JP2001056566A - Production of composition for underlayer film of resist and composition for underlayer film of resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a composition for the underlayer film of a resist excellent in the reproducibility and resolution of a resist pattern when the composition is kept warm over a long period of time and excellent also in adhesion to the resist and resistance to a developing solution used after the exposure of the resist. SOLUTION: Water is added to at least one compound selected from compounds of the formula R1aSi(OR2)4-a [where R1 is H, F or a monovalent organic group, R2 is a monovalent organic group and (a) is an integer of 0-2] and the formula R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c [where R3-R6 may be the same or different and are each a monovalent organic group, (b) and (c) may be the same or different and are each 0-2, R7 is O or -(CH2)n-, (d) is 0 or 1 and (n) is 1-6] by 0.2-2 mol per 1 mol alkoxyl groups of the selected compound, and they are hydrolyzed and condensed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a resist underlayer film, and more particularly, to a resist pattern having excellent reproducibility and resolution when the composition is kept for a long period of time, excellent adhesion to a resist, and The present invention relates to a composition for a resist underlayer film having excellent resistance to a developer used after exposure.

[0002]

2. Description of the Related Art Fine patterning of organic materials and inorganic materials is performed by lithography technology, resist development process, and pattern transfer after resist development for pattern formation of semiconductor devices and the like. However, as the degree of integration of semiconductor elements and the like increases, it becomes difficult to accurately transfer a pattern to a resist in an exposure step, and the processing dimensions may be deviated in a substrate processing step. Therefore, an anti-reflection film for reducing the effect of standing waves, which is a cause of an irregular processing size, is indispensable in a fine processing process. As such an anti-reflection film, there is a lower anti-reflection film formed between the resist and the substrate.

On the other hand, when a substrate such as a silicon oxide film or an interlayer insulating film is processed, a resist pattern is used as a mask. It becomes difficult to process the oxide film without giving. Therefore, a process is first performed in which the resist pattern is first transferred to a lower layer film for processing an oxide film / interlayer insulating film, and then the oxide film / interlayer insulating film is dry-etched using the film as a mask. The lower film for processing an oxide film or an interlayer insulating film refers to a film which also functions as a lower antireflection film or a film formed below the antireflection film. In this process, since the etching rate of the resist and the lower layer film for processing the oxide film / interlayer insulating film are close to each other, the distance between the resist and the lower layer film is
It is necessary to form a mask capable of processing the lower layer film. In other words, on the oxide film, the lower film for processing the oxide film and the interlayer insulating film is formed.
A multilayer film of a mask and a resist for processing the lower layer film is formed.

[0004] The characteristics required for a mask for processing an underlayer film include the ability to form a resist pattern without tailing and undeveloped portions, excellent adhesion to a resist, and sufficient properties for processing an underlayer film for processing an oxide film. It has excellent masking properties and excellent storage stability as a solution, but there is no material that meets all requirements.

According to the present invention, in order to solve the above-mentioned problems, by providing the resist under the resist, the reproducibility of the pattern is improved without peeling of the resist or the undeveloped residue, and the resist is resistant to an alkali developing solution and has a stable storage. It is an object of the present invention to provide a resist underlayer composition having excellent properties.

The present invention relates to (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) wherein R ¹ is hydrogen An atom, a fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) represented by the following general formula (2) that compound _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ····· (2) (R 3, R 4, R 5 and R ⁶ may be the same or different and each represents a monovalent organic group, b and c may be the same or different and each represent a number of 0 to 2, and R ⁷ represents an oxygen atom or-( CH ₂ ) _n- , d is 0 or 1
And n represents a number of 1 to 6. )) (At least one compound selected from the group consisting of
), 0.5 mol or more and 2 mol or less of water per 1 mol of the total of the alkoxyl group of the compound represented by the general formula (1) and the alkoxyl group of the compound represented by the general formula (2). And a method for producing a composition for a resist underlayer film, which comprises subjecting the composition to hydrolysis and condensation.

[0007] In (A) (A-1) component above general formula (1), the monovalent organic group R ¹ and R ^2, an alkyl group, an aryl group, an allyl group, and the like glycidyl group it can. Further, in the general formula (1), R ¹ is preferably a monovalent organic group, particularly an alkyl group or a phenyl group. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, preferably having 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched, Further, a hydrogen atom may be substituted with a fluorine atom or the like. In the general formula (1), as the aryl group,
Examples include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.

Specific examples of the compound represented by the general formula (1) include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, tri-n-butoxysilane, tri- sec-butoxysilane, tri-tert-butoxysilane, triphenoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotri-iso-propoxysilane,
Fluorotri-n-butoxysilane, fluorotri-s
ec-butoxysilane, fluorotri-tert-butoxysilane, fluorotriphenoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane,
Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane, etc .; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltrimethylsilane -N-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane,
Methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-s
ec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, vinyltri-n-butoxysilane, vinyltri- sec-butoxysilane, vinyl tri-tert
-Butoxysilane, vinyltriphenoxysilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane,
n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-
sec-butoxysilane, n-propyltri-tert
-Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-te
rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-
n-propoxysilane, sec-butyl-tri-iso
-Propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxy Silane, t-butyltriethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-
n-butoxysilane, t-butyltri-sec-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltrisilane -Iso-
Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, etc .; dimethyldimethoxysilane , Dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, dimethyl-di-sec
-Butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n -Butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-
tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso- Propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di-tert-butoxysilane, di-n-propyl-di- Phenoxysilane, di-i
so-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-
Propoxysilane, di-iso-propyl-di-iso
-Propoxysilane, di-iso-propyl-di-n-
Butoxysilane, di-iso-propyl-di-sec-
Butoxysilane, di-iso-propyl-di-tert
-Butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n
-Butyldiethoxysilane, di-n-butyl-di-n-
Propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec-butoxysilane, di-n-butyl-di- tert-butoxysilane, di-n
-Butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane,
Di-sec-butyl-di-iso-propoxysilane,
Di-sec-butyl-di-n-butoxysilane, di-s
ec-butyl-di-sec-butoxysilane, di-se
c-butyl-di-tert-butoxysilane, di-se
c-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxy Silane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxy Silane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-s
ec-butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane, and the like. (A
-1) Of the components, preferably, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n- Propoxysilane,
Methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n- Butyltriethoxysilane, i-butyltrimethoxysilane,
i-butyltriethoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyl Dimethoxysilane, diphenyldiethoxysilane, trimethylmonomethoxysilane,
Examples thereof include trimethylmonoethoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triphenylmonomethoxysilane, and triphenylmonoethoxysilane. These may be used alone or in combination of two or more.

(A-2) Component In the above general formula (2), examples of the monovalent organic group include the same organic groups as those in the above general formula (1).
In the general formula (2), as the compound in which R ⁷ is an oxygen atom, hexamethoxydisiloxane, hexaethoxydisiloxane, hexaphenoxydisiloxane, 1,1,1
1,3,3-pentamethoxy-3-methyldisiloxane, 1,1,1,3,3-pentaethoxy-3-methyldisiloxane, 1,1,1,3,3-pentamethoxy-
3-phenyldisiloxane, 1,1,1,3,3-pentaethoxy-3-phenyldisiloxane, 1,1,3,
3-tetramethoxy-1,3-dimethyldisiloxane,
1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3
-Diphenyldisiloxane, 1,1,3,3-tetraethoxy-1,3-diphenyldisiloxane, 1,1,3
-Trimethoxy-1,3,3-trimethyldisiloxane, 1,1,3-triethoxy-1,3,3-trimethyldisiloxane, 1,1,3-trimethoxy-1,3,3
3-triphenyldisiloxane, 1,1,3-triethoxy-1,3,3-triphenyldisiloxane, 1,3
Dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3
Examples thereof include 3-tetraphenyldisiloxane and 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane. Of these, hexamethoxydisiloxane, hexaethoxydisiloxane, 1,1,
3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-
1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3
-Diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,
Preferred examples include 3,3-tetraphenyldisiloxane. In the general formula (2), d
As compounds having 0, hexamethoxydisilane, hexaethoxydisilane, hexaphenixidisilane, 1,
1,1,2,2-pentamethoxy-2-methyldisilane, 1,1,1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-
Phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-
Tetraethoxy-1,2-dimethyldisilane, 1,1,
2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2-trimethoxy-1,2,2
-Trimethyldisilane, 1,1,2-triethoxy-
1,2,2-trimethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,
2-triethoxy-1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,1
Examples of the compound in which R ⁷ is — (CH ₂ ) _n — in the general formula (2) include 2,2-tetraphenyldisilane and 1,2-diethoxy-1,1,2,2-tetraphenyldisilane. (Hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (hexaphenoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (dimethoxyphenylsilyl) methane, bis ( Diethoxyphenylsilyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane,
Bis (methoxydiphenylsilyl) methane, bis (ethoxydiphenylsilyl) methane, bis (hexamethoxysilyl) ethane, bis (hexaethoxysilyl) ethane, bis (hexaphenoxysilyl) ethane, bis (dimethoxymethylsilyl) ethane, bis ( Diethoxymethylsilyl) ethane, bis (dimethoxyphenylsilyl)
Ethane, bis (diethoxyphenylsilyl) ethane, bis (methoxydimethylsilyl) ethane, bis (ethoxydimethylsilyl) ethane, bis (methoxydiphenylsilyl) ethane, bis (ethoxydiphenylsilyl) ethane, 1,3-bis (hexa Methoxysilyl) propane,
1,3-bis (hexaethoxysilyl) propane, 1,
3-bis (hexaphenoxysilyl) propane, 1,3
-Bis (dimethoxymethylsilyl) propane, 1,3-
Bis (diethoxymethylsilyl) propane, 1,3-bis (dimethoxyphenylsilyl) propane, 1,3-bis (diethoxyphenylsilyl) propane, 1,3-bis (methoxydimethylsilyl) propane, 1,3- Examples thereof include bis (ethoxydimethylsilyl) propane, 1,3-bis (methoxydiphenylsilyl) propane, and 1,3-bis (ethoxydiphenylsilyl) propane. Of these, hexamethoxydisilane,
Hexaethoxydisilane, hexaphenixidisilane,
1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-
1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,
2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-
Tetraphenyldisilane, bis (hexamethoxysilyl) methane, bis (hexaethoxysilyl) methane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (dimethoxyphenylsilyl) methane, bis (diethoxyphenyl) Preferred examples include (silyl) methane, bis (methoxydimethylsilyl) methane, bis (ethoxydimethylsilyl) methane, bis (methoxydiphenylsilyl) methane, and bis (ethoxydiphenylsilyl) methane.
In the present invention, the component (A) includes the above (A-1)
Component and / or Component (A-2) are used, and Component (A-1) and Component (A-2) are 2
More than one species can be used.

In the present invention, it is particularly preferable that the component (A) is as follows or is particularly preferable since the adhesion to the resist is better. Compound represented by the following general formula (6): Si (OR ² ) ₄ (6) (R ² represents a monovalent organic group, and specific examples are the same as those in the above general formula (1)) compound represented by (6) and a silane compound comprising a compound represented by the following general formula _{^{(7) R 1 n Si (}} oR 2) 4 _{over n} (7) (R ¹ and R ^2, are identical or different And each represents a monovalent organic group, and specific examples are the same as in the general formula (1), and n represents an integer of 1 to 3.) In the above case, the compound represented by the general formula (7) (In terms of complete hydrolysis condensate)
Is 0.5 to 30 parts by weight, more preferably 0.5 to 25 parts by weight, based on 100 parts by weight of the compound represented by the general formula (6) (in terms of a completely hydrolyzed condensate). Department.

In the present invention, the compound (1) is usually hydrolyzed and condensed in an organic solvent. Examples of the organic solvent used in the present invention include n-pentane, i-pentane, and n-pentane.
Hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane,
Aliphatic hydrocarbon solvents such as i-octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene , Di-i-propyl benzene, n-amylnaphthalene, trimethylbenzene, and other aromatic hydrocarbon solvents; methanol, ethanol, n-propanol,
i-propanol, n-butanol, i-butanol,
sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec
-Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol,
sec-hexanol, 2-ethylbutanol, sec
-Heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol,
n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, Monoalcohol solvents such as 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol; ethylene glycol, propylene glycol, 1,
3-butylene glycol, pentanediol-2,4,
2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, etc. Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n- Hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone,
Ketone solvents such as 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone and fenchone; ethyl ether, i-propyl ether,
n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-methyldioxolan, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether , Ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether , Diethylene glycol mono-n-butyl Ether, diethylene glycol di -n- butyl ether, diethylene glycol mono -n
-Hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether solvents such as ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone , N-propyl acetate, i-acetic acid
Propyl, n-butyl acetate, i-butyl acetate, acetic acid se
c-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, acetoacetate Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate, propylene glycol monoethyl acetate Ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropyl acetate Glycol monomethyl ether acetate, dipropylene glycol monoethyl ether,
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactic acid n Ester solvents such as amyl, diethyl malonate, dimethyl phthalate and diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Nitrogen-containing solvents such as dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone; Can be mentioned.

Among these organic solvents, those represented by the following general formula (4) are preferred. R ⁸ O (R ¹² O) _e R ⁹ (4) (R ⁸ and R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—. 1
R ¹² represents an alkylene group having 2 to 4 carbon atoms, particularly preferably a group represented by —CH (CH ₃ ) CH ₂ —, and e represents an integer of 1 to 2. As the organic solvent represented by the general formula (4), preferably, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether,
Propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether,
Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate,
Propylene glycol monobutyl ether acetate,
Dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol diacetate, propylene glycol, and the like. Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Call monopropyl ether acetate it is particularly preferred in view of storage stability of the solution. These can be used alone or in combination of two or more.

When the compound (1) is hydrolyzed and condensed, a catalyst may be used. Examples of the catalyst used at this time include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base. Examples of the metal chelate compound include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetylacetonate) titanium, and tri-n-
Butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxybis (acetylacetonate) titanium, di- n-propoxybis (acetylacetonato) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonato) titanium, di-sec-butoxy.
Bis (acetylacetonato) titanium, di-t-butoxybis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n
-Propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxytris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonate) ) Titanium, mono-t-butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri I-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl) Acetoace Over G) titanium, diethoxy-bis (ethylacetoacetate) titanium, di -n- propoxy bis (ethylacetoacetate) titanium, di -i-
Propoxy bis (ethyl acetoacetate) titanium,
Di-n-butoxybis (ethylacetoacetate) titanium, di-sec-butoxybis (ethylacetoacetate) titanium, di-t-butoxybis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) ) Titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium,
Mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, Titanium chelate compounds such as mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy. Mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxymono (acetylacetonato) zirconium, tri-n-butoxymono ( Acetylacetonate) zirconium, tri -sec- butoxy mono (acetylacetonate) zirconium, tri -t- butoxy mono (acetylacetonate) zirconium, diethoxy ·
Bis (acetylacetonate) zirconium, di-n-
Propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxybis (acetylacetonate) zirconium, di-sec-butoxy.
Bis (acetylacetonate) zirconium, di-t-
Butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonato) zirconium, mono-i-propoxy.
Tris (acetylacetonate) zirconium, mono-
n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy. Mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, Tri-s
ec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy.
Bis (ethylacetoacetate) zirconium, di-i
-Propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) ) Zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-
n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy.
Tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetonate) Zirconium chelate compounds such as mono (ethylacetoacetate) zirconium;
Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; and the like. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid , Butyric acid, melitic acid, arachidonic acid, mykimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p
-Toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like. Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine,
Monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane,
Examples thereof include diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. As the inorganic base, for example, ammonia,
Sodium hydroxide, potassium hydroxide, barium hydroxide,
Calcium hydroxide and the like can be mentioned. Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These may be used alone or in combination of two or more.

The amount of the catalyst used is usually 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the component (A) (in terms of complete hydrolysis condensate).
The range is 0 parts by weight.

In the present invention, when the compound (1) is hydrolyzed and condensed, R ¹ O—, R ⁴ O— or R ⁵ O—
It is preferable to use 0.5 mol or more and 2 mol or less of water per 1 mol of the group represented by The amount of water to add is 0.5
When the amount is less than mol, the alkali developing solution resistance of the composition for a resist underlayer film decreases, and when the amount of water added exceeds 2 mol, the storage stability of the obtained composition for a resist underlayer film deteriorates. Specifically, water is intermittently or continuously added to an organic solvent in which the compound (1) is dissolved. At this time, the catalyst may be added in advance to the organic solvent, or may be dissolved or dispersed in water at the time of adding water. The reaction temperature at this time is usually 0 to 100 ° C, preferably 1 to 100 ° C.
5 to 80 ° C. When two or more compounds (1) are used, (a) two or more compounds (1) may be mixed and then hydrolyzed and condensed, or (b) two or more compounds (1) may be used. ) May be separately mixed after hydrolysis and condensation, but (b) is particularly preferred.

[0016] Set for resist underlayer film obtained as described above
Other compounds may be added to the product if necessary.
Can be. (C) component  In the present invention, a latent thermal acid generator is used as the acid generator.
Agents and latent photoacid generators. In the present invention
The latent thermal acid generator used is usually 50 to 450 ° C,
Preferably the acid is heated by heating to 200-350 ° C.
Generated compound, sulfonium salt, benzothiazo
Onium such as ium salt, ammonium salt, phosphonium salt
Um salts are used.

A specific example of the above sulfonium salt is 4
-Acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-
4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-
Alkylsulfonium salts such as 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate; benzyl -4-Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl -2-methyl-4-hydroxyphenylmethylsulfonium hexafluoro Nchimoneto, benzyl-3-chloro-4-hydroxyphenyl methyl sulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl methyl sulfonium hexafluorophosphate, benzoin tosylate, 2
Benzylsulfonium salts such as -nitrobenzyl tosylate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, Dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-
tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-
Dibenzylsulfonium salts such as 4-hydroxyphenylsulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chloro Benzyl-4
-Hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-
4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4
Substituted benzylsulfonium salts such as -hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate;

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, and 3-benzylbenzothiazolium tetrafluoroborate. (P-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5
Benzylbenzothiazolium salts such as -chlorobenzothiazolium hexafluoroantimonate. Furthermore, as thermal acid generators other than the above, 2, 4,
4,6-tetrabromocyclohexadienone can be exemplified.

Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium
Hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate Nates and the like are preferably used. These commercial products include Sun-Aid SI-L85,
I-L110, SI-L145, SI-L150,
And SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.). These compounds can be used alone or in combination of two or more.

The latent photoacid generator used in the present invention comprises:
It is a compound that generates an acid when irradiated with ultraviolet light of usually 1 to 100 mJ, preferably 10 to 50 mJ. Examples of the photoacid generator include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, and diphenyliodonium. Nonafluoro n-
Butanesulfonate, bis (4-t-butylphenyl)
Iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4 -T-butylphenyl) iodonium nonafluoro n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl (4- Methylphenyl) sulfonium trifluoromethanesulfonate, diphenyl (4-methoxyphenyl) sulfate Trifluoromethanesulfonate, (hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfoniumtrifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfoniumtrifluoromethanesulfonate, dimethyl (2-oxocyclohexyl) sulfoniumtrifluoromethane Sulfonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfone 4-cyano 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyl-diethylsulfonium Trifluoromethanesulfonate, 4
-Nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfoniumtrifluoromethanesulfonate,
4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-ethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxyethoxy) -1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-methoxyethoxy) -1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbenyloxy-1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- n-butoxycarbyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1- Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-
(2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-
Onium salt-based photoacid generators such as (naphthyl acetomethyl) tetrahydrothiophenium trifluoromethanesulfonate; phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl- Halogen-containing compound-based photoacid generators such as bis (trichloromethyl) -s-triazine; 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,3,4 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,4'-tetrabenzophenone or 1,2-naphthoquinonediazide-5
Diazoketone compound-based photoacid generators such as sulfonic acid esters; sulfonic acid compound-based photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane; benzoin tosylate, pyrogallol Trinitrotrifluoromethanesulfonate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-
Examples thereof include sulfonic acid compound-based photoacid generators such as dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate. These can be used alone or in combination of two or more. The proportion of the component (C) used in the composition for a resist underlayer film of the present invention is 1 to 30 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight of the component (A) (in terms of a completely hydrolyzed condensate). 10 parts by weight. When the content of the component (C) is less than 1 part by weight, resist tailing increases,
When the content of the component (C) exceeds 30 parts by weight, undercut of the resist pattern increases.

The content of water in the composition for a resist underlayer film obtained by the method of the present invention is more than 0.1% by weight and 15% by weight.
The following is preferred. When the water content is less than 0.1% by weight, when the composition is stored for a long period of time, residual development tends to occur on the surface during resist development, and the water content is 15% by weight.
If it exceeds, the coating properties of the composition will be poor.

Further, the content of sodium and iron in the composition is preferably 20 ppb or less, particularly preferably 15 ppb or less, from the viewpoint of the resolution of the resist. Sodium and iron may be mixed in from the raw materials used,
Preferably, the raw material is purified by distillation or the like.

The following components may be further added to the composition for a resist underlayer film obtained by the method of the present invention. β-diketones β-diketones include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2
6,6-tetramethyl-3,5-heptanedione, 1,
One or more kinds such as 1,1,5,5,5-hexafluoro-2,4-heptanedione. In the present invention, the content of β-diketone in the composition for a resist underlayer film is preferably 1 to 50% by weight, more preferably 3 to 30% by weight of the total solvent. If β-diketone is added in such a range, a certain storage stability can be obtained, and there is little possibility that the properties such as coating uniformity of the composition for a resist underlayer film are reduced.

Other components such as colloidal silica, colloidal alumina, an organic polymer, and a surfactant may be further added to the composition for a resist underlayer film obtained in the present invention. The colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5%.
-30 μm, preferably 10-20 μm, and the solid content concentration is about 10-40% by weight. As such colloidal silica, for example, Nissan Chemical Industries, Ltd.
Methanol silica sol and isopropanol silica sol; Oscar, etc., manufactured by Sekiyu Kasei Kogyo Co., Ltd. Nissan Chemical Industry Co., Ltd.
Alumina Sols 520, 100, and 200 manufactured by Kawaken Fine Chemical Co., Ltd .; Examples of the organic polymer include a compound having a polyalkylene oxide structure, a compound having a sugar chain structure, a vinylamide-based polymer, a (meth) acrylate compound, an aromatic vinyl compound, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, and a polyamine. Examples thereof include quinoxaline, polyoxadiazole, and a fluoropolymer. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a silicone surfactant, a polyalkylene oxide surfactant And fluorinated surfactants and acrylic surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; In addition to the following product names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products), Gafakku (Dainippon Ink & Chemicals Co., Ltd.), (Sumitomo 3M Co., Ltd.) Fluorad, Asahi guard, Surflon (or more,
Asahi Glass Co., Ltd.), Disperbyk (Big Chemie Japan Co., Ltd.), Solsperse (Zeneca Co., Ltd.)
Manufactured). These surfactants can be used alone or in combination of two or more.

The total solid content of the composition for a resist underlayer film obtained by the method of the present invention is preferably 1 to 20% by weight.
It is appropriately adjusted according to the purpose of use. When the total solid content of the composition is 1 to 20% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is more excellent.
The weight average molecular weight of all the polyorganosiloxane components [the hydrolyzed condensate of the component (A)] in the composition thus obtained is usually about 500 to 120,000, preferably about 800 to 100,000. It is.

In order to further improve the adhesion between the resist underlayer film formed from the composition for a resist underlayer film obtained by the method of the present invention and the resist, the surface of the resist underlayer film may be subjected to a methylsilylation treatment. . Examples of the silylation agent include allyloxytrimethylsilane, N, O-
Bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, bis (trimethylsilyl) urea, trimethylchlorosilane, N- (trimethylsilyl) acetamide, trimethylsilyl azide, trimethylsilyl cyananide, N- (trimethylsilyl) imidazole, 3-trimethylsilyl-2- Oxazolidinone, trimethylsilyl trifluoromethanesulfonate, hexamethyldisilazane, heptamethyldisilazane, hexamethyldisiloxane, N-methyl-
N-trimethylsilyl trifluoroacetamide,
(N, N-dimethylamino) trimethylsilane, nonamethyltrisilazane, 1,1,3,3-tetramethyldisilazane, trimethyliodosilane, and the like can be given. Methylsilylation of the resist underlayer film can be performed by dip coating or spin coating the above silylating agent on the resist underlayer film, or by exposing the resist underlayer film to a vapor atmosphere of the silylating agent. After that, the coating may be heated to 50 to 300 ° C.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described.
A description will be given based on examples. However, the following description generally shows an example of the embodiment of the present invention, and without any particular reason,
The description is not intended to limit the invention.

The composition for a resist underlayer film was evaluated by the following method. (Evaluation of Resist Adhesion) An antireflection film (NFC B007 manufactured by JSR) was applied on a silicon wafer by spin coating, and dried on a hot plate at 190 ° C. for 1 minute. The thickness of the obtained antireflection film was 300 nm.
Next, the resist underlayer film composition was applied by spin coating, and dried on a 180 ° C hot plate for 1 minute and on a 300 ° C hot plate for 1 minute. At this time, the thickness of the resist underlayer film was controlled to 70 nm. Further, a resist (M20G manufactured by JSR) is applied on the resist underlayer film,
Dry at 135 ° C. for 90 seconds. At this time, the thickness of the resist was controlled to 700 nm. Nikon KrF excimer laser irradiator (trade name: NSR-2205 EX)
8A) using a KrF excimer laser (wavelength 248 n)
m) was applied to the substrate at 22 mJ via a quartz mask having a line and space pattern of 0.13 to 0.25 μm (every 0.1 μm). After this, the substrate is
Heated at 5 ° C. for 90 seconds. The resist pattern was observed with a SEM on the substrate after developing with a 2.38% aqueous solution of tetramethylammonium hydroxide for 30 seconds, and a case where no development peeling of the resist pattern occurred was determined as "no peeling".

(Evaluation of Resolution of Resist Pattern) On the substrate after the development, the resist pattern was observed with an SEM, and a resist pattern in which no undeveloped resist remained on the exposed portion was defined as a minimum resolution.

(Evaluation of Alkali Resistance) The resist underlayer film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and the change in the film thickness before and after the immersion was 2%.
In the case of nm or less, it was judged as “good”.

Storage stability The composition for a resist underlayer film stored for 7 days at 45 ° C.
It was applied on an inch silicon wafer using a spin coater. Then, it was dried on a hot plate at 180 ° C. for 1 minute and on a hot plate at 300 ° C. for 1 minute.
The film thickness of the coating film thus obtained was measured using an optical film thickness meter (manufactured by Rudolph Technologies, S
Spectra Laser 200) was used to measure 50 points in the coating film surface. The film thickness of the obtained film thickness was measured, and the storage stability was evaluated based on the film thickness increase rate determined by the following equation. Film thickness increase rate (%) = ((film thickness after storage) − (film thickness before storage)) ÷ (film thickness before storage) × 100 〇: film thickness change rate ≦ 10% △: 10% <film Thickness change rate ≦ 20% ×: 20% <Thickness change rate

Synthesis Example 1 In a quartz separable flask, 60.2 g of distilled tetramethoxysilane was dissolved in 410 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. . Next, 28.5 ion-exchanged water in which 1.25 g of maleic acid was dissolved.
g was added to the solution over 1 hour. Then, at 60 ° C, 4
After reacting for an hour, the reaction solution was cooled to room temperature. 50 ℃
After removing 65 g of a solution containing methanol from the reaction solution by evaporation, 65 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution.

Synthesis Example 2 In a quartz separable flask, 60.2 g of distilled tetramethoxysilane and 0.3 g of diisopropoxytitanium bisethylacetyl acetate were dissolved in 410 g of distilled propylene glycol monoethyl ether, followed by stirring with a three-one motor. Then, the solution temperature was stabilized at 60 ° C. Next, 28.5 g of ion-exchanged water in which 1.25 g of maleic acid was dissolved was added to the solution over 1 hour. afterwards,
After reacting at 60 ° C. for 4 hours, the reaction solution was cooled to room temperature. 65 g of a solution containing methanol from the reaction solution at 50 ° C.
After removal by evaporation, 65 g of distilled propylene glycol monoethyl ether was added to obtain a reaction solution.

Synthesis Example 3 In a quartz separable flask, 60.2 g of distilled tetramethoxysilane was dissolved in 410 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. . Next, 14.2 g of ion-exchanged water in which 1.25 g of oxalic acid was dissolved
Was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 4 hours, the reaction solution was cooled to room temperature. After removing 51 g of a solution containing methanol from the reaction solution at 50 ° C. by evaporation, 51 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution.

Synthesis Example 4 In a quartz separable flask, 60.2 g of distilled tetramethoxysilane was dissolved in 410 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. . Next, 56.9 g of ion-exchanged water in which 1.25 g of malonic acid was dissolved
Was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 4 hours, the reaction solution was cooled to room temperature. After removing 93 g of a solution containing methanol from the reaction solution at 50 ° C. by evaporation, 93 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution.

Synthesis Example 5 In a quartz separable flask, 48.2 g of distilled methyltrimethoxysilane was dissolved in 431 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Was. Next, ion-exchanged water in which 1.25 g of malonic acid is dissolved.
1 g was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 4 hours, the reaction solution was cooled to room temperature. 50
After removing 44 g of a solution containing methanol from the reaction solution by evaporating at 44 ° C., 44 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution.

Synthesis Example 6 In a quartz separable flask, 48.2 g of distilled methyltrimethoxysilane was dissolved in 431 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Was. Next, ion-exchanged water 3 in which 1.25 g of maleic acid was dissolved
4.8 g was added to the solution over 1 hour. Then 60
After reacting at 4 ° C. for 4 hours, the reaction solution was cooled to room temperature.
After removing 60 g of a solution containing methanol from the reaction solution at 50 ° C. by evaporation, 60 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution.

Comparative Synthesis Example 1 In a quartz separable flask, 60.2 g of distilled tetramethoxysilane was dissolved in 431 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Was. Next, 7.1 g of ion-exchanged water in which 1.25 g of maleic acid was dissolved
Was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 4 hours, the reaction solution was cooled to room temperature. After removing 44 g of a solution containing methanol from the reaction solution at 50 ° C. by evaporation, 44 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution.

Comparative Synthesis Example 2 In a quartz separable flask, 60.2 g of distilled tetramethoxysilane was dissolved in 367 g of distilled propylene glycol monopropyl ether, followed by stirring with a three-one motor to stabilize the solution temperature at 60 ° C. Was. Next, 71.2 ion-exchanged water in which 1.25 g of maleic acid was dissolved.
g was added to the solution over 1 hour. Then, at 60 ° C, 4
After reacting for an hour, the reaction solution was cooled to room temperature. 50 ℃
After removing 107 g of a solution containing methanol from the reaction solution by evaporation, 107 g of distilled propylene glycol monopropyl ether was added to obtain a reaction solution.

Example 1 To 50 g of the reaction solution obtained in Synthesis Example 1, 0.09 g of triphenylsulfonium trifluoromethanesulfonate was added as the component (C), the mixture was sufficiently stirred, and filtered through a Teflon filter having a pore size of 0.2 μm. An evaluation was performed. Evaluation results : Adhesion of resist: no peeling Resolution of resist pattern: 0.17 μm Alkali resistance: good (change in film thickness: 0.4 nm) Storage stability: good (film change ratio: 6.3%)

Example 2 To 50 g of the reaction solution obtained in Synthesis Example 1 was added 0.09 g of triphenylsulfonium nonafluoro-n-butanesulfonate as the component (C), and the mixture was sufficiently stirred, and evaluated in the same manner as in Example 1. Was done. Evaluation result Adhesion of resist: no peeling Resolution of resist pattern: 0.18 μm Alkali resistance: good (change in film thickness: 0.6 nm) Storage stability: good (film change ratio: 6.8%)

Example 3 To 50 g of the reaction solution obtained in Synthesis Example 2 was added 0.09 g of triphenylsulfonium trifluoromethanesulfonate as the component (C), and the mixture was sufficiently stirred, and evaluated in the same manner as in Example 1. Evaluation results : Adhesion of resist: no peeling Resolution of resist pattern: 0.18 μm Alkali resistance: good (0.8 nm change in film thickness) Solution storage stability: good (3.7% increase in film thickness)

Example 4 To 50 g of the reaction solution obtained in Synthesis Example 3, 0.09 g of triphenylsulfonium trifluoromethanesulfonate was added as the component (C), and the mixture was sufficiently stirred, and evaluated in the same manner as in Example 1. Evaluation result Adhesion of resist: no peeling Resolution of resist pattern: 0.18 μm Alkali resistance: good (change in film thickness: 1.2 nm) Solution storage stability: good (film growth rate: 7.5%)

Example 5 To 50 g of the reaction solution obtained in Synthesis Example 4 was added 0.09 g of triphenylsulfonium trifluoromethanesulfonate as the component (C), and the mixture was sufficiently stirred, and evaluated in the same manner as in Example 1. Evaluation result : Adhesion of resist: no peeling Resolution of resist pattern: 0.16 μm Alkali resistance: good (film thickness change: 0.2 nm) Solution storage stability: good (film thickness increase rate: 8.2%)

Example 6 To 45 g of the reaction solution obtained in Synthesis Example 1, 5 g of the reaction solution obtained in Synthesis Example 5 and 0.09 g of triphenylsulfonium trifluoromethanesulfonate as the component (C) were added, and the mixture was sufficiently stirred. Evaluation was performed in the same manner as in Example 1. Evaluation results Resist adhesion: no peeling Resist pattern resolution: 0.16 μm Alkali resistance: good (change in film thickness: 0.3 nm) Solution storage stability: good (film growth rate: 5.7%)

Example 7 To 45 g of the reaction solution obtained in Synthesis Example 1, 5 g of the reaction solution obtained in Synthesis Example 6 and 0.09 g of triphenylsulfonium trifluoromethanesulfonate as the component (C) were added, and the mixture was sufficiently stirred. Evaluation was performed in the same manner as in Example 1. Evaluation result : Adhesion of resist: no peeling Resolution of resist pattern: 0.16 μm Alkali resistance: good (change in film thickness: 0.3 nm) Solution storage stability: good (film growth rate: 6.2%)

Comparative Example 1 Triphenylsulfonium trifluoromethanesulfonate (0.09 g) was added as a component (C) to 50 g of the reaction solution obtained in Synthesis Example 7, and the mixture was sufficiently stirred, and evaluated in the same manner as in Example 1. Evaluation result : Adhesion of resist: peeling Alkali resistance: poor (change in film thickness: 2.9 nm)

Comparative Example 2 Triphenylsulfonium trifluoromethanesulfonate (0.09 g) was added as a component (C) to 50 g of the reaction solution obtained in Synthesis Example 8, and the mixture was sufficiently stirred. Evaluation result : Adhesion of resist: No peeling Resolution of resist pattern: Poor (0.25 μm resolution not possible, residual development occurred) Alkali resistance: Good (Film thickness change: 0.2 nm) Solution storage stability: Poor (Film thickness increase rate) 15.9%)

[0050]

According to the present invention, the resolution of the resist pattern and the resist can be improved by adjusting the amount of water added to the hydrolysis condensate of the alkoxysilane to 0.5 mol or more and 2 mol or less per 1 mol of the alkoxyl group. Good adhesion, good resistance to the developer used after exposing the resist,
It is possible to produce a composition for a resist underlayer film having excellent storage stability.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Kinji Yamada 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Akio Saito 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Inside (72) Inventor Yoshihisa Ota 2--11-2, Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd.F-term (reference) 2H025 AA08 AA14 AB16 AC01 AC04 BE00 CB33 CC03 CC20 DA34 DA35 FA12 5F046 CA08 PA08

Claims (9)

[Claims] (A) (A-1) a compound represented by the following general formula (1): R ¹ _a Si (OR ² ) _4-a (1) (R ¹ is a hydrogen atom, A fluorine atom or a monovalent organic group, R ² represents a monovalent organic group, a represents an integer of 0 to 2) and (A-2) a compound represented by the following general formula (2) _{^{R 3 b (R 4 O)}} 3-b Si- (R 7) d -Si (oR 5) 3-c R 6 c ··· (2) (R 3, R 4, R 5 and R ^6, May be the same or different, each represents a monovalent organic group, b and c may be the same or different, each represents a number of 0 to 2, and R ⁷ represents an oxygen atom or — (CH ₂ ) _n Represents-, d is 0 or 1
And n represents a number of 1 to 6. ), At least one compound selected from the group consisting of the alkoxyl group of the compound represented by the general formula (1) and the alkoxyl group of the compound represented by the general formula (2) is added in an amount of 0 per mole. 0.5 to 2 moles of water are added, hydrolyzed,
A method for producing a composition for a resist underlayer film, comprising condensation. 2. The hydrolysis and condensation of the component (A) in the presence of a metal chelate compound represented by the following general formula (3) and / or an acid catalyst. The method for producing the composition for a resist underlayer film according to the above. R ¹⁰ _f M (OR ¹¹ ) _gf (3) (R ¹⁰ is a chelating agent, M is a metal atom, and R ¹¹ is a compound having 2 to 2 carbon atoms.
5 represents an alkyl group or an aryl group having 6 to 20 carbon atoms, g represents the valence of the metal M, and f represents an integer of 1 to g. ) 3. The method for producing a composition for a resist underlayer film according to claim 1, wherein the hydrolysis and condensation of the component (A) are performed in the presence of an organic solvent (B). 4. The method for producing a composition for a resist underlayer film according to claim 3, wherein (B) the organic solvent is a solvent represented by the following general formula (4). R ⁸ O (R ¹² O) _e R ⁹ (4) (R ⁸ and R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or CH ₃ CO—. 1
Represents a valent organic group, R ¹² represents an alkylene group having 2 to 4 carbon atoms, and e represents an integer of 1 to 2. ) 5. The method for producing a composition for a resist underlayer film according to claim 1, wherein the component (A) contains a compound represented by the following general formula (5). Si (OR ² ) ₄ (5) (R ² represents a monovalent organic group.) 6. The composition for a resist underlayer film according to claim 1, wherein the component (A) comprises a compound represented by the following general formula (6) and a compound represented by the following general formula (7). Method of manufacturing a product. _{^{Si (OR 2) 4 ····· (}} 6) (R 2 is a monovalent organic _{^{group.) R 1 n Si (OR}} 2) 4 _{over n ·····} (7) (R ¹ And R ² may be the same or different and each represents a monovalent organic group, and n represents an integer of 1 to ^3. ) 7. A composition for a resist underlayer film obtained by the production method according to claim 1. 8. The composition for a resist underlayer film according to claim 7, further comprising (C) a compound capable of generating an acid by irradiation with ultraviolet light and / or heating. 9. Component (A) (complete hydrolyzed condensate) 1
9. The composition for a resist underlayer film according to claim 8, wherein the content of the component (C) is 1 to 30 parts by weight with respect to 00 parts by weight.