Resist underlay film-forming composition using cyclic carbonyl compound

Abstract

To provide a resist underlay film-forming composition that shows high etching resistance, a good dry etching rate ratio and a good optical constant and that has good coatability for the so-called level difference substrate, shows little difference in film thickness after embedding, and can form a flat surface, and also to provide: a method for producing a polymer suitable for the resist underlay film-forming composition; a resist underlay film using the resist underlay film-forming composition; and a method for producing a semiconductor device.SOLUTION: A resist underlay film-forming composition comprises: a reaction product of a C6-60 aromatic compound (A) and a carbonyl group possessed by a C3-60 cyclic carbonyl compound (B); and a solvent. The reaction product has such a structure that one carbon atom of the cyclic carbonyl compound (B) has two aromatic compounds (A) bonded thereto.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist underlayer film-forming composition that exhibits high etching resistance, a good dry etching rate ratio and optical constants, has good coverage even on uneven substrates, has a small film thickness difference after filling, and is capable of forming a flat film; a method for producing a polymer suitable for the resist underlayer film-forming composition; a resist underlayer film using the resist underlayer film-forming composition; and a method for producing a semiconductor device. [Background technology]

[0002] In recent years, resist underlayer film materials for multilayer resist processes have been required to function as anti-reflective coatings, particularly for short-wavelength exposure, have appropriate optical constants, and also have etching resistance during substrate processing. For this reason, the use of polymers having repeating units containing benzene rings has been proposed (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2004-354554 Summary of the Invention [Problem to be solved by the invention]

[0004] To achieve thinner resist layers as resist patterns become finer, a lithography process is known in which at least two resist underlayer films are formed and used as a mask. This involves providing at least one organic film (underlayer organic film) and at least one inorganic underlayer film on a semiconductor substrate, patterning the inorganic underlayer film using a resist pattern formed on an upper resist film as a mask, and then patterning the lower organic film using the pattern as a mask. This method is said to be capable of forming patterns with high aspect ratios. Examples of materials for forming the at least two layers include combinations of organic resins (e.g., acrylic resins, novolac resins) and inorganic materials (e.g., silicon resins (e.g., organopolysiloxanes), inorganic silicon compounds (e.g., SiON, SiO2), etc.). Furthermore, in recent years, double patterning technology, which involves two lithography processes and two etching processes to obtain a single pattern, has been widely applied, with the above-mentioned multilayer process being used in each step. In this case, the organic film formed after the initial pattern is required to have the property of flattening steps.

[0005] However, there is a problem that the coating ability of the composition for forming a resist underlayer film is low for so-called uneven substrates in which the resist pattern formed on the substrate to be processed has differences in height or density, resulting in large differences in film thickness after filling, making it difficult to form a flat film.

[0006] The present invention has been made based on the solution to these problems, and an object of the present invention is to provide a resist underlayer film-forming composition that exhibits high etching resistance, a good dry etching rate ratio and optical constants, has good coverage even on so-called uneven substrates, has small film thickness differences after filling, and is capable of forming a flat film. Another object of the present invention is to provide a method for producing a polymer suitable for the resist underlayer film-forming composition, and a method for producing a resist underlayer film and a semiconductor device using the resist underlayer film-forming composition. [Means for solving the problem]

[0007] The present invention encompasses the following. [1] A reaction product of an aromatic compound (A) having 6 to 60 carbon atoms with a carbonyl group possessed by a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, and a solvent, the cyclic carbonyl compound (B) contains 5% by mass or more of heteroatoms, The reaction product has one carbon atom of the cyclic carbonyl compound (B) linking two of the aromatic compounds (A). A resist underlayer film-forming composition. [2] The resist underlayer film forming composition according to [1], wherein the cyclic carbonyl compound (B) has at least four heteroatoms in one molecule. [3] The cyclic carbonyl compound (B) is represented by the following formula (1): [ka] [In the formula, X is O, NH, or CH; Ring Y is a 3- to 8-membered ring which may have as a substituent a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group or a carbonyl group and which may be interrupted by an oxygen atom or a sulfur atom, a hydroxy group, an oxo group, a carboxy group, a cyano group, a nitro group, a sulfo group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an amino group, a glycidyl group, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and which may be interrupted by a heteroatom, or a linked ring or fused ring thereof. The resist underlayer film-forming composition according to [1] or [2], [4] A reaction product of an aromatic compound (A) having 6 to 60 carbon atoms with a carbonyl group of a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, and a solvent, The cyclic carbonyl compound (B) is represented by the following formula (1): [ka] [In the formula, X is CH2, Ring Y is a 3- to 8-membered ring which may have as a substituent a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group or a carbonyl group and which may be interrupted by an oxygen atom or a sulfur atom, a hydroxy group, an oxo group, a carboxy group, a cyano group, a nitro group, a sulfo group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an amino group, a glycidyl group, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, or a linked ring thereof. A resist underlayer film-forming composition. [5] The resist underlayer film-forming composition according to [4], wherein the reaction product comprises two of the aromatic compounds (A) linked via one carbon atom of the cyclic carbonyl compound (B). [6] The resist underlayer film forming composition according to any one of [3] to [5], wherein the cyclic carbonyl compound (B) is an alicyclic compound. [7] The resist underlayer film forming composition according to any one of [1] to [6], wherein the cyclic carbonyl compound (B) does not contain a benzene ring. [8] The resist underlayer film-forming composition according to any one of [1] to [7], wherein the compound (A) contains one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or combinations thereof. [9] The resist underlayer film-forming composition according to any one of [1] to [7], wherein the compound (A) contains two or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or a combination thereof.

[10] The resist underlayer film forming composition according to any one of [1] to [9], further comprising a crosslinking agent.

[11] The resist underlayer film forming composition according to any one of [1] to

[10] , further comprising an acid and / or an acid generator.

[12] The resist underlayer film forming composition according to any one of [1] to

[11] , wherein the boiling point of the solvent is 160° C. or higher.

[13] A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film-forming composition according to any one of [1] to

[12] .

[14] A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of [1] to

[12] ; forming a resist film thereon; forming a resist pattern by irradiating with light or an electron beam and developing; etching the underlayer film using the resist pattern; and processing a semiconductor substrate using the patterned underlayer film.

[15] A method for producing a polymer for a resist underlayer film-forming composition, comprising a step of reacting an aromatic compound (A) having 6 to 60 carbon atoms with a carbonyl group possessed by a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, The reaction product of the present invention is a method in which one carbon atom of the cyclic carbonyl compound (B) links two of the aromatic compounds (A).

[16] A method for producing a polymer for a resist underlayer film-forming composition, comprising a step of reacting an aromatic compound (A) having 6 to 60 carbon atoms with a carbonyl group possessed by a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, the cyclic carbonyl compound (B) contains 5% by mass or more of heteroatoms, The reaction product of the present invention is a method in which one carbon atom of the cyclic carbonyl compound (B) links two of the aromatic compounds (A). [Effects of the Invention]

[0008] The resist underlayer film-forming composition of the present invention not only has high etching resistance, a good dry etching rate ratio, and good optical constants, but also the resist underlayer film obtained has good coverage even on so-called uneven substrates, has a small film thickness difference after filling, forms a flat film, and achieves finer substrate processing. In particular, the resist underlayer film forming composition of the present invention is effective in a lithography process in which at least two resist underlayer films are formed to reduce the resist film thickness, and the resist underlayer film is used as an etching mask. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a diagram illustrating iso-dense bias. (ba) in FIG. 1 is the iso-dense bias. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Resist underlayer film-forming composition] The resist underlayer film-forming composition according to the present invention contains a reaction product of an aromatic compound (A) having 6 to 60 carbon atoms with a carbonyl group possessed by a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, a solvent, and other components, which will be explained in order below.

[0011] [Aromatic compounds (A) having 6 to 60 carbon atoms]

[0012] The aromatic compound (A) having 6 to 60 carbon atoms is (a) may be a monocyclic compound such as benzene, phenol, or phloroglucinol; (b) may be a condensed ring compound such as naphthalene or dihydroxynaphthalene; (c) may be a heterocyclic compound such as furan, thiophene, pyridine, or carbazole; (d) A compound in which the aromatic rings of (a) to (c) are bonded together by a single bond, such as biphenyl, phenylindole, 9,9-bis(4-hydroxyphenyl)fluorene, and α,α,α',α'-tetrakis(4-hydroxyphenyl)-p-xylene, (e) -CH-, -(CH2) such as phenylnaphthylamine n The aromatic rings (a) to (d) may be compounds in which the aromatic rings are linked with a spacer exemplified by -(n=1 to 20), -CH=CH-, -CH≡CH-, -N=N-, -NH-, -NHR-, -NHCO-, -NRCO-, -S-, -COO-, -O-, -CO- and -CH=N-.

[0013] Examples of aromatic compounds include benzene, thiophene, furan, pyridine, pyrimidine, pyrazine, pyrrole, oxazole, thiazole, imidazole, naphthalene, anthracene, quinoline, carbazole, quinazoline, purine, indolizine, benzothiophene, benzofuran, indole, phenylindole, and acridine.

[0014] The aromatic compound (A) may be an aromatic compound containing an amino group, a hydroxyl group, or both, or an arylamine compound, a phenol compound, or both. Aromatic amines or phenolic hydroxy group-containing compounds are preferred. Examples of aromatic amines include aniline, diphenylamine, phenylnaphthylamine, hydroxydiphenylamine, phenylnaphthylamine, N,N'-diphenylethylenediamine, and N,N'-diphenyl-1,4-phenylenediamine. Examples of the phenolic hydroxy group-containing compound include phenol, dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, and polynuclear phenols.

[0015] Examples of the polynuclear phenol include dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 2,2'-biphenol, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane.

[0016] The hydrogen atoms of the aromatic compound (A) having 6 to 60 carbon atoms may be substituted with an alkyl group, a fused ring group, a heterocyclic group, a hydroxy group, an amino group, a nitro group, an ether group, an alkoxy group, a cyano group, or a carboxyl group having 1 to 20 carbon atoms.

[0017] Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups that may or may not have a substituent, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, cyclohexyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, p-tert-butylcyclohexyl group, n-decyl group, n-dodecylnonyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. Preferably, it is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0018] Examples of alkyl groups having 1 to 20 carbon atoms interrupted by an oxygen atom, a sulfur atom, or an amide bond include those containing the structural unit -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. The -O-, -S-, -NHCO-, or -CONH- may be present in one unit or in two or more units in the alkyl group. Specific examples of alkyl groups having 1 to 20 carbon atoms interrupted by -O-, -S-, -NHCO-, or -CONH- units include methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butyl ... and the like, and further, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl groups, each of which is substituted with a methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, or the like. Preferred are methoxy, ethoxy, methylthio, and ethylthio groups, and more preferred are methoxy and ethoxy groups.

[0019] The fused ring group is a substituent derived from a fused ring compound, and specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a naphthacenyl group, a triphenylenyl group, a pyrenyl group, and a chrysenyl group. Of these, a phenyl group, a naphthyl group, an anthracenyl group, and a pyrenyl group are preferred.

[0020] The heterocyclic group is a substituent derived from a heterocyclic compound, and specific examples thereof include a thiophene group, a furan group, a pyridine group, a pyrimidine group, a pyrazine group, a pyrrole group, an oxazole group, a thiazole group, an imidazole group, a quinoline group, a carbazole group, a quinazoline group, a purine group, an indolizine group, a benzothiophene group, a benzofuran group, an indole group, an acridine group, an isoindole group, a benzimidazole group, an isoquinoline group, a quinoxaline group, a cinnoline group, a pteridine group, a chromene group (benzopyran group), an isochromene group (benzopyran group), a xanthene group, Examples of such groups include a thiazole group, a pyrazole group, an imidazoline group, and an azine group. Among these, a thiophene group, a furan group, a pyridine group, a pyrimidine group, a pyrazine group, a pyrrole group, an oxazole group, a thiazole group, an imidazole group, a quinoline group, a carbazole group, a quinazoline group, a purine group, an indolizine group, a benzothiophene group, a benzofuran group, an indole group, and an acridine group are preferred, and a thiophene group, a furan group, a pyridine group, a pyrimidine group, a pyrrole group, an oxazole group, a thiazole group, an imidazole group, and a carbazole group are most preferred.

[0021] The above aromatic compounds may be linked together via a single bond or a spacer. Examples of spacers are -CH-, -(CH2) n Examples include one or a combination of two or more of -(n=1 to 20), -CH=CH-, -CH≡CH-, -N=N-, -NH-, -NHR-, -NHCO-, -NRCO-, -S-, -COO-, -O-, -CO- and -CH=N-. Two or more of these spacers may be linked together.

[0022] The aromatic compound (A) preferably contains one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or a combination thereof, and more preferably contains two or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or a combination thereof.

[0023] The aromatic compound (A) may be one or two or more types, but is preferably one or two types.

[0024] [Cyclic carbonyl compounds (B) having 3 to 60 carbon atoms] The cyclic carbonyl compound (B) having 3 to 60 carbon atoms is one in which one carbon atom of the cyclic carbonyl compound (B) connects two of the aromatic compounds (A) described above.

[0025] The cyclic carbonyl compound (B) preferably contains 5% by mass or more of heteroatoms, more preferably 10% by mass or more of heteroatoms, and preferably does not contain a benzene ring.

[0026] Examples of heteroatoms include nitrogen, oxygen, sulfur, phosphorus, and halogens. The cyclic carbonyl compound (B) preferably has at least one heteroatom per molecule. Preferably, it has at least two heteroatoms per molecule. Preferably, it has at least three heteroatoms per molecule. Preferably, it has at least four heteroatoms per molecule.

[0027] Preferably, the cyclic carbonyl compound (B) is represented by the following formula (1): [ka] [In the formula, X is O, NH, or CH; Ring Y is a 3- to 8-membered ring which may have as a substituent a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group or a carbonyl group and which may be interrupted by an oxygen atom or a sulfur atom, a hydroxy group, an oxo group, a carboxy group, a cyano group, a nitro group, a sulfo group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an amino group, a glycidyl group, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and which may be interrupted by a heteroatom, or a linked ring or fused ring thereof. It is shown as follows.

[0028] The alkyl group having 1 to 20 carbon atoms is as described above. Examples of the acyl group having 1 to 6 carbon atoms include a formyl group and an acetyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, etc. Examples of the alkoxycarbonyl group having 1 to 6 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, etc. Examples of aryl groups having 6 to 20 carbon atoms include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-methoxyphenyl, p-methoxyphenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and fluorene. Examples of alkenyl groups having 2 to 10 carbon atoms include vinyl and allyl. Examples of alkynyl groups having 2 to 10 carbon atoms include ethynyl. The heteroatoms, ring compounds, connecting rings, and fused rings are as described above.

[0029] The cyclic carbonyl compound (B) is preferably an alicyclic compound. The cyclic carbonyl compound (B) may be one or more types, preferably one or two types.

[0030] Particularly preferred examples of the cyclic carbonyl compound (B) include dehydrocholic acid, cortisone acetate, gluconolactone, camphorsulfonic acid, araboascorbic acid, isocyanuric acid and its derivatives (e.g., diallyl isocyanurate, monoallyl isocyanurate, mono-n-butyl isocyanurate), tricyclo[5.2.1.0] 2,6 ] decan-8-one, bicyclohexane-4,4'-dione monoethylene ketal, 1,4-cyclohexanedione monoethylene ketal, 2-adamantanone, cyclohexanone, 2-cyclopentyl cyclopentanone, and 2-cyclohexyl cyclohexanone.

[0031] [Reaction products] By reacting the aromatic compound (A) with the carbonyl group of the cyclic carbonyl compound (B), a reaction product (polymer) can be obtained in which one carbon atom of the cyclic carbonyl compound (B) links two of the aromatic compounds (A).

[0032] Examples of the acid catalyst used in the reaction include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, and methanesulfonic acid; and carboxylic acids such as formic acid and oxalic acid. The amount of the acid catalyst used varies depending on the type of acid used. The amount is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.1 to 100 parts by mass, per 100 parts by mass of the aromatic compound (A).

[0033] The above condensation and addition reactions can be carried out without solvent, but are usually carried out using a solvent. Any solvent that does not inhibit the reaction can be used. Examples of solvents include ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, and dioxane. The reaction temperature is usually 40° C. to 200° C. The reaction time varies depending on the reaction temperature, but is usually about 30 minutes to 50 hours. The weight average molecular weight Mw of the polymer obtained as described above is usually 500 to 1,000,000, or 600 to 500,000.

[0034] The reaction products suitable for use in the present invention will be described in the examples.

[0035] [solvent]

[0033] The solvent for the resist underlayer film-forming composition of the present invention is not particularly limited, as long as it can dissolve the reaction product. In particular, since the resist underlayer film-forming composition of the present invention is used in the form of a homogeneous solution, it is recommended to use a solvent that is generally used in lithography processes in combination with the composition, taking into consideration its coating performance.

[0036] Examples of such solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate,Butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl Examples of suitable solvents include 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

[0037] In addition, the following compound described in Japanese Patent Application No. 2017-140193 can also be used. [ka] (R in formula (i) 1 , R 2 and R 3 each represents a hydrogen atom, an oxygen atom, a sulfur atom, or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and may be the same or different and may be bonded to each other to form a ring structure.

[0038] Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups that may or may not have a substituent, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, cyclohexyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, p-tert-butylcyclohexyl group, n-decyl group, n-dodecylnonyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. Preferably, it is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0039] Examples of alkyl groups having 1 to 20 carbon atoms interrupted by an oxygen atom, a sulfur atom, or an amide bond include those containing the structural unit -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. The -O-, -S-, -NHCO-, or -CONH- may be present in one unit or in two or more units in the alkyl group. Specific examples of alkyl groups having 1 to 20 carbon atoms interrupted by -O-, -S-, -NHCO-, or -CONH- units include methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butyl ... and the like, and further, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl groups, each of which is substituted with a methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, or the like. Preferred are methoxy, ethoxy, methylthio, and ethylthio groups, and more preferred are methoxy and ethoxy groups.

[0040] These solvents have a relatively high boiling point, and are therefore effective in imparting high embedding properties and high planarization properties to the resist underlayer film-forming composition.

[0041] Specific examples of preferred compounds represented by formula (i) are shown below. [ka]

[0042] Among the above, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylisobutyramide, and The following formula: [ka] Compounds represented by the formula (i) are preferably 3-methoxy-N,N-dimethylpropionamide and N,N-dimethylisobutyramide.

[0043] These solvents can be used alone or in combination. Among these solvents, those with a boiling point of 160°C or higher are preferred, including propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylisobutyramide, 2,5-dimethylhexane-1,6-diyl diacetate (DAH; cas. 89182-68-3), and 1,6-diacetoxyhexane (cas. 6222-17-9). Particularly preferred are propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutyramide.

[0044] [Crosslinking agent component] The resist underlayer film-forming composition of the present invention may contain a crosslinker component. Examples of such crosslinkers include melamine-based crosslinkers, substituted urea-based crosslinkers, and polymers thereof. A crosslinker having at least two crosslink-forming substituents is preferred, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. Condensates of these compounds may also be used.

[0045] In addition, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As a crosslinking agent having high heat resistance, a compound containing a crosslink-forming substituent having an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule can be preferably used.

[0046] This compound may be a compound having a partial structure of the following formula (4), or a polymer or oligomer having a repeating unit of the following formula (5). [ka] Above R 11 , R 12 , R 13 , and R 14 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl groups mentioned above can be used.

[0047] Examples of the compounds, polymers and oligomers of formula (4) and formula (5) are shown below. [ka] [ka]

[0048] The above compounds are available as products of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (4-24) is available from Asahi Organic Chemicals Co., Ltd. under the trade name TM-BIP-A. The amount of crosslinking agent added varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80 mass % of the total solids content, preferably 0.01 to 50 mass %, and more preferably 0.05 to 40 mass %. These crosslinking agents may undergo a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the above-mentioned reaction product of the present invention, they can undergo a crosslinking reaction with these crosslinkable substituents.

[0049] [Acid and / or Acid Generator] The resist underlayer film forming composition of the present invention may contain an acid and / or an acid generator. Examples of the acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid. The amount of the acid to be used is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total solid content.

[0050] Examples of the acid generator include a thermal acid generator and a photoacid generator. Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters.

[0051] Photoacid generators generate acid when the resist is exposed to light. This allows the acidity of the underlayer film to be adjusted. This is one way to match the acidity of the underlayer film to that of the upper layer resist. Adjusting the acidity of the underlayer film also allows for adjustment of the pattern shape of the upper layer resist. Examples of the photoacid generator contained in the resist underlayer film-forming composition of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0052] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0053] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0054] 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.

[0055] The acid generators may be used singly or in combination of two or more. When an acid generator is used, the proportion thereof is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.5 to 1 part by mass, relative to 100 parts by mass of the solid content of the resist underlayer film-forming composition.

[0056] [Other ingredients] The resist undercoat forming composition of the present invention may contain a surfactant to further improve coating properties against surface irregularities without generating pinholes or striations. Examples of the surfactant 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 octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitan monolaurate; polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitan monostearate; polyoxyethylene sorbitan monooleate; polyoxyethylene sorbitan trioleate; polyoxyethylene sorbitan monolaurate; polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitan monoole ... Examples of suitable surfactants include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-containing surfactants such as F-TOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-40, R-40N, and R-40LM (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film material. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass, based on 100 parts by mass of the solid content of the resist underlayer film-forming composition.

[0057] The resist underlayer film-forming composition of the present invention may contain a light absorber, a rheology modifier, an adhesion promoter, etc. The rheology modifier is effective in improving the fluidity of the underlayer film-forming composition. The adhesion promoter is effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

[0058] Examples of the light-absorbing agent include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; CI Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI Disperse Violet 43; CI Disperse Blue 96; and CI Fluorescent Brightening Agent. Suitable examples of the light absorbent that can be used include CI Solvent Orange 2 and 45, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pigment Green 10, and CI Pigment Brown 2. The light absorbent is typically blended in an amount of 10% by mass or less, and preferably 5% by mass or less, based on the total solid content of the resist undercoat-forming composition.

[0059] Rheology modifiers are added primarily to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically added in an amount of less than 30% by mass based on the total solids content of the resist underlayer film-forming composition.

[0060] The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the resist underlayer film-forming composition, and particularly to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; methyloltrimethylsilane; and methyloltrimethylsilane. Examples of suitable adhesion promoters include silanes such as chlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesion promoters are typically blended in an amount of less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the resist undercoat-forming composition.

[0061] The solids content of the resist underlayer film-forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solids content is the content of all components of the resist underlayer film-forming composition excluding the solvent. The proportion of the reaction product in the solids content is preferably 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass, in that order.

[0062] One measure for evaluating whether a resist underlayer film-forming composition is in a uniform solution state is to observe its passability through a specific microfilter. The resist underlayer film-forming composition of the present invention passes through a microfilter with a pore size of 0.1 μm and exhibits a uniform solution state.

[0063] Examples of the microfilter material include fluorine-based resins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, with PTFE (polytetrafluoroethylene) being preferred.

[0064] [Method of manufacturing resist underlayer film and semiconductor device] Hereinafter, a method for producing a resist underlayer film and a semiconductor device using the resist underlayer film-forming composition according to the present invention will be described.

[0065] The resist underlayer film-forming composition of the present invention is applied to a substrate used in the manufacture of a semiconductor device (e.g., a silicon wafer substrate, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, or a low-dielectric-constant material (low-k material)-coated substrate, etc.) by a suitable application method such as a spinner or coater, and then baked to form a resist underlayer film. Baking conditions are appropriately selected from a baking temperature of 80°C to 250°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 150°C to 250°C and the baking time is 0.5 to 2 minutes. The thickness of the underlayer film formed here is, for example, 10 to 1000 nm, or 20 to 500 nm, or 30 to 300 nm, or 50 to 200 nm.

[0066] Furthermore, an inorganic resist underlayer film (hard mask) can be formed on the organic resist underlayer film according to the present invention. For example, a silicon-containing resist underlayer film (inorganic resist underlayer film)-forming composition described in WO2009 / 104552A1 can be formed by spin coating, or a Si-based inorganic material film can be formed by a CVD method or the like.

[0067] Furthermore, by applying the resist underlayer film-forming composition according to the present invention to a semiconductor substrate having a portion with a step and a portion without a step (a so-called stepped substrate) and baking it, a resist underlayer film can be formed in which the step between the portion with a step and the portion without a step is in the range of 3 to 50 nm.

[0068] A resist film, such as a photoresist layer, is then formed on the resist underlayer film. The photoresist layer can be formed by a well-known method, i.e., by coating a photoresist composition solution on the underlayer film and baking it. The photoresist film thickness is, for example, 50 to 10,000 nm, or 100 to 2,000 nm, or 200 to 1,000 nm.

[0069] The photoresist formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. Examples include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; and chemically amplified photoresists composed of a binder having a group that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, a low-molecular-weight compound that decomposes in the presence of acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator. Examples include APEX-E (trade name) manufactured by Shipley Chemical Co., Ltd., PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Further examples include fluorine-containing polymer photoresists such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0070] Next, a resist pattern is formed by irradiation with light or electron beams and development. First, exposure is performed through a predetermined mask. Near ultraviolet, far ultraviolet, or extreme ultraviolet (e.g., EUV (wavelength 13.5 nm)) is used for exposure. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 excimer laser (wavelength 157 nm) can be used. Among these, ArF excimer laser (wavelength 193 nm) and EUV (wavelength 13.5 nm) are preferred. After exposure, post-exposure bake can also be performed as needed. The post-exposure bake is performed under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 to 10 minutes.

[0071] In addition, in the present invention, a resist for electron beam lithography can be used instead of a photoresist. Either a negative or positive type electron beam resist can be used. Examples of such resists include chemically amplified resists consisting of an acid generator and a binder having a group that decomposes in the presence of acid to change the alkaline dissolution rate; chemically amplified resists consisting of an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes in the presence of acid to change the alkaline dissolution rate of the resist; chemically amplified resists consisting of an acid generator, a binder having a group that decomposes in the presence of acid to change the alkaline dissolution rate, and a low-molecular-weight compound that decomposes in the presence of acid to change the alkaline dissolution rate of the resist; non-chemically amplified resists consisting of a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate; and non-chemically amplified resists consisting of a binder having a moiety that is cleaved by an electron beam to change the alkaline dissolution rate. When using these electron beam resists, resist patterns can be formed in the same manner as when using a photoresist using an electron beam as the irradiation source.

[0072] Next, development is carried out with a developer, whereby, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed, and a photoresist pattern is formed. Examples of the developer include aqueous alkaline solutions such as aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0073] Then, the inorganic lower layer film (middle layer) is removed using the photoresist (upper layer) pattern thus formed as a protective film, and then the organic lower layer film (lower layer) is removed using the film consisting of the patterned photoresist and inorganic lower layer film (middle layer) as a protective film. Finally, the semiconductor substrate is processed using the patterned inorganic lower layer film (middle layer) and organic lower layer film (lower layer) as protective films.

[0074] First, the inorganic underlayer film (intermediate layer) in the area where the photoresist was removed is removed by dry etching to expose the semiconductor substrate. Gases such as tetrafluoromethane (CF), perfluorocyclobutane (C), perfluoropropane (C), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used for dry etching of the inorganic underlayer film. A halogen-based gas is preferably used for dry etching of the inorganic underlayer film, and a fluorine-based gas is more preferred. Examples of fluorine-based gases include tetrafluoromethane (CF), perfluorocyclobutane (C), perfluoropropane (C), trifluoromethane, and difluoromethane (CH).

[0075] Thereafter, the organic underlayer film is removed using the patterned photoresist and inorganic underlayer film as a protective film. The organic underlayer film (underlayer) is preferably removed by dry etching using an oxygen-based gas. This is because inorganic underlayer films containing a large amount of silicon atoms are difficult to remove by dry etching using an oxygen-based gas.

[0076] Finally, the semiconductor substrate is processed, preferably by dry etching using a fluorine-based gas. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0077] Furthermore, an organic antireflective coating can be formed on the resist underlayer coating before the formation of the photoresist. The antireflective coating composition used therein is not particularly limited, and any one can be selected from those conventionally used in lithography processes. The antireflective coating can be formed by a conventional method, such as coating with a spinner or coater and baking.

[0078] In the present invention, an organic underlayer film is formed on a substrate, and then an inorganic underlayer film is formed thereon, and a photoresist is then coated on top of that. This narrows the pattern width of the photoresist, and even if a thin layer of photoresist is applied to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, a fluorine-based gas that has a sufficiently high etching rate for the photoresist can be used as an etching gas to process the resist underlayer film, and a fluorine-based gas that has a sufficiently high etching rate for the inorganic underlayer film can be used as an etching gas to process the substrate, and an oxygen-based gas that has a sufficiently high etching rate for the organic underlayer film can be used as an etching gas to process the substrate.

[0079] The resist underlayer film formed from the resist underlayer film-forming composition may also absorb light depending on the wavelength of the light used in the lithography process. In such cases, it can function as an antireflective film that prevents light from being reflected from the substrate. Furthermore, the underlayer film formed from the resist underlayer film-forming composition of the present invention can also function as a hard mask. The underlayer film of the present invention can also be used as a layer for preventing interaction between the substrate and the photoresist, a layer having the function of preventing adverse effects on the substrate of materials used in the photoresist or substances generated during exposure of the photoresist, a layer having the function of preventing diffusion of substances generated from the substrate during heating and baking into an upper photoresist layer, and a barrier layer for reducing the poisoning effect of the photoresist layer due to a dielectric layer of the semiconductor substrate.

[0080] In addition, an underlayer film formed from the resist underlayer film-forming composition can be applied to a substrate having via holes formed therein for use in a dual damascene process, and can be used as a filling material capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the surface of an uneven semiconductor substrate. [Example]

[0081] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used to measure the weight-average molecular weight of the polymers obtained in the following synthesis examples is shown below. Apparatus: Tosoh Corporation HLC-8320GPC GPC column: Shodex (registered trademark) Asahipak (registered trademark) (Showa Denko K.K.) Column temperature: 40℃ Flow rate: 0.6mL / min Eluent: N,N-dimethylformamide (DMF) Standard sample: Polystyrene (Tosoh Corporation)

[0082] <Synthesis Example 1> A 100 mL two-neck flask was charged with 5.94 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 7.00 g of TEP-TPA (α,α,α',α'-tetrakis(4-hydroxyphenyl)-p-xylene, Asahi Organic Chemicals Co., Ltd.), 15.07 g of propylene glycol monomethyl ether, 2.13 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.18 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 16 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate the polymer. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-1). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 96,600. [ka]

[0083] <Synthesis Example 2> A 100 mL two-neck flask was charged with 9.57 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 3.00 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.), 16.00 g of propylene glycol monomethyl ether, 3.43 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.89 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 36 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-2). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,300. [ka]

[0084] <Synthesis Example 3> A 100 mL two-neck flask was charged with 10.42 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 5.00 g of 2-phenylindole (Tokyo Chemical Industry Co., Ltd.), 19.14 g of propylene glycol monomethyl ether, 3.73 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.06 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 15 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-3). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,250. [ka]

[0085] <Synthesis Example 4> A 100 mL two-neck flask was charged with 12.84 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 7.00 g of N-phenyl-1-naphthylamine (Tokyo Chemical Industry Co., Ltd.), 24.44 g of propylene glycol monomethyl ether, 4.60 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.54 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 15 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-4). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,260. [ka]

[0086] <Synthesis Example 5> A 100 mL two-neck flask was charged with 8.04 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 7.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 17.92 g of propylene glycol monomethyl ether, 2.88 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.59 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 26 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-5). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,000. [ka]

[0087] <Synthesis Example 6> A 100 mL two-neck flask was charged with 12.57 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 5.00 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 22.07 g of propylene glycol monomethyl ether, 4.50 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.49 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 15 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-6). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,690. [ka]

[0088] <Synthesis Example 7> A 100 mL two-neck flask was charged with 12.04 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 5.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 21.35 g of propylene glycol monomethyl ether, 4.31 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.38 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 15 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-7). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,000. [ka]

[0089] <Synthesis Example 8> A 100 mL two-neck flask was charged with 5.09 g of cortisone acetate (Tokyo Chemical Industry Co., Ltd.), 6.00 g of TEP-TPA (Asahi Organic Chemicals Co., Ltd.), 12.31 g of propylene glycol monomethyl ether, 1.22 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.67 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 16 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-8). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,000. [ka]

[0090] <Synthesis Example 9> A 100 mL two-neck flask was charged with 2.25 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 6.00 g of TEP-TPA (Asahi Organic Chemicals Co., Ltd.), 9.47 g of propylene glycol monomethyl ether, 1.22 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.67 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 16 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-9). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 347,200. [ka]

[0091] <Synthesis Example 10> A 100 mL two-neck flask was charged with 8.47 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 6.00 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.), 16.00 g of propylene glycol monomethyl ether, 4.57 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.52 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 36 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-10). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,300. [ka]

[0092] <Synthesis Example 11> A 100 mL two-neck flask was charged with 8.29 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 9.00 g of 2-phenylindole (Tokyo Chemical Industry Co., Ltd.), 21.77 g of propylene glycol monomethyl ether, 4.48 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.47 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-11). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,600. [ka]

[0093] <Synthesis Example 12> A 100 mL two-neck flask was charged with 7.31 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 9.00 g of N-phenyl-1-naphthylamine (Tokyo Chemical Industry Co., Ltd.), 20.25 g of propylene glycol monomethyl ether, 3.94 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.18 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-12). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,100. [ka]

[0094] <Synthesis Example 13> A 100 mL two-neck flask was charged with 4.57 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 9.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 16.04 g of propylene glycol monomethyl ether, 2.47 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.36 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-13). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,000. [ka]

[0095] <Synthesis Example 14> A 100 mL two-neck flask was charged with 7.78 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 7.00 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 18.98 g of propylene glycol monomethyl ether, 4.20 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.32 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-14). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,050. [ka]

[0096] <Synthesis Example 15> A 100 mL two-neck flask was charged with 8.53 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 8.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 21.13 g of propylene glycol monomethyl ether, 4.60 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.54 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 10 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-15). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,300. [ka]

[0097] <Synthesis Example 16> A 100 mL two-neck flask was charged with 4.89 g of (+)-10-camphorsulfonic acid (Tokyo Chemical Industry Co., Ltd.), 10.00 g of TEP-TPA (Asahi Organic Chemicals Co., Ltd.), 16.92 g of propylene glycol monomethyl ether, 2.03 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.12 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 15 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-16). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 18,700. [ka]

[0098] <Synthesis Example 17> A 100 mL two-neck flask was charged with 9.20 g of (+)-10-camphorsulfonic acid (Tokyo Chemical Industry Co., Ltd.), 5.00 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.), 18.01 g of propylene glycol monomethyl ether, 3.81 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.10 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 10 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-17). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,400. [ka]

[0099] <Synthesis Example 18> A 100 mL two-neck flask was charged with 4.08 g of D-glucurono-6,3-lactone (Tokyo Chemical Industry Co., Ltd.), 11.00 g of TEP-TPA (Asahi Organic Chemicals Co., Ltd.), 17.31 g of propylene glycol monomethyl ether, 2.23 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.23 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 10 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-18). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 6,700. [ka]

[0100] <Synthesis Example 19> A 100 mL two-neck flask was charged with 4.08 g of D-araboascorbic acid (Tokyo Chemical Industry Co., Ltd.), 11.00 g of TEP-TPA (Asahi Organic Chemicals Co., Ltd.), 17.31 g of propylene glycol monomethyl ether, 2.23 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.23 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 16 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-19). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 12,600. [ka]

[0101] <Synthesis Example 20> A 100 mL two-neck flask was charged with 9.07 g of D-araboascorbic acid (Tokyo Chemical Industry Co., Ltd.), 6.50 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.), 20.53 g of propylene glycol monomethyl ether, 4.95 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.74 g of 3-mercaptopropionic acid. The mixture was then heated to 140°C and refluxed with stirring for approximately 0.5 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-20). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,740. [ka]

[0102] <Synthesis Example 21> A 100 mL two-neck flask was charged with 5.29 g of DA-ICA (diallyl isocyanurate, manufactured by Shikoku Chemical Industries Co., Ltd.), 12.00 g of TEP-TPA (manufactured by Asahi Organic Chemicals Co., Ltd.), 16.75 g of propylene glycol monomethyl ether, 4.19 g of N-methylpyrrolidone, 3.65 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Inc.), and 2.01 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 43 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate the precipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-21). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 9,050. [ka]

[0103] <Synthesis Example 22> A 100 mL two-neck flask was charged with 4.28 g of MA-ICA (monoallyl isocyanurate, manufactured by Shikoku Chemical Industries Co., Ltd.), 12.00 g of TEP-TPA (manufactured by Asahi Organic Chemicals Co., Ltd.), 14.97 g of propylene glycol monomethyl ether, 3.74 g of N-methylpyrrolidone, 2.43 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Inc.), and 1.34 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 43 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate the precipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-22). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,500. [ka]

[0104] <Synthesis Example 23> A 100 mL two-neck flask was charged with 4.68 g of MB-ICA (mono-n-butyl isocyanurate, Kobe Natural Products Chemicals Co., Ltd.), 12.00 g of TEP-TPA (Asahi Organic Chemicals Co., Ltd.), 16.27 g of propylene glycol monomethyl ether, 4.07 g of N-methylpyrrolidone, 3.65 g of methanesulfonic acid (Kanto Chemical Co., Ltd.), and 2.01 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 43 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-23). ​​The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 22,100. [ka]

[0105] <Synthesis Example 24> A 100 mL two-neck flask was charged with 11.61 g of DA-ICA (diallyl isocyanurate, manufactured by Shikoku Chemical Industry Co., Ltd.), 7.00 g of phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.29 g of propylene glycol monomethyl ether, 5.32 g of N-methylpyrrolidone, 4.19 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Ltd.), 8.00 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4.42 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 100 hours. After completion of the reaction, the solution was added dropwise to a methanol / water solution to reprecipitate the precipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-24). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,090. [ka]

[0106] <Synthesis Example 25> A 100 mL two-neck flask was charged with 8.66 g of DA-ICA (diallyl isocyanurate, Shikoku Chemical Industry Co., Ltd.), 8.00 g of 2-phenylindole (Tokyo Chemical Industry Co., Ltd.), 18.10 g of propylene glycol monomethyl ether, 4.53 g of N-methylpyrrolidone, 5.97 g of methanesulfonic acid (Kanto Chemical Co., Ltd.), 3.30 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 2.06 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 59 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-25). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,000. [ka]

[0107] <Synthesis Example 26> A 100 mL two-neck flask was charged with 8.59 g of DA-ICA (diallyl isocyanurate, manufactured by Shikoku Chemical Industry Co., Ltd.), 9.00 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 18.80 g of propylene glycol monomethyl ether, 4.70 g of N-methylpyrrolidone, 4.19 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Ltd.), 5.97 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 3.27 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 59 hours. After completion of the reaction, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-26). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 770. [ka]

[0108] <Synthesis Example 27> A 100 mL two-neck flask was charged with 5.97 g of DA-ICA (diallyl isocyanurate, manufactured by Shikoku Chemical Industry Co., Ltd.), 10.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 16.07 g of propylene glycol monomethyl ether, 4.02 g of N-methylpyrrolidone, 4.11 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Inc.), and 2.27 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 59 hours. After completion of the reaction, the solution was added dropwise to a methanol / water solution to reprecipitate the precipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-27). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,780. [ka]

[0109] <Synthesis Example 28> A 100 mL two-neck flask was charged with 10.45 g of DA-ICA (diallyl isocyanurate, manufactured by Shikoku Chemical Industries Co., Ltd.), 8.00 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.52 g of propylene glycol monomethyl ether, 5.13 g of N-methylpyrrolidone, 7.20 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Inc.), and 3.98 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 59 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate the precipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-28). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,300. [ka]

[0110] <Synthesis Example 29> A 100 mL two-neck flask was charged with 8.76 g of DA-ICA (diallyl isocyanurate, manufactured by Shikoku Chemical Industries Co., Ltd.), 7.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.44 g of propylene glycol monomethyl ether, 4.36 g of N-methylpyrrolidone, 6.04 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Inc.), and 3.34 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 44 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate the precipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-29). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,700. [ka]

[0111] <Synthesis Example 30> A 100 mL two-neck flask was charged with 8.09 g of MA-ICA (monoallyl isocyanurate, manufactured by Shikoku Chemical Industries Co., Ltd.), 8.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 16.55 g of propylene glycol monomethyl ether, 4.14 g of N-methylpyrrolidone, 4.60 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Inc.), and 2.54 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 44 hours. After completion of the reaction, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-30). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,100. [ka]

[0112] <Synthesis Example 31> A 100 mL two-neck flask was charged with 8.85 g of MB-ICA (mono-n-butyl isocyanurate, manufactured by Kobe Natural Products Chemical Co., Ltd.), 8.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 19.00 g of propylene glycol monomethyl ether, 4.75 g of N-methylpyrrolidone, 6.90 g of methanesulfonic acid (manufactured by Kanto Chemical Co., Ltd.), and 3.81 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 44 hours. After completion of the reaction, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-31). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,900. [ka]

[0113] <Synthesis Example 32> A 100 mL two-neck flask was charged with 12.00 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 2.49 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 5.22 g of 9,9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 22.47 g of propylene glycol monomethyl ether acetate, 0.86 g of methanesulfonic acid (Kanto Chemical Co., Ltd.), and 1.90 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 12 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-32). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,200. [ka]

[0114] <Synthesis Example 33> A 100 mL two-neck flask was charged with 8.42 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 4.38 g of DA-ICA (Shikoku Chemical Industry Co., Ltd.), 7.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 24.39 g of propylene glycol monomethyl ether, 6.10 g of N-methylpyrrolidone, 4.02 g of methanesulfonic acid (Kanto Chemical Co., Ltd.), and 6.67 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-33). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,000. [ka]

[0115] <Synthesis Example 34> A 100 mL two-neck flask was charged with 9.02 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 7.50 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 4.00 g of D-(+)-glucono-1,5-lactone (Tokyo Chemical Industry Co., Ltd.), 24.67 g of propylene glycol monomethyl ether, 1.29 g of methanesulfonic acid (Kanto Chemical Co., Ltd.), and 2.86 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 12 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-34). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,200. [ka]

[0116] <Synthesis Example 35> A 100 mL two-neck flask was charged with 9.58 g of dehydrocholic acid (Tokyo Chemical Industry Co., Ltd.), 6.00 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.), 3.72 g of 1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 23.69 g of propylene glycol monomethyl ether, 1.37 g of methanesulfonic acid (Kanto Chemical Co., Ltd.), and 3.03 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 16 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-35). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,300. [ka]

[0117] <Comparative Synthesis Example 1> A 100 mL two-neck flask was charged with 4.48 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 10.00 g of TEP-TPA (Asahi Organic Chemicals Co., Ltd.), 35.67 g of propylene glycol monomethyl ether, and 0.91 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150°C and refluxed with stirring for approximately 4 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to cause reprecipitation. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-1). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 195,900. [ka]

[0118] <Comparative Synthesis Example 2> A 100 mL two-neck flask was charged with 8.41 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 10.00 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.), 43.86 g of propylene glycol monomethyl ether, and 0.38 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150°C and refluxed with stirring for approximately 4 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to cause reprecipitation. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-2). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 8,100. [ka]

[0119] <Comparative Synthesis Example 3> A 100 mL two-neck flask was charged with 5.49 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 10.00 g of 2-phenylindole (Tokyo Chemical Industry Co., Ltd.), 16.49 g of propylene glycol monomethyl ether acetate, and 0.99 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150°C and refluxed with stirring for approximately 5 hours. After the reaction was completed, the solution was added dropwise to methanol to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-3). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,600. [ka]

[0120] <Comparative Synthesis Example 4> A 100 mL two-neck flask was charged with 4.84 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 10.00 g of N-phenyl-1-naphthylamine (Tokyo Chemical Industry Co., Ltd.), 36.67 g of propylene glycol monomethyl ether acetate, and 0.88 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150°C and refluxed with stirring for approximately 15 minutes. After the reaction was completed, the solution was added dropwise to methanol to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-4). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 5,900. [ka]

[0121] <Comparative Synthesis Example 5> A 100 mL two-neck flask was charged with 3.03 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 10.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 32.68 g of propylene glycol monomethyl ether acetate, and 0.55 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150 °C and refluxed with stirring for approximately 17.5 hours. After the reaction was completed, the solution was added dropwise to methanol to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (1-5). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 910,300. [ka]

[0122] <Comparative Synthesis Example 6> A 100 mL two-neck flask was charged with 6.62 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 10.00 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 41.58 g of propylene glycol monomethyl ether acetate, and 1.20 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150°C and refluxed with stirring for approximately 1.5 hours. After the reaction was completed, the solution was added dropwise to methanol to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-6). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 5,300. [ka]

[0123] <Comparative Synthesis Example 7> A 100 mL two-neck flask was charged with 6.35 g of benzaldehyde (Tokyo Chemical Industry Co., Ltd.), 10.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 40.84 g of propylene glycol monomethyl ether acetate, and 1.15 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150°C and refluxed with stirring for approximately 30 minutes. After the reaction was completed, the solution was added dropwise to methanol to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-7). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 52,300. [ka]

[0124] Example 1 The resin (i.e., polymer, hereinafter the same) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.86% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.69 g of propylene glycol monomethyl ether were added to 3.45 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0125] <Example 2> The resin obtained in Synthesis Example 2 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 19.80% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.85 g of propylene glycol monomethyl ether were added to 3.28 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0126] Example 3 The resin obtained in Synthesis Example 3 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.33% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.34 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.48 g of propylene glycol monomethyl ether were added to 3.24 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0127] Example 4 The resin obtained in Synthesis Example 4 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 19.84% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.34 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.73 g of propylene glycol monomethyl ether were added to 3.00 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0128] <Example 5> The resin obtained in Synthesis Example 5 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.64% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.65 g of propylene glycol monomethyl ether were added to 3.49 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0129] Example 6 The resin obtained in Synthesis Example 6 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 17.66% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.34 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.36 g of propylene glycol monomethyl ether were added to 3.57 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0130] Example 7 The resin obtained in Synthesis Example 7 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 24.32% by mass). 2.67 g of this resin solution was dissolved in 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 3.46 g of propylene glycol monomethyl ether, and the solution was filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0131] Example 8 The resin obtained in Synthesis Example 8 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.86% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.69 g of propylene glycol monomethyl ether were added to 3.45 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0132] Example 9 The resin obtained in Synthesis Example 9 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 14.20% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.56 g of propylene glycol monomethyl ether were added to 4.58 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0133] Example 10 The resin obtained in Synthesis Example 10 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 15.92% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.05 g of propylene glycol monomethyl ether were added to 4.08 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0134] Example 11 The resin obtained in Synthesis Example 11 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 19.67% by mass). 2.98 g of this resin solution was dissolved in 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.17 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 2.18 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.93 g of propylene glycol monomethyl ether, and the solution was filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0135] Example 12 The resin obtained in Synthesis Example 12 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 12.29% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 0.85 g of propylene glycol monomethyl ether were added to 5.29 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0136] Example 13 The resin obtained in Synthesis Example 13 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content: 19.35% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.78 g of propylene glycol monomethyl ether were added to 3.36 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0137] Example 14 The resin obtained in Synthesis Example 14 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.26% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.58 g of propylene glycol monomethyl ether were added to 3.56 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0138] Example 15 The resin obtained in Synthesis Example 15 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.34% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.59 g of propylene glycol monomethyl ether were added to 3.54 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0139] Example 16 The resin obtained in Synthesis Example 16 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.26% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.58 g of propylene glycol monomethyl ether were added to 3.56 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0140] Example 17 The resin obtained in Synthesis Example 17 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 15.77% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFACE R-40, manufactured by DIC Corporation), 0.26 g of PGME-BIP-A (manufactured by Finechem Co., Ltd.), 1.16 g of propylene glycol monomethyl ether containing 2% by mass K-PURE (registered trademark) TAG2689 (manufactured by King Industries Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.98 g of propylene glycol monomethyl ether were added to 3.94 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0141] Example 18 The resin obtained in Synthesis Example 18 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.26% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.16 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.58 g of propylene glycol monomethyl ether were added to 3.56 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0142] Example 19 The resin obtained in Synthesis Example 19 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.43% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.61 g of propylene glycol monomethyl ether were added to 3.53 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0143] Example 20 The resin obtained in Synthesis Example 20 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 13.21% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.21 g of propylene glycol monomethyl ether were added to 4.92 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0144] <Example 21> The resin obtained in Synthesis Example 21 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content: 13.71% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.39 g of propylene glycol monomethyl ether were added to 4.74 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0145] Example 22 The resin obtained in Synthesis Example 22 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 16.47% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.19 g of propylene glycol monomethyl ether were added to 3.95 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0146] Example 23 The resin obtained in Synthesis Example 23 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 15.50% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.94 g of propylene glycol monomethyl ether were added to 4.19 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0147] Example 24 The resin obtained in Synthesis Example 24 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content: 16.99% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 1.34 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.25 g of propylene glycol monomethyl ether were added to 3.50 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0148] Example 25 The resin obtained in Synthesis Example 25 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content: 13.71% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.39 g of propylene glycol monomethyl ether were added to 4.74 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0149] <Example 26> The resin obtained in Synthesis Example 26 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 14.29% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.59 g of propylene glycol monomethyl ether were added to 4.55 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0150] Example 27 The resin obtained in Synthesis Example 27 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 16.73% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.25 g of propylene glycol monomethyl ether were added to 3.85 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0151] Example 28 The resin obtained in Synthesis Example 28 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 17.06% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.33 g of propylene glycol monomethyl ether were added to 3.81 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0152] Example 29 The resin obtained in Synthesis Example 29 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.46% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.61 g of propylene glycol monomethyl ether were added to 3.52 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0153] Example 30 The resin obtained in Synthesis Example 30 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 16.49% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.19 g of propylene glycol monomethyl ether were added to 3.94 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0154] Example 31 The resin obtained in Synthesis Example 31 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 21.90% by mass). 2.97 g of this resin solution was dissolved in 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 3.17 g of propylene glycol monomethyl ether, and the solution was filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0155] Example 32 The resin obtained in Synthesis Example 31 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 21.90% by mass). 2.97 g of this resin solution was dissolved in 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.78 g of propylene glycol monomethyl ether acetate, 2.25 g of propylene glycol monomethyl ether, and 1.84 g of N,N-dimethylisobutyramide, and the resulting mixture was filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0156] Example 33 The resin obtained in Synthesis Example 32 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 23.28% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.55 g of propylene glycol monomethyl ether acetate, and 5.48 g of propylene glycol monomethyl ether were added to 2.79 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0157] Example 34 The resin obtained in Synthesis Example 33 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 19.84% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.86 g of propylene glycol monomethyl ether were added to 3.28 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0158] Example 35 The resin obtained in Synthesis Example 34 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 21.71% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.35 g of propylene glycol monomethyl ether acetate, and 5.48 g of propylene glycol monomethyl ether were added to 2.99 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0159] Example 36 The resin obtained in Synthesis Example 35 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 20.10% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.11 g of propylene glycol monomethyl ether acetate, and 5.48 g of propylene glycol monomethyl ether were added to 3.23 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0160] <Comparative Example 1> The resin obtained in Comparative Synthesis Example 1 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 15.22% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 1.86 g of propylene glycol monomethyl ether were added to 4.27 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0161] <Comparative Example 2> The resin obtained in Comparative Synthesis Example 2 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 16.80% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.27 g of propylene glycol monomethyl ether were added to 3.87 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0162] <Comparative Example 3> The resin obtained in Comparative Synthesis Example 3 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 22.51% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.14 g of propylene glycol monomethyl ether acetate, and 1.80 g of propylene glycol monomethyl ether were added to 2.89 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0163] <Comparative Example 4> The resin obtained in Comparative Synthesis Example 4 was dissolved in cyclohexanone and then subjected to ion exchange to obtain a resin solution (solid content 17.72% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.86 g of propylene glycol monomethyl ether acetate, and 0.88 g of propylene glycol monomethyl ether were added to 3.67 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0164] <Comparative Example 5> The resin obtained in Comparative Synthesis Example 5 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 15.86% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.97 g of propylene glycol monomethyl ether acetate, and 1.80 g of propylene glycol monomethyl ether were added to 4.10 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0165] <Comparative Example 6> The resin obtained in Comparative Synthesis Example 6 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 18.21% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.70 g of propylene glycol monomethyl ether acetate, and 2.57 g of propylene glycol monomethyl ether were added to 3.57 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0166] <Comparative Example 7> The resin obtained in Comparative Synthesis Example 7 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 18.38% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.97 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.49 g of propylene glycol monomethyl ether acetate, and 1.80 g of propylene glycol monomethyl ether were added to 3.54 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0167] [Resist solvent elution test] The resist underlayer film-forming composition solutions prepared in Comparative Examples 1 to 7 and Examples 1 to 36 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 250°C for 60 seconds to form resist underlayer films (film thickness 0.20 μm). These resist underlayer films were immersed in solvents used in resists: ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. These resist underlayer films were insoluble in these solvents.

[0168] [Optical constant measurement] The solutions of the resist underlayer film-forming compositions prepared in Comparative Examples 1 to 7 and Examples 1 to 36 were each applied onto a silicon wafer using a spin coater. The resist underlayer films were baked on a hot plate at 250°C for 60 seconds to form resist underlayer films (film thickness 0.05 μm). The refractive index (n value) and optical absorption coefficient (k value, also called extinction coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer. The results are shown in Table 1.

[0169] [Table 1-1] [Table 1-2]

[0170] [Dry etching rate measurement] The etcher and etching gas used to measure the dry etching rate were as follows: there was. RIE-10NR (Samco): CF4 The resist underlayer film-forming composition solutions prepared in Comparative Examples 1-7 and Examples 1-36 were each applied to a silicon wafer using a spin coater. Resist underlayer films (film thickness 0.20 μm) were formed by baking on a hot plate at 250°C for 60 seconds. The dry etching rates were measured using CF4 gas as the etching gas, and the dry etching rates of the resist underlayer films in Comparative Examples 1-7 and Examples 1-36 were compared with those of the resist underlayer films. The results are shown in Table 2. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film) / (KrF photoresist).

[0171] [Table 2-1] [Table 2-2]

[0172] [Embeddability evaluation] The embedding ability was confirmed in a dense pattern area of ​​a 200 nm thick SiO2 substrate with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film-forming compositions prepared in Comparative Examples 1-3, 6, and 7 and Examples 1-36 were applied to the substrate and baked at 250°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the presence or absence of the resist underlayer film-forming composition filling the interior of the pattern was confirmed (Table 3). ○ indicates good, and × indicates poor.

[0173] [Table 3-1] [Table 3-2]

[0174] <Synthesis Example 51> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,615.96 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 10.00 g of phenol (Tokyo Chemical Industry Co., Ltd.), 22.76 g of propylene glycol monomethyl ether acetate, 10.92 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 16.93 g of 3-mercaptopropionic acid were added. The mixture was then heated to 140°C and refluxed with stirring for approximately 23 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to cause reprecipitation. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-51). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,000. [ka]

[0175] <Synthesis Example 52> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,6 6.29 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 7.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 28.25 g of propylene glycol monomethyl ether acetate, 1.21 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.67 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 17 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-52). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,400. [ka]

[0176] <Synthesis Example 53> A 100 mL two-neck flask was charged with 7.13 g of bicyclohexane-4,4'-dione monoethylene ketal (Tokyo Chemical Industry Co., Ltd.), 5.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 20.20 g of propylene glycol monomethyl ether acetate, 0.86 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.48 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 2 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-53). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,300. [ka]

[0177] <Synthesis Example 54> A 100 mL two-neck flask was charged with 6.54 g of 1,4-cyclohexanedione monoethylene ketal (Tokyo Chemical Industry Co., Ltd.), 7.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 23.12 g of propylene glycol monomethyl ether acetate, 1.21 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.67 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 17 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-54). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,200. [ka]

[0178] <Synthesis Example 55> A 100 mL two-neck flask was charged with 6.29 g of 2-adamantanone (Tokyo Chemical Industry Co., Ltd.), 7.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 22.75 g of propylene glycol monomethyl ether acetate, 1.21 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.67 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 17 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-55). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 4,700. [ka]

[0179] <Synthesis Example 56> A 100 mL two-neck flask was charged with 6.46 g of cyclohexanone (Tokyo Chemical Industry Co., Ltd.), 11.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 47.61 g of propylene glycol monomethyl ether acetate, 1.90 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.05 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 40 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-56). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,800. [ka]

[0180] <Synthesis Example 57> A 100 mL two-neck flask was charged with 6.37 g of 2-cyclopentylcyclopentanone (Tokyo Chemical Industry Co., Ltd.), 7.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 22.87 g of propylene glycol monomethyl ether acetate, 1.21 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.67 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 40 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered under suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-57). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,900. [ka]

[0181] <Synthesis Example 58> A 100 mL two-neck flask was charged with 6.47 g of 2-cyclohexylcyclohexanone (Tokyo Chemical Industry Co., Ltd.), 6.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 21.12 g of propylene glycol monomethyl ether acetate, 1.04 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 0.57 g of 3-mercaptopropionic acid. The mixture was then heated to 150 °C and refluxed with stirring for approximately 40 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-58). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 6,200. [ka]

[0182] <Synthesis Example 59> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,6] 4.49 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 10.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 4.67 g of 1-naphthaldehyde (Tokyo Chemical Industry Co., Ltd.), 24.69 g of propylene glycol monomethyl ether acetate, 1.72 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 3.81 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 2.5 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-59). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,900. [ka]

[0183] <Synthesis Example 60> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,6 ] 3.80 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 12.00 g of TEP-TPA (Tokyo Chemical Industry Co., Ltd.), 22.55 g of propylene glycol monomethyl ether, 2.43 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 4.03 g of 3-mercaptopropionic acid were added. The mixture was then heated to 140°C and refluxed with stirring for approximately 12 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to cause reprecipitation. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-60). The weight-average molecular weight Mw measured by GPC in terms of polystyrene was 2,500. [ka]

[0184] <Synthesis Example 61> A 100 mL two-neck flask was charged with 12.08 g of 2-cyclopentylcyclopentanone (Tokyo Chemical Industry Co., Ltd.), 10.00 g of phloroglucinol (Tokyo Chemical Industry Co., Ltd.), 42.34 g of propylene glycol monomethyl ether, 7.63 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 12.63 g of 3-mercaptopropionic acid. The mixture was then heated to 140 °C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponded to formula (2-61). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 600. [ka]

[0185] <Synthesis Example 62> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,6 6.99 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 9.00 g of 2-phenylindole (Tokyo Chemical Industry Co., Ltd.), 27.88 g of propylene glycol monomethyl ether acetate, 4.48 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 7.42 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 12 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to cause reprecipitation. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-62). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 600. [ka]

[0186] <Synthesis Example 63> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,66.16 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 9.00 g of N-phenyl-1-naphthylamine (Tokyo Chemical Industry Co., Ltd.), 25.44 g of propylene glycol monomethyl ether acetate, 3.94 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 6.54 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-63). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,400. [ka]

[0187] <Synthesis Example 64> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,6 6.14 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 12.00 g of 9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 19.22 g of propylene glycol monomethyl ether acetate, 0.99 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 1.09 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 16 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-64). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 2,400. [ka]

[0188] <Synthesis Example 65> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,66.14 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 8.00 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 28.25 g of propylene glycol monomethyl ether acetate, 4.80 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 7.95 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol / water solution to cause reprecipitation. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-65). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,400. [ka]

[0189] <Synthesis Example 66> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,6 ] 4.69 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 4.75 g of 2-cyclopentylcyclopentanone (Tokyo Chemical Industry Co., Ltd.), 10.0 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 35.38 g of propylene glycol monomethyl ether acetate, 6.00 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 9.94 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-66). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,000. [ka]

[0190] <Synthesis Example 67> In a 100 mL two-neck flask, add tricyclo[5.2.1.0 2,67.00 g of decan-8-one (Tokyo Chemical Industry Co., Ltd.), 3.73 g of 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.), 8.17 g of 9-bis(4-hydroxyphenyl)fluorene (Tokyo Chemical Industry Co., Ltd.), 30.81 g of propylene glycol monomethyl ether acetate, 4.48 g of methanesulfonic acid (Tokyo Chemical Industry Co., Ltd.), and 7.42 g of 3-mercaptopropionic acid were added. The mixture was then heated to 150°C and refluxed with stirring for approximately 21 hours. After the reaction was completed, the solution was added dropwise to a methanol solution to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (2-67). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 1,700. [ka]

[0191] <Comparative Synthesis Example 51> A 100 mL two-neck flask was charged with 18.8 g of phenol (Tokyo Chemical Industry Co., Ltd.) and 0.01 g of trifluoromethanesulfonic acid, and 8.00 g of dicyclopentadiene (Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring at 50°C. After stirring at the same temperature for 1 hour, the temperature was raised to 150°C and the mixture was stirred for 2 hours to terminate the reaction. Unreacted material was removed by reprecipitation. The resulting precipitate was suction filtered, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-51). The weight-average molecular weight Mw measured by GPC in terms of polystyrene was 1,000. [ka]

[0192] <Comparative Synthesis Example 52> A 100 mL two-neck flask was charged with 7.91 g of dicyclopentadiene (Tokyo Chemical Industry Co., Ltd.), 10.00 g of carbazole (Tokyo Chemical Industry Co., Ltd.), 18.00 g of propylene glycol monomethyl ether acetate, and 0.09 g of trifluoromethanesulfonic acid (Tokyo Chemical Industry Co., Ltd.). The mixture was then heated to 150°C and refluxed with stirring for approximately 12 hours. After the reaction was completed, the solution was added dropwise to methanol to reprecipitate. The resulting precipitate was filtered by suction, and the residue was dried under reduced pressure at 60°C overnight. The resulting polymer corresponded to formula (1-52). The weight-average molecular weight (Mw) measured by GPC in terms of polystyrene was 3,000. [ka]

[0193] <Example 51> The resin (i.e., polymer, hereinafter the same) obtained in Synthesis Example 51 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 21.57% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 1.01 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.27 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0194] <Example 52> The resin obtained in Synthesis Example 52 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content: 19.86% by mass). 2.53 g of this resin solution was dissolved in 0.05 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.13 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.63 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.69 g of propylene glycol monomethyl ether acetate, 0.31 g of propylene glycol monomethyl ether, and 3.68 g of cyclohexanone, and the resulting solution was filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0195] <Example 53> The resin obtained in Synthesis Example 53 was dissolved in cyclohexanone and then subjected to ion exchange to obtain a resin solution (solid content: 19.45% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFACE R-40, manufactured by DIC Corporation), 3.58 g of propylene glycol monomethyl ether acetate, 0.08 g of propylene glycol monomethyl ether, and 1.74 g of cyclohexanone were added to 3.51 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0196] <Example 54> The resin obtained in Synthesis Example 54 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content: 23.34% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFACE R-40, manufactured by DIC Corporation), 3.57 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.02 g of this resin solution and dissolved, and the mixture was filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0197] Example 55 The resin obtained in Synthesis Example 55 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 21.53% by mass). 2.62 g of this resin solution was dissolved in 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.14 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.71 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.80 g of propylene glycol monomethyl ether acetate, 0.04 g of propylene glycol monomethyl ether, and 3.64 g of cyclohexanone, and the resulting solution was filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0198] Example 56 The resin obtained in Synthesis Example 56 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 17.65% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.14 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.71 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.22 g of propylene glycol monomethyl ether acetate, 0.04 g of propylene glycol monomethyl ether, and 3.64 g of cyclohexanone were added to 3.20 g of this resin solution and dissolved. The mixture was then filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0199] Example 57 The resin obtained in Synthesis Example 57 was dissolved in cyclohexanone and then subjected to ion exchange to obtain a resin solution (solid content 18.19% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.14 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.71 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.67 g of propylene glycol monomethyl ether acetate, 2.22 g of propylene glycol monomethyl ether, and 1.10 g of cyclohexanone were added to 3.10 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0200] <Example 58> The resin obtained in Synthesis Example 58 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 18.05% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.14 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.71 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.29 g of propylene glycol monomethyl ether acetate, 0.04 g of propylene glycol monomethyl ether, and 3.64 g of cyclohexanone were added to 3.13 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0201] Example 59 The resin obtained in Synthesis Example 59 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 22.47% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 1.14 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.14 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0202] Example 60 The resin obtained in Synthesis Example 60 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 21.31% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 3.57 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.31 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0203] <Example 61> The resin obtained in Synthesis Example 61 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 19.80% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.71 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.56 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0204] <Example 62> The resin obtained in Synthesis Example 62 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 19.52% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 3.57 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.61 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0205] Example 63 The resin obtained in Synthesis Example 63 was dissolved in cyclohexanone and then subjected to ion exchange to obtain a resin solution (solid content 18.98% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.16 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.78 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.86 g of propylene glycol monomethyl ether acetate, 0.15 g of propylene glycol monomethyl ether, and 4.68 g of cyclohexanone were added to 3.30 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0206] <Example 64> The resin obtained in Synthesis Example 64 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 19.00% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.16 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.82 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.79 g of propylene glycol monomethyl ether acetate, 0.11 g of propylene glycol monomethyl ether, and 4.58 g of cyclohexanone were added to 3.46 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0207] Example 65 The resin obtained in Synthesis Example 65 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 20.75% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 3.57 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.40 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0208] <Example 66> The resin obtained in Synthesis Example 66 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content 23.14% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 3.57 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.05 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0209] Example 67 The resin obtained in Synthesis Example 67 was dissolved in propylene glycol monomethyl ether acetate and then subjected to ion exchange to obtain a resin solution (solid content 20.43% by mass). 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.82 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone were added to 3.45 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0210] <Comparative Example 51> The resin obtained in Comparative Synthesis Example 51 was dissolved in propylene glycol monomethyl ether and then subjected to ion exchange to obtain a resin solution (solid content: 23.68% by mass). 2.98 g of this resin solution was dissolved in 0.07 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.18 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.88 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 1.30 g of propylene glycol monomethyl ether acetate, 0.05 g of propylene glycol monomethyl ether, and 4.55 g of cyclohexanone, and the resulting solution was filtered through a 0.1 μm diameter polytetrafluoroethylene microfilter to prepare a solution of a resist underlayer film-forming composition.

[0211] <Comparative Example 52> The resin obtained in Comparative Synthesis Example 52 was dissolved in cyclohexanone and then subjected to ion exchange to obtain a resin solution (solid content 34.12% by mass). 0.06 g of propylene glycol monomethyl ether acetate containing 1% surfactant (MEGAFAC R-40, manufactured by DIC Corporation), 0.14 g of PL-LI (manufactured by Midori Chemical Co., Ltd.), 0.71 g of propylene glycol monomethyl ether containing 2% by mass pyridinium benzenesulfonate, 0.67 g of propylene glycol monomethyl ether acetate, 2.22 g of propylene glycol monomethyl ether, and 2.55 g of cyclohexanone were added to 1.65 g of this resin solution and dissolved. The mixture was then filtered through a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a resist underlayer film-forming composition.

[0212] [Resist solvent elution test] The resist underlayer film-forming composition solutions prepared in Comparative Examples 51 and 52 and Examples 51 to 67 were each applied to a silicon wafer using a spin coater and baked on a hot plate at 250°C for 60 seconds or 350°C for 60 seconds to form resist underlayer films (film thickness 0.20 μm). These resist underlayer films were immersed in solvents used in resists: ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. These resist underlayer films were insoluble in these solvents.

[0213] [Optical constant measurement] The resist underlayer film-forming composition solutions prepared in Comparative Examples 51 and 52 and Examples 51 to 67 were each applied to a silicon wafer using a spin coater. The resist underlayer films were baked on a hot plate at 250°C for 60 seconds or at 350°C for 60 seconds to form resist underlayer films (film thickness 0.05 μm). The refractive index (n value) and optical extinction coefficient (k value, also called extinction coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer. The results are shown in Table 4. [Table 4]

[0214] [Dry etching rate measurement] The etcher and etching gas used to measure the dry etching rate were as follows: there was. RIE-10NR (Samco): CF4 The resist underlayer film-forming composition solutions prepared in Comparative Examples 51-52 and Examples 51-67 were each applied to a silicon wafer using a spin coater. Resist underlayer films (film thickness 0.20 μm) were formed by baking on a hot plate at 250°C for 60 seconds or at 350°C for 60 seconds. Dry etching rates were measured using CF4 gas as the etching gas, and the dry etching rates of the resist underlayer films in Comparative Examples 51-52 and Examples 51-67 were compared with those of the resist underlayer films. The results are shown in Table 5. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film) / (KrF photoresist).

[0215] [Table 5]

[0216] [Embeddability evaluation] The embedding ability was confirmed in a dense pattern area of ​​a 150 nm thick SiO2 substrate with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film-forming compositions prepared in Comparative Examples 51 and 52 and Examples 51 to 67 were applied to the substrate and then baked at 250°C for 60 seconds or at 350°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the presence or absence of filling of the resist underlayer film-forming composition into the pattern was confirmed (Table 6). ○ indicates good, and × indicates poor.

[0217] [Table 6]

[0218] [Coating test on uneven substrate] In a coating test for a stepped substrate, a comparison of coating film thickness was performed on a 200 nm-thick SiO2 substrate in an open area (OPEN) where no pattern was formed and a dense pattern area (DENSE) with a trench width of 50 nm and a pitch of 100 nm. The resist underlayer film-forming compositions prepared in Comparative Examples 51 and 52 and Examples 51-67 were applied to the substrate, and then baked at 250°C for 60 seconds or at 350°C for 60 seconds to form a resist underlayer film of approximately 150 nm. The planarization of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the planarization was evaluated by measuring the film thickness difference between the trench area (patterned area) and the open area (non-patterned area) of the stepped substrate (the coating step between the trench area and the open area, referred to as the bias). Here, planarization refers to a small difference in film thickness (iso-dense bias) between the area where a pattern exists (trench area (pattern area)) and the area where no pattern exists (open area (no pattern area)) of the coating material applied on top of the pattern (Table 7). Specifically, (ba) shown in Figure 1 is the iso-dense bias. In the figure, a is the recess depth of the coating film at the center of the dense space area, b is the recess depth of the coating film at the center of the open area area, c is the initial space depth in the stepped substrate used, d is the coating film, and e is the stepped substrate.

[0219] [Table 7] [Industrial Applicability]

[0220] According to the present invention, there is provided a resist underlayer film-forming composition that exhibits high etching resistance, a good dry etching rate ratio and optical constants, has good coverage even on uneven substrates, has small film thickness differences after filling, and is capable of forming a flat film. The present invention also provides a method for producing a polymer suitable for the resist underlayer film-forming composition, a resist underlayer film using the resist underlayer film-forming composition, and a method for producing a semiconductor device.

Claims

1. The reaction product comprises a reaction product of an aromatic compound (A) having 6 to 60 carbon atoms with a carbonyl group possessed by a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, and a solvent; the cyclic carbonyl compound (B) contains 5% by mass or more of heteroatoms, In the reaction product, one carbon atom of the cyclic carbonyl compound (B) connects two of the aromatic compounds (A). A resist underlayer film-forming composition.

2. The resist underlayer film forming composition according to claim 1 , wherein the cyclic carbonyl compound (B) has at least one heteroatom in one molecule.

3. The cyclic carbonyl compound (B) is represented by the following formula (1): 【Chemical 71】 [In the formula, X is O, NH, or CH ２ and Ring Y is a 3- to 8-membered ring which may have as a substituent a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group or a carbonyl group and which may be interrupted by an oxygen atom or a sulfur atom, a hydroxy group, an oxo group, a carboxy group, a cyano group, a nitro group, a sulfo group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an amino group, a glycidyl group, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, and which may be interrupted by a heteroatom, or a connected ring or fused ring thereof.] The resist underlayer film forming composition according to claim 1 or 2, wherein

4. The reaction product comprises an aromatic compound (A) having 6 to 60 carbon atoms and a carbonyl group possessed by a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, and a solvent; The cyclic carbonyl compound (B) is represented by the following formula (1): 【Chemical 72】 [In the formula, X is CH ２ and Ring Y is a 3- to 8-membered ring which may have as a substituent a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group or a carbonyl group and which may be interrupted by an oxygen atom or a sulfur atom, a hydroxy group, an oxo group, a carboxy group, a cyano group, a nitro group, a sulfo group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an amino group, a glycidyl group, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, or a linked ring thereof. A resist underlayer film-forming composition.

5. 5. The resist underlayer film forming composition according to claim 4, wherein the reaction product has one carbon atom of the cyclic carbonyl compound (B) linking two of the aromatic compounds (A).

6. The resist underlayer film forming composition according to any one of claims 3 to 5, wherein the cyclic carbonyl compound (B) is an alicyclic compound.

7. The resist underlayer film forming composition according to any one of claims 1 to 6, wherein the cyclic carbonyl compound (B) does not contain a benzene ring.

8. The resist underlayer film forming composition according to any one of claims 1 to 7, wherein the compound (A) contains one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or combinations thereof.

9. 8. The resist underlayer film forming composition according to claim 1, wherein the compound (A) contains two or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or a combination thereof.

10. The resist underlayer film forming composition according to any one of claims 1 to 9, further comprising a crosslinking agent.

11. The resist underlayer film forming composition according to any one of claims 1 to 10, further comprising an acid and / or an acid generator.

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

13. A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film-forming composition according to any one of claims 1 to 12.

14. A method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a semiconductor substrate from the resist underlayer film-forming composition according to any one of claims 1 to 12; a step of forming a resist film thereon; a step of forming a resist pattern by irradiating with light or an electron beam and developing; a step of etching the underlayer film using the resist pattern; and a step of processing a semiconductor substrate with the patterned underlayer film.

15. A method for producing a polymer for a resist underlayer film-forming composition, the method comprising the step of reacting an aromatic compound (A) having 6 to 60 carbon atoms with a carbonyl group possessed by a cyclic carbonyl compound (B) having 3 to 60 carbon atoms, The reaction product of the present invention is a reaction product in which one carbon atom of the cyclic carbonyl compound (B) links two of the aromatic compounds (A).

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