattern liquefies due to the capillary pressure generated by the curable composition, eliminating bubbles and resulting in superior filling performance. The condensable gas may be dissolved in the curable composition.

[0164] The boiling point of the condensable gas is not limited as long as it is below the ambient temperature of this process, but is preferably -10°C or higher, or +10°C or higher and +23°C or lower.

[0165] The vapor pressure of the condensable gas at the ambient temperature of this process is not particularly limited as long as it is below the mold pressure. Preferably, it is in the range of 0.1 MPa to 0.4 MPa.

[0166] Examples of condensable gases include chlorofluorocarbons (CFCs) such as trichlorofluoromethane, fluorocarbons (FCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) such as 1,1,1,3,3-pentafluoropropane (CHF2CH2CF3, HFC-245fa, PFP), and hydrofluoroethers (HFEs) such as pentafluoroethyl methyl ether (CF3CF2OCH3, HFE-245mc).

[0167] Condensible gases may be used individually or in mixtures of two or more. These condensable gases may also be mixed with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. Air and helium are preferred non-condensable gases to be mixed with condensable gases.

[0168] (A process of curing a curable composition by irradiating it with light or an electron beam to form a cured film.) In this process, the curable composition is irradiated with light or an electron beam to form a cured film. Specifically, the curable composition filled in the fine pattern of the mold is irradiated with light or an electron beam through the mold, and the curable composition filled in the fine pattern of the mold is cured in that state, thereby forming a cured film with a patterned shape.

[0169] The light or electron beam is selected according to the sensitivity wavelength of the curable composition. Specifically, ultraviolet light, X-rays, electron beams, etc. with wavelengths of 150 nm to 400 nm can be appropriately selected and used. Examples of light or electron beam light sources include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, F2 excimer lasers, etc. There may be one or more light sources. Irradiation may be performed on the entire curable composition filled in the fine pattern of the mold, or on only a part of it. Light irradiation may be performed intermittently multiple times over the entire area of ​​the substrate, or it may be performed continuously over the entire area. It is also possible to perform the first irradiation on a part of the substrate and the second irradiation on a different area.

[0170] The cured film obtained in this manner preferably has a pattern with a size of 1 nm or more, or 10 nm or more, 10 mm or less, or 100 μm or less.

[0171] (The process of separating the hardened film from the mold) In this step, the cured film and the mold are separated. By separating the cured film having a pattern shape from the mold, a cured film having a pattern shape that is an inverse pattern of the fine pattern formed on the mold is obtained in a self-supporting state.

[0172] The method for separating the patterned cured film from the mold is not particularly limited, as long as it involves moving the cured film and the mold in a direction that moves them apart relative to each other, and there are no particular limitations on the physical damage to any part of the patterned cured film, nor are there any particular limitations on the various conditions. For example, the substrate may be fixed and the mold may be moved away from the substrate to separate them, or the mold may be fixed and the substrate may be moved away from the mold to separate them. Alternatively, the substrate and the mold may be pulled and moved in opposite directions to separate them.

[0173] Furthermore, if the process of bringing the curable composition into contact with the mold is carried out under a condensable gas atmosphere, the condensable gas vaporizes as the pressure at the interface where the cured film and the mold come into contact decreases when the cured film and the mold are separated in this process. This reduces the release force required to separate the cured film and the mold.

[0174] Through the above process, a cured film can be prepared that has a desired uneven pattern shape derived from the uneven shape of the mold, at a desired position. [Examples]

[0175] The following examples illustrate specific compositions according to the present invention, but this does not limit the present invention.

[0176] The equipment used to measure the weight-average molecular weight of the reaction products obtained in the following synthesis example is shown. Equipment: HLC-8320GPC manufactured by Tosoh Corporation GPC column: TSKgel Super-MultiporeHZ-N (2 tubes) Column temperature: 40℃ Flow rate: 0.35ml / min Eluent:THF Standard sample: Polystyrene

[0177] The chemical structures (examples) and abbreviations of the main raw materials used are as follows: [ka]

[0178] [ka]

[0179] [ka]

[0180] [Synthesis Example 1] 260.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 1,430 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) were placed in a flask. Then, the mixture was heated to approximately 90°C under nitrogen, and 17.26 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 130.00 g of PGME, was added dropwise. After approximately 45 hours, the mixture was precipitated with methanol and water and dried to obtain polymer (1-I). Note that the actual structural units consist of crosslinks formed by the bonding of arbitrary ROCH2- groups containing methoxymethyl groups to hydroxyl groups, or to ROCH2- groups themselves. However, showing this state in a chemical formula would be extremely complicated, so only the structural units are shown. The same applies hereafter. The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 4,500. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0181] [ka]

[0182] [Synthesis Example 2] 68.99 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 379.44 g of PGME were placed in a flask. Then, under nitrogen, the mixture was heated to approximately 90°C, and 4.57 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 34.50 g of PGME, was added dropwise. After approximately 47.5 hours, the mixture was precipitated with methanol and water, and dried to obtain polymer (1-2). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 5,400. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0183] [ka]

[0184] [Synthesis Example 3] 30.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 165.07 g of 1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a flask. Then, under nitrogen, the mixture was heated to approximately 90°C, and 1.99 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 15.05 g of 1-butanol, was added dropwise. After approximately 81.5 hours, the mixture was precipitated with methanol and water, and dried to obtain polymer (1-3). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 3,487. Furthermore, the introduction of 1-butyl groups was also considered. 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGME, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0185] [ka]

[0186] [Synthesis Example 4] 34.50 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 33.16 g of TM-BIP-A, and 379.44 g of PGME were placed in a flask. Then, under nitrogen, the mixture was heated to approximately 90°C. 2.29 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 34.50 g of PGME, was added dropwise. After approximately 125.5 hours, the mixture was precipitated with methanol and water, and dried to obtain polymer (1-4). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 4,296. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGME, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0187] [ka]

[0188] [Synthesis Example 5] 34.50 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 0.31 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), and 189.73 g of PGME were placed in a flask. Then, under nitrogen, the mixture was heated to approximately 90°C, and 2.29 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 17.25 g of PGME, was added dropwise. After approximately 48 hours, the mixture was precipitated with methanol and water, and dried to obtain polymer (1-5). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 3,978. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGME, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0189] [ka]

[0190] [Synthesis Example 6] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 5.46 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 58.72 g of PGME were placed in a 100 mL flask. Then, the mixture was heated to 90°C under nitrogen, and 0.47 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of PGME, was added dropwise. After about 2 hours, the mixture was precipitated with methanol and dried to obtain polymers (1-6). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 4,000. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0191] [ka]

[0192] [Synthesis Example 7] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 7.16 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 65.52 g of PGME were placed in a 100 mL flask. Then, the mixture was heated to 90°C under nitrogen, and 0.47 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of PGME, was added dropwise. After approximately 3 hours, the mixture was precipitated with methanol and dried to obtain polymer (1-7). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 4,500. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0193] [ka]

[0194] [Synthesis Example 8] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 11.44 g of 9,9-bis(4-hydroxyphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 60.73 g of PGME were placed in a 100 mL flask. The mixture was then heated under nitrogen until reflux was achieved. 0.47 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of PGME, was added dropwise. After approximately 4 hours, the mixture was precipitated with methanol and water and dried to obtain polymer (1-8). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 4,100. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0195] [ka]

[0196] [Synthesis Example 9] 12.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 7.29 g of 2,2'-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 54.58 g of PGME were placed in a 100 mL flask. The mixture was then heated under nitrogen until reflux was achieved. 0.56 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of PGME, was added dropwise. After approximately 1.5 hours, the mixture was precipitated with methanol and water and dried to obtain polymer (1-9). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 3,700. Furthermore, the introduction of PGME was also considered. 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0197] [ka]

[0198] [Synthesis Example 10] 12.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 6.27 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 70.36 g of PGME were placed in a 100 mL flask. The mixture was then heated under nitrogen until reflux was achieved. 0.56 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of PGME, was added dropwise. After approximately 1 hour, the mixture was precipitated with methanol and water and dried to obtain polymer (1-10). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 10,000. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0199] [ka]

[0200] [Synthesis Example 11] 68.99 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 40.00 g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 379.42 g of PGME were placed in a flask. Then, under nitrogen, the mixture was heated to approximately 90°C, and 4.57 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 34.49 g of PGME, was added dropwise. After approximately 26.5 hours, the mixture was precipitated with methanol, water, and aqueous ammonia, and dried to obtain polymer (1-11). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 4,200. Furthermore, the introduction of PGME... 1 This was confirmed by 1H-NMR. The obtained resin was dissolved in PGME, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0201] [ka]

[0202] [Synthesis Example 12] 8.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.63 g of 9-fluorenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.30 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.93 g of PGMEA were placed in a 100 mL flask. The mixture was then heated under nitrogen until reflux was achieved, and after approximately 1.5 hours, it was precipitated with methanol and dried to obtain polymer (1-12). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 2,600. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0203] [ka]

[0204] [Comparative Synthesis Example 1] 15.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 35.55 g of 1,4-dioxane were placed in a 100 mL flask. Then, the mixture was heated to 120 °C under nitrogen, and 0.24 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of 1,4-dioxane, was added dropwise. After about 6 hours, the mixture was precipitated with methanol and dried to obtain polymer (2-1). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 4,600. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0205] [ka]

[0206] [Comparative Synthesis Example 2] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 5.46 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.70 g of 1,4-dioxane were placed in a 100 mL flask. Then, the mixture was heated to 120 °C under nitrogen, and 0.16 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of 1,4-dioxane, was added dropwise. After about 1 hour, the mixture was precipitated with methanol and dried to obtain polymer (2-2). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 3,200. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0207] [ka]

[0208] [Comparative Synthesis Example 3] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 7.16 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.70 g of 1,4-dioxane were placed in a 100 mL flask. Then, the mixture was heated to 120 °C under nitrogen, and 0.16 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of 1,4-dioxane, was added dropwise. After about 1 hour, the mixture was precipitated with methanol and water and dried to obtain polymer (2-3). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 2,800. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and anion exchange resin to obtain the target polymer solution.

[0209] [ka]

[0210] [Comparative Synthesis Example 4] 12.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 8.23 ​​g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 23.88 g of 1,4-dioxane were placed in a flask. Then, under nitrogen, the mixture was heated to approximately 120°C, and 0.38 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), dissolved in 5 g of PGME, was added dropwise, and the mixture was allowed to react for approximately 5 hours.

[0211] [Comparative Synthesis Example 5] 69.92 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 40.88 g of 2-ethylhexylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.19 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 80.00 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were placed in a 200 mL flask. The mixture was then heated under nitrogen until reflux was achieved, and after approximately 24 hours, it was precipitated with methanol and dried to obtain polymer (2-4). The weight-average molecular weight Mw, measured in polystyrene equivalent by GPC, was approximately 1,700. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain the target polymer solution.

[0212] [ka]

[0213] [Example 1] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. To 9.12 g of this resin solution, 0.39 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 4.96 g of PGMEA, and 2.41 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0214] [Example 2] In Synthesis Example 3, a resin solution (solid content 26.93% by mass) was obtained. To 6.03 g of this resin solution, 0.33 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.43 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.16 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 5.24 g of PGMEA, and 5.80 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0215] [Example 3] In Synthesis Example 4, a resin solution (solid content 22.01% by mass) was obtained. To 7.38 g of this resin solution, 0.33 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.43 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.16 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 5.24 g of PGMEA, and 4.46 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0216] [Example 4] In Synthesis Example 5, a resin solution (solid content 20.12% by mass) was obtained. To 8.08 g of this resin solution, 0.33 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.43 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.16 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 5.24 g of PGMEA, and 3.76 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0217] [Example 5] In Synthesis Example 6, a resin solution (solid content of 17.85% by mass) was obtained. To 10.92 g of this resin solution, 0.39 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 3.15 g of PGMEA, and 2.41 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0218] [Example 6] In Synthesis Example 7, a resin solution (solid content 16.62% by mass) was obtained. To 11.73 g of this resin solution, 0.39 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 2.35 g of PGMEA, and 2.41 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0219] [Example 7] In Synthesis Example 8, a resin solution (solid content 18.61% by mass) was obtained. To 10.48 g of this resin solution, 0.39 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 3.61 g of PGMEA, and 2.41 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0220] [Example 8] In Synthesis Example 9, a resin solution (solid content 16.88% by mass) was obtained. To 11.55 g of this resin solution, 0.39 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 2.52 g of PGMEA, and 2.41 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0221] [Example 9] In Synthesis Example 10, a resin solution (solid content of 18.06% by mass) was obtained. To 10.80 g of this resin solution, 0.39 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 3.28 g of PGMEA, and 2.41 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0222] [Example 10] In Synthesis Example 11, a resin solution (solid content of 17.62% by mass) was obtained. To 13.82 g of this resin solution, 0.49 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 1.44 g of PGME containing 5% by mass pyridinium p-hydroxybenzene sulfonate, 0.49 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 6.12 g of PGMEA, and 2.64 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0223] [Example 11] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. To 11.80 g of this resin solution, 0.39 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 3.78 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.25 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 2.66 g of PGMEA, and 1.51 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0224] [Example 12] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. To 12.15 g of this resin solution, 0.26 g of PGMEA containing 1% by mass surfactant (DIC Corporation, Megafac R-40), 2.37 g of PGMEA, and 5.22 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0225] [Example 13] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. To 14.02 g of this resin solution, 0.30 g of PGMEA containing 1% by mass surfactant (DIC Corporation, Megafac R-40), 0.58 g of PGMEA, and 5.10 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0226] [Example 14] A resin solution (solid content 30.00% by mass) was obtained in Synthesis Example 12. To 4.33 g of this resin solution, 1.22 g of the polymer solution (solid content 21.38% by mass) obtained in Synthesis Example 1, 1.95 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.13 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 10.63 g of PGMEA, and 1.77 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0227] [Comparative Example 1] In comparative synthesis example 5, a resin solution (solid content of 24.24% by mass) was obtained. To 7.54 g of this resin solution, 0.37 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.73 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.18 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 3.03 g of PGMEA, and 1.14 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0228] [Comparative Example 2] A resin solution (solid content 30.00% by mass) was obtained in Synthesis Example 12. To 4.33 g of this resin solution, 0.26 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 1.95 g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.13 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafac R-40), 11.56 g of PGMEA, and 1.77 g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[0229] (Polymer solubility test) When synthesis was carried out according to Synthesis Examples 2, 6, 7, and 11 and Comparative Synthesis Examples 1, 2, 3, and 4, the solubility of the monomers and polymers in the reaction solvent was visually confirmed. Solutions that were not suspended were considered good, and solutions that were suspended were considered poor. In addition, the polymers obtained in Synthesis Examples 2, 6, 7, and 11 and the polymers obtained in Comparative Synthesis Examples 1, 2, and 3 were dissolved in PGME or PGMEA so that the solid content was 20% by mass. Subsequently, ion exchange treatment was carried out according to the synthesis examples and comparative examples, and the solubility of the polymers was determined. Solutions that were not suspended after ion exchange treatment were considered good, and solutions that were suspended after ion exchange treatment were considered poor. The results are shown in Table 1.

[0230] [Table 1]

[0231] By synthesizing polymers in PGME, which contains non-phenolic hydroxyl groups within the molecule, methoxypropoxy groups are introduced into the side chains. Therefore, these polymers exhibit higher solubility in PGME or PGMEA after ion exchange compared to polymers synthesized in 1,4-dioxane, which does not contain non-phenolic hydroxyl groups within the molecule. Furthermore, this method offers the advantage of synthesizing polymers in PGME, a solvent commonly used in the semiconductor industry, without using 1,4-dioxane, a highly hazardous solvent classified as a specific hazardous industrial waste. Additionally, as shown in Synthesis Example 11 and Comparative Synthesis Example 4, when highly polar monomers are used, they do not dissolve in low-polarity solvents such as 1,4-dioxane, and polymerization does not proceed. On the other hand, using a highly polar alcohol solvent like PGME allows polymerization to proceed, and it is advantageous that materials with high solubility even after ion exchange can be obtained. Next, the properties of polymers and crosslinking agents containing these alcohol-substituted compounds were evaluated.

[0232] (Leaching test into resist solvent) Solutions of the resist underlayer-forming compositions prepared in Comparative Examples 1-2 and Examples 1-14 were applied onto silicon wafers using a spin coater, and then baked on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form a resist underlayer (thickness 200 nm). These resist underlayers were immersed in a general-purpose thinner, PGME / PGMEA = 7 / 3, to confirm their curability. All resist underlayers were insoluble in this thinner, confirming that they possessed sufficient curability.

[0233] (Optical constant measurement) Solutions of the resist underlayer-forming compositions prepared in Comparative Example 1 and Examples 1-13 were applied onto silicon wafers using a spin coater. The wafers were then baked on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form a resist underlayer (50 nm thick). The refractive index (n-value) and optical absorption coefficient (k-value, also called the attenuation coefficient) at a wavelength of 193 nm were measured for these resist underlayers using a spectroscopic ellipsometer. The results are shown in Table 2.

[0234] [Table 2]

[0235] As described above, the optical constants of the resist underlayer can be freely controlled by changing the type of compound being reacted.

[0236] [Measurement of dry etching rate] The etcher and etching gas used to measure the dry etching rate are as follows: RIE-10NR (Samco): CF4

[0237] Solutions of the resist underlayer-forming compositions prepared in Comparative Example 1 and Examples 1-13 were applied onto silicon wafers using a spin coater. A resist underlayer (200 nm thick) was formed by baking on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds. The dry etching rate was measured using CF4 gas as the etching gas, and the dry etching rate ratio for Comparative Example 1 and Examples 1-13 was determined. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer) / (KrF photoresist). The results are shown in Table 3.

[0238] [Table 3]

[0239] As described above, the etching resistance of the resist underlayer can be freely controlled by changing the type of compound used in the reaction.

[0240] (Measurement of sublimation volume) The amount of sublimation was measured using the sublimation measurement device described in International Publication No. 2007 / 111147. The resist underlayer film forming compositions prepared in Comparative Example 1 and Examples 1-13 were applied to silicon wafers, and the amount of sublimation was measured when the film thickness reached 200 nm after firing at 240°C for 60 seconds or 350°C for 60 seconds. The results are shown in Table 4. Note that the values ​​in the table are (amount of sublimation in Examples 1-13) / (amount of sublimation in Comparative Example 1).

[0241] [Table 4]

[0242] As described above, by using a material with a cross-linked structure, it is possible to significantly reduce the amount of sublimation material in the resist underlayer film forming composition, thereby reducing concerns about equipment contamination.

[0243] (Evaluation of implantability) The embedding properties were confirmed in a dense pattern area with a 200 nm thick SiO2 substrate, a trench width of 50 nm, and a pitch of 100 nm. The resist underlayer film forming compositions prepared in Comparative Example 1 and Examples 1-13 were applied to the above substrates and then baked at 240°C for 60 seconds or 350°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarity of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation to confirm whether or not the resist underlayer film forming composition filled the inside of the pattern. The results are shown in Table 5.

[0244] [Table 5]

[0245] Examples 1-13 exhibit high embedding properties similar to conventional materials.

[0246] (Hardness test) The resist underlayer-forming compositions prepared in Comparative Example 1 and Examples 1-13 were applied to silicon wafers, respectively, and then baked at 240°C for 60 seconds or 350°C for 60 seconds to form a 200 nm resist underlayer film. The hardness of these cured resist films was evaluated using a Bruker TI-980 triboidentor. Films with higher hardness than Comparative Example 1 were rated as ○. The results are shown in Table 6.

[0247] [Table 6]

[0248] As described above, by using a material with a cross-linked structure in the polymer, the hardness of the resist underlayer can be significantly increased.

[0249] (Bending resistance evaluation) Solutions of the resist underlayer-forming compositions prepared in Comparative Example 1 and Examples 1-13 were applied to silicon wafers coated with silicon oxide using a spin coater. A resist underlayer (thickness 200 nm) was formed by baking on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds. A silicon hard mask-forming composition solution was applied to the resist underlayer and baked at 240°C for 1 minute to form a silicon hard mask layer (thickness 30 nm). A resist solution was applied on top of that and baked at 100°C for 1 minute to form a resist layer (thickness 150 nm). Exposure was performed at a wavelength of 193 nm using a mask, followed by post-exposure heating with PEB (105°C for 1 minute), and then development to obtain a resist pattern. Subsequently, dry etching was performed using a fluorine-based gas and an oxygen-based gas to transfer the resist pattern to a silicon wafer coated with silicon oxide, and the shape of each pattern was observed using a Hitachi High-Technologies Corporation CG-4100.

[0250] When forming a resist pattern on a substrate to be processed through lithography and etching processes, irregular pattern bending becomes more likely as the width of the formed pattern narrows. Specifically, this occurs in the resist underlayer film used as a mask material when etching the target substrate, particularly in the pattern formed from the organic resin layer, which bends from side to side. This makes it difficult to process the substrate accurately. Therefore, the less bending occurs, the finer the substrate processing becomes possible. The results are shown in Table 7. A circle (○) indicates higher bending resistance compared to Comparative Example 1.

[0251] [Table 7]

[0252] As shown in the results above, the example demonstrated higher bending resistance compared to the comparative example.

[0253] [Evaluation as a crosslinking agent] (Measurement of sublimation volume of the resist underlayer) The amount of sublimation was measured using the sublimation measurement device described in International Publication No. 2007 / 111147. The resist underlayer film forming compositions prepared in Comparative Example 2 and Example 14 were applied to silicon wafers, and the amount of sublimation was measured when the film thickness reached 200 nm after firing at 240°C for 60 seconds. The results are shown in Table 8. Note that the values ​​listed in the table are (amount of sublimation in Example 14) / (amount of sublimation in Comparative Example 2).

[0254] [Table 8]

[0255] As described above, by using a polymer-type crosslinking agent, the amount of sublimation in the resist underlayer film-forming composition can be significantly reduced compared to conventional crosslinking agents, thus reducing concerns about equipment contamination.

[0256] (Coating test on stepped substrates) As a coating test on stepped substrates, the coating thickness was compared on a 200 nm thick SiO2 substrate in an open area (OPEN) where no pattern was formed and in a dense pattern area (DENSE) with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer forming compositions prepared in Comparative Example 2 and Example 14 were applied to the substrate and then baked at 240°C for 60 seconds to form a resist underlayer of approximately 200 nm. The planarity of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarity was evaluated by measuring the difference in film thickness between the trench area (patterned area) and the open area (unpatterned area) of the stepped substrate (this is the coating step difference between the trench area and the open area, and is called the bias). Here, planarity means that the difference in film thickness of the coated material on top of the area where a pattern exists (trench area (patterned area)) and the area where a pattern does not exist (open area (unpatterned area)) is small (Iso-dense bias). The results are shown in Table 9.

[0257] [Table 9]

[0258] As described above, the introduction of alcohol compounds into the side chains leads to a decrease in glass transition temperature and viscosity, significantly improving the planarity of the resist underlayer film-forming composition. [Industrial applicability]

[0259] According to the present invention, a novel resist underlayer forming composition is provided that eliminates the need to use harmful chemicals in the preparation of the resin, meets the requirements for improved solubility in PGME and PGMEA, reduction of the amount of sublimation contaminating the equipment, improved coating planarity on stepped substrates, and increased hardness of the resulting resist underlayer film, while maintaining other desirable properties.

Claims

1. RoCheese groups other than methoxymethyl groups ２ A resist underlayer film forming composition comprising a polymer (X) having a plurality of identical or different structural units having a monovalent organic group (R is a hydrogen atom or a mixture thereof), and a linking group that links the plurality of structural units, and a solvent, wherein at least one of the plurality of structural units is an aromatic ring having a phenolic hydroxyl group.

2. R may be substituted with a phenyl group, a naphthyl group, or an anthracenyl group, and may be interrupted by an oxygen atom or a carbonyl group, a saturated or unsaturated linear or branched C ２ -C ２０ Aliphatic hydrocarbon group, C ３ -C ２０ The resist underlayer film forming composition according to claim 1, comprising an alicyclic hydrocarbon group, a hydrogen atom, or a mixture thereof.

3. The resist underlayer forming composition according to claim 1 or 2, wherein the linking group comprises an alkylene group, an ether group, or a carbonyl group.

4. The resist underlayer forming composition according to claim 1 or 2, wherein the structural unit comprises an aromatic ring, heterocycle, or fused ring which may have a substituted or unsubstituted amino group.

5. The resist underlayer film forming composition according to claim 1 or 2, further comprising a polymer (X) and a crosslinkable film material (Y).

6. A resist underlayer film forming composition according to claim 1 or 2, further comprising a crosslinking agent.

7. A resist underlayer film forming composition according to claim 1 or 2, further comprising an acid and / or an acid generator.

8. A resist underlayer film forming composition according to claim 1 or 2, further comprising a surfactant.

9. The resist underlayer film forming composition according to claim 1 or 2, wherein the solvent comprises a solvent having a boiling point of 160°C or higher.

10. A resist underlayer film characterized by being a fired product of a coated film comprising the composition described in any one of claims 1 to 9.

11. A step of forming a resist underlayer film on a semiconductor substrate using the composition described in any one of claims 1 to 9, A step of forming a resist film on the formed resist underlayer film, A process of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it. A step of etching and patterning the resist underlayer film through the formed resist pattern, and Process of processing a semiconductor substrate via a patterned resist underlayer film. A method for manufacturing a semiconductor device containing [a specific component].

12. A step of forming a resist underlayer film on a semiconductor substrate using the composition described in any one of claims 1 to 9, A step of forming a hard mask on the formed resist underlayer film, A step of forming a resist film on the formed hard mask, A process of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it. A step of etching and patterning the hard mask through the formed resist pattern, and A step of etching and patterning the resist underlayer film through a patterned hard mask, and Process of processing a semiconductor substrate via a patterned resist underlayer film. A method for manufacturing a semiconductor device containing [a specific component].

13. A method for manufacturing a semiconductor device according to claim 11 or 12, wherein the step of forming a resist underlayer film is performed by a nanoimprint method.

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