Resistor underlayer film formation composition, resistor underlayer film, and method for manufacturing semiconductor device.

Abstract

This invention provides a novel inhibitor underlayer film forming composition. An inhibitor underlayer film forming composition comprises a polymer (X) and a solvent, wherein the polymer (X) comprises a plurality of identical or different structural units having ROCH2- groups other than methoxymethyl (R being a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group connecting the aforementioned plurality of structural units.

Description

Technical Field

[0001] This invention relates to a resist underlayer film forming composition, a sintered product of a coating film composed of the composition (i.e., a resist underlayer film), and a method for manufacturing a semiconductor device using the composition. Prior Technology

[0002] In the manufacture of semiconductor devices, microfabrication is performed using lithography. During this lithography process, when the resist layer on a substrate is exposed to ultraviolet lasers such as KrF excimer lasers or ArF excimer lasers, it is known that the desired resist pattern cannot be formed due to the standing waves generated by the reflection of the ultraviolet laser light from the substrate surface. To solve this problem, a resist underlayer film (anti-reflective film) is disposed between the substrate and the resist layer. Furthermore, phenolic varnish resin is known to be used as a component in forming the resist underlayer film.

[0003] Furthermore, it is also known that due to the need for thinning of the resist layer accompanying the miniaturization of the resist pattern, at least two resist underlayer films are formed, and these resist underlayer films are used as masking materials in lithography processes. Examples of materials for forming at least two layers include organic resins (e.g., acrylic resins, phenolic varnish resins), silicone resins (e.g., organopolysiloxanes), and inorganic silicone compounds (e.g., SiON, SiO2). When using the pattern formed from the aforementioned organic resin layer as a mask for dry etching, it is necessary for the pattern to be etch-resistant to etching gases (e.g., fluorocarbons).

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

[0005]

[0006] (In the formula, X1 represents a divalent organic group having at least one aromatic ring with 6 to 20 carbon atoms that can be substituted by a halogen group, nitro group, amino group or hydroxyl group, and X2 represents an organic group or methoxy group having at least one aromatic ring with 6 to 20 carbon atoms that can be substituted by a halogen group, nitro group, amino group or hydroxyl group). [Previous Technical Documents] [Patent Literature]

[0007] [Patent Document 1] WO2014 / 171326A1 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] However, in previous resist underlayer film formation compositions, there are still shortcomings in meeting the requirements for improving the solubility of solvents commonly used in the semiconductor industry, such as PGME or PGMEA, reducing the amount of sublimation that contaminates devices, improving the planarization of the coating on stepped substrates, and achieving high hardness of the resulting resist underlayer film. Furthermore, maintaining or improving characteristics such as not using harmful chemicals in resin preparation, not dissolving in the resist solvent, obtaining the desired optical constants, and being able to follow irregular patterns generated based on the width of the pattern are also important. [Methods for solving problems]

[0010] The present invention addresses the aforementioned problems. That is, the present invention includes the following. [1] An inhibitor underlayer film forming composition comprising a polymer (X) and a solvent, wherein the polymer (X) comprises a plurality of identical or different structural units having ROCH2- groups other than methoxymethyl (R being a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group connecting the plurality of structural units. [2] As described in [1], the inhibitor lower film forming composition, wherein R is a saturated or unsaturated straight or branched C2-C20 aliphatic hydrocarbon group, C3-C20 alicyclic hydrocarbon group, hydrogen atom or a mixture thereof that can be substituted by phenyl, naphthyl or anthracene and interrupted by oxygen atom or carbonyl group. [3] The inhibitor underlayer film forming composition as described in [1] or [2], wherein the linking group comprises an alkyl group, an ether group or a carbonyl group. [4] The inhibitor underlayer film forming composition described in any of [1] to [3], wherein the building unit comprises an aromatic ring, heterocycle or condensed ring that may have phenolic hydroxyl groups and may have substituted or unsubstituted amine groups. [5] The inhibitor underlayer film forming composition described in any of [1] to [4] further comprises a film material (Y) that can crosslink with polymer (X). [6] The inhibitory underlayer film forming composition described in any of [1] to [5] further includes a crosslinking agent. [7] The inhibitory lower film forming composition described in any of [1] to [6] further comprises an acid and / or an acid generating agent. [8] The inhibitory underlayer film forming composition described in any of [1] to [7] further includes a surfactant. [9] The inhibitor underlayer film forming composition described in any of [1] to [8], wherein the solvent comprises a solvent having a boiling point of 160°C or higher.

[10] A resistive underlayer film, characterized as a sintered product of a coated film consisting of any of the compositions described in [1] to [9].

[11] A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film by using a composition as described in any one of [1] to [9] on a semiconductor substrate. The steps of forming a resist film on top of the formed resist lower layer film, The process of forming a resist pattern by irradiating and developing the formed resist film with light or electron beams. The process involves etching the underlying resist film using the formed resist pattern, and then patterning it. The process of fabricating a semiconductor substrate through a patterned resist underlayer film.

[12] A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film by using a composition as described in any one of [1] to [9] on a semiconductor substrate; The step of forming a hard mask on top of the formed resist underlayer film. The step of forming a resist film on top of the hard mask is as follows: The process of forming a resist pattern by irradiating and developing the formed resist film with light or electron beams. Through the formed resist pattern, the aforementioned hard mask is etched, and the patterning steps are performed. The process involves etching the aforementioned resist underlayer film using a patterned hard mask, followed by patterning steps. The process of fabricating a semiconductor substrate through a patterned resist underlayer film.

[13] The method of manufacturing a semiconductor device as described in

[11] or

[12] is to perform the step of forming a resist underlayer film by nanoprinting. [Invention Effects]

[0011] According to the present invention, a novel resist underlayer film forming composition is provided that addresses the requirements of not using harmful chemicals in resin preparation, improving the solubility of PGME or PGMEA, reducing the amount of sublimation in contaminating devices, improving the planarization of the coating on stepped substrates, and increasing the hardness of the resulting resist underlayer film, while maintaining other good properties. Implementation

[0012] The inhibitor underlayer film forming composition of the present invention comprises a polymer (X) and a solvent, wherein the polymer (X) comprises a plurality of identical or different structural units having ROCH2- groups other than methoxymethyl (R being a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group connecting the aforementioned plurality of structural units.

[0013] [Polymer(X)] The polymer (X) comprises a plurality of identical or different building units having ROCH2- groups other than methoxymethyl (R being a monovalent organic group, a hydrogen atom, or a mixture thereof), and a linking group connecting the plurality of building units.

[0014] The R of the monovalent organometallic group is preferably a phenyl, naphthyl, or anthracene-based substituted group, and can be a saturated or unsaturated straight-chain or branched C2-C20 aliphatic hydrocarbon group, C3-C20 alicyclic hydrocarbon group, or a mixture thereof, which can be interrupted by an oxygen atom or a carbonyl group. The term "mixture" means that the plurality of ROCH2- groups existing in a single building unit may be different, and also means that the individual ROCH2- groups in two or more building units may be different.

[0015] Typical examples of the aforementioned saturated aliphatic hydrocarbon groups are alkyl groups having a straight chain or branches with 2 to 20 carbon atoms. Examples include 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, 3-methyl -n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, and 1-methoxy-2-propyl, etc.

[0016] Alternatively, cyclic alkyl groups may be used, for example, cyclic alkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1, 3-Dimethyl-cyclobutyl, 2,2-Dimethyl-cyclobutyl, 2,3-Dimethyl-cyclobutyl, 2,4-Dimethyl-cyclobutyl, 3,3-Dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0017] Typical examples of the aforementioned unsaturated aliphatic hydrocarbon groups are alkenyl groups with 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, and 2-methyl-2-butenyl. 2-Methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 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, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-s-butylvinyl, 1, 3-Dimethyl-1-butenyl, 1,3-Dimethyl-2-butenyl, 1,3-Dimethyl-3-butenyl, 1-i-Butylvinyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 2-i-propyl-2-propenyl, 3,3-Dimethyl-1-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-t-Butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-I-propyl-1-propenyl, 1-I-propyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl Alkenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, etc.

[0018] The aforementioned saturated aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, and cyclic alkyl groups may be interrupted by an oxygen atom and / or a carbonyl group to one or more degrees. Preferably, R is a -CH2CH2CH2CH3 group or a -CH(CH3)CH2OCH3 group.

[0019] Polymer (X) can be synthesized by polymerization of a compound having a methoxymethyl group, a compound having a phenolic hydroxyl group, a compound that reacts with a methoxymethyl group to give a ROCH2- group other than a methoxymethyl group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and a compound that, if necessary, includes a functional group that serves as a linker (e.g., aldehyde, ketone, ROCH2-Ar-CH2 OR (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).

[0020] Compounds containing methoxymethyl groups or phenolic hydroxyl groups, which are used in the synthesis of polymer (X), can be exemplified by 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl.

[0021] As a compound that reacts with the methoxymethyl group used in the synthesis of polymer (X) to donate a ROCH2- group other than methoxymethyl (R being a monovalent organic group, a hydrogen atom, or a mixture thereof), it is preferably an organic compound having a non-phenolic hydroxyl group within the molecule. The non-phenolic hydroxyl group may not be present within the molecule; functional groups that can chemically modify the non-phenolic hydroxyl group may be, for example, organic compounds having alkoxy (-OR), aldehyde (-CHO), carboxyl (-COOH), ester (-COOR), or ketone (-COR). The functional group that can chemically modify the non-phenolic hydroxyl group or non-phenolic hydroxyl group may be one or more within the molecule. The organic compound may be an aliphatic hydrocarbon (preferably with 10 or fewer carbon atoms), an alicyclic hydrocarbon (preferably with 20 or fewer carbon atoms), or an aromatic hydrocarbon (e.g., the α-carbon has at least one aliphatic hydroxyl group). Examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, aliphatic alcohols (e.g., n-butanol), compounds represented by Ar-CH2OH (Ar such as benzene, naphthalene, anthracene, pyrene, fumonisin, or m-terphenyl), aldehydes, ketones, hydroxymethyl compounds, etc. Furthermore, since dioxane is not a compound that does not possess a ROCH2- group other than methoxymethyl (R is a monovalent organic group, a hydrogen atom, or a mixture thereof), and is also a substance harmful to the human body, it is preferable not to use it.

[0022] Examples of organic compounds containing an aldehyde group include aliphatic aldehydes such as formaldehyde, trioxymethylene, butylaldehyde, and crotonaldehyde; aromatic aldehydes such as furfural, pyridine carboxylaldehyde, benzaldehyde, naphthylaldehyde, anthracene aldehyde, phenanthrene aldehyde, salicylaldehyde, phenylacetaldehyde, biphenylaldehyde, 3-phenylpropanal, toluene aldehyde, (N,N-dimethylamino)benzaldehyde, acetoxybenzaldehyde, 1-pyrene carboxylaldehyde, and anisaldehyde.

[0023] Examples of organic compounds with ketone groups include diaryl ketones such as diphenyl ketones, phenylnaphthyl ketones, dinaphthyl ketones, phenyltolyl ketones, xylyl ketones, 9-furonones, anthraquinones, acenaphthoquinones, etc.; spiroketones such as 11H-benzo[b]furon-11-ones, 9H-tribenzo[a,f,l]triindene-9,14,15-triones, and indene[1,2-b]furon-6,12-diones.

[0024] The resulting polymer (X) preferably comprises an aromatic ring, heterocyclic ring, or condensed ring that may have phenolic hydroxyl groups, substituted or unsubstituted amine groups. Furthermore, the linking group connecting the plurality of structural units preferably comprises an alkyl group, an ether group, or a carbonyl group.

[0025] The compounds used in the synthesis of polymer (X) are not limited to one type of compound, and two or more compounds may be used together. Accordingly, a plurality of structural units having ROCH2- groups other than methoxymethyl (R is a monovalent organic group, a hydrogen atom, or a mixture thereof) may be the same or different.

[0026] The weight average molecular weight of the polymer (X) contained in the inhibitor lower film forming composition of the present invention is not particularly limited. It is converted to a standard polystyrene value, for example, 1,000 or more, for example, 2,000 or more, for example, 500,000 or less, for example, 100,000 or less.

[0027] [solvent] The inhibitor lower film forming composition of the present invention can be used in a homogeneous solution state by dissolving the above-mentioned components in a suitable solvent.

[0028] 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 ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 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.

[0029] Furthermore, high-boiling-point solvents with a boiling point above 180°C 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-propanediol, 1,3-butanediol, 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, glycerol, n-nonyl acetate, ethylene glycol monohexyl ether, and ethylene glycol monohexyl ether. 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, triacetyl glycerol (tri... Acetin), 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-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc.

[0030] These solvents can be used alone or in combination of two or more. The proportion of solid components of the organic solvent removed from the aforementioned composition is, for example, 0.5% to 30% by mass, preferably 0.8% to 15% by mass.

[0031] Alternatively, the following compounds described in WO2018 / 131562A1 may also be used. (In formula (i), R1, R2 and R3 represent alkyl groups with 1 to 20 carbon atoms that can be interrupted by hydrogen atoms, oxygen atoms, sulfur atoms or amide bonds. They can be the same or different from each other and can bond together to form a ring structure.)

[0032] Alkyl groups having 1 to 20 carbon atoms can be listed as linear or branched alkyl groups, which may or may not have substituents. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, cyclohexyl, 2-ethylhexyl, n-nonyl, isononyl, p-tert-butylcyclohexyl, n-decyl, n-dodecylnonyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl. Preferably, the alkyl group has 1 to 12 carbon atoms; more preferably, it has 1 to 8 carbon atoms; and even more preferably, it has 1 to 4 carbon atoms.

[0033] Alkyl groups having 1 to 20 carbon atoms interrupted by oxygen, sulfur, or amide bonds can be exemplified by those containing the structural units -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. -O-, -S-, -NHCO-, or -CONH- can be one or more units in the aforementioned alkyl groups. Specific examples of alkyl groups with 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, butylaminocarbonyl, etc., and further include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl, each of which is substituted by methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, etc. Methoxy, ethoxy, methylthio, and ethylthio are preferred, and methoxy and ethoxy are even more preferred.

[0034] Because these solvents have relatively high boiling points, they are also effective in imparting high embedding or high planarization properties to the composition of the inhibitor underlayer film.

[0035] Specific examples of preferred compounds represented by the following formula (i).

[0036] Of the above, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamide, and compounds represented by the following formulas are preferred. The compounds represented by formula (i) are preferably 3-methoxy-N,N-dimethylpropionic acid and N,N-dimethylisobutylamide.

[0037] These solvents can be used alone or in combination of two or more. Among these solvents, those with a boiling point above 160°C are preferred, and more preferably are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamide, 2,5-dimethylhexane-1,6-dimethyldiacetate (DAH; CAS, 89182-68-3), and 1,6-diethoxyhexane (CAS, 6222-17-9). Particularly preferred are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutylamide.

[0038] [Any ingredients] The inhibitor lower film forming composition of the present invention, as an arbitrary component, may contain at least one of a crosslinking agent, an acid and / or an acid generating agent, a thermal acid generating agent, and a surfactant.

[0039] (Cross-linking agent) The inhibitor lower film forming composition of the present invention may further contain a crosslinking agent. Preferably, the crosslinking agent is a crosslinking compound having at least two crosslinking-forming substituents. Examples include melamine-based compounds, substituted urea-based compounds, and phenolic compounds or polymers thereof, which have crosslinking-forming substituents such as hydroxymethyl and methoxymethyl. Specifically, it includes compounds such as methoxymethylated glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, etc., for example, tetramethoxymethylglycourea, tetrabutoxymethylglycourea, and hexamethoxymethylmelamine. Furthermore, as substituted urea-based compounds, it includes compounds such as methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea, for example, tetramethoxymethylurea and tetrabutoxymethylurea. Condensations of these compounds may also be used. Examples of phenolic compounds include tetrahydroxymethylbiphenol, tetramethoxymethylbiphenol, tetrahydroxymethylbisphenol, tetramethoxymethylbisphenol, and compounds represented by the following formulas.

[0040] As a crosslinking agent, compounds having at least two epoxy groups can also be used. Examples of such compounds include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexane dicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, trimethylolethane triglycidyl ether, bisphenol- A-Diglycidyl Ether, Daicel's EPOLEAD [Registered Trademark] GT-401, GT-403, GT-301, GT-302, CELLOXIDE [Registered Trademark] 2021, 3000, Mitsubishi Chemical's 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828, 807, 152, 154, 180S75, 871, 872, Nippon Kayaku's EPPN201, 202, EOCN-102, 103S, 104S, 1020, 1025, 1027, Nagase ChemteX (stock) manufactures DENACOL (registered trademark) EX-252, 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 (stock) manufactures CY175, CY177, CY179, CY182, CY184, and CY192; DIC (stock) manufactures Epihlone 200, 400, 7015, 835LV, and 850CRP. As compounds having at least two epoxy groups, epoxy resins having amine groups may also be used. Examples of such epoxy resins include YH-434 and YH-434L (manufactured by Shin-Nippon Chemical Epoxy Manufacturing Co., Ltd.).

[0041] As a crosslinking agent as mentioned above, a compound having at least two terminal isocyanate groups may also be used. Examples of such compounds include TAKENATE B-830 and B-870N manufactured by Mitsui Chemicals, Ltd., and VESTANAT B1358 / 100 manufactured by Evonik Degussa.

[0042] Alternatively, compounds having at least two vinyl ether groups can be used as the aforementioned crosslinking agent. Examples of such compounds include bis(4-(vinyloxymethyl)cyclohexylmethyl)pentanediol, tri(ethylene glycol) divinyl ether, divinyl adipate, diethylene glycol divinyl ether, 1,2,4-tris(4-vinyloxybutyl)trimethacrylate, 1,3,5-tris(4-vinyloxybutyl)trimethacrylate, 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 cyclohexanediol divinyl ether.

[0043] Furthermore, a crosslinking agent with high heat resistance can be used as the aforementioned crosslinking agent. Preferably, a compound containing a crosslinking substituent with an aromatic ring (e.g., benzene ring, naphthalene ring) within the molecule is used.

[0044] This compound can be listed as a compound having a partial structure of the following formula (4), or a polymer or oligomer having repeating units of the following formula (5). R11, R12, R13, and R14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, as illustrated above. n1 is an integer from 1 to 4, n2 is an integer from 1 to (5-n1), and (n1+n2) represents an integer from 2 to 5. n3 represents an integer from 1 to 4, n4 is from 0 to (4-n3), and (n3+n4) represents an integer from 1 to 4. Oligomers and polymers can be used in the range of 2 to 100 or 2 to 50 repeating unit structures.

[0045] Examples of compounds, polymers, and oligomers of formulas (4) and (5) are shown below.

[0046] The aforementioned compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, among the aforementioned crosslinking agents, the compound of formula (4-23) can be obtained by Honshu Chemical Co., Ltd. under the trade name TMOM-BP, the compound of formula (4-24) can be obtained by Asahi Organic Materials Co., Ltd. under the trade name TM-BIP-A, and the compound of formula (4-28) can be obtained by Finechem Co., Ltd. under the trade name PGME-BIP-A. Although the amount of crosslinking agent added varies depending on the coating solvent used, the substrate used, the required solution viscosity, and the required film shape, it is generally 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 is less than 80% by mass, less than 50% by mass, less than 40% by mass, less than 20% by mass, or less than 10% by mass relative to the total solids content. Although such crosslinking agents can also cause crosslinking reactions due to self-condensation, when crosslinking substituents are present in the polymer of the present invention, they can cause crosslinking reactions with such crosslinking substituents.

[0047] One type of crosslinking agent selected from these can be added, or two or more types can be added in combination.

[0048] (Acids and / or acid-generating agents) The inhibitor underlayer film forming composition of the present invention may contain acid and / or acid generating agent.

[0049] Examples of acids include carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, pyridinium phenolsulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphtholic acid, as well as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Acids may be used alone or in combination of two or more. The amount of admixture relative to the total solids content is typically 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and even more preferably 0.01 to 5% by mass.

[0050] Examples of acid-generating agents include thermal acid-generating agents and photoacid-generating agents. As heat-generating agents, in addition to 2,4,4,6-tetrabromocyclohexadienone, benzoin toluenesulfonate, 2-toluenesulfonic acid nitrobenzyl ester, K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), the fourth-order ammonium salt of trifluoroacetic acid and alkyl esters of organic sulfonic acids can be listed.

[0051] Examples of ononium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nonafluoron-butane sulfonate, diphenyliodonium perfluoron-octane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, as well as strontium salt compounds such as triphenylstrontium hexafluoroantimonate, triphenylstrontium nonafluoron-butane sulfonate, triphenylstrontium camphor sulfonate, and triphenylstrontium trifluoromethane sulfonate.

[0052] Examples of sulfonamide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0053] 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.

[0054] Acid-generating agents can be used in isolation or in combination of two or more. When using an acid-generating agent, its proportion 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 component of the lower layer film forming composition of the inhibitor.

[0055] (surfactants) The inhibitor-forming composition of the present invention may further contain a surfactant. Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol monolaurate. Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, as well as polyoxyethylene sorbitan fatty acid esters; EFTOP [registered trademark] EF301, same as EF303, same as EF352 (Mitsubishi Materials Electronics & Chemicals Co., Ltd.); MEGAFACE [registered trademark] F171, same as F173, same as R-30, same as R-30-N, same as R-40, same as R-40-LM (DIC Co., Ltd.); FLUORAD Fluoropolymer surfactants such as FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard AG710 (registered trademark), SURFLON S-382 (registered trademark), SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may be added. One type of surfactant selected from these surfactants may be added, or two or more may be added in combination. The proportion of the aforementioned surfactant relative to the solid content of the resistive film-forming composition of the present invention after removing the solvent described later is, for example, 0.01% by mass to 5% by mass.

[0056] [Membrane Material (Y)] The polymer (X) of this invention can also be used as a crosslinking agent for the membrane material (Y). That is, the inhibitory lower membrane forming composition of this invention may further include a membrane material (Y) that can crosslink with the polymer (X). The membrane material (Y) can be described as a membrane material that can crosslink with the polymer (X).

[0057] The membrane material (Y) used in this invention can be chosen arbitrarily and is not particularly limited to any material that can crosslink with the polymer (X) described above. The membrane material can be a polymer, an oligomer, or a low-molecular-weight compound with a molecular weight of 1,000 or less. Examples of crosslinking-forming groups present in the membrane material include hydroxyl, carboxyl, amino, and alkoxy groups, but these are not limited to these.

[0058] (a) As a crosslinkable membrane material, examples include alicyclic epoxy polymers having repeating structural units represented by the following formula (1) as disclosed in WO 2011 / 021555 A1. (T indicates that the polymer backbone has a repeating unit structure of aliphatic rings, and E indicates an organic group with epoxy groups or epoxy groups).

[0059] E is a substituent for the aforementioned aliphatic ring. The epoxy group can be directly bonded to the aliphatic group, or an organic group with an epoxy group (such as a glycidyl group) can be bonded to the aliphatic group. The aforementioned aliphatic ring is, for example, formed by 4 to 10 carbon atoms linked together, especially by 6 carbon atoms linked together. The aliphatic ring may have other substituents besides the substituent E (epoxy group or an organogroup having an epoxy group). Examples of such substituents include alkyl groups with 1 to 10 carbon atoms, aryl groups with 6 to 20 carbon atoms, halogen atoms, nitro groups, and amino groups. The weight-average molecular weight of the alicyclic epoxy polymer system represented by formula (1) above is 600 to 1,000,000, preferably 1,000 to 200,000. The number of repeating units in the alicyclic epoxy polymer (A) represented by formula (1) above is 2 to 3,000 or 3 to 600.

[0060] For example, the following polymers are exemplified.

[0061] (b) As a crosslinkable membrane material, polymers having one or more repeating building blocks as disclosed in WO 2014 / 024836 A1, such as those having repeating building blocks as represented by formulas (1a), (1b) and (1c) below, may be listed. In the formula, the two R1s independently represent alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, aromatic hydrocarbon groups, halogen atoms, nitro groups, or amino groups; the two R2s independently represent hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, acetal groups, acetyls, or glycidyl groups; R3 represents an aromatic hydrocarbon group that may have substituents; R4 represents a hydrogen atom, a phenyl group, or a naphthyl group. When R3 and R4, which are bonded to the same carbon atom, represent phenyl groups, they can bond with each other to form a ring. In formula (1b), the groups represented by the two R3s and the atoms or groups represented by the two R4s can be different from each other; the two ks independently represent 0 or 1; m represents an integer from 3 to 500; n, n1, and n2... represents an integer from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or heteroatom, and the two Qs independently represent the building units represented by the following formula (2). (In the formula, 2 R1, 2 R2, 2 R3, 2 R4, 2 k, n1, n2 and X are synonyms of formula (1b), and 2 Q1 independently represent the building units represented by the aforementioned formula (2)).

[0062] Preferably, the aromatic hydrocarbon group represented by R3 mentioned above is phenyl, naphthyl, anthryl, or pyrene.

[0063] (c) As a crosslinkable membrane material, examples include polymers containing the unit structure represented by the following formula (1) as disclosed in WO 2010 / 147155 A1. (in formula (1),) R1 and R2 are respectively selected from the group consisting of hydrogen atom, halogen group, nitro group, amino group, hydroxyl group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl, alkenyl, or aryl group indicates that it may contain ether bond, ketone bond, or ester bond. R3 is selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl, alkenyl, or aryl group may contain ether, ketone, or ester bonds. R4 represents an aryl or heterocyclic group with 6 to 40 carbon atoms that can be substituted by a halogen group, nitro group, amino group, or hydroxyl group. R5 represents an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 40 carbon atoms, or a heterocyclic group that can be substituted with hydrogen atoms, halogen groups, nitro groups, amino groups, or hydroxyl groups. R4 and R5 can bond with these carbon atoms to form a ring, and n1 and n2 are integers from 1 to 3.

[0064] Preferably, in the aforementioned formula (1), R1, R2, R3 and R5 represent hydrogen atoms, and R4 is a polymer containing a unit structure representing a phenyl or naphthyl group. Preferred is the polymer as described in claim 1, wherein in the aforementioned formula (1), R1, R2 and R3 represent hydrogen atoms respectively, and R4 and R5 are bonded together with the carbon atoms to form a ring, wherein the carbon atom is a unit structure containing the carbon atom at the 9th position of the formed ring.

[0065] Preferred polymers are those comprising the unit structures represented by formula (2) and / or formula (3) below. (in equations (2) and (3),) R1, R2, R6, R7, and R8 are selected from the group consisting of hydrogen atoms, halogen groups, nitro groups, amino groups, hydroxyl groups, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl, alkenyl, or aryl group indicates that it may contain ether bonds, ketone bonds, or ester bonds. R3 is selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl, alkenyl, or aryl group may contain an ether bond, a ketone bond, or an ester bond. R4 represents an aryl or heterocyclic group with 6 to 40 carbon atoms that can be substituted by a halogen group, nitro group, amino group, or hydroxyl group. R5 represents an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 40 carbon atoms, or a heterocyclic group that can be substituted with hydrogen atoms, halogen groups, nitro groups, amino groups, or hydroxyl groups. R4 and R5 can bond together with these carbon atoms to form a ring. n1 and n2 are integers from 1 to 3 respectively. n3 to n5 are integers from 1 to 4 respectively.

[0066] Preferably, in the aforementioned formula (2) and / or formula (3), R1, R2, R3, R5, R6, R7 and R8 represent hydrogen atoms, and R4 is a polymer containing a unit structure representing a phenyl or naphthyl group.

[0067] (d) As a cross-linkable membrane material, examples include polymers disclosed in WO 2013 / 005797 A1 that contain a unit structure composed of reactants of condensed heterocyclic compounds and bicyclic compounds.

[0068] Preferably, the condensed heterocyclic compound is a carbazole compound or a substituted carbazole compound. Preferably, the above-mentioned bicyclic compound is dicyclopentadiene, substituted dicyclopentadiene, tetracyclo[4.4.0.12,5.17,10]dodec-3,8-diene or substituted tetracyclo[4.4.0.12,5.17,10]dodec-3,8-diene.

[0069] Preferably, the polymer is a polymer with a unit structure represented by formula (1), formula (2), formula (3), or a combination thereof. (In the formula, R1 to R14 are substituents for hydrogen atoms, which are alkyl groups with 1 to 10 carbon atoms or aryl groups with 6 to 40 carbon atoms that can be replaced by halogen groups, nitro groups, amino groups or hydroxyl groups or such groups, Ar is an aromatic cyclic group with 6 to 40 carbon atoms, n1, n2, n5, n6, n9, n10, n13, n14 and n15 are integers from 0 to 3, and n3, n4, n7, n8, n11 and n12 are integers from 0 to 4). Preferably, in formula (3) above, Ar is phenyl or naphthyl.

[0070] (e) As a crosslinkable membrane material, polymers containing the unit structure of formula (1) as disclosed in WO 2012 / 176767 A1 can be cited. (In formula (1), A is a hydroxy-substituted phenyl group derived from polyhydroxybenzene, and B is a monovalent condensed aromatic hydrocarbon cyclic group of 2 to 4 benzene rings).

[0071] Preferably, A is a hydroxyl-substituted phenyl group derived from phenylene glycol or phenyltriol. Preferably, A is a hydroxylated phenyl group derived from catechol, resorcinol, hydroquinone, phloroglucinol, hydroxyquinoline, or phloroglucinol. Preferably, the condensed aromatic hydrocarbon ring group of B is naphthyl, anthracene, or pyrene. The preferred condensed aromatic hydrocarbon cyclic system of type B has a halogen group, hydroxyl group, nitro group, amino group, carboxyl group, carboxylic acid ester group, nitrile group, or a combination thereof as a substituent.

[0072] (f) As a crosslinkable membrane material, examples include polymers containing a unit structure (A) as disclosed in WO 2013 / 047516 A1. In formula (1), Ar1 and Ar2 represent benzene rings or naphthalene rings, respectively, and R1 and R2 are substituents for hydrogen atoms on these rings, selected from the group consisting of halogen groups, nitro groups, amino groups, hydroxyl groups, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, aryl groups with 6 to 40 carbon atoms, and combinations thereof. The alkyl, alkenyl, and aryl groups represent organic groups that may contain ether bonds, ketone bonds, or ester bonds. R3 is a group selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and combinations thereof, wherein the alkyl, alkenyl, and aryl groups represent organic groups that may contain ether, ketone, or ester bonds. R4 is a group selected from aryl and heterocyclic groups having 6 to 40 carbon atoms, wherein the aryl and heterocyclic groups represent organic groups that can be substituted with halogen, nitro, amino, alkyl, alkoxy, aryl, formyl, carboxyl, or hydroxyl groups having 1 to 10 carbon atoms. R5 is selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 40 carbon atoms, and heterocyclic groups, wherein the alkyl, aryl, and heterocyclic groups represent organic groups that can be substituted with halogen groups, nitro groups, amino groups, or hydroxyl groups, and R4 and R5 can bond these carbon atoms together to form a ring. n1 and n2 are integers from 0 to 3.

[0073] Preferably, R5 in formula (1) above is a hydrogen atom, and R4 is a substituted phenyl, naphthyl, anthryl, or pyrene. Preferably, R3 in formula (1) above is a hydrogen atom or a phenyl group. Preferably, it includes the above-mentioned unit structure (a1), in which either Ar1 or Ar2 is a benzene ring and the other is a naphthalene ring. Preferably, Ar1 and Ar2 together form a benzene ring in the aforementioned unit structure (a2). Preferably, it is a copolymer comprising unit structure (a1) and unit structure (a2).

[0074] Preferably, it is a copolymer comprising unit structure (A) of formula (1) and unit structure (B) of formula (2) below. (In formula (2), R6 is a group consisting of aryl and heterocyclic groups selected from 6 to 40 carbon atoms, and the aryl and heterocyclic groups represent organic groups that can be substituted by halogen, nitro, amino, alkyl, alkoxy, aryl, formyl, carboxyl or hydroxyl groups with 1 to 10 carbon atoms, and R7 is a group consisting of hydrogen atoms, alkyl with 1 to 10 carbon atoms, aryl and heterocyclic groups with 6 to 40 carbon atoms, and the alkyl, aryl and heterocyclic groups represent organic groups that can be substituted by halogen, nitro, amino or hydroxyl groups, and R6 and R7 can be bonded to these carbon atoms to form a ring). Preferably, it is a copolymer comprising unit structure (a1) and unit structure (B).

[0075] (g) As a cross-linkable membrane material, examples include polymers having a unit structure represented by the following formula (1) as disclosed in WO 2013 / 146670 A1. In formula (1), R1, R2, and R3 are substituents for the hydrogen atoms of the ring, which are independently halogenated, nitro, amino, hydroxyl, alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, aryl with 6 to 40 carbon atoms, or may include combinations of ether, ketone, or ester bonds. R4 is a hydrogen atom, alkyl with 1 to 10 carbon atoms, alkenyl with 2 to 10 carbon atoms, aryl with 6 to 40 carbon atoms, or may include combinations of ether, ketone, or ester bonds. R5 is an aryl or heterocyclic group with 6 to 40 carbon atoms that may be substituted with hydrogen atoms or halogenated, nitro, amino, methyl, carboxyl, alkyl ester of carboxylic acid, phenyl, alkoxy or hydroxyl groups with 1 to 10 carbon atoms, and R6 is a halogenated or heterocyclic group with 6 to 40 carbon atoms. The ring is an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 40 carbon atoms, which can be substituted by a hydrogen atom, 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, or R5 and R6 can bond with such carbon atoms to form a ring. Ring A and ring B represent a benzene ring, a naphthalene ring, or an anthracene ring, respectively. n1, n2, and n3 are integers greater than or equal to 0, up to the largest number of rings that can be substituted.

[0076] Preferably, rings A and B are both benzene rings, n1, n2 and n3 are 0, and R4 is a hydrogen atom. Preferably, R5 is a phenyl group that can be substituted with hydrogen atom or halogen group, nitro group, amino group, methyl group, carboxyl group, alkyl ester group of carboxylic acid, phenyl, alkoxy group with 1 to 10 carbon atoms or hydroxyl group, naphthyl, anthryl or pyrene group, and R6 is a hydrogen atom.

[0077] (h) As a crosslinkable membrane material, polymers having one or more repeating building blocks represented by formulas (1a), (1b) and (1c) as disclosed in WO 2014 / 129582 A1 can be listed. In the formula, the two R1s independently represent alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, aromatic hydrocarbon groups, halogen atoms, nitro groups, or amino groups; the two R2s independently represent hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, acetal groups, acetyls, or glycidyl groups; R3 represents an aromatic hydrocarbon group that may have substituents; R4 represents a hydrogen atom, a phenyl group, or a naphthyl group. When R3 and R4, which are bonded to the same carbon atom, represent phenyl groups, they can bond with each other to form a ring. In formula (1b), the groups represented by the two R3s and the atoms or groups represented by the two R4s can be different from each other; the two ks independently represent 0 or 1; m represents an integer from 3 to 500; n, n1, and n2... represents an integer from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or heteroatom, and the two Qs independently represent the building units represented by the following formula (2). (In the formula, 2 R1, 2 R2, 2 R3, 2 R4, 2 k, n1, n2 and X are synonyms of formula (1b), and 2 Q1 independently represent the building units represented by the aforementioned formula (2)).

[0078] Preferably, the aromatic hydrocarbon group represented by R3 mentioned above is phenyl, naphthyl, anthryl, or pyrene.

[0079] (i) As a crosslinkable membrane material, examples include polymers containing a unit structure represented by the following formula (1) as disclosed in WO 2016 / 072316 A1. (In formula (1), R1 to R4 represent hydrogen atoms or methyl groups, respectively. X1 represents a divalent organogroup containing at least one aryl group that can be substituted by an alkyl, amino, or hydroxyl group.)

[0080] Preferably, in formula (1), the aryl group defined in X1 is arylphenyl, arylbiphenyl, aryltriphenyl, arylpyrrolyl, arylnaphthyl, arylanthryl, arylpyrene or arylcarbazolylene.

[0081] Preferably, in formula (1), X1 is an organic group represented by formula (2). In formula (2), A1 represents pentylenyl or pentylenyl. A2 represents pentylenyl, pentylenyl, or an organic group represented by formula (3). (In formula (3), A3 and A4 represent phenyl or naphthyl groups respectively, and the dashed line represents the bond).

[0082] (j) As a cross-linkable membrane material, examples include phenolic varnish resins obtained by reacting an aromatic compound (A) with an aldehyde (B) having a formaldehyde group bonded to a second or third carbon atom of an alkyl group having 2 to 26 carbon atoms, as disclosed in WO 2017 / 069063 A1.

[0083] The preferred phenolic varnish resin is one that contains the unit structure represented by the following formula (1). (In formula (1), A represents a divalent group derived from an aromatic compound with 6 to 40 carbon atoms, b1 represents an alkyl group with 1 to 16 carbon atoms, and b2 represents a hydrogen atom or an alkyl group with 1 to 9 carbon atoms).

[0084] Preferably, A is a divalent group derived from an amino group, a hydroxyl group (Hydroxyl), or an aromatic compound containing both. Preferably, A is a divalent group derived from arylamine compounds, phenolic compounds, or aromatic compounds containing 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 polyphenols. Preferred polyphenols include dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, s(4-hydroxyphenyl)methane, s(4-hydroxyphenyl)ethane, 2,2'-biphenol, or 1,1,2,2-tetra(4-hydroxyphenyl)ethane.

[0085] The preferred phenolic varnish resin is one that contains the unit structure represented by the following formula (2). (In formula (2), a1 and a2 represent substituted benzene rings or naphthalene rings, respectively; R1 represents a secondary or tertiary amino group, a divalent hydrocarbon group with 1 to 10 carbon atoms that can be substituted, an aryl group, or a divalent group arbitrarily bonded to such a group; b3 represents an alkyl group with 1 to 16 carbon atoms; and b4 represents a hydrogen atom or an alkyl group with 1 to 9 carbon atoms).

[0086] (k) As a crosslinkable membrane material, examples include polymers having repeating structural units represented by the following formulas (1a) and / or (1b) as disclosed in WO 2017 / 199768 A1. [In formulas (1a) and (1b), the two R1s independently represent alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, aromatic hydrocarbon groups, halogen atoms, nitro groups, or amino groups, respectively; the two R2s independently represent hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 6 carbon atoms, acetal groups, acetyl groups, or glycidyl groups, respectively; R3 represents aromatic hydrocarbon groups or heterocyclic groups that may have substituents; R4 represents hydrogen atoms, phenyl groups, or naphthyl groups. When R3 and R4, which are bonded to the same carbon atom, represent phenyl groups, they can bond to each other to form a cyclopentadienyl ring. The two k groups independently represent 0 or 1, m represents an integer from 3 to 500, p represents an integer from 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.]

[0087] Preferably, the aforementioned polymer is a polymer of at least one bisphenol compound and at least one aromatic aldehyde or aromatic ketone. Preferably, the aromatic hydrocarbon group represented by R3 mentioned above is phenyl, naphthyl, anthryl, or pyrene.

[0088] (l) As a membrane material that can undergo cross-linking reaction, examples include poly(epoxide) resins with an epoxy functional valence greater than 2.0 but less than 10 disclosed in Japanese Patent Application Publication No. 11-511194.

[0089] Preferred poly(epoxide) resin is selected from the group consisting of bisphenol A-epoxychlorohydrin resin products, epoxy phenolic varnishes, o-cresol epoxy phenolic varnishes, polyglycidyl ethers, polyglycidyl amines, alicyclic epoxides, and polyglycidyl esters. Preferably, the poly(epoxide) resin has a higher epoxy functional valence than 3.5.

[0090] (m) can be used as a cross-linkable membrane material or phenolic varnish membrane material, such as the compound or phenolic varnish membrane material represented by the following formula (1) as disclosed in WO 2018 / 198960 A1. In formula (1), Indicates a single or double bond. X1 represents -N(R1)- or -CH(R1)-. X2 represents -N(R2)- or -CH(R2)-. X3 represents -N=, -CH=, -N(R3)-, or -CH(R3)-. X4 represents -N=, -CH=, -N(R4)-, or -CH(R4)-. R1, R2, R3, and R4 may be the same or different, representing a hydrogen atom, a C1-20 straight-chain, 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, respectively. The aforementioned alkyl and aryl groups may be substituted by a C1-6 acetyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or a hydroxyl group, and may be interrupted by an oxygen or sulfur atom. R5, R6, R9, and R10 are the same or different, representing hydrogen atom, hydroxyl group, C1-6 acetyl group, C1-6 alkoxy group, C1-6 alkoxycarbonyl group, C1-10 linear, branched, or cyclic alkyl group, C6-20 aryl group, C2-20 alkenyl group, or C2-10 alkynyl group, respectively. The aforementioned acetyl, alkoxy, alkoxycarbonyl, alkyl, aryl, alkenyl, and alkynyl groups may have one or more groups selected from the group consisting of amino, nitro, cyano, hydroxyl, glycidyl, and carboxyl groups. R7 and R8 are the same or different, representing benzene rings or naphthalene rings, respectively. n and o are 0 or 1.

[0091] Preferably, R1, R2, R3 or R4 in formula (1) are C1 to 20 straight-chain, branched or cyclic alkyl groups that can be substituted with hydroxyl groups and interrupted by oxygen or sulfur atoms.

[0092] Preferably, it contains one or more of the repeating units a, b, c, d, e, f, g, h, i represented by the following formula (2) with one or more units. In formula (2), Indicates a single or double bond. X1 represents -N(R1)-, -CH(R1)-, -N< or -CH<, X2 represents -N(R2)-, -CH(R2)-, -N< or -CH<, X3 represents -N=, -CH=, -N(R3)-, -CH(R3)-, -N< or -CH<. X4 represents -N=, -CH=, -N(R4)-, -CH(R4)-, -N< or -CH<. R1, R2, R3, and R4 may be the same or different, representing a hydrogen atom, a C1-20 straight-chain, 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, respectively. The aforementioned alkyl and aryl groups may be substituted by a C1-6 acetyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or a hydroxyl group, and may be interrupted by an oxygen or sulfur atom. R5, R6, R9, and R10 are the same or different, representing hydrogen atom, hydroxyl group, C1-6 acetyl group, C1-6 alkoxy group, C1-6 alkoxycarbonyl group, C1-10 linear, branched, or cyclic alkyl group, C6-20 aryl group, C2-20 alkenyl group, or C2-10 alkynyl group, respectively. The aforementioned acetyl, alkoxy, alkoxycarbonyl, alkyl, aryl, alkenyl, and alkynyl groups may have one or more groups selected from the group consisting of amino, nitro, cyano, hydroxyl, glycidyl, and carboxyl groups. R7 and R8 are the same or different, representing benzene rings or naphthalene rings, respectively. n and o are 0 or 1. B1 and B2 are the same or different, respectively representing the groups of aromatic compounds derived from linear, branched or cyclic alkyl groups of C1-20 or aryl and heterocyclic groups of C6-40 that can be interrupted by hydrogen, oxygen or sulfur atoms. B1 and B2 can form a ring together with the carbon atoms of these groups. The hydrogen atoms of the groups of the aforementioned aromatic compounds can be replaced by alkyl, phenyl, condensed cycloyl, heterocyclic, hydroxyl, amino, ether, alkoxy, cyano, nitro or carboxyl groups of C1-20.

[0093] Preferably, it is a compound containing one or more of the repeating units j, k, l, m, r, s, t, u, v, w represented by the following formula (3) with one or more units. In formula (3), Indicates a single or double bond. X1 represents -N< or -CH<, X2 represents -N< or -CH<, X3 represents -N=, -CH=, -N(R3)-, or -CH(R3)-. X4 represents -N=, -CH=, -N(R4)-, or -CH(R4)-. R3 and R4 may be the same or different, representing a hydrogen atom, a C1-20 straight-chain, 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, respectively. The aforementioned alkyl and aryl groups may be substituted by a C1-6 acetyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or a hydroxyl group, and may be interrupted by an oxygen or sulfur atom. R5, R6, R9, and R10 are the same or different, representing hydrogen atom, hydroxyl group, C1-6 acetyl group, C1-6 alkoxy group, C1-6 alkoxycarbonyl group, C1-10 linear, branched, or cyclic alkyl group, C6-20 aryl group, C2-20 alkenyl group, or C2-10 alkynyl group, respectively. The aforementioned acetyl, alkoxy, alkoxycarbonyl, alkyl, aryl, alkenyl, and alkynyl groups may have one or more groups selected from the group consisting of amino, nitro, cyano, hydroxyl, glycidyl, and carboxyl groups. R7 and R8 are the same or different, representing benzene rings or naphthalene rings, respectively. n and o are 0 or 1. p and q are integers from 0 to 20. When there are p methylene groups and q methylene groups (two or more), the sequence can be interrupted by an oxygen atom or a sulfur atom. B3 indicates a direct bond, or a group derived from an aromatic compound of C6-40 that can be substituted with an alkyl, phenyl, condensed cycloyl, heterocyclic, hydroxyl, amino, ether, alkoxy, cyano, nitro, or carboxyl group of C1-20.

[0094] Preferably, R1, R2, R3 or R4 in formula (1) are C1 to 20 straight-chain, branched or cyclic alkyl groups that can be substituted with hydroxyl groups and interrupted by oxygen or sulfur atoms.

[0095] (n) As a cross-linkable membrane material, examples include epoxy adducts formed by the reaction of an epoxy-containing compound having at least two epoxy groups with an epoxy adduct having one epoxy addition reactive group, as disclosed in WO 2017 / 002653 A1. The epoxy adduct can be exemplified as follows.

[0096]

[0097]

[0098]

[0099] (In the formula, a, b, c, and d are 0 or 1 respectively, and a+b+c+d=1).

[0100] (o) As a membrane material capable of cross-linking reaction, examples include polymers with the structure represented by formula (1) as disclosed in WO 2005 / 098542 A1.

[0101] (In the formula, A1, A2, A3, A4, A5 and A6 represent hydrogen atoms, methyl or ethyl atoms, respectively, and X1 represents formula (2), formula (3), formula (4) or formula (5):

[0102] (In the formula, R1 and R2 represent hydrogen atoms, alkyl with 1 to 6 carbon atoms, alkenyl with 3 to 6 carbon atoms, benzyl or phenyl, and the aforementioned phenyl can be substituted by a radical selected from the group consisting of alkyl with 1 to 6 carbon atoms, halogen atoms, alkoxy with 1 to 6 carbon atoms, nitro, cyano, hydroxyl and alkylthio with 1 to 6 carbon atoms. Also, R1 and R2 can be bonded to each other to form a ring with 3 to 6 carbon atoms. R3 represents alkyl with 1 to 6 carbon atoms, alkenyl with 3 to 6 carbon atoms, benzyl or phenyl, and the aforementioned phenyl can be substituted by a radical selected from the group consisting of alkyl with 1 to 6 carbon atoms, halogen atoms, alkoxy with 1 to 6 carbon atoms, nitro, cyano, hydroxyl and alkylthio with 1 to 6 carbon atoms.) Q represents formula (6) or formula (7): (In the formula, Q1 represents alkyl, phenyl, naphthyl or anthracene with 1 to 10 carbon atoms, and the aforementioned phenyl, naphthyl and anthracene can be substituted by groups selected from the group consisting of alkyl, halogen, alkoxy, nitro, cyano, hydroxy and alkylthio with 1 to 6 carbon atoms, n1 and n2 represent the number 0 or 1 respectively, and X2 represents formula (2), formula (3) or formula (5)).

[0103] It is preferable that the structure represented by the aforementioned formula (1) is represented by formula (12) or formula (13). (In the formula, R1, R2, and Q have the same meaning as the above definition). (In the formula, X1 represents the same meaning as defined above, Y represents alkyl, halogen, alkoxy, nitro, cyano, hydroxyl or alkylthio group with 1 to 6 carbon atoms, and m represents an integer from 0 to 4. When m is 2 to 4, it can be the same as or different from the aforementioned Y).

[0104] (p) As a crosslinkable membrane material, polymers having a repeating unit structure represented by formula (1) or formula (2) as disclosed in WO 2006 / 115074 A1 can be cited as examples. {In the formula, R1 and R2 represent hydrogen atoms, methyl, ethyl or halogen atoms respectively, A1, A2, A3, A4, A5 and A6 represent hydrogen atoms, methyl or ethyl atoms respectively, and Q represents formula (3) or formula (4):} [In the formula, Q1 represents an alkyl, phenyl, naphthyl, or anthracene group having 1 to 15 carbon atoms, and the aforementioned phenyl, naphthyl, and anthracene groups can be substituted with groups selected from the group consisting of alkyl, halogen, alkoxy, nitro, cyano, hydroxyl, and alkylthio groups having 1 to 6 carbon atoms, respectively; n1 and n2 represent the number 0 or 1, respectively; X1 represents formula (5), (6), or (7):] (In the formula, R3 and R4 represent hydrogen atoms, alkyl with 1 to 6 carbon atoms, alkenyl with 3 to 6 carbon atoms, benzyl or phenyl, and the aforementioned phenyl can be substituted by any group in the group consisting of alkyl with 1 to 6 carbon atoms, halogen atoms, alkoxy with 1 to 6 carbon atoms, nitro, cyano, hydroxyl, and alkylthio with 1 to 6 carbon atoms. Also, R3 and R4 can bond to each other to form a ring with 3 to 6 carbon atoms. R5 represents alkyl with 1 to 6 carbon atoms, alkenyl with 3 to 6 carbon atoms, benzyl or phenyl, and the aforementioned phenyl can be substituted by any group in the group consisting of alkyl with 1 to 6 carbon atoms, halogen atoms, alkoxy with 1 to 6 carbon atoms, nitro, cyano, hydroxyl, and alkylthio with 1 to 6 carbon atoms.)

[0105] Preferably, the polymer is a polymer having the repeating unit structure represented by formula (12). (In the formula, Q is synonymous with the above).

[0106] Preferably, the aforementioned polymer is a polymer having a repeating unit structure represented by formulas (13) and (14). [In the formula, Q2 represents equation (15), equation (16), or equation (17):] (In the formula, Y, m, R3, R4 and R5 are synonyms with those mentioned above), Q3 is expressed as (18): (In the formula, Q4 represents an alkyl group with 1 to 15 carbon atoms, and n3 and n4 represent the number 0 or 1 respectively).

[0107] (q) As a crosslinkable membrane material, examples include polymers disclosed in WO 2008 / 069047 A1 that comprise at least one unit structure selected from the group consisting of unit structures represented by formulas (1), (2) and (3) below, or combinations thereof. (in the above formula, X represents a hydrogen atom or an aromatic condensation ring. Y represents an aromatic condensation ring; X and Y can bond together to form a condensation ring. R1, R2, R3, R4, R5, R10, R11, and R12 represent hydrogen atoms, halogen atoms, or alkyl groups with 1 to 3 carbon atoms, respectively. R6, R7, and R8 represent alkyl groups consisting of 1 to 10 hydrogen atoms or carbon atoms, either in a chain or cyclic configuration. R9 represents a chain or cyclic alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. R7 and R8 can bond together to form a ring. M and Q represent direct bonding or linker bases, respectively. (n represents an integer of 0 or 1) When the total number of all unit structures constituting the polymer is set to 1.0, the proportions of the number of unit structures (a) represented by equation (1), the proportions of the number of unit structures (b) represented by equation (2), and the proportions of the number of unit structures (c) represented by equation (3) become polymers with a ratio of 0.3≦a≦0.95, 0.005≦b≦0.7, and 0≦c≦0.45.

[0108] Preferably, the polymer comprises the unit structures represented by formulas (1) and (2). When the total number of all unit structures constituting the polymer is set to 1.0, the proportion of the number of unit structures (a) represented by formula (1) and the proportion of the number of unit structures (b) represented by formula (2) are 0.305≦a+b≦1, 0.3≦a≦0.95, and 0.005≦b≦0.7, respectively. Preferably, the polymer comprises the unit structures represented by formulas (1) and (3). When the total number of all unit structures constituting the polymer is set to 1.0, the ratio of the number of unit structures (a) represented by formula (1) and the ratio of the number of unit structures (c) represented by formula (3) are 0.35≦a+c≦1, 0.3≦a≦0.95, and 0.05≦c≦0.7, respectively. Preferably, the polymer comprises the unit structures represented by formulas (1), (2) and (3). When the total number of all unit structures constituting the polymer is set to 1.0, the proportions of the number of unit structures (a) represented by formula (1), the proportions of the number of unit structures (b) represented by formula (2) and the proportions of the number of unit structures (c) represented by formula (3) are 0.355≦a+b+c≦1, 0.3≦a≦0.9, 0.005≦b≦0.65, and 0.05≦c≦0.65. Preferably, the unit structure represented by formula (1) is a unit structure composed of vinylnaphthalene, acenaphthylene, vinylanthracene, vinylcarbazole, or derivatives thereof.

[0109] (r) As a cross-linkable membrane material, examples include compounds represented by the following formula (2) as disclosed in WO 2018 / 203464 A1. (In formula (2), the two Ars represent aryl groups, which are substituents and have at least one hydroxyl group. Q represents a divalent linker, methylene group, or single bond with at least one benzene ring or naphthalene ring.) Its molecular weight is, for example, 150 to 600.

[0110] In formula (2), aryl groups represented by Ar can be exemplified by, for example, phenyl, biphenyl, naphthyl, anthryl, and phenanthrene. Furthermore, when Q represents a divalent linker having at least one benzene or naphthyl ring, such divalent linkers can be exemplified by, for example, divalent groups in which at least one of the two hydrogen atoms of the methylene group is replaced by a phenyl, biphenyl, or naphthyl group; divalent aromatic groups selected from the group consisting of extended phenyl, extended biphenyl, and extended naphthyl groups; and divalent groups having the divalent aromatic group and a methylene, ether (-O- group), or sulfide (-S- group). Compounds represented by formulas (2-1) to (2-6) can be exemplified as monomers. (In equation (2-6), m represents an integer from 0 to 3).

[0111] (s) As a crosslinkable membrane material, examples include fullerene derivatives of malonate diesters represented by the following formula (1) disclosed in WO 2011 / 108365 A1 and WO 2016 / 143436 A1, which add 1 to 6 molecules to 1 molecule of fullerene. (In the formula, R independently represents alkyl groups with 1 to 10 carbon atoms).

[0112] (t) As a crosslinkable membrane material, examples include polyfunctional (meth)acrylate compounds with molecular weights of 300 to 10,000 that are in a liquid state at room temperature and atmospheric pressure, as disclosed in WO 2011 / 132640 A1.

[0113] Preferably, the aforementioned compounds are compounds having 2 to 20 (meth)acrylate groups in the molecule. Preferably, the molecular weight of the aforementioned compound is between 300 and 2,300.

[0114] The compound can be exemplified as follows.

[0115]

[0116]

[0117] (u) As a crosslinkable membrane material, examples include compounds (E) disclosed in WO 2017 / 154921 A1, which comprise partial structures (I) and partial structures (II), wherein partial structure (II) comprises hydroxyl groups generated by the reaction of an epoxy group with a proton-generating compound, wherein 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 is 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 (1-8), wherein partial structure (II) is a compound (E) consisting of a partial structure represented by formula (2-1) or (2-2) below. (In the formula, R1, R1a, R3, R5, R5a, and R6a represent saturated hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 40 carbon atoms, oxygen atoms, carbonyl groups, sulfur atoms, nitrogen atoms, amide groups, amino groups, or groups composed of combinations thereof; R2, R2a, R4, and R6 represent hydrogen atoms, saturated hydrocarbon groups with 1 to 10 carbon atoms, unsaturated hydrocarbon groups with 2 to 10 carbon atoms, oxygen atoms, carbonyl groups, amide groups, amino groups, or groups composed of combinations thereof; R2, R2a, R4, and R6 represent monovalent groups; R1, R1a, R3, R5a, and R6a represent divalent groups; R5 represents trivalent groups; R7, R8, R9, R10, and R11...) The numbers represent 1 to 10 saturated hydrocarbon groups with hydrogen or carbon atoms, respectively; n represents the number of repeating units from 1 to 10; and the dashed line represents the chemical bond with adjacent atoms.

[0118] The preferred compound (E) comprises epoxy groups and hydroxyl groups in a molar ratio of 0 ≦ (epoxy group) / (hydroxyl group) ≦ 0.5, and in a molar ratio of 0.01 ≦ (partial structure (II)) / (partial structure (I) + partial structure (II)) ≦ 0.8. Preferably, compound (E) is a compound comprising at least one partial structure (I) and at least one partial structure (II). Preferably, R5a and R6a are respectively an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, or a divalent group composed of combinations thereof. Preferably, compound (E) comprises partial structures (I) and partial structures (II) in an amount of 1 to 1000.

[0119] (v) As a crosslinkable membrane material, examples include compounds disclosed in WO 2018 / 030198 A1 that contain at least one photodegradable nitrogen-containing structure and / or a photodegradable sulfur-containing structure and a hydrocarbon structure.

[0120] Preferably, the above-mentioned compound is a compound having one or more photodegradable nitrogen-containing structures and / or photodegradable sulfur-containing structures within the molecule. Preferably, the above-mentioned compounds are compounds containing photodegradable nitrogen-containing structures and / or photodegradable sulfur-containing structures and hydrocarbon structures within the same molecule, or combinations of compounds containing different structures. Preferably, the above-mentioned hydrocarbon structure is a saturated or unsaturated group with 1 to 40 carbon atoms, and is a straight-chain, branched or cyclic hydrocarbon group. Preferably, the above-mentioned photodegradable nitrogen-containing structure includes a structure that generates reactive nitrogen-containing functional groups or reactive carbon functional groups by ultraviolet irradiation, or a structure that generates reactive nitrogen-containing functional groups or reactive carbon functional groups by ultraviolet irradiation. Preferably, the above-mentioned photodegradable nitrogen-containing structure is a photodegradable nitrogen-containing structure that may contain sulfur atoms, such structure being an azide structure, a tetrazolium structure, a triazole structure, an imidazole structure, a pyrazole structure, an azole structure, a diazo structure, or a structure containing a combination of these. Preferably, the aforementioned photodegradable sulfur-containing structure includes a structure that generates organosulfur free radicals or carbon free radicals by ultraviolet irradiation, or a structure that generates organosulfur free radicals or carbon free radicals by ultraviolet irradiation. Preferably, the above-mentioned photodegradable sulfur-containing structure is a photodegradable sulfur-containing structure that may contain nitrogen atoms, and the structure is a trisulfide structure, a disulfide structure, a sulfide structure, a thione structure, a thiophene structure, a thiol structure, or a structure containing a combination of the above.

[0121] The following compounds are preferred.

[0122] (w) As a cross-linkable membrane material, compounds represented by the following formula (1) as disclosed in WO 2019 / 013293 A1 can be listed. (In formula (1), R1 is a divalent group with 1 to 30 carbon atoms, R2 to R7 are linear, branched or cyclic alkyl groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, thiols or hydroxyl groups, at least one of R5 is a hydroxyl or thiol group, m2, m3 and m6 are integers from 0 to 9, m4 and m7 are integers from 0 to 8, m5 is an integer from 1 to 9, n is an integer from 0 to 4, and p2 to p7 are integers from 0 to 2).

[0123] The following compounds are preferred.

[0124] (x) can be used as a cross-linkable membrane material, such as the compound represented by the following general formula (1) disclosed in Japanese Patent Application Publication No. 2016-216367. (In the formula, n1 and n2 represent 0 or 1 respectively, 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 represent integers from 0 to 7 respectively. However, m1+m2 is 1 to 14). (In the formula, l represents an integer from 0 to 3, Ra to Rf represent alkyl, phenyl or phenylethyl groups with 1 to 10 carbon atoms that can be replaced by hydrogen atoms or fluorine, and Ra and Rb can bond to form cyclic compounds). (In the formula, * indicates the bonding site of the aromatic ring, Q1 represents a straight-chain or branched saturated or unsaturated hydrocarbon group with 1 to 30 carbon atoms, an alicyclic group with 4 to 20 carbon atoms, or a substituted or unsubstituted phenyl, naphthyl, anthracene, or pyrene group. When Q1 represents a straight-chain or branched saturated or unsaturated hydrocarbon group with 1 to 30 carbon atoms, the methylene group constituting Q1 can be substituted by an oxygen atom or a carbonyl group.)

[0125] The compound represented by the aforementioned general formula (1) is preferably represented by the compound represented by the following general formula (4). (In the formula, m3 and m4 represent 1 or 2, and W and R1 are the same as above).

[0126] Preferably, W is either a single bond or a structure represented by the following formula (5). (In the formula, l is the same as above).

[0127] Preferably, the compound represented by the aforementioned general formula (1) has two or more Q1s in the molecule and includes one or more structures represented by the following general formula (6) and the following general formula (7) as the aforementioned Q1s. (In the formula, ** represents the bonding site of the carbonyl group, Rh represents a straight-chain, branched, saturated or unsaturated hydrocarbon group with 1 to 30 carbon atoms, and the methylene group constituting Rh can be replaced by an oxygen atom or a carbonyl group). (In the formula, ** represents the bonding site of the carbonyl group, Ri represents a hydrogen atom or a straight-chain or branched hydrocarbon group with 1 to 10 carbon atoms, Rj represents a straight-chain or branched hydrocarbon group with 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxy carbonyl group with 1 to 10 carbon atoms, or an alkanoyloxy group with 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, which are integers from 0 to 7 respectively. However, n3+n4 is more than 0 and less than 7. n5 represents 0 to 2).

[0128] (y) As a membrane material capable of cross-linking reaction, compounds represented by the following general formula (1A) disclosed in Japanese Patent Application Publication No. 2017-119670 can be listed as examples. (In the formula, R is a single bond, an organic group with 1 to 50 carbon atoms, an ether bond, a -SO- group or a -SO2- group, R1 is a group represented by the following general formula (1B), m1 and m2 are 1≦m1≦5 and 1≦m2≦5, and are integers that satisfy 2≦m1+m2≦8). (In the formula, X1 is the basis of the following general formula (1C), and X is the basis of the following general formula (1D). (In the formula, (X) represents the bond node with the aforementioned X). (In the formula, X2 is a divalent organic group with 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, X3 is a group represented by the following general formula (1E), and n5 is 0, 1 or 2). (In the formula, R10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring can be replaced by a methyl or methoxy group).

[0129] Preferably, the molecular weight of the aforementioned compound is below 2,500.

[0130] The preferred compounds are those represented by the following general formula (2A) and those represented by the following general formula (3A). (In the formula, R is a single bond, an organic group with 1 to 50 carbon atoms, an ether bond, a -SO- group or a -SO2- group, R2 is a group represented by the following general formula (2B), m3 and m4 are 1≦m3≦5 and 1≦m4≦5, and are integers that satisfy 2≦m3+m4≦8). (In the formula, X11 is the basis of the following general formula (2C), and X' is the basis of the following general formula (2D). (In the formula, (X') represents the key node with the aforementioned X'). (In the formula, n3 is 0 or 1, n4 is 1 or 2, X4 is the basis of the following general formula (2E), and n6 is 0, 1 or 2). (In the formula, R11 is a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring can be replaced by a methyl or methoxy group). (In the formula, R101, R102, R103, and R104 are each independently a hydroxyl group, m100 is 1, 2, or 3. When m100 is 1, R100 is a hydrogen atom or a hydroxyl group; when m100 is 2, it is a single bond or a group represented by the following general formula (3B); when m100 is 3, it is a group represented by the following general formula (3C). The hydrogen atoms on the aromatic ring in the formula can be replaced by methyl or methoxy groups. 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, n1 01 and n102 are 0≦n101≦3 and 0≦n102≦3, and are integers satisfying 1≦n101+n102≦4. When m101 is 1, n101, n102, n103 and n104 are 0≦n101≦2, 0≦n102≦2, 0≦n103≦2, 0≦n104≦2, and are integers satisfying 2≦n101+n102+n103+n104≦8. (In the formula, * indicates the bonding position, R106 and R107 are organic groups that do not contain hydrogen atoms or ester bonds with 1 to 24 carbon atoms. R106 and R107 can bond together to form a ring structure.) (In the formula, * indicates the bonding position, and R108 is a hydrogen atom or an organic group with 1 to 15 carbon atoms).

[0131] (z) As a polyether film material, polymers represented by the following general formula (1) as disclosed in WO2012 / 050064 can be listed. The following formula (1) represents the unit construction, (In formula (1), Ar1 represents an organogroup containing an aryl or heterocyclic group with 6 to 50 carbon atoms) Polymers that contain a unit structure represented by formula (2) below, or a combination of unit structures represented by formula (1) and unit structures represented by formula (2). (However, in formula (2), Ar2, Ar3 and Ar4 represent organic groups containing aryl or heterocyclic groups with 6 to 50 carbon atoms, respectively, and T represents carbonyl or sulfonyl groups).

[0132] The aforementioned crosslinkable membrane material (Y) preferably contains selected... (Y1) Membrane materials containing aliphatic rings (e.g., (a)(m) above), (Y2) Phenolic varnish film materials (e.g., as mentioned above (b)(c)(d)(e)(f)(g)(h) (i)(j)(k)(l)), (Y3) Polyether film materials (e.g., the above (z)), (Y4) Polyester film material (e.g., the above (o)(p)), (Y5) Compounds that are different from cross-linking compound (A) (e.g., the above-mentioned (m)(n)(r)(s)(t)(u)(v)(w)(x)(y)), (Y6) Membrane materials containing aromatic condensation rings (e.g., (q) above), (Y7) acrylic resin and (Y8) Methacrylate resin At least one of the groups formed.

[0133] When the inhibitor lower layer film forming composition of the present invention includes a crosslinkable membrane material (Y) (membrane material or polymer), the content ratio of the aforementioned crosslinkable membrane material (Y) relative to the total solids content is generally 1 to 99.9% by mass, preferably 50 to 99.9% by mass, more preferably 50 to 95% by mass, and even more preferably 50 to 90% by mass.

[0134] In the resist underlayer film formation composition of the present invention, light absorbers, rheology modifiers, adhesion promoters, etc., may be further added. Rheology modifiers are effective in improving the flowability of the underlayer film formation composition. Adhesion promoters are effective in improving the adhesion between the semiconductor substrate or the resist and the underlayer film.

[0135] (Light absorber) As light absorbers, commercially available light absorbers listed in publications such as "Technology and Market of Industrial Pigments" (CMC publication) or "Dye Handbook" (organic synthetic chemists' association) are suitable for use, such as CIDisperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,60,64,66,68,79,82,88,90,93,102,114 and 124; CIDisperse Orange 1,5,13,25,29,30,31,44,57,72 and 73; CIDisperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199 and 210; CIDisperse Violet 43; CIDisperse Blue 96; CIFluorescent Brightening Agent 112, 135 and 163; CISolvent Orange 2 and 45; CISolvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CIPigment Green 10; CIPigment Brown 2, etc. The above-mentioned light absorbers are generally blended in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solids content of the composition forming the underlying film of the resist.

[0136] (Rheology modifier) Rheology modifiers are primarily added to improve the flowability of the resist underlayer film composition, especially during the baking process, to enhance the uniformity of the resist underlayer film thickness or improve the filling performance of the resist underlayer film composition within the pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecanyl 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 blended in proportions of less than 30% by mass relative to the total solids content of the resistive underlayer film composition.

[0137] (Followed by adjuvants) Next, the auxiliary agents are mainly added to improve the adhesion between the substrate or the resist and the composition of the resist underlying film, especially during development, with the aim of preventing the resist from peeling off. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylhydroxymethylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylhydroxymethylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; hexamethyldisilazane; N,N'-bis(trimethylsilyl)urea; dimethyltrimethylsilylamine; and trimethylsilylimidazolium, etc. The adhesives include silanes such as chlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzoimidazole, indazole, imidazole, 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesives are typically blended in a proportion of less than 5% by mass, preferably less than 2% by mass, relative to the total solid content of the resistive underlayer film-forming composition.

[0138] The solid content of the inhibitor underlayer film-forming composition of the present invention is typically defined as 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content refers to the percentage of the total components of the inhibitor underlayer film-forming composition after removing the solvent. The proportion of the aforementioned polymer in the solid content is preferably in the following order: 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.

[0139] One of the criteria for evaluating whether the resist underlayer membrane formation composition is a homogeneous solution state is to observe the permeability of a specific microfilter. However, the resist underlayer membrane formation composition of the present invention presents a homogeneous solution state when passing through a microfilter with a pore size of 0.1 μm.

[0140] While fluorinated resins such as PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polyurethane), PES (polyether ether), and nylon can be listed as materials for the aforementioned microfilters, PTFE (polytetrafluoroethylene) is preferred.

[0141] [Resistor Lower Layer Film] The resist underlayer film can be formed using the resist underlayer film formation composition of the present invention, as follows. The resist underlayer film of this invention is formed by coating a substrate used in the manufacture of semiconductor devices (such as silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low-k material coated substrates) with a suitable coating method such as a spinner or coating machine, and then firing it using a heating means such as a hot plate. The firing conditions are appropriately selected from a firing temperature of 80°C to 600°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 350°C and the firing time is 0.5 to 2 minutes. The ambient gas used during firing can be air, or an inert gas such as nitrogen or argon. Here, the thickness of the underlying film formed is, for example, 10 to 1000 nm, or 20 to 500 nm, or 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz embossing mold (mold replica) can be made.

[0142] Alternatively, an adhesion layer and / or a polysiloxane layer containing 99% by mass or less or 50% by mass of Si can be formed on the resist lower film of the present invention by coating or vapor deposition. For example, in addition to the adhesion layer described in Japanese Patent Application Publication No. 2013-202982 or Japanese Patent No. 5827180, and the silicon-containing resist lower film (inorganic resist lower film) formation composition described in WO2009 / 104552A1, a Si-based inorganic material film can be formed by CVD or the like.

[0143] Furthermore, by coating the resist lower layer film forming composition of the present invention onto a semiconductor substrate (i.e., a step substrate) having a stepped portion and a non-stepped portion, and then firing it, a resist lower layer film with a step difference of 3 to 70 nm between the stepped portion and the non-stepped portion can be formed.

[0144] [Semiconductor device manufacturing method] The method for manufacturing the semiconductor device of the present invention comprises: The steps for forming the resistive underlayer film using the composition of the present invention are as follows: The steps of forming a resist film on top of the formed resist lower layer film, The process of forming a resist pattern by irradiating and developing the formed resist film with light or electron beams. The steps of etching the underlying resist film based on the formed resist pattern and patterning are as follows: The process of fabricating a semiconductor substrate through a patterned resist underlayer film.

[0145] Furthermore, the method for manufacturing the semiconductor device of the present invention comprises: The steps for forming the resistive underlayer film using the composition of the present invention are as follows: The step of forming a hard mask on top of the formed resist underlayer film. The step of forming a resist film on top of the hard mask is as follows: The process of forming a resist pattern by irradiating and developing the formed resist film with light or electron beams. Through the formed resist pattern, the aforementioned hard mask is etched, and the patterning steps are performed. The process involves etching the aforementioned resist underlayer film using a patterned hard mask, followed by patterning steps. The process of fabricating a semiconductor substrate through a patterned resist underlayer film.

[0146] The composition is formed using the resistive underlayer film of the present invention, and the steps for forming the resistive underlayer film are as described above.

[0147] An organopolysiloxane film can be formed as a second resist lower layer film on the resist lower layer film formed in the aforementioned steps, and a resist pattern can be formed on it. This second resist lower layer film can be a SiON film or a SiN film formed by vapor deposition methods such as CVD or PVD. Furthermore, an antireflective film (BARC) can be formed on this second resist lower layer film as a third resist lower layer film. This third resist lower layer film can be a resist shape correction film that does not have antireflective properties.

[0148] In the step of forming the aforementioned resist pattern, exposure is performed either by using a reticle to form the specified pattern or by direct drawing. Exposure sources can include, for example, g-lines, i-lines, KrF excimer lasers, ArF excimer lasers, EUV, and electron beams. After exposure, post-exposure baking is performed if necessary. Then, development is performed with a developer (e.g., a 2.38% by mass tetramethylammonium hydroxide aqueous solution), followed by rinsing with a rinsing solution or pure water to remove the used developer. Finally, post-baking is performed to improve the drying of the resist pattern and its adhesion to the substrate.

[0149] The etching step performed after the formation of the aforementioned resist pattern is carried out by dry etching. Examples of etching gases used in the dry etching process include CHF3, CF4, and C2F6 for the second resist underlayer film (organopolysiloxane film); O2, N2O, and NO2 for the first resist underlayer film formed from the resist underlayer film forming composition of the present invention; and CHF3, CF4, and C2F6 for surfaces having steps, recesses, and / or protrusions. Furthermore, argon, nitrogen, or carbon dioxide can be mixed with these gases.

[0150] [Formation of the resist underlayer film via nanoprinting] Alternatively, the step of forming the above-mentioned resist underlayer film can be performed by nanoprinting. This method includes: The step of applying a curable composition to the formed inhibitor lower film. The steps of contacting the aforementioned hardened components with the mold, The steps of irradiating the aforementioned curable components with light or an electron beam to form a curable film, and The step of separating the aforementioned hardened film from the aforementioned mold.

[0151] In the demolding process of photopolymer nanoprinting, the adhesion between the resist composition and the substrate is crucial. This is because low adhesion can lead to defects during demolding, where a portion of the photocured material obtained by hardening the resist composition may adhere directly to the mold and peel off, resulting in pattern delamination. To improve adhesion between the resist composition and the substrate, a proposed technique is to form an adhesion layer between the resist composition and the substrate.

[0152] Furthermore, there are cases where highly etch-resistant layers are formed in the pattern formation of nanoprinted designs. Organic materials and polysiloxane-based materials are generally used as materials for these highly etch-resistant layers. Moreover, an adhesion layer or a Si-containing polysiloxane layer can be formed on the resist underlayer film for nanoprinting by coating or vapor deposition. If this adhesion layer or Si-containing polysiloxane layer is hydrophobic and exhibits a high-purity water contact angle, and the underlayer film is also hydrophobic and exhibits a high-purity water contact angle, it is expected to improve the adhesion between the films or make them difficult to peel off. Conversely, if the adhesion layer or polysiloxane layer is hydrophilic and exhibits a low-purity contact angle, and the underlayer film is also hydrophilic and exhibits a low-purity contact angle, it is expected to improve the adhesion between the films or make them difficult to peel off.

[0153] Furthermore, depending on the characteristics of the aforementioned adhesion membrane, polysiloxane layer, and underlayer membrane, He, H2, N2, air, etc., can be used.

[0154] The polymer (X) of this invention is not limited to low-temperature calcination; it also exhibits the desired pure water contact angle during high-temperature calcination. When used as a material, it combines a crosslinking agent, an acid catalyst, and a surfactant, and also exhibits the desired pure water contact angle. This is expected to improve adhesion to the upper film and provide good permeability to gases such as He, H2, N2, and air. Furthermore, by exhibiting good planarization properties, the polymer (X) of this invention can be modified to adapt to the optical constants or etching speeds of the process.

[0155] (hardening components) As a photoresist formed on the lower layer of the resist film, there are no particular limitations if it is intended for use in photosensitizing applications. Both negative and positive photoresists can be used. Types include positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazidesulfonate; chemically amplified photoresists composed of a binder with a group that enhances the alkali dissolution rate through acid decomposition and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that enhances the alkali dissolution rate of the photoresist through acid decomposition and an alkali-soluble binder and a photoacid generator; and chemically amplified photoresists composed of a binder with a group that enhances the alkali dissolution rate of the photoresist through acid decomposition and a low-molecular-weight compound that enhances the alkali dissolution rate of the photoresist through acid decomposition and a photoacid generator. Examples include Shipley's APEX-E, Sumitomo Chemical Industries Co., Ltd.'s PAR710, and Shin-Etsu Chemical Industries Co., Ltd.'s SEPR430. For example, examples include fluorine-containing polymer photoresists described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), or Proc. SPIE, Vol. 3999, 365-374 (2000).

[0156] (Steps applicable to hardening compositions) This step involves applying a curable composition to the formed resist underlayer film using the manufacturing method of the present invention. Methods for applying the curable composition include, for example, inkjet printing, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spin coating, and slot scanning. Inkjet printing is suitable for applying the curable composition as droplets, while spin coating is suitable for coating the curable composition. In this step, an adhesion layer and / or a polysiloxane layer containing 99% by mass or less or 50% by mass or less Si can also be formed on the resist underlayer film by coating or vapor deposition, and the curable composition can then be applied thereon.

[0157] (Steps for contacting hardening components with the mold) In this step, the curing composition comes into contact with the mold. For example, if the curing composition comes into contact with a liquid and a mold having a prototype pattern for transferring the pattern shape, a liquid film of the curing composition fills the recesses of the fine pattern on the surface of the mold.

[0158] Considering the steps involved in irradiation with light or electron beams, it is recommended to use a mold with a light-transmitting material as the substrate. Specifically, the mold substrate is preferably made of light-transmitting resins such as glass, quartz, PMMA, and polycarbonate resin; transparent metal vapor-deposited films; flexible films such as polydimethylsiloxane; photocurable films; or metal films. Due to its low coefficient of thermal expansion and minimal pattern deformation, quartz is particularly preferred as the mold substrate.

[0159] The mold surface preferably has a pattern height of 4nm or higher and 200nm or lower. While a certain pattern height is necessary to improve substrate processing accuracy, a lower pattern height results in less force pulling the mold from the hardened film during the separation process (described later), and also reduces the number of defects remaining on the mask side after removing the resist pattern. Considering these factors, it is recommended to select and adopt an appropriately balanced pattern height. Furthermore, due to the elastic deformation of the resist patterns during the impact when the mold is pulled out, adjacent resist patterns may come into contact with each other, resulting in resist patterns sticking or breaking. This can be avoided by setting the pattern height to about twice or less (length-to-width ratio less than 2) relative to the pattern width.

[0160] To improve the peelability of the hardened component from the mold surface, the mold can be pre-treated. Methods of surface treatment include applying a release agent to the mold surface to form a release agent layer. Examples of release agents include polysiloxane-based, fluorine-based, hydrocarbon-based, polyethylene-based, polypropylene-based, paraffin-based, lignite-based, 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. Release agents can be used alone or in combination of two or more.

[0161] In this step, when the mold comes into contact with the hardening component, the pressure applied to the hardening component is not particularly limited. A pressure of 0 MPa or higher and 100 MPa or lower is recommended. Preferably, the pressure is 0 MPa or higher, 50 MPa or lower, 30 MPa or lower, or 20 MPa or lower.

[0162] In the previous step (the step applicable to hardening compositions), during the pre-diffusion of the droplets of the hardening composition, the diffusion of the hardening composition in this step is completed rapidly. As a result, the contact time between the mold and the hardening composition can be shortened. Although the contact time is not particularly limited, it is preferably 0.1 seconds or more, 600 seconds or less, 3 seconds or less, or 1 second or less. If the contact time is too short, the diffusion and filling will not be sufficient, and there is a risk of producing a defect known as an unfilled defect.

[0163] This step can be performed under atmospheric, reduced pressure, or inert gas conditions, but is preferably performed at a pressure above 0.0001 atm and below 10 atm. To prevent interference with the hardening reaction by oxygen or moisture, it is recommended to perform the procedure under reduced pressure or inert gas conditions. Specific examples of inert gases that can be used to create an inert gas environment include nitrogen, carbon dioxide, helium, argon, CFCs, HCFCs, HFCs, or mixtures thereof.

[0164] This step can be performed in an environment containing condensable gases (hereinafter referred to as a "condensable gas environment"). In this specification, condensable gas refers to the gas that condenses and liquefies under capillary pressure generated during filling the recesses of the micro-pattern formed on the mold and the gap between the mold and the substrate, together with the curing composition. Furthermore, the condensable gas system exists as a gas in the environment before contacting the curing composition and the mold in this step. When this step is performed in a condensable gas environment, the gas filling the recesses of the micro-pattern is liquefied by the capillary pressure generated by the curing composition, eliminating bubbles and resulting in excellent filling performance. The condensable gas is soluble in the curing composition.

[0165] If the boiling point of the condensable gas is below the ambient temperature of this step, although there is no particular limitation, it is preferably above -10°C or above +10°C and below +23°C.

[0166] If the vapor pressure of the condensable gas at the ambient temperature in this step is below the mold pressure, there is no particular limitation. It is preferably in the range of 0.1 MPa to 0.4 MPa.

[0167] As condensable gases, examples include chlorofluorocarbons (CFCs) such as trichlorofluoromethane, fluorocarbons (FCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) such as 1,1,1,3,3-pentafluoropropane (CHF2 CH2 CF3, HFC-245fa, PFP), and hydrofluoroethers (HFEs) such as pentafluoroethyl methyl ether (CF3 CF2 OCH3, HFE-245mc).

[0168] Condensable gases can be used alone or in mixtures of two or more. Furthermore, these condensable gases can be mixed with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. Air and helium are preferred non-condensable gases that can be mixed with condensable gases.

[0169] (The step of irradiating a hardening component with light or an electron beam to form a hardened film) In this step, the curable composition is irradiated with light or an electron beam to form a curable film. That is, by passing the curable composition with a fine pattern filled in the mold through the mold and irradiating it with light or an electron beam, the curable composition with a fine pattern filled in the mold is directly cured in this state to form a curable film with a pattern shape.

[0170] The wavelength of the light or electron beam is selected according to the sensitivity of the curing composition. Specifically, ultraviolet light, X-rays, electron beams, etc., with wavelengths between 150 nm and 400 nm can be appropriately selected. 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. There can be one or multiple light sources. Irradiation can be performed on the entire curing composition of the micro-pattern filled in the mold, or only on a portion of the area. Light irradiation can be performed intermittently multiple times over the entire area of ​​the substrate, or continuously over the entire area. Alternatively, a portion of the substrate can be irradiated first, and a different area can be irradiated a second time.

[0171] The resulting hardened film is preferably a pattern with dimensions of 1 nm or more, 10 nm or more, 10 mm or less, or 100 μm or less.

[0172] (Steps for separating the hardened film from the mold) In this step, the hardened film and the mold are separated. The hardened film with a patterned shape is separated from the mold, and the hardened film with a patterned shape that is a reversed pattern of the micro-pattern formed on the mold is obtained in a free-standing state.

[0173] As a method for separating a patterned hardened film from a mold, if it involves moving the hardened film and the mold in a direction of relative separation, there are no particular limitations as long as a portion of the patterned hardened film is not physically damaged, nor are there any particular limitations on the conditions. For example, the substrate can be fixed so that the mold can be moved away from the substrate and peeled off, or the mold can be fixed so that the substrate can be moved away from the mold and peeled off. Alternatively, the substrate and the mold can be stretched in opposite directions and moved to peel them off.

[0174] Furthermore, when the step of contacting the aforementioned hardened component with the mold is carried out in a condensing gas environment, during the separation of the hardened film and the mold in this step, the pressure at the interface between the hardened film and the mold decreases, causing the condensing gas to vaporize. This reduces the force necessary to separate the hardened film and the mold, i.e., the demolding force.

[0175] Through the above steps, the desired convex and concave pattern shape derived from the mold can be modulated into a hardened film at the desired location. [Example]

[0176] The following description of specific examples of the components of the present invention is not intended to limit the present invention.

[0177] The apparatus used to determine the weight-average molecular weight of the reaction products obtained in the following synthesis example is shown. Device: HLC-8320GPC manufactured by Tosoh Corporation GPC tubing: TSKgel Super-MultiporeHZ-N (2 tubing) Column temperature: 40℃ Flow rate: 0.35 ml / min Dissolution solution: THF Standard sample: polystyrene

[0178] The chemical structures (examples) and abbreviations of the main raw materials used are as follows.

[0179]

[0180]

[0181] [Synthesis example 1] 260.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 1,430 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) were placed in a flask. Then, under nitrogen atmosphere, the mixture was heated to approximately 90°C, and 17.26 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 130.00 g of PGME was added dropwise. After approximately 45 hours, the mixture was precipitated with methanol and water and dried to obtain polymer (1-I). While the actual building block consists of crosslinked ROCH2- groups containing methoxymethyl groups and hydroxyl or ROCH2- groups, representing its state in a chemical formula is extremely complex; therefore, only the building block is shown. The same applies below. The weight-average molecular weight (Mw) determined by GPC to be converted to polystyrene was approximately 4,500. Furthermore, the introduction of PGME was confirmed by 1H-NMR. The desired polymer solution was obtained by dissolving the resulting resin in PGMEA and performing ion exchange for 4 hours using cation exchange resin and anion exchange resin.

[0182]

[0183] [Synthesis example 2] 68.99 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 379.44 g of PGME were placed in a flask. Then, under nitrogen atmosphere, the mixture was heated to approximately 90°C, and 4.57 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 34.50 g of PGME was added dropwise. After approximately 47.5 hours, the mixture was precipitated with methanol and water and dried to obtain polymers (1-2). The weight-average molecular weight (Mw) determined by GPC to be approximately 5,400 (converted to polystyrene). The introduction of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange and anion exchange resins for 4 hours to obtain the desired polymer solution.

[0184]

[0185] [Synthesis example 3] 30.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 165.07 g of 1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a flask. Then, under nitrogen atmosphere, the mixture was heated to approximately 90°C, and 1.99 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 15.05 g of 1-butanol was added dropwise. After approximately 81.5 hours, the mixture was precipitated with methanol and water and dried to obtain polymers (1-3). The weight-average molecular weight (Mw) determined by GPC to be approximately 3,487 (converted to polystyrene). The introduction of the 1-butyl group was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0186]

[0187] [Synthesis Example 4] 34.50 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 33.16 g of TM-BIP-A, and 379.44 g of PGME were placed in a flask. The mixture was then heated to approximately 90°C under nitrogen atmosphere, and 2.29 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 34.50 g of PGME was added dropwise. After approximately 125.5 hours, the mixture was precipitated with methanol and water and dried to obtain polymers (1-4). The weight-average molecular weight (Mw) determined by GPC to be approximately 4,296 (converted to polystyrene). The presence of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange and anion exchange resins for 4 hours to obtain the desired polymer solution.

[0188]

[0189] [Synthesis Example 5] 34.50 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 0.31 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), and 189.73 g of PGME were placed in a flask. The mixture was then heated to approximately 90°C under nitrogen atmosphere, and 2.29 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 17.25 g of PGME was added dropwise. After approximately 48 hours, the mixture was precipitated with methanol and water and dried to obtain polymers (1-5). The weight-average molecular weight (Mw) determined by GPC to be approximately 3,978 (converted to polystyrene). The presence of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange and anion exchange resins for 4 hours to obtain the desired polymer solution.

[0190]

[0191] [Synthesis example 6] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 5.46 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 58.72 g of PGME were placed in a 100 mL flask. The mixture was then heated to 90 °C under nitrogen atmosphere, and 0.47 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise. After approximately 2 hours, the mixture was precipitated with methanol and dried to obtain polymers (1-6). The weight-average molecular weight (Mw) determined by GPC to be approximately 4,000 (converted to polystyrene). The introduction of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0192]

[0193] [Synthesis Example 7] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 7.16 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 65.52 g of PGME were placed in a 100 mL flask. The mixture was then heated to 90 °C under nitrogen atmosphere, and 0.47 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise. After approximately 3 hours, the mixture was precipitated with methanol and dried to obtain polymers (1-7). The weight-average molecular weight (Mw) determined by GPC to be approximately 4,500 (converted to polystyrene). The introduction of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0194]

[0195] [Synthesis example 8] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 11.44 g of 9,9-bis(4-hydroxyphenyl)pyrene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.73 g of PGME were placed in a 100 mL flask. The mixture was then heated to reflux under nitrogen, and 0.47 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise. After approximately 4 hours, the mixture was precipitated with methanol and water and dried to obtain polymers (1-8). The weight-average molecular weight (Mw) determined by GPC to be approximately 4,100 (converted to polystyrene). The introduction of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange and anion exchange resins for 4 hours to obtain the desired polymer solution.

[0196]

[0197] [Synthesis Example 9] 12.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 7.29 g of 2,2'-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 54.58 g of PGME were placed in a 100 mL flask. The mixture was then heated to reflux under nitrogen, and 0.56 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise. After approximately 1.5 hours, the mixture was precipitated with methanol and water and dried to obtain polymers (1-9). The weight-average molecular weight (Mw) determined by GPC to be approximately 3,700 (converted to polystyrene). The introduction of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange and anion exchange resins for 4 hours to obtain the desired polymer solution.

[0198]

[0199] [Synthesis Example 10] 12.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 6.27 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of PGME were placed in a 100 mL flask. The mixture was then heated to reflux under nitrogen, and 0.56 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise. After approximately 1 hour, the mixture was precipitated with methanol and water and dried to obtain polymer (1-10). The weight-average molecular weight (Mw) determined by GPC to be approximately 10,000 (converted to polystyrene). The introduction of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0200]

[0201] [Synthesis Example 11] 68.99 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 40.00 g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 379.42 g of PGME were placed in a flask. The mixture was then heated to approximately 90°C under nitrogen atmosphere, 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 ammonia, and then dried to obtain polymer (1-11). The weight-average molecular weight (Mw) determined by GPC to be approximately 4,200 (converted to polystyrene). The presence of PGME was confirmed by 1H-NMR. The resulting resin was dissolved in PGMEA, and ion exchange was performed using cation exchange and anion exchange resins for 4 hours to obtain the desired polymer solution.

[0202]

[0203] [Synthesis Example 12] 8.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.63 g of 9-fentanyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.30 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.93 g of PGMEA were placed in a 100 mL flask. The mixture was then heated to reflux under nitrogen atmosphere for approximately 1.5 hours, precipitated with methanol, and dried to obtain polymer (1-12). The weight-average molecular weight (Mw) determined by GPC to be approximately 2,600 (converted to polystyrene). The resulting resin was dissolved in PGMEA, and ion exchange was performed using both cation and anion exchange resins for 4 hours to obtain the desired polymer solution.

[0204]

[0205] [Comparative Synthesis Example 1] 15.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.) and 35.55 g of 1,4-dioxane were placed in a 100 mL flask. The mixture was then heated to 120 °C under nitrogen atmosphere, and 0.24 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of 1,4-dioxane was added dropwise. After approximately 6 hours, the mixture was precipitated with methanol and dried to obtain polymer (2-1). The weight-average molecular weight (Mw) determined by GPC to be approximately 4,600 (converted to polystyrene). The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0206]

[0207] [Comparative Synthesis Example 2] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 5.46 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.70 g of 1,4-dioxane were placed in a 100 mL flask. The mixture was then heated to 120 °C under nitrogen atmosphere, and 0.16 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of 1,4-dioxane was added dropwise. After approximately 1 hour, the mixture was precipitated with methanol and dried to obtain polymer (2-2). The weight-average molecular weight (Mw) determined by GPC to be approximately 3,200 (converted to polystyrene). The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0208]

[0209] [Comparative Synthesis Example 3] 10.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 7.16 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18.70 g of 1,4-dioxane were placed in a 100 mL flask. The mixture was then heated to 120 °C under nitrogen atmosphere, and 0.16 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of 1,4-dioxane was added dropwise. After approximately 1 hour, the mixture was precipitated with methanol and water and dried to obtain polymer (2-3). The weight-average molecular weight (Mw) determined by GPC to be approximately 2,800 (converted to polystyrene). The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0210]

[0211] [Comparative Synthesis Example 4] 12.00 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 8.23 ​​g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 23.88 g of 1,4-dioxane were placed in a flask. Then, the mixture was heated to 120°C under nitrogen atmosphere, and 0.38 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5 g of PGME was added dropwise, allowing the reaction to proceed for approximately 5 hours.

[0212] [Comparative Synthesis Example 5] 69.92 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 40.88 g of 2-ethylhexylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.19 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 80.00 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were placed in a 200 mL flask. The mixture was then heated to reflux under nitrogen, and after approximately 24 hours, it was precipitated with methanol and dried to obtain polymer (2-4). The weight-average molecular weight (Mw) determined by GPC to be approximately 1,700 (converted to polystyrene). The obtained resin was dissolved in PGMEA, and ion exchange was performed using cation exchange resin and anion exchange resin for 4 hours to obtain the desired polymer solution.

[0213]

[0214] [Example 1] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. 9.12g of this resin solution was added to 0.39g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20g of PGMEA containing 1% by mass of surfactant (manufactured by DIC, MEGAFACER-40), 4.96g of PGMEA, and 2.41g of PGME, and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator lower membrane.

[0215] [Example 2] In Synthesis Example 3, a resin solution (solid content 26.93% by mass) was obtained. To this resin solution, 0.33g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.43g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.16g of PGMEA containing 1% by mass of surfactant (manufactured by DIC, MEGAFACER-40), 5.24g of PGMEA, and 5.80g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator membrane.

[0216] [Example 3] In Synthesis Example 4, a resin solution (solid content 22.01 wt%) was obtained. 7.38 g of this resin solution was added to 0.33 g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.43 g of PGME containing 2 wt% K-PURE TAG2689 (manufactured by King Industries), 0.16 g of PGMEA (manufactured by DIC, MEGAFACER-40) and 5.24 g of PGMEA, and 4.46 g of PGME, and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to form a solution of the composition under the modulator membrane.

[0217] [Example 4] In Synthesis Example 5, a resin solution (solid content 20.12% by mass) was obtained. 8.08g of this resin solution was added to 0.33g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.43g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.16g of PGMEA containing 1% by mass of surfactant (manufactured by DIC, MEGAFACER-40), 5.24g of PGMEA, and 3.76g of PGME, and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator lower membrane.

[0218] [Example 5] In Synthesis Example 6, a resin solution (solid content 17.85% by mass) was obtained. To this resin solution, 0.39g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20g of PGMEA containing 1% by mass MEGAFACER-40 (manufactured by DIC Co., Ltd.), 3.15g of PGMEA, and 2.41g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator membrane.

[0219] [Example 6] In Synthesis Example 7, a resin solution (solid content 16.62% by mass) was obtained. To this resin solution, 0.39g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20g of PGMEA containing 1% by mass MEGAFACER-40 (manufactured by DIC Co., Ltd.), 2.35g of PGMEA, and 2.41g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator lower membrane.

[0220] [Example 7] In Synthesis Example 8, a resin solution (solid content 18.61% by mass) was obtained. To this resin solution, 0.39g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20g of PGMEA containing 1% by mass MEGAFACER-40 (manufactured by DIC Co., Ltd.), 3.61g of PGMEA, and 2.41g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator membrane.

[0221] [Example 8] In Synthesis Example 9, a resin solution (solid content 16.88% by mass) was obtained. To this resin solution, 0.39g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20g of PGMEA containing 1% by mass MEGAFACER-40 (manufactured by DIC Co., Ltd.), 2.52g of PGMEA, and 2.41g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator membrane.

[0222] [Example 9] In Synthesis Example 10, a resin solution (solid content 18.06% by mass) was obtained. To this resin solution, 0.39g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.92g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.20g of PGMEA containing 1% by mass MEGAFACER-40 (manufactured by DIC Co., Ltd.), 3.28g of PGMEA, and 2.41g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator membrane.

[0223] [Example 10] In Synthesis Example 11, a resin solution (solid content 17.62% by mass) was obtained. To this resin solution, 0.49g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 1.44g of PGME containing 5% by mass of pyridinium p-hydroxybenzenesulfonate, 0.49g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Co., Ltd., MEGAFACER-40), 6.12g of PGMEA, and 2.64g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator lower membrane.

[0224] [Example 11] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. To this resin solution, 0.39g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 3.78g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.25g of PGMEA containing 1% by mass MEGAFACER-40 (manufactured by DIC Co., Ltd.), 2.66g of PGMEA, and 1.51g of PGME were added and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator lower membrane.

[0225] [Example 12] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. 0.26g of PGMEA, 2.37g of PGMEA, and 5.22g of PGME, each containing 1% by mass of surfactant (DIC (manufactured by DIC), MEGAFACER-40), were added to 12.15g of this resin solution and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator lower membrane.

[0226] [Example 13] In Synthesis Example 1, a resin solution (solid content 21.38% by mass) was obtained. 0.30g of PGMEA, 0.58g of PGMEA, and 5.10g of PGME, containing 1% by mass of surfactant (DIC (manufactured by DIC), MEGAFACER-40), were added to 14.02g of this resin solution and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator lower membrane.

[0227] [Example 14] In Synthesis Example 12, a resin solution (solid content 30.00% by mass) was obtained. 4.33g of this resin solution was added to 1.22g of the polymer solution (solid content 21.38% by mass) obtained in Synthesis Example 1, 1.95g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.13g of PGMEA containing 1% by mass of surfactant (manufactured by DIC, MEGAFACER-40), 10.63g of PGMEA, and 1.77g of PGME, and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulating inhibitor membrane.

[0228] [Comparative Example 1] In Comparative Synthesis Example 5, a resin solution (solid content 24.24% by mass) was obtained. 7.54g of this resin solution was added to 0.37g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 2.73g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.18g of PGMEA containing 1% by mass of surfactant (manufactured by DIC, MEGAFACER-40), 3.03g of PGMEA, and 1.14g of PGME, and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator membrane.

[0229] [Comparative Example 2] In Synthesis Example 12, a resin solution (solid content 30.00% by mass) was obtained. 4.33g of this resin solution was added to 0.26g of TMOM-BP (manufactured by Honshu Chemical Co., Ltd.), 1.95g of PGME containing 2% by mass K-PURE TAG2689 (manufactured by King Industries), 0.13g of PGMEA (manufactured by DIC, MEGAFACER-40) and 11.56g of PGMEA, and 1.77g of PGME, and dissolved. The solution was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1μm to form a solution of the composition under the modulator membrane.

[0230] (Polymer solubility test) Based on Synthetic Examples 2, 6, 7, and 11 and Comparative Synthetic Examples 1, 2, 3, and 4, during the synthesis, the dissolution of monomers and polymers in the reaction solvent was visually confirmed. Solutions without suspension were defined as good, and solutions with suspension were defined as poor. Furthermore, the polymers obtained in Synthetic Examples 2, 6, 7, and 11, and the polymers obtained in Comparative Synthetic Examples 1, 2, and 3, were dissolved in PGME or PGMEA with a solid content of 20% by mass. Then, according to the synthetic and comparative examples, ion exchange treatment was performed to determine the solubility of the polymers. Solutions without suspension after ion exchange treatment were defined as good, and solutions with suspension after ion exchange treatment were defined as poor. The results are shown in Table 1.

[0231]

[0232] By synthesizing polymers in PGME, which contains non-phenolic hydroxyl groups within the molecule, methoxypropoxy groups are introduced into the side chain. Therefore, compared to polymers synthesized in 1,4-dioxane, which does not contain non-phenolic hydroxyl groups within the molecule, polymers exhibit higher solubility after ion exchange compared to PGME or PGMEA. Furthermore, it is advantageous that polymers can be synthesized in PGME, a solvent commonly used in the semiconductor industry, instead of using highly hazardous solvents such as 1,4-dioxane, which are classified as hazardous industrial waste. Moreover, as shown in Synthesis Example 11 and Comparative Synthesis Example 4, when using highly polar monomers, low-polarity solvents such as 1,4-dioxane cannot dissolve the monomers, preventing polymerization. On the other hand, it is also advantageous that polymerization can be carried out using highly polar alcohol solvents such as PGME, resulting in materials with high solubility after ion exchange. Next, the properties of polymers and crosslinking agents having these alcohol-structured substitutes are evaluated.

[0233] (Dissolution test of inhibitor solvent) Solutions of the resist underlayer film formation compositions prepared in Comparative Examples 1-2 and Examples 1-14 were spin-coated onto silicon wafers and then fired at 240°C for 60 seconds or 350°C for 60 seconds on a hot plate to form resist underlayer films (film thickness 200 nm). These resist underlayer films were impregnated with a common diluent of PGME / PGMEA = 7 / 3 to confirm curability. Neither resist underlayer film was soluble in this diluent, confirming sufficient curability.

[0234] (Optical constant measurement) Solutions of the resist underlayer film formation compositions prepared in Comparative Example 1 and Examples 1-13 were spin-coated onto silicon wafers. The wafers were then fired at 240°C for 60 seconds or 350°C for 60 seconds on a hot plate to form resist underlayer films (50 nm thick). The refractive index (n-value) and optical absorption coefficient (also known as k-value or attenuation coefficient) at a wavelength of 193 nm were measured using a spectroelastic ellipsometry for these resist underlayer films. The results are shown in Table 2.

[0235]

[0236] As mentioned above, by changing the types of compounds involved in the reaction, the optical constant of the lower layer of the resist can be freely controlled.

[0237] [Determination of dry etching rate] The etching machine and etching gas system used in the measurement of dry etching rate are as follows. RIE-10NR (manufactured by SAMCO): CF4

[0238] The solutions of the resist underlayer film composition prepared in Comparative Example 1 and Examples 1-13 were spin-coated onto silicon wafers. The wafers were then heated on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form the resist underlayer film (200 nm thick). CF4 gas was used as the etching gas, and the dry etching rate was measured to determine the dry etching rate ratio between Comparative Example 1 and Examples 1-13. The dry etching rate ratio is the ratio of (resist underlayer film) / (KrF photoresist). The results are shown in Table 3.

[0239]

[0240] As mentioned above, by changing the types of compounds involved in the reaction, the etching resistance of the resist underlayer film can be freely controlled.

[0241] (Determination of sublimation content) The amount of sublimation was determined using the sublimation measuring apparatus described in International Publication No. 2007 / 111147. The resist underlayer film formation compositions prepared in Comparative Example 1 and Examples 1-13 were coated onto silicon wafers and fired at 240°C for 60 seconds or 350°C for 60 seconds, respectively. The amount of sublimation was measured when the film thickness was 200 nm. The results are shown in Table 4. Note that the values ​​recorded in the table are (sublimation amount of Examples 1-13) / (sublimation amount of Comparative Example 1).

[0242]

[0243] As mentioned above, by becoming a material with a cross-linked structure, the amount of sublimation in the composition of the lower layer film of the resist can be significantly reduced, thereby reducing concerns about device contamination.

[0244] (Embeddedness assessment) Embedding was confirmed in a densely patterned region with a SiO2 substrate of 200 nm thickness, a trench width of 50 nm, and a spacing of 100 nm. The resist underlayer film formation compositions modulated in Comparative Example 1 and Examples 1-13 were coated onto the above substrates and then fired 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 High-Technologies scanning electron microscope (S-4800) to confirm the presence or absence of filling of the resist underlayer film formation composition within the pattern. The results are shown in Table 5.

[0245]

[0246] Examples 1-13, using the same materials as before, exhibit high embeddability.

[0247] (Hardness test) The resist underlayer film formation compositions prepared in Comparative Example 1 and Examples 1-13 were respectively coated onto silicon wafers and then fired at 240°C for 60 seconds or 350°C for 60 seconds to form 200 nm resist underlayer films. The hardness of this resist-cured film was evaluated using a Bruker TI-980 triboidentor. Films with higher hardness than Comparative Example 1 were rated as 0. The results are shown in Table 6.

[0248]

[0249] As mentioned above, by becoming a material with a cross-linked structure in the polymer, the hardness of the resist underlayer film can be greatly improved.

[0250] (Bending resistance assessment) Solutions of the resist underlayer films prepared in Comparative Example 1 and Examples 1-13 were spin-coated onto silicon wafers coated with silicon oxide films. The resist underlayer films (200 nm thick) were formed by heating at 240°C for 60 seconds or 350°C for 60 seconds on a hot plate. A silicon hard mask composition solution was then coated onto the resist underlayer film and heated at 240°C for 1 minute to form a silicon hard mask layer (30 nm thick). A resist solution was then coated onto this mask and heated at 100°C for 1 minute to form a resist layer (150 nm thick). The mask was then exposed at a wavelength of 193 nm, followed by heating with PEB (at 105°C for 1 minute) and development to obtain the resist pattern. Then, using fluorine-based and oxygen-based gases, dry etching is performed to transfer the resist pattern onto a silicon wafer coated with a silicon oxide film. The individual pattern shapes are then observed using a CG-4100 manufactured by Hitachi High Technology Co., Ltd.

[0251] During the formation of resist patterns on the substrate to be processed through lithography and etching processes, irregular bending of the pattern can easily occur depending on its width. Specifically, when etching a substrate for etching purposes, the pattern formed under the resist layer used as a masking material, especially the pattern formed from an organic resin layer, may exhibit left-right bending. This makes it impossible to faithfully process the substrate based on the resulting condition. Therefore, the more difficult it is to produce bending, the more possible it is to process fine substrates. The results are shown in Table 7. The one with higher bending resistance compared to Comparative Example 1 is rated as 0.

[0252]

[0253] As the results described above show, the embodiments exhibit higher flexural toughness compared to the comparative examples.

[0254] [Evaluation as a crosslinking agent] (Determination of sublimation content in the lower layer of the inhibitor film) The amount of sublimation was determined using the sublimation measuring apparatus described in International Publication No. 2007 / 111147. The resist underlayer film formation compositions prepared in Comparative Example 2 and Example 14 were coated onto silicon wafers, and after firing at 240°C for 60 seconds, the amount of sublimation was measured at a film thickness of 200 nm. The results are shown in Table 8. Note that the values ​​recorded in the table are (sublimation amount of Example 14) / (sublimation amount of Comparative Example 2).

[0255]

[0256] As mentioned above, by becoming a polymer-type crosslinking agent, the amount of sublimation in the composition of the barrier film can be significantly reduced compared to previous crosslinking agents, thus reducing concerns about equipment contamination.

[0257] (Coating test on stepped substrate) As a coating test on a stepped substrate, the coating thickness was compared between the open region (OPEN) without a pattern and the densely patterned region (DENSE) with a trench width of 50 nm and a spacing of 100 nm on a 200 nm thick SiO2 substrate. The resist underlayer film formation composition prepared in Comparative Example 2 and Example 14 was coated onto the above substrate and then fired 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 High-Technologies scanning electron microscope (S-4800). The planarization was evaluated by measuring the difference in film thickness between the trench region (patterned area) and the open region (unpatterned area) of the stepped substrate (the coating step difference between the trench region and the open region, referred to as bias). Here, planarization refers to the small difference in film thickness (iso-dense bias) between the patterned areas (grooved regions (patterned areas)) and the unpatterned areas (open regions (unpatterned areas)). The results are shown in Table 9.

[0258]

[0259] As mentioned above, by introducing alcohol compounds into the side chains, the glass transition temperature or viscosity is reduced, thus significantly improving the planarization of the resist underlayer film composition. [Industrial Applicability]

[0260] According to the present invention, a novel resist underlayer film forming composition is provided that addresses the requirements of not using harmful chemicals in resin preparation, improving the solubility of PGME or PGMEA, reducing the amount of sublimation in contaminating devices, improving the planarization of the coating on stepped substrates, and increasing the hardness of the resulting resist underlayer film, while maintaining other good properties.

Claims

1. A resistive underlayer film forming composition comprising a polymer (X) and a solvent, wherein the polymer (X) comprises a plurality of identical or different structural units having ROCH2- groups other than methoxymethyl (R being a saturated or unsaturated straight-chain or branched C2-C20 aliphatic hydrocarbon group, C3-C20 alicyclic hydrocarbon group, hydrogen atom, or a mixture thereof that can be substituted by phenyl, naphthyl, or anthracene and interrupted by an oxygen atom or carbonyl group), and a linking group connecting the plurality of structural units, characterized in that at least one of the structural units is an aromatic ring having a phenolic hydroxyl group.

2. As in claim 1, the resistive lower film forming composition, wherein, Linking groups include alkyl, ether, or carbonyl groups.

3. As in claim 1 or 2, the resistive lower film forming composition, wherein, The building blocks include aromatic rings, heterocycles, or condensed rings that may have substituted or unsubstituted amine groups.

4. The resistive underlayer film forming composition of claim 1 or 2 further comprises a film material (Y) that can crosslink with polymer (X).

5. The resistive underlayer film forming composition as claimed in claim 1 or 2 further includes a crosslinking agent.

6. The resistive underlayer film forming composition as claimed in claim 1 or 2 further comprises an acid and / or an acid-generating agent.

7. The resistive underlayer film forming composition of claim 1 or 2 further includes a surfactant.

8. As in claim 1 or 2, the resistive lower film forming composition, wherein, The aforementioned solvent includes solvents with a boiling point of 160°C or higher.

9. A resistive underlayer film, characterized in that it is a sintered product of a coated film composed of any one of the components of claims 1 to 8.

10. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using any one of the components of claims 1 to 8; forming a resist film on the formed resist underlayer film; forming a resist pattern by irradiating and developing the formed resist film with light or an electron beam; etching the aforementioned resist underlayer film through the formed resist pattern and patterning it; and processing a semiconductor substrate through the patterned resist underlayer film.

11. A method for manufacturing a semiconductor device, comprising: forming a resist underlayer film on a semiconductor substrate using any one of the components of claims 1 to 8; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating and developing the formed resist film with light or an electron beam; etching the hard mask through the formed resist pattern and patterning it; etching the resist underlayer film through the patterned hard mask and patterning it; and processing a semiconductor substrate through the patterned resist underlayer film.

12. The method of manufacturing a semiconductor device as claimed in claim 10 or 11, wherein the step of forming a resist underlayer film is performed by nanoprinting.