Resist underlayer film-forming composition

Abstract

Provided is a novel composition for forming a resist underlayer film. This composition for forming a resist underlayer film includes a polymer (X) and a solvent, the polymer (X) containing: a plurality of structural units which are the same as or different from each other and have a methoxymethyl group and a ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof) other than the methoxymethyl group; and a linking group that links the plurality of structural units.

Description

[Technical Field]

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

[0002] In the manufacture of semiconductor devices, microfabrication is performed by a lithography process. In this lithography process, when a resist layer on a substrate is exposed to an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser, a known problem occurs in that a resist pattern having the desired shape cannot be formed due to the influence of standing waves generated by the reflection of the ultraviolet laser on the substrate surface. To solve this problem, a resist underlayer film (anti-reflective film) is provided between the substrate and the resist layer. It is known that novolac resins are used as compositions for forming the resist underlayer film.

[0003] In addition, a lithography process is also known in which at least two resist underlayer films are formed and used as a mask material to achieve thinner resist layers as the resist pattern becomes finer. 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 is performed using a pattern formed from the organic resin layer as a mask, the pattern must be resistant to etching gases (e.g., fluorocarbons).

[0004] As a composition for forming such a resist underlayer film, for example, Patent Document 1 discloses a composition containing a compound represented by the following formula (1):

[0005] [ka]

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

[0007] [Patent Document 1] WO2014 / 171326A1 Summary of the Invention [Problem to be solved by the invention]

[0008] However, conventional resist underlayer film-forming compositions still lack sufficient solubility in PGME and PGMEA, which are solvents commonly used in the semiconductor industry, to reduce the amount of sublimation that contaminates equipment, to improve the coating planarization properties for uneven substrates, and to increase the hardness of the resulting resist underlayer film.It is also important to maintain or improve properties such as not using hazardous chemicals in the preparation of the resin, not eluting in resist solvents, being able to obtain desired optical constants, and being able to follow irregular patterns that occur as the pattern width narrows. [Means for solving the problem]

[0009] The present invention is intended to solve the above problems. That is, the present invention includes the following. [1] A resist underlayer film-forming composition comprising: a polymer (X) containing a plurality of identical or different structural units each having a methoxymethyl group and a ROCH2- group other than a methoxymethyl group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group connecting the plurality of structural units; and a solvent. [2] R is a saturated or unsaturated, linear or branched C2-C alkyl group optionally substituted with a phenyl group, a naphthyl group, or an anthracenyl group, optionally interrupted by an oxygen atom or a carbonyl group. 20 Aliphatic hydrocarbon groups, C3-C 20 The resist underlayer film forming composition according to [1], wherein the alicyclic hydrocarbon group is a hydrogen atom, or a mixture thereof. [3] The resist underlayer film forming composition according to [1] or [2], wherein the linking group contains an alkylene group, an ether group, or a carbonyl group. [4] The resist underlayer film-forming composition according to any one of [1] to [3], wherein the structural unit contains an aromatic ring, a heterocycle, or a fused ring, which may have a phenolic hydroxyl group and which may have a substituted or unsubstituted amino group. [5] The resist underlayer film-forming composition according to any one of [1] to [4], further comprising a film material (Y) capable of undergoing a crosslinking reaction with the polymer (X). [6] The resist underlayer film-forming composition according to any one of [1] to [5], further comprising a crosslinking agent. [7] The resist underlayer film forming composition according to any one of [1] to [6], further comprising an acid and / or an acid generator. [8] The 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 includes a solvent having a boiling point of 160°C or higher.

[10] A resist underlayer film, which is a baked product of a coating film made of the composition according to any one of [1] to [9].

[11] A step of forming a resist underlayer film on a semiconductor substrate using the composition according to any one of [1] to [9]. forming a resist film on the formed resist underlayer film; a step 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 A process of processing a semiconductor substrate through a patterned resist underlayer film A method for manufacturing a semiconductor device comprising:

[12] A step of forming a resist underlayer film on a semiconductor substrate using the composition according to any one of [1] to [9]. forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; a step of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it; Etching and patterning the hard mask through the formed resist pattern; and Etching and patterning the resist underlayer film through a patterned hard mask; and A process of processing a semiconductor substrate through a patterned resist underlayer film A method for manufacturing a semiconductor device comprising:

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

[11] or

[12] , wherein the step of forming the resist underlayer film is carried out by a nanoimprint method. [Effects of the Invention]

[0010] According to the present invention, there is provided a novel resist underlayer film-forming composition that does not require the use of hazardous chemicals in the preparation of a resin, meets requirements such as improved solubility in PGME or PGMEA, reduced amount of sublimation that contaminates equipment, improved coating planarization properties for substrates with uneven surfaces, and high hardness of the resulting resist underlayer film, while maintaining other favorable properties. DETAILED DESCRIPTION OF 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 each having a methoxymethyl group and a ROCH2- group other than a methoxymethyl group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group connecting the plurality of structural units, and a solvent.

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

[0013] The monovalent organic group R is preferably a saturated or unsaturated, linear or branched C-C alkyl group which may be substituted with a phenyl group, a naphthyl group, or an anthracenyl group and which may be interrupted by an oxygen atom or a carbonyl group. 20 Aliphatic hydrocarbon groups, C3-C 20 The term "mixed" means that the ROCH2- groups present in a single structural unit may be different from each other, and also means that the ROCH2- groups in two or more structural units may be different from each other.

[0014] Typical saturated aliphatic hydrocarbon groups are straight-chain or branched alkyl groups having 2 to 20 carbon atoms, such as ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl ... Examples of alkyl groups include 1-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. Examples of cyclic alkyl groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl Examples of such cyclopropyl groups include methyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.

[0016] Typical unsaturated aliphatic hydrocarbon groups are alkenyl groups having 2 to 20 carbon atoms, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-prop ... -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-hexenyl group phenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylethenyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 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 of the alkyl group 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 times by an oxygen atom and / or a carbonyl group. Particularly preferred are —CH2CH2CH2CH3 and —CH(CH3)CH2OCH3 groups.

[0018] Polymer (X) can be synthesized by polymerizing a compound having a methoxymethyl group and optionally having a phenolic hydroxyl group, a compound that reacts with the methoxymethyl group to give a ROCH- group other than a methoxymethyl group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and, if necessary, a compound containing a functional group that can serve as a linking group (e.g., an aldehyde, a ketone, ROCH-Ar-CHOR (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] An example of the compound having a methoxymethyl group and optionally having a phenolic hydroxyl group, which is used in the synthesis of polymer (X), is 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 (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof) other than a methoxymethyl group, an organic compound having a non-phenolic hydroxyl group in the molecule is preferred. Even if the compound does not have a non-phenolic hydroxyl group in the molecule, it may have a functional group that can be chemically converted to 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). The non-phenolic hydroxyl group or the functional group that can be chemically converted to a non-phenolic hydroxyl group may be one or more in the molecule. The organic compound may be an aliphatic hydrocarbon (preferably having 10 or fewer carbon atoms), an alicyclic hydrocarbon (preferably having 20 or fewer carbon atoms), or an aromatic hydrocarbon (e.g., having at least one hydroxyl group whose α-carbon is aliphatic). Examples of such compounds include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, aliphatic alcohols (e.g., n-butanol), compounds represented by Ar-CHOH (Ar is, for example, benzene, naphthalene, anthracene, pyrene, fluorene, or m-terphenyl), aldehydes, ketones, and methylol compounds. Note that dioxane is not a compound that provides a ROCH- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof) other than a methoxymethyl group, and is also a substance that is harmful to the human body, so it is preferable not to use it.

[0021] Examples of the organic compound 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 the organic compound having a 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 spiro ketones such as 11H-benzo[b]fluoren-11-one, 9H-tribenzo[a,f,l]triindene-9,14,15-trione, and indeno[1,2-b]fluorene-6,12-dione.

[0023] The structural units of the polymer (X) thus obtained preferably contain an aromatic ring, a heterocyclic ring, or a fused ring, which may have a phenolic hydroxyl group and a substituted or unsubstituted amino group, and the linking group connecting the structural units preferably contains an alkylene group, an ether group, or a carbonyl group.

[0024] The compound used in the synthesis of polymer (X) is not limited to one type of compound, and two or more types of compounds may be used in combination. Therefore, the multiple structural units having a methoxymethyl group and a ROCH2- group other than a methoxymethyl group (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, and is, in standard polystyrene equivalent, for example, 1,000 or more, for example, 2,000 or more, and for example, 500,000 or less, for example, 100,000 or less.

[0026] [solvent] The resist underlayer film forming composition of the present invention can be prepared by dissolving the above-mentioned components in an appropriate solvent, and is used in the form of a homogeneous solution.

[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 acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0028] Furthermore, a high boiling point solvent having 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 of suitable esters include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate.

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

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

[0031] Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups that may or may not have a substituent, such as a 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 unit -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. The -O-, -S-, -NHCO-, or -CONH- may be present in one unit or in two or more units in 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, butyl ... and the like, and further, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl groups, each of which is substituted with a methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, or the like. Preferred are methoxy, ethoxy, methylthio, and ethylthio groups, and more preferred are methoxy and ethoxy groups.

[0033] These solvents have a relatively high boiling point, and are therefore effective in imparting high embedding properties and high planarization properties to the resist underlayer film-forming composition.

[0034] Specific examples of preferred compounds represented by formula (i) are shown below. [ka]

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

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

[0037] [Optional ingredients] The resist underlayer film-forming composition of the present invention may further contain, as an optional component, at least one of 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. A crosslinking compound having at least two crosslinking substituents is preferably used as the crosslinking agent. Examples include melamine-based compounds, substituted urea-based compounds, and phenol-based compounds, or polymers thereof, each having a crosslinking substituent such as a methylol group or a methoxymethyl group. Specific examples include compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, and butoxymethylated benzoguwanamine, such as tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, and hexamethoxymethylmelamine. Substituted urea-based compounds include compounds such as methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea, such as tetramethoxymethylurea and tetrabutoxymethylurea. Condensates of these compounds may also be used. Examples of the phenolic compound include tetrahydroxymethylbiphenol, tetramethoxymethylbiphenol, tetrahydroxymethylbisphenol, tetramethoxymethylbisphenol, and compounds represented by the following formula: [ka] [ka]

[0039] The crosslinking agent may also be a compound having at least two epoxy groups. 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 Epolead (registered trademark) GT-401, GT-403, GT-301, and GT-30 manufactured by Daicel Corporation. 2. Celloxide (registered trademark) 2021, 3000; 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, 807, 152, 154, 180S75, 871, 872 manufactured by Mitsubishi Chemical Corporation; EPPN201, 202, EOCN-102, 103S, 104S, 1020, 1025, 1027 manufactured by Nippon Kayaku Co., Ltd.; and Denacol (registered trademark) EX-25 manufactured by Nagase ChemteX Corporation. Examples of epoxy resins include EX-2, EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, and EX-321; BASF Japan Ltd.'s CY175, CY177, CY179, CY182, CY184, and CY192; and DIC Corporation's Epiclon 200, 400, 7015, 835LV, and 850CRP. The compound having at least two epoxy groups can also be an epoxy resin having an amino group. Examples of such epoxy resins include YH-434 and YH-434L (manufactured by Shin-Nichika Epoxy Manufacturing Co., Ltd.).

[0040] The crosslinking agent may also be a compound having at least two blocked isocyanate groups, such as Takenate (registered trademark) B-830 and B-870N manufactured by Mitsui Chemicals, Inc., and VESTANAT (registered trademark) 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, adipic acid divinyl 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] In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As a crosslinking agent having high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0043] This compound may be a compound having a partial structure of the following formula (4), or a polymer or oligomer having a repeating unit of the following formula (5). [ka] Above R 11 , R 12 , R 13 , and R 14 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups mentioned above can be used. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5-n1), and (n1+n2) is an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is an integer of 0 to (4-n3), and (n3+n4) is an integer of 1 to 4. Oligomers and polymers having a repeating unit structure number of 2 to 100 or 2 to 50 can be used.

[0044] Examples of the compounds, polymers and oligomers of formula (4) and formula (5) are shown below. [ka] [ka] [ka]

[0045] The above compounds are available as products from Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (4-23) is available from Honshu Chemical Industry Co., Ltd. under the trade name TMOM-BP, the compound of formula (4-24) is available from Asahi Organic Chemicals Co., Ltd. under the trade name TM-BIP-A, and the compound of formula (4-28) is available 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, and 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, based on the total solids content. These crosslinking agents may cause a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the polymer of the present invention, they can cause a crosslinking reaction with those crosslinkable substituents.

[0046] One type selected from these various crosslinking agents may be added, or two or more types may be added in combination.

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

[0048] Examples of the acid 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; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. The amount of the acid to be used is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass, based on the total solid content.

[0049] Examples of the acid generator include a thermal acid generator and a photoacid generator. Examples of thermal acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), as well as quaternary ammonium salts of trifluoroacetic acid and organic alkyl sulfonates.

[0050] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0051] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

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

[0053] The acid generators may be used singly or in combination of two or more. When an acid generator is used, the proportion thereof is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass, relative to 100 parts by mass of the solid content of the resist underlayer film-forming composition.

[0054] (surfactant) 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 monostearate. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; F-Top (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); Megafac (registered trademark) F171, F173, R-30, R-30-N, R-40, and R-4 Examples of suitable surfactants include fluorine-based surfactants such as O-LM (manufactured by DIC Corporation), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710, Surflon (registered trademark) 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 surfactant selected from these surfactants may be added, or two or more surfactants may be added in combination. The content of the surfactant is, for example, 0.01 to 5% by mass based on the solid content of the resist underlayer film-forming composition of the present invention, excluding the solvent described below.

[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 contains a film material (Y) capable of undergoing a crosslinking reaction with the polymer (X). It can be said that the film material (Y) is a film material capable of undergoing a crosslinking reaction with the polymer (X).

[0056] The membrane material (Y) optionally used in the present invention can be any material capable of undergoing a crosslinking reaction with the polymer (X). The membrane material may be a polymer, an oligomer, or a low-molecular-weight compound having a molecular weight of 1,000 or less. Examples of crosslinking groups present in the membrane material include, but are not limited to, hydroxyl groups, carboxyl groups, amino groups, and alkoxy groups.

[0057] (a) Examples of the film material capable of undergoing a crosslinking reaction include alicyclic epoxy polymers having a repeating structural unit represented by the following formula (1), as disclosed in WO 2011 / 021555 A1. [ka] (T represents a repeating unit structure having an aliphatic ring in the main chain of the polymer, and E represents an epoxy group or an organic group having an epoxy group.)

[0058] E is a substituent on the aliphatic ring, and may be either an epoxy group directly bonded to the aliphatic group, or an organic group having an epoxy group (for example, a glycidyl group) bonded to the aliphatic group. The aliphatic ring is, for example, one in which 4 to 10 carbon atoms are linked in a ring, and particularly one in which 6 carbon atoms are linked in a ring. The aliphatic ring may have other substituents in addition to the substituent E (epoxy group or organic group having an epoxy group). Such substituents include 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 the formula (1) 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 the formula (1) is 2 to 3,000, or 3 to 600.

[0059] For example, the following polymers are exemplified. [ka]

[0060] (b) Examples of the crosslinkable membrane material include those represented by the following formula (1a), formula (1b), and formula (1c): [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, and R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring, and in formula (1b), two R 3 and two R 4 may be different from each other, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, n, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent the following formula (2): [ka] (wherein two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are the same as in formula (1b), and two Q 1 each independently represents a structural unit represented by the formula (2). Examples of the polymer include a polymer having one or more repeating structural units represented by the following formula:

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

[0062] (c) Examples of the crosslinkable membrane material include those of 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 hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; and R4 and R5 may together with the carbon atoms to which they are attached form a ring; and n1 and n2 are each an integer of 1 to 3.

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

[0064] Preferably, the compound represented by the following formula (2) and / or formula (3): [ka] (In formula (2) and formula (3), R1, R2, R6, R7, and R8 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; and R4 and R5 may together with the carbon atoms to which they are attached form a ring; n1 and n2 are each an integer from 1 to 3, and n3 to n5 are each an integer of 1 to 4.

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

[0066] (d) Examples of the crosslinkable membrane material include polymers containing a unit structure formed from a reaction product of a fused heterocyclic compound and a bicyclic compound, as disclosed in WO 2013 / 005797 A1.

[0067] Preferably, the fused heterocyclic compound is a carbazole compound or a substituted carbazole compound. Preferably, the 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 ]dodeca-3,8-diene.

[0068] Preferably, the polymer is a polymer containing a unit structure represented by the following formula (1), a unit structure represented by the following formula (2), a unit structure represented by the following formula (3), or a combination thereof. [ka] (In the formula, R 1 ~R 14 are substituents of a hydrogen atom, each independently representing a halogen group, a nitro group, an amino group, or a hydroxy group, or an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms which may be substituted by such a group; Ar is an aromatic ring group having 6 to 40 carbon atoms; and n1, n2, n5, n6, n9, and n 10 , n 13 , n 14 and n 15 are integers from 0 to 3, and n3, n4, n7, n8, n 11 and n 12 are each an integer between 0 and 4.) Preferably, in the above formula (3), Ar is a phenyl group or a naphthyl group.

[0069] (e) Examples of crosslinkable membrane materials include those of formula (1): [ka] (In formula (1), A is a hydroxy-substituted phenylene group derived from polyhydroxybenzene, and B is a monovalent fused aromatic hydrocarbon ring group in which 2 to 4 benzene rings are fused.)

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

[0071] (f) Examples of the crosslinkable membrane material include those of the following formula (1): [ka] (In formula (1), Ar 1 , and Ar 2 represents a benzene ring or a naphthalene ring, and R 1 and R 2 are each a substituent for a hydrogen atom on these rings and are selected from the group consisting of a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, and the aryl group represent an organic group which may contain an ether bond, a ketone bond, or an ester bond; R 3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, and the aryl group represent an organic group which may contain an ether bond, a ketone bond, or an ester bond; R 4 is selected from the group consisting of aryl groups and heterocyclic groups having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group; R 5is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R 4 and R 5 may form a ring together with the carbon atom to which they are attached. n1 and n2 are each an integer of 0 to 3.

[0072] Preferably, R in the above formula (1) 5 is a hydrogen atom, and R 4 is an optionally substituted phenyl group, naphthyl group, anthryl group, or pyrenyl group. Preferably, R in the above formula (1) 3 is a hydrogen atom or a phenyl group. Preferably, in the unit structure (A), Ar 1 and Ar 2 contains a unit structure (a1) in which one of the units is a benzene ring and the other is a naphthalene ring. Preferably, in the unit structure (A), Ar 1 and Ar 2 Both of these contain a unit structure (a2) which is a benzene ring. A copolymer containing the unit structure (a1) and the unit structure (a2) is preferred.

[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 is selected from the group consisting of aryl groups and heterocyclic groups having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group; R7 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group represent an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R 6 and R 7 may form a ring together with the carbon atoms to which they are attached. A copolymer containing the unit structure (a1) and the unit structure (B) is preferred.

[0074] (g) Examples of the crosslinkable membrane material include those of the following formula (1): [ka] (In formula (1), R 1 , R 2 , and R 3 are substituents for hydrogen atoms in the ring, and each independently represents a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond. 4 R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond. 5 is a hydrogen atom, or a halogen atom, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms which may be substituted with a hydroxyl group, or a heterocyclic group; R 6 is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, or a hydroxyl group, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, or R5 and R 6 may form a ring together with the carbon atom to which they are attached. Ring A and ring B each represent a benzene ring, a naphthalene ring, or an anthracene ring. n1, n2, and n3 each represent an integer of 0 or more up to the maximum number that can be substituted on the ring. Examples include polymers having a unit structure represented by the following formula:

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

[0076] (h) Examples of the crosslinkable membrane material include those represented by the following formula (1a), formula (1b), and formula (1c), as disclosed in WO 2014 / 129582 A1: [ka] [Wherein, two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group which may have a substituent, and R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring, and in formula (1b), two R 3 and two R4 may be different from each other, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, n, n1, and n2 each independently represent an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Q's each independently represent the following formula (2): [ka] (wherein two R 1 , two R 2 , two R 3 , two R 4 , two k, n1, n2 and X are the same as in formula (1b), and two Q 1 each independently represents a structural unit represented by the formula (2). represents a structural unit represented by the formula: Examples of the polymer include a polymer having one or more repeating structural units represented by the following formula:

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

[0078] (i) Examples of the crosslinkable membrane material include those of the following formula (1): [ka] (In formula (1), R 1 ~R 4 Each of X independently represents a hydrogen atom or a methyl group. 1 represents a divalent organic group containing at least one arylene group which may be substituted with an alkyl group, an amino group, or a hydroxyl group.

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

[0081] (j) Examples of crosslinkable film materials include novolak resins obtained by reacting an aromatic compound (A) with an aldehyde (B) having a formyl group bonded to a secondary or tertiary carbon atom of an alkyl group having 2 to 26 carbon atoms, as disclosed in WO 2017 / 069063 A1.

[0082] Preferably, the novolac resin is represented by the following formula (1): [ka] (In formula (1), A represents a divalent group derived from an aromatic compound having 6 to 40 carbon atoms, and b 1 represents an alkyl group having 1 to 16 carbon atoms; b 2 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

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

[0084] Preferably, the novolac resin is represented by the following formula (2): [ka] (In formula (2), a 1 and a 2 represents an optionally substituted benzene ring or naphthalene ring, and R 1 represents a secondary amino group or a tertiary amino group, a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, an arylene group, or a divalent group to which any of these groups are optionally bonded. 3 represents an alkyl group having 1 to 16 carbon atoms; b 4 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0085] (k) Examples of the crosslinkable membrane material include those represented by the following formula (1a) and / or formula (1b): [ka] [In formulas (1a) and (1b), two R 1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group; 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group; R 3 represents an aromatic hydrocarbon group or a heterocyclic group which may have a substituent, and R 4 represents a hydrogen atom, a phenyl group, or a naphthyl group, and R 3 and R 4 each represent a phenyl group, they may be bonded to each other to form a fluorene ring, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, p represents an integer of 3 to 500, X represents a benzene ring, and the two -C(CH3)2- groups bonded to the benzene ring are in a meta or para position relationship. Examples of the polymer include a polymer having a repeating structural unit represented by the following formula:

[0086] Preferably, the polymer is a polymerization reaction product of at least one bisphenol compound and at least one aromatic aldehyde or aromatic ketone. Preferably, the R 3 The aromatic hydrocarbon group represented by is a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.

[0087] (l) Examples of cross-linkable membrane materials include poly(epoxide) resins having an epoxy functionality of greater than 2.0 and less than 10, such as those disclosed in JP-A-11-511194.

[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, polyglycidyl amines, cycloaliphatic epoxides, and polyglycidyl esters. Preferably, the poly(epoxide) resin has an epoxy functionality greater than 3.5.

[0089] (m) Examples of crosslinkable film materials or novolac film materials include compounds represented by the following formula (1) and novolac film materials, as disclosed in WO 2018 / 198960 A1. [ka] [In formula (1), [ka] represents a single bond or a double bond, X 1 is -N(R 1 )- or -CH(R 1 )-, X 2 is -N(R 2 )- or -CH(R 2 )-, X 3 are -N=, -CH=, -N(R 3 )- or -CH(R 3 )-, X 4 are -N=, -CH=, -N(R 4 )- or -CH(R 4 )-, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, and the alkyl group and aryl group 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 hydroxy group and may be interrupted by an oxygen atom or a sulfur atom; R 5 , R 6 , R 9and R 10 are the same or different and each represent a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1.]

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

[0091] Preferably, the compound contains one or more units of one or more of repeating units a, b, c, d, e, f, g, h, and i represented by the following formula (2). [ka] [ka] Formula (2) [In formula (2), [ka] represents a single bond or a double bond, X 1 is -N(R 1 )-, -CH(R 1)-, -N< or -CH<; X 2 is -N(R 2 )-, -CH(R 2 )-, -N< or -CH<; X 3 are -N=, -CH=, -N(R 3 )-, -CH(R 3 )-, -N< or -CH<; X 4 are -N=, -CH=, -N(R 4 )-, -CH(R 4 )-, -N< or -CH<; R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, and the alkyl group and aryl group 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 hydroxy group and may be interrupted by an oxygen atom or a sulfur atom; R 5 , R 6 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1; B 1 and B 2 are the same or different and each represents a group derived from an aromatic compound selected from the group consisting of a C1-20 linear, branched or cyclic alkyl group optionally interrupted by a hydrogen atom, an oxygen atom or a sulfur atom, a C6-40 aryl group and a C6-40 heterocyclic group; B 1 and B 2 may form a ring together with the carbon atom to which they are bonded, and a hydrogen atom of the group derived from the aromatic compound may be substituted with a C1-20 alkyl group, a phenyl group, a fused ring group, a heterocyclic group, a hydroxy group, an amino group, an ether group, an alkoxy group, a cyano group, a nitro group, or a carboxyl group.]

[0092] Preferably, the compound contains one or more units of one or more of repeating units j, k, l, m, r, s, t, u, v, and w represented by the following formula (3). [ka] [ka] Formula (3) [In formula (3), [ka] represents a single bond or a double bond, X 1 represents -N< or -CH<, X 2 represents -N< or -CH<, X 3 are -N=, -CH=, -N(R 3 )- or -CH(R 3 )-, X 4 are -N=, -CH=, -N(R 4 )- or -CH(R 4 )-, R 3 and R 4are the same or different and each represents a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group, a carboxyl group or a cyano group, and the alkyl group and aryl group 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 hydroxy group and may be interrupted by an oxygen atom or a sulfur atom; R 5 , R 6 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-20 alkenyl group or a C2-10 alkynyl group, and the acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group, alkenyl group and alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group and a carboxyl group, R 7 and R 8 are the same or different and each represents a benzene ring or a naphthalene ring, n and o are 0 or 1; p and q are integers from 0 to 20, When the number of methylene groups is two or more, the number of methylene groups p and the number of methylene groups q may be interrupted by an oxygen atom or a sulfur atom. B 3 represents a direct bond or a group derived from a C6-40 aromatic compound which may be substituted with a C1-20 alkyl group, a phenyl group, a fused ring group, a heterocyclic group, a hydroxy group, an amino group, an ether group, an alkoxy group, a cyano group, a nitro group, or a carboxyl group.]

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

[0094] (n) Examples of crosslinkable film materials include epoxy adducts formed by reacting an epoxy group-containing compound having at least two epoxy groups with an epoxy adduct-forming compound having one epoxy addition reactive group, as disclosed in WO 2017 / 002653 A1. Examples of such epoxy adducts include the following.

[0095] [ka] [ka]

[0096] [ka]

[0097] [ka]

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

[0099] (o) Examples of the crosslinkable membrane material include those of formula (1):

[0100] [ka] (In the formula, A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group, and X1 represents a compound represented by formula (2), formula (3), formula (4), or formula (5):

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

[0102] Preferably, the structure represented by formula (1) is represented by formula (12): [ka] (wherein R1, R2, and Q have the same meanings as defined above) Or, equation (13): [ka] (wherein X1 has 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, and m represents an integer of 0 to 4, and when m is 2 to 4, the Ys may be the same or different.) The structure is expressed as follows.

[0103] (p) Examples of the crosslinkable membrane material include those represented by formula (1) or (2): [ka] In the formula, R1 and R2 each represent a hydrogen atom, a methyl group, an ethyl group, or a halogen atom; A1, A2, A3, A4, A5, and A6 each represent a hydrogen atom, a methyl group, or an ethyl group; and Q is a group represented by formula (3) or formula (4): [ka] [In the formula, Q1 represents an alkylene group having 1 to 15 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and the phenylene group, naphthylene group, and anthrylene group are each optionally substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms; n1 and n2 each represent the number 0 or 1; X1 represents a group represented by formula (5), (6), or formula (7): [ka] (wherein R3 and R4 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is 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, and R3 and R4 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R5 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is 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).)

[0104] Preferably, the polymer has the formula (12): [ka] (wherein Q has the same meaning as above)

[0105] Preferably, the polymer has formula (13) and formula (14): [ka] [Wherein Q2 is the formula (15), the formula (16) or the formula (17): [ka] (wherein Y, m, R3, R4 and R5 are as defined above), and Q3 represents a group represented by formula (18): [ka] (wherein Q4 represents an alkylene group having 1 to 15 carbon atoms, and n3 and n4 each represent the number 0 or 1.)

[0106] (q) Examples of the crosslinkable membrane material include those represented by the following 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 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, R6, R7, and R8 each represent a hydrogen atom or a linear or cyclic alkyl group having 1 to 10 carbon atoms; R9 represents a linear or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms; R7 and R8 may be bonded to each other to form a ring; M and Q each represent a direct bond or a linking group; and n represents an integer of 0 or 1.) or a combination of such polymers, wherein, when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) satisfy the following ranges: 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 taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1) and the ratio of the number (b) of unit structures represented by formula (2) satisfy the following conditions: 0.305≦a+b≦1, 0.3≦a≦0.95, 0.005≦b≦0.7. Preferably, the polymer contains unit structures represented by formula (1) and formula (3), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1) and the ratio of the number (c) of unit structures represented by formula (3) 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 formula (1), formula (2), and formula (3), and when the total number of all unit structures constituting the polymer is taken as 1.0, the ratio of the number (a) of unit structures represented by formula (1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) satisfy the following conditions: 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 the crosslinkable membrane material include those of the following formula (2): [ka] (In formula (2), each of the two Ar represents an aryl group, the aryl group having at least one hydroxy group as a substituent, and Q represents a divalent linking group having at least one benzene ring or naphthalene ring, a methylene group, or a single bond.) The molecular weight of the compound 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, an anthryl group, and a phenanthryl group. When Q represents a divalent linking group having at least one benzene ring or a naphthalene ring, examples of the divalent linking group include a divalent group in which at least one of the two hydrogen atoms of a methylene group is 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 the divalent aromatic group and a methylene group, an ether group (-O- group), or a sulfide group (-S- group). Examples of the monomer include compounds represented by the following formulas (2-1) to (2-6). [ka] (In formula (2-6), m represents an integer of 0 to 3.)

[0110] (s) Examples of the film material capable of crosslinking include those having a structure in which one fullerene molecule is reacted with a compound represented by the following formula (1): [ka] (In the formula, each R independently represents an alkyl group having 1 to 10 carbon atoms.) Examples of the fullerene derivative include a fullerene derivative having one to six molecules of malonic acid diester added thereto, which is represented by the following formula:

[0111] (t) Examples of the crosslinkable membrane material include polyfunctional (meth)acrylate compounds having a molecular weight 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 has 2 to 20 (meth)acrylate groups in the molecule. Preferably, the molecular weight of the compound is between 300 and 2,300.

[0113] Examples of such compounds include the following:

[0114] [ka]

[0115] [ka]

[0116] (u) Examples of membrane materials capable of crosslinking include compound (E) containing partial structure (I) and partial structure (II), as disclosed in WO 2017 / 154921 A1, in which partial structure (II) contains a hydroxy group generated by the reaction of an epoxy group with a proton-generating compound, partial structure (I) is at least one partial structure selected from the group consisting of partial structures represented by formulas (1-1) to (1-5) below, or a partial structure consisting of a combination of a partial structure represented by formula (1-6) and a partial structure represented by formula (1-7) or formula (1-8), and partial structure (II) is a partial structure represented by formula (2-1) or formula (2-2) below. [ka] (In the formula, R 1 , R 1a , R 3 , R 5 , R 5a , and R 6a each represents a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a group consisting of a combination thereof; R 2 , R 2a , R 4 , and R 6each represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R 2 , R 2a , R 4 , R 6 represents a monovalent group, R 1 , R 1a , R 3 , R 5a , and R 6a represents a divalent group, R 5 represents a trivalent group, and R 7 , R 8 , R 9 , R 10 and R 11 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 dotted lines represent chemical bonds with adjacent atoms.

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

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

[0119] Preferably, the compound is a compound having one or more photodegradable nitrogen-containing structures and / or photodegradable sulfur-containing structures in the molecule. Preferably, the compound is a compound in which a photodegradable nitrogen-containing structure and / or a photodegradable sulfur-containing structure and a hydrocarbon structure are present in the same molecule, or a combination of compounds in which the structures are present in different molecules. Preferably, the hydrocarbon structure is a saturated or unsaturated group having 1 to 40 carbon atoms, and is a linear, branched, or cyclic hydrocarbon group. Preferably, the photodecomposable nitrogen-containing structure is a structure that generates a reactive nitrogen-containing functional group or a reactive carbon-containing functional group upon irradiation with ultraviolet light, or a structure that contains a reactive nitrogen-containing functional group or a reactive carbon-containing functional group generated upon irradiation with ultraviolet light. Preferably, the photodecomposable nitrogen-containing structure is a photodecomposable nitrogen-containing structure which may contain a sulfur atom, and the structure is an azide structure, a tetraazole structure, a triazole structure, an imidazole structure, a pyrazole structure, an azole structure, a diazo structure, or a structure containing a combination thereof. Preferably, the photodecomposable sulfur-containing structure is a structure that generates an organic sulfur radical or a carbon radical upon irradiation with ultraviolet light, or a structure that contains an organic sulfur radical or a carbon radical generated upon irradiation with ultraviolet light. Preferably, the photodecomposable sulfur-containing structure is a photodecomposable sulfur-containing structure which may contain a nitrogen atom, and the structure is a trisulfide structure, a disulfide structure, a sulfide structure, a thioketone structure, a thiophene structure, a thiol structure, or a structure containing a combination thereof.

[0120] Preferred are the following compounds: [ka] [ka]

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

[0122] Preferred are the following compounds: [ka]

[0123] (x) Examples of a film material capable of undergoing a crosslinking reaction include compounds represented by the following general formula (1), as disclosed in JP-A-2016-216367: [ka] (In the formula, n1 and n2 each independently represent 0 or 1, W is a single bond or any of the structures represented by the following formula (2), R1 is any of the structures represented by the following general formula (3), and m1 and m2 each independently represent an integer of 0 to 7, with the proviso that m1+m2 is 1 or more and 14 or less.) [ka] (In the formula, l represents an integer of 0 to 3, and R a ~R f each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group; R a and R b may be bonded to form a cyclic compound.) [ka] (In the formula, * represents a bonding site to the aromatic ring, and Q1 represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, anthracenyl group, or pyrenyl group. When Q1 represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, a methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group.)

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

[0125] Preferably, the W is either a single bond or a structure represented by the following formula (5). [ka] (wherein l is the same as above).

[0126] Preferably, the compound represented by the general formula (1) has two or more Q1s in the molecule, and the Q1s include one or more types of structures represented by the following general formula (6) and one or more types of structures represented by the following general formula (7). [ka] (wherein ** represents the bonding site to the carbonyl group, R h represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and R h The methylene group constituting the formula (I) may be substituted with an oxygen atom or a carbonyl group. [ka] (wherein ** represents the bonding site to the carbonyl group, R i represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7, provided that n3 + n4 is 0 or more and 7 or less. n5 represents 0 to 2.

[0127] (y) Examples of a film material capable of undergoing a crosslinking reaction include compounds represented by the following general formula (1A), as disclosed in JP-A-2017-119670. [ka] (In the formula, R represents a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO2- group; R1 represents a group represented by the following general formula (1B); and m1 and m2 represent integers satisfying 1 ≦ m1 ≦ 5, 1 ≦ m2 ≦ 5, and 2 ≦ m1 + m2 ≦ 8.) [ka] (In the formula, X 1 is a group represented by the following general formula (1C), and X is a group represented by the following general formula (1D). [ka] (In the formula, (X) represents the bonding site to the X.) [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (1E), and n5 is 0, 1, or 2. [ka] (In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group.

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

[0129] Preferred are compounds represented by the following general formula (2A) and compounds represented by the following general formula (3A). [ka] (In the formula, R represents a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO2- group; R2 represents a group represented by the following general formula (2B); and m3 and m4 represent integers satisfying 1 ≦ m3 ≦ 5, 1 ≦ m4 ≦ 5, and 2 ≦ m3 + m4 ≦ 8.) [ka] (In the formula, X 11 is a group represented by the following general formula (2C), and X' is a group represented by the following general formula (2D). [ka] (In the formula, (X') represents the bonding site to the X'.) [ka] (wherein n3 is 0 or 1, n4 is 1 or 2, and X 4 is a group represented by the following general formula (2E), and n6 is 0, 1, or 2. [ka] (In the formula, R 11 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. [ka] (In the formula, R 101 , R 102 , R 103 , R 104 are each independently a hydroxyl group, m100 is 1, 2, or 3, and R 100 represents a hydrogen atom or a hydroxyl group when m100 is 1, a single bond or a group represented by the following general formula (3B) when m100 is 2, and a group represented by the following general formula (3C) when m100 is 3, wherein the hydrogen atom on the aromatic ring may be substituted with a methyl group or a methoxy group. m101 is 0 or 1, m102 is 1 or 2, m103 is 0 or 1, m104 is 1 or 2, and m105 is 0 or 1. When m101 is 0, n101 and n102 are integers that satisfy 0≦n101≦3, 0≦n102≦3, and 1≦n101+n102≦4, and when m101 is 1, n101, n102, n103, and n104 are integers that satisfy 0≦n101≦2, 0≦n102≦2, 0≦n103≦2, 0≦n104≦2, and 2≦n101+n102+n103+n104≦8. [ka] (where * indicates a bonding position, and R 106 , R 107is a hydrogen atom or an organic group having 1 to 24 carbon atoms and not containing an ester bond, and R 106 and R 107 may be bonded to form a cyclic structure. [ka] (where * indicates a bonding position, and R 108 is a hydrogen atom or an organic group having 1 to 15 carbon atoms.

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

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

[0132] When the resist underlayer film-forming composition of 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 mass %, preferably 50 to 99.9 mass %, more preferably 50 to 95 mass %, and even more preferably 50 to 90 mass %, based on the total solid content.

[0133] The resist underlayer film-forming composition of the present invention may further contain a light absorber, a rheology modifier, an adhesion promoter, etc. The rheology modifier is effective in improving the fluidity of the underlayer film-forming composition. The adhesion promoter is effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

[0134] (light absorber) Examples of the light-absorbing agent include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI Disperse Violet 43; CI Disperse Blue 96; and CI Fluorescent Brightening Agent. Suitable examples of the light absorbent that can be used include CI Solvent Orange 2 and 45, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pigment Green 10, and CI Pigment Brown 2. The light absorbent is typically blended in an amount of 10% by mass or less, and preferably 5% by mass or less, based on the total solids content of the resist underlayer film-forming composition.

[0135] (Rheology modifier) Rheology modifiers are added primarily to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically added in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition.

[0136] (adhesion aid) The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film-forming composition, and particularly 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; methyloltrimethylsilane; and methyltrimethylsilane. Examples of suitable adhesion aids include silanes such as chlorosilane, 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 urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion aids are typically blended in an amount of less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the resist underlayer film-forming composition.

[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 content of all components of the resist underlayer film-forming composition excluding the solvent. The proportion of the polymer in the solid content is preferably 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, in that order.

[0138] One measure for evaluating 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 of the present invention passes through a microfilter with a pore size of 0.1 μm and exhibits a uniform solution state.

[0139] Examples of the microfilter material include fluorine-based resins 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, with PTFE (polytetrafluoroethylene) being preferred.

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

[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 of the present invention by coating or vapor deposition. For example, an adhesion layer can be formed by spin coating using the adhesion layer described in JP-A-2013-202982 and Japanese Patent No. 5827180, or a silicon-containing resist underlayer film (inorganic resist underlayer film)-forming composition described in WO2009 / 104552A1, or a Si-based inorganic material film can be formed by CVD or the like.

[0142] Furthermore, by applying the resist underlayer film-forming composition according to the present invention to a semiconductor substrate having a portion with a step and a portion without a step (a so-called stepped substrate) and baking it, a resist underlayer film can be formed in which the step between the portion with a step and the portion without a step is in the range of 3 to 70 nm.

[0143] [Method of manufacturing a semiconductor device] The method for manufacturing a semiconductor device according to the present invention includes the steps of: a step of forming a resist underlayer film using the resist underlayer film-forming composition according to the present invention; forming a resist film on the formed resist underlayer film; a step 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 A process of processing a semiconductor substrate through a patterned resist underlayer film Includes:

[0144] Further, a method for manufacturing a semiconductor device according to the present invention includes the steps of: a step of forming a resist underlayer film using the resist underlayer film-forming composition according to the present invention; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; a step of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it; Etching and patterning the hard mask through the formed resist pattern; and Etching and patterning the resist underlayer film through a patterned hard mask; and A process of processing a semiconductor substrate through a patterned resist underlayer film Includes:

[0145] The step 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 film on the resist underlayer film formed by the above process, and a resist pattern may be formed thereon. This second resist underlayer film may be a SiON film or a 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 film on the second resist underlayer film, and the third resist underlayer film may be a resist shape correction film without anti-reflective properties.

[0147] In the process of forming the resist pattern, exposure is performed through a mask (reticle) to form a predetermined pattern or by direct writing. Examples of exposure sources that can be used include g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, and electron beam. After exposure, post-exposure baking is performed as needed. The resist is then developed with a developer (e.g., a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), and rinsed with a rinse solution or pure water to remove the used developer. Post-baking is then performed to dry the resist pattern and improve adhesion to the underlying layer.

[0148] The etching step performed after the formation of the resist pattern is carried out by dry etching. Examples of etching gases used in dry etching include CHF3, CF4, and C2F6 for the second resist underlayer film (organopolysiloxane film), O2, NO2, 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 or recesses and / or protrusions. Furthermore, these gases can be mixed with argon, nitrogen, or carbon dioxide.

[0149] [Formation of resist underlayer film by nanoimprint method] The step of forming the resist underlayer film can also be carried out by a nanoimprint method. applying a curable composition onto the formed resist underlayer film; contacting the curable composition with a 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 mold release process of photo-nanoimprint technology, adhesion between the resist composition and the substrate is important. If the adhesion between the resist composition and the substrate is low, when the mold is released in the mold release process, part of the photocured product obtained by curing the resist composition may peel off while still adhering to the mold, resulting in pattern peeling defects. As a technique for improving adhesion between the resist composition and the substrate, a technique has been proposed in which an adhesion layer is formed between the resist composition and the substrate, which is a layer for adhering the resist composition to the substrate.

[0151] In addition, a highly etch-resistant layer may be used for pattern formation in nanoimprinting. Organic materials and silicone materials are commonly used as materials for the highly etch-resistant layer. Furthermore, an adhesion layer or a silicon-containing silicone layer can be formed on the nanoimprint resist underlayer film by coating or vapor deposition. When these adhesion layers or silicon-containing silicone layers are hydrophobic and exhibit a high pure water contact angle, it is expected that the underlayer film will also be hydrophobic and exhibit a high pure water contact angle, thereby enhancing adhesion between the films and reducing peeling resistance. Conversely, when the adhesion layer or silicone layer is hydrophilic and exhibits a low pure water contact angle, it is expected that the underlayer film will also be hydrophilic and exhibit a low pure water contact angle, thereby enhancing adhesion between the films and reducing peeling resistance.

[0152] Furthermore, He, H2, N2, air, etc. can be used depending on the properties of the adhesive film, silicone layer, and underlayer film.

[0153] The polymer (X) according to the present invention exhibits a desired pure water contact angle not only when baked at low temperatures but also when baked at high temperatures. It also exhibits a desired pure water contact angle when mixed with a crosslinker, an acid catalyst, and a surfactant. This enables enhanced adhesion to an overlying 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 modifying the molecular skeleton, 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 composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; and chemically amplified photoresists composed of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, a low-molecular-weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator. Examples include APEX-E (trade name) manufactured by Shipley Chemical Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples include fluorine-containing polymer 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 is a step of applying a curable composition onto the resist underlayer film formed by the method for producing a resist underlayer film according to the present invention. Examples of methods that can be used to apply the curable composition include inkjet coating, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scanning. The inkjet method is suitable for applying the curable composition as droplets, and the spin coating method 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 be formed on the resist underlayer film by coating or vapor deposition, and the curable composition can be applied thereon.

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

[0157] Considering the light or electron beam irradiation process described below, it is recommended to use a mold whose substrate is made of a light-transmitting material. Specific examples of the mold substrate include glass, quartz, optically transparent resins such as PMMA and polycarbonate resin, transparent metal vapor deposition films, flexible films such as polydimethylsiloxane, photocured films, and metal films. Quartz is more preferable as the mold substrate because of its small thermal expansion coefficient and small pattern distortion.

[0158] The fine pattern on the surface of the mold preferably has a pattern height of 4 nm or more and 200 nm or less. A certain level of pattern height is necessary to increase the processing accuracy of the substrate, but a lower pattern height reduces the force required to peel the mold from the cured film in the step of separating the cured film and the mold (described later), and also reduces the number of defects remaining on the mask side after the resist pattern is torn off. Taking these factors into consideration, it is recommended to select and adopt a pattern height with an appropriate balance. Furthermore, when the mold is peeled off, the elastic deformation of the resist pattern due to the impact can cause adjacent resist patterns to come into contact with each other, resulting in adhesion or damage to the resist patterns. This can sometimes be avoided by making the pattern height approximately twice the pattern width (aspect ratio of 2 or less).

[0159] To improve the releasability of the curable composition from the surface of the mold, the mold may be subjected to a surface treatment in advance. Examples of surface treatment methods include applying a release agent to the surface of the mold 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. Fluorine-based and hydrocarbon-based release agents are preferred. Commercially available products include, for example, Optool (registered trademark) 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 step, the pressure applied to the curable composition when contacting the mold with the curable composition is not particularly limited. A pressure of 0 MPa or more and 100 MPa or less is recommended. The pressure is preferably 0 MPa or more and 50 MPa or less, 30 MPa or less, or 20 MPa or less.

[0161] If pre-spreading of the droplets of the curable composition has progressed in the previous step (the step of applying the curable composition), spreading of the curable composition in this step is completed quickly. As a result, the time for contacting the mold with the curable composition can be shortened. The contact time is not particularly limited, but is preferably 0.1 seconds or more and 600 seconds or less, 3 seconds or less, or 1 second or less. If the contact time is too short, spreading and filling may be insufficient, resulting in the risk of defects known as unfilled defects.

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

[0163] This step may be carried out in an atmosphere containing a condensable gas (hereinafter referred to as a "condensable gas atmosphere"). In this specification, the condensable gas refers to a gas that condenses and liquefies due to the capillary pressure generated when the gas is filled together with the curable composition into the recesses of the fine pattern formed on the mold and the gap between the mold and the substrate. The condensable gas exists as a gas in the atmosphere before the curable composition comes into contact with the mold in this step. When this step is carried out in a condensable gas atmosphere, the gas filled into the recesses of the fine pattern is liquefied by the capillary pressure generated by the curable composition, thereby eliminating bubbles, resulting in excellent filling properties. 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 equal to or lower than the atmospheric temperature in this step, 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 in this step is not particularly limited as long as it is equal to or lower than the mold pressure, and is preferably in the range of 0.1 MPa to 0.4 MPa.

[0166] Specific 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] The condensable gas may be used alone or in combination of two or more. These condensable gases may also be used in combination with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. Air and helium are preferred as non-condensable gases to be mixed with the condensable gas.

[0168] (Step of irradiating the curable composition with light or electron beam to form a cured film) In this step, the curable composition is irradiated with light or an electron beam to form a cured film. That is, 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 to form a cured film having the pattern shape.

[0169] The light or electron beam is selected depending on the wavelength sensitivity of the curable composition. Specifically, ultraviolet light, X-rays, electron beams, etc. having a wavelength of 150 nm or more and 400 nm or less 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, and F2 excimer lasers. The number of light sources may be one or more. Irradiation may be performed on the entire curable composition filled into the fine pattern of the mold, or on only a partial region. Light irradiation may be performed intermittently multiple times over the entire region on the substrate, or may be performed continuously over the entire region. Alternatively, a partial region on the substrate may be irradiated a first time, and a different region from the partial region may be irradiated a second time.

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

[0171] (Step of separating the cured film from the mold) In this step, the cured film is separated from the mold. The patterned cured film is separated from the mold, yielding a free-standing cured film having a pattern that is a reverse pattern of the fine pattern formed on the mold.

[0172] The method for separating the patterned cured film from the mold is not particularly limited as long as it is a method for moving the cured film and the mold in directions that move them apart relatively, as long as a portion of the patterned cured film is not physically damaged, and various conditions are also not particularly limited. 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] If the above-described step of contacting the curable composition with the mold is carried out in a condensable gas atmosphere, when the cured film is separated from the mold in this step, the condensable gas evaporates as the pressure at the interface where the cured film and the mold contact each other decreases, thereby reducing the mold release force required to separate the cured film from the mold.

[0174] Through the above steps, a cured film can be prepared that has a desired concave-convex pattern shape derived from the concave-convex shape of the mold at desired positions. [Example]

[0175] Specific examples of the composition according to the present invention will be described below using the following examples, but the present invention is not limited thereto.

[0176] The apparatus used to measure the weight-average molecular weight of the reaction products obtained in the following synthesis examples is shown below. Apparatus: Tosoh Corporation HLC-8320GPC GPC column: TSKgel Super-MultiporeHZ-N (2 columns) 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] A flask was charged with 260.00 g of TMOM-BP (Honshu Chemical Co., Ltd.) and 1,430 g of propylene glycol monomethyl ether (hereinafter referred to as PGME). The mixture was then heated to approximately 90°C under nitrogen, and 17.26 g of methanesulfonic acid (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 unit is a crosslink formed by bonding any ROCH2- group containing a methoxymethyl group to a hydroxy group, or between ROCH2- groups. However, since the chemical formula would be extremely complicated to represent this state, only the structural unit is shown. The same applies below. The weight-average molecular weight Mw measured by GPC in terms of polystyrene was approximately 4,500. Furthermore, the introduction of PGME was 1 The resulting resin was dissolved in PGMEA and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours 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. The mixture was then heated to approximately 90°C under nitrogen, 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 by GPC in terms of polystyrene was approximately 5,400. The introduction of PGME was 1 The resulting resin was dissolved in PGMEA and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0183] [ka]

[0184] [Synthesis Example 3] 30.00 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.) and 165.07 g of 1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a flask. The mixture was then heated to approximately 90°C under nitrogen, 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 by GPC in terms of polystyrene was approximately 3,487. The introduction of 1-butyl groups was also confirmed. 1 The resulting resin was dissolved in PGME and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0185] [ka]

[0186] [Synthesis Example 4] A flask was charged with 34.50 g of TMOM-BP (Honshu Chemical Co., Ltd.), 33.16 g of TM-BIP-A, and 379.44 g of PGME. The mixture was then heated to approximately 90°C under nitrogen, and 2.29 g of methanesulfonic acid (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 by GPC in terms of polystyrene was approximately 4,296. The introduction of PGME was also 1 The resulting resin was dissolved in PGME and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0187] [ka]

[0188] [Synthesis Example 5] A flask was charged with 34.50 g of TMOM-BP (Honshu Chemical Co., Ltd.), 0.31 g of PL-LI (Midori Chemical Co., Ltd.), and 189.73 g of PGME. The mixture was then heated to approximately 90°C under nitrogen, and 2.29 g of methanesulfonic acid (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 by GPC in terms of polystyrene was approximately 3,978. The introduction of PGME was also 1 The resulting resin was dissolved in PGME and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0189] [ka]

[0190] [Synthesis Example 6] A 100 mL flask was charged with 10.00 g of TMOM-BP (Honshu Chemical Co., Ltd.), 5.46 g of carbazole (Tokyo Chemical Industry Co., Ltd.), and 58.72 g of PGME. The mixture was then heated to 90°C under nitrogen, and 0.47 g of methanesulfonic acid (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 polymer (1-6). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 4,000. The introduction of PGME was 1 The resulting resin was dissolved in PGMEA and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0191] [ka]

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

[0193] [ka]

[0194] [Synthesis Example 8] A 100 mL flask was charged with 10.00 g of TMOM-BP (Honshu Chemical Co., Ltd.), 11.44 g of 9,9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), and 60.73 g of PGME. The mixture was then heated to reflux under nitrogen, and 0.47 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise. After about 4 hours, the mixture was precipitated with methanol and water and dried to obtain polymer (1-8). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 4,100. The introduction of PGME was also 1 The resulting resin was dissolved in PGMEA and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0195] [ka]

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

[0197] [ka]

[0198] [Synthesis Example 10] A 100 mL flask was charged with 12.00 g of TMOM-BP (Honshu Chemical Co., Ltd.), 6.27 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), and 70.36 g of PGME. The mixture was then heated to reflux under nitrogen, and 0.56 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise. After about an hour, the polymer was precipitated with methanol and water and dried to obtain polymer (1-10). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 10,000. The introduction of PGME was also 1 The resulting resin was dissolved in PGMEA and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0199] [ka]

[0200] [Synthesis Example 11] A flask was charged with 68.99 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 40.00 g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 379.42 g of PGME. The mixture was then heated to approximately 90°C under nitrogen, 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 by GPC in terms of polystyrene was approximately 4,200. The introduction of PGME was 1 The resulting resin was dissolved in PGME and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the target polymer solution.

[0201] [ka]

[0202] [Synthesis Example 12] A 100 mL flask was charged with 8.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 8.63 g of 9-fluorenone (Tokyo Chemical Industry Co., Ltd.), 2.30 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 18.93 g of PGMEA. The mixture was then heated to reflux under nitrogen. After approximately 1.5 hours, the mixture was precipitated with methanol and dried to obtain polymer (1-12). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 2,600. The resulting resin was dissolved in PGMEA and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the desired polymer solution.

[0203] [ka]

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

[0205] [ka]

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

[0207] [ka]

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

[0209] [ka]

[0210] [Comparative Synthesis Example 4] A flask was charged with 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. The mixture was then heated to approximately 120°C under nitrogen, and 0.38 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise, followed by a reaction for approximately 5 hours.

[0211] [Comparative Synthesis Example 5] A 200 mL flask was charged with 69.92 g of N-phenyl-1-naphthylamine (Tokyo Chemical Industry Co., Ltd.), 40.88 g of 2-ethylhexylaldehyde (Tokyo Chemical Industry Co., Ltd.), 9.19 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 80.00 g of propylene glycol monomethyl ether acetate (PGMEA). The mixture was then heated to reflux under nitrogen. After approximately 24 hours, the mixture was precipitated with methanol and dried to obtain polymer (2-4). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was approximately 1,700. The resulting resin was dissolved in PGMEA and subjected to ion exchange using a cation exchange resin and an anion exchange resin for 4 hours to obtain the desired polymer solution.

[0212] [ka]

[0213] [Example 1] A resin solution (solid content 21.38% by mass) was obtained in Synthesis Example 1. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.20 g of PGMEA containing 1% by mass of surfactant (Megafac R-40, manufactured by DIC Corporation), 4.96 g of PGMEA, and 2.41 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0214] [Example 2] A resin solution (solid content 26.93% by mass) was obtained in Synthesis Example 3. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.16 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 5.24 g of PGMEA, and 5.80 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0215] [Example 3] A resin solution (solid content 22.01% by mass) was obtained in Synthesis Example 4. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.16 g of PGMEA containing 1% by mass of surfactant (Megafac R-40, manufactured by DIC Corporation), 5.24 g of PGMEA, and 4.46 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0216] [Example 4] A resin solution (solid content 20.12% by mass) was obtained in Synthesis Example 5. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.16 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 5.24 g of PGMEA, and 3.76 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0217] [Example 5] A resin solution (solid content 17.85% by mass) was obtained in Synthesis Example 6. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.20 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 3.15 g of PGMEA, and 2.41 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0218] [Example 6] A resin solution (solid content: 16.62% by mass) was obtained in Synthesis Example 7. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.20 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 2.35 g of PGMEA, and 2.41 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0219] [Example 7] A resin solution (solid content: 18.61% by mass) was obtained in Synthesis Example 8. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.20 g of PGMEA containing 1% by mass of surfactant (Megafac R-40, manufactured by DIC Corporation), 3.61 g of PGMEA, and 2.41 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0220] [Example 8] A resin solution (solid content: 16.88% by mass) was obtained in Synthesis Example 9. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.20 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 2.52 g of PGMEA, and 2.41 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0221] [Example 9] A resin solution (solid content: 18.06% by mass) was obtained in Synthesis Example 10. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.20 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 3.28 g of PGMEA, and 2.41 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0222] [Example 10] A resin solution (solid content: 17.62% by mass) was obtained in Synthesis Example 11. 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 of pyridinium p-hydroxybenzenesulfonate, 0.49 g of PGMEA containing 1% by mass of a surfactant (manufactured by DIC Corporation, Megafac R-40), 6.12 g of PGMEA, and 2.64 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0223] [Example 11] A resin solution (solid content 21.38% by mass) was obtained in Synthesis Example 1. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.25 g of PGMEA containing 1% by mass of surfactant (Megafac R-40, manufactured by DIC Corporation), 2.66 g of PGMEA, and 1.51 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

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

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

[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 of K-PURE TAG2689 (manufactured by King Industries), 0.13 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 10.63 g of PGMEA, and 1.77 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0227] [Comparative Example 1] A resin solution (solid content 24.24% by mass) was obtained in Comparative Synthesis Example 5. 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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.18 g of PGMEA containing 1% by mass of surfactant (Megafac R-40, manufactured by DIC Corporation), 3.03 g of PGMEA, and 1.14 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[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 of K-PURE TAG2689 (manufactured by King Industries Ltd.), 0.13 g of PGMEA containing 1% by mass of surfactant (Megafac R-40, manufactured by DIC Corporation), 11.56 g of PGMEA, and 1.77 g of PGME were added and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter having a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0229] (Polymer solubility test) When syntheses were performed 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 rated as good, and solutions that were suspended were rated as bad. 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 to a solids content of 20% by mass. Ion exchange treatment was then performed according to the Synthesis Examples and Comparative Examples, and the solubility of the polymers was evaluated. Solutions that were not suspended after the ion exchange treatment were rated as good, and solutions that were suspended after the ion exchange treatment were rated as bad. The results are shown in Table 1.

[0230] [Table 1]

[0231] By synthesizing the polymer in PGME, which contains non-phenolic hydroxyl groups in the molecule, methoxypropoxy groups are introduced into the side chains. Therefore, the polymer exhibits higher solubility in PGME or PGMEA after ion exchange than polymers synthesized in 1,4-dioxane, which does not contain non-phenolic hydroxyl groups in the molecule. This method is also advantageous in that it allows the polymer to be synthesized in PGME, a solvent commonly used in the semiconductor industry, without using 1,4-dioxane, a highly hazardous solvent classified as specified hazardous industrial waste. Furthermore, as shown in Synthesis Example 11 and Comparative Synthesis Example 4, when highly polar monomers are used, the monomers 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 such as PGME promotes polymerization, resulting in highly soluble materials even after ion exchange. Subsequently, the polymers and crosslinkers with these alcohol structural substituents were characterized.

[0232] (Test for elution into resist solvent) The solutions of the resist underlayer film-forming compositions prepared in Comparative Examples 1-2 and Examples 1-14 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form resist underlayer films (thickness: 200 nm). These resist underlayer films were immersed in a commonly used thinner, PGME / PGMEA = 7 / 3, to confirm their curability. All resist underlayer films were insoluble in this thinner, confirming that they had sufficient curability.

[0233] (Optical constant measurement) The resist underlayer film-forming composition solutions prepared in Comparative Example 1 and Examples 1-13 were each applied to a silicon wafer using a spin coater. The resist underlayer films were baked on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form resist underlayer films (film thickness 50 nm). The refractive index (n value) and optical extinction coefficient (k value, also called extinction coefficient) at a wavelength of 193 nm were measured for these resist underlayer films using a spectroscopic ellipsometer. The results are shown in Table 2.

[0234] [Table 2]

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

[0236] [Dry etching rate measurement] The etcher and etching gas used for measuring the dry etching rate are as follows: RIE-10NR (Samco): CF4

[0237] The solutions of the resist underlayer film-forming compositions prepared in Comparative Example 1 and Examples 1-13 were each applied to a silicon wafer using a spin coater. Resist underlayer films (200 nm thick) were formed by baking on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds. Dry etching rates were measured using CF4 gas as the etching gas, and the dry etching rate ratios for Comparative Example 1 and Examples 1-13 were calculated. The dry etching rate ratio was the dry etching rate ratio of (resist underlayer film) / (KrF photoresist). The results are shown in Table 3.

[0238] [Table 3]

[0239] As described above, by changing the type of compound to be reacted, the etching resistance of the resist underlayer film can be freely controlled.

[0240] (Sublimation amount measurement) The amount of sublimated material was measured using the sublimated material amount measuring device described in International Publication No. 2007 / 111147. The resist underlayer film-forming compositions prepared in Comparative Example 1 and Examples 1-13 were each applied to a silicon wafer, and the amount of sublimated material was measured when a film thickness of 200 nm was achieved after baking at 240°C for 60 seconds or 350°C for 60 seconds. The results are shown in Table 4. The values ​​shown in the table are (amount of sublimated material in Examples 1-13) / (amount of sublimated material in Comparative Example 1).

[0241] [Table 4]

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

[0243] (Embeddability evaluation) The embedding ability was confirmed in a dense pattern area of ​​a 200 nm thick SiO2 substrate with 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 substrate 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 planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation to confirm whether the resist underlayer film-forming composition had filled the interior of the pattern. The results are shown in Table 5.

[0244] [Table 5]

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

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

[0247] [Table 6]

[0248] As described above, by using a material having a crosslinked structure in the polymer, the hardness of the resist underlayer film can be significantly increased.

[0249] (Bending resistance evaluation) The solutions of the resist underlayer film-forming compositions prepared in Comparative Example 1 and Examples 1-13 were applied to silicon wafers coated with a silicon oxide film using a spin coater. Baking was performed on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form resist underlayer films (200 nm thick). A silicon hard mask-forming composition solution was applied to the resist underlayer film and baked at 240°C for 1 minute to form a silicon hard mask layer (30 nm thick). A resist solution was applied thereon and baked at 100°C for 1 minute to form a resist layer (150 nm thick). The wafers were exposed to light at a wavelength of 193 nm using a mask, followed by post-exposure baking (PEB) (105°C for 1 minute) and development to obtain resist patterns. Subsequently, dry etching was performed using fluorine-based gas and oxygen-based gas. The resist patterns were transferred to silicon wafers coated with a silicon oxide film, and the respective pattern shapes were observed using a CG-4100 (Hitachi High-Technologies Corporation).

[0250] When a resist pattern is formed on a substrate to be processed through a lithography process and an etching process, irregular bending of the pattern becomes more likely as the width of the formed pattern narrows. Specifically, this occurs when a pattern formed from an organic resin layer, particularly a resist underlayer film used as a mask material when etching the target substrate, bends left and right. This makes it difficult to faithfully process the substrate. Therefore, the less bending occurs, the more precise the substrate processing becomes. The results are shown in Table 7. A sample with higher bending resistance than Comparative Example 1 was evaluated as ○.

[0251] [Table 7]

[0252] As shown in the above results, the examples showed higher bending resistance than the comparative examples.

[0253] [Evaluation as a crosslinker] (Measurement of the amount of sublimated material from the resist underlayer film) The amount of sublimation was measured using a sublimation amount measuring device described in International Publication No. 2007 / 111147. The resist underlayer film-forming compositions prepared in Comparative Example 2 and Example 14 were each applied to a silicon wafer, and the amount of sublimation was measured when the film thickness reached 200 nm after baking at 240°C for 60 seconds. The results are shown in Table 1. 8 The values ​​shown in the table are (amount of sublimated product in Example 14) / (amount of sublimated product in Comparative Example 2).

[0254] [Table 8]

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

[0256] (Coating test on uneven substrate) In a coating test for a stepped substrate, a comparison of coating film thickness was conducted on a 200 nm-thick SiO2 substrate in an open area (OPEN) where no pattern was formed and a dense pattern area (DENSE) with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film-forming compositions prepared in Comparative Example 2 and Example 14 were applied to the substrate and baked at 240°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference between the trench area (patterned area) and the open area (non-patterned area) of the stepped substrate (the coating step between the trench area and the open area, referred to as the bias). Here, planarization refers to a small difference in film thickness (iso-dense bias) of the coating present on the upper part of the patterned area (trench area (patterned area)) and the non-patterned area (open area (non-patterned area)). The results are shown in Table 1. 9 Shown below.

[0257] [Table 9]

[0258] As described above, by introducing an alcohol compound into the side chain, the glass transition temperature and viscosity are lowered, and therefore the planarization properties of the resist underlayer film-forming composition are significantly improved. [Industrial Applicability]

[0259] According to the present invention, there is provided a novel resist underlayer film-forming composition that does not require the use of hazardous chemicals in the preparation of a resin, meets requirements such as improved solubility in PGME or PGMEA, reduced amount of sublimation that contaminates equipment, improved coating planarization properties for substrates with uneven surfaces, and high hardness of the resulting resist underlayer film, while maintaining other favorable properties.

Claims

1. A polymer (X), a cross-linking agent, and A resist underlayer film-forming composition containing a solvent, The polymer (X) is a methoxymethyl group and a ROCH group other than a methoxymethyl group. ２ a polymer comprising a plurality of identical or different structural units each having a - group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group connecting the plurality of structural units, wherein at least one structural unit among the plurality of structural units is an aromatic ring having a phenolic hydroxyl group; The crosslinking agent has the formula: 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 The resist underlayer film-forming composition according to claim 1, wherein the compound is selected from the group consisting of the compounds listed above.

2. 2. The resist underlayer film forming composition according to claim 1, wherein R is —CH(CH 3 )CH 2 OCH 3.

3. 3. The resist underlayer film forming composition according to claim 1, wherein the linking group is —CH 2 — or —CH 2 O—.

4. The resist underlayer film forming composition according to claim 1, wherein the polymer (X) is selected from the following group: 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】

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

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

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

8. A resist underlayer film, characterized in that it is a fired product of a coating film made of the composition described in any one of claims 1 to 7.

9. A process for forming a resist underlayer film on a semiconductor substrate using the composition according to any one of claims 1 to 7; forming a resist film on the formed resist underlayer film; a step 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 A process of processing a semiconductor substrate through a patterned resist underlayer film A method for manufacturing a semiconductor device comprising:

10. A process for forming a resist underlayer film on a semiconductor substrate using the composition according to claim 1. forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; a step of forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it; Etching and patterning the hard mask through the formed resist pattern; and Etching and patterning the resist underlayer film through a patterned hard mask; and A process of processing a semiconductor substrate through a patterned resist underlayer film A method for manufacturing a semiconductor device comprising:

11. A method for manufacturing a semiconductor device as described in claim 10, wherein the step of forming a resist underlayer film is carried out by a nanoimprint method.

Images