JPH1090908A - Composition for reflection preventing film material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having a high reflection preventing effect, capable of providing an excellent resist pattern without causing the intermixing with a resist layer, and having a high dry etching speed by containing a polymer compound having a specified repeat unit and a specified melamine compound. SOLUTION: This composition contains a polymer compound having a repeat unit represented by the formula, and a melamine compound, guanamine compound, glycol uril compound or urea compound substituted by a group selected from methylol group, alkoxymethyl group, and acyloxymethyl group. In the formula, R<1> represent hydrogen atom, methyl group, cholorine atom, bromine atom or cyano group, X represent a divalent connecting group, P represents 6-14 (n+1)-valent aromatic ring groups or 5-membered to 14-membered heteroaromatic cyclic groups, Y represents an electron donating group, and Z represents a monovalent organic group. (n) represents an integer of 0-3, and when (n) is 2 or more, Y may be the same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for an antireflection film material, which is effective for reducing the adverse effect of reflection from an underlying substrate, and a composition for an antireflection film material in a lithography process using various radiations. The present invention relates to a method for forming a resist pattern.

[0002]

2. Description of the Related Art A photoresist is a semiconductor wafer,
It is applied to a substrate of glass, ceramic or metal by a spin coating method or a roller coating method to a thickness of 0.5 to 2 μm. After that, it is heated and dried, and the circuit pattern and the like are baked with radiation such as ultraviolet rays through an exposure mask,
An image is formed by performing baking after exposure if necessary and then developing. Further, by etching using this image as a mask, a pattern-like processing can be performed on the substrate. Typical application fields include semiconductor manufacturing processes such as ICs, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes.

In microfabrication of a semiconductor using a photoresist, prevention of light reflection from a substrate surface has become an important issue with miniaturization of dimensions. Conventionally, a photoresist containing a light absorbing agent has been used for this purpose, but there is a problem that the resolution is impaired. Therefore, an anti-reflective coating (Bottom Anti-Reflective Coating,
BARC) has been widely considered. As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and α-silicon, and an organic film type including a light absorbing agent and a polymer material are known. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation, whereas the latter is advantageous in that it does not require special equipment,
A number of considerations have been made. For example, Tokiko 7-69
No. 611, comprising a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, a light absorbing agent, and US Pat. No. 5,294,680.
Reaction product of a maleic anhydride copolymer and a diamine type light absorber described in JP-A-6-118631, a resin containing a resin binder and a methylolmelamine-based thermal crosslinking agent described in JP-A-6-118631, JP-A-6-118656. Acrylic resin type anti-reflection coating having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule as described above, a composition comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, JP-A-8-179509 Examples thereof include those obtained by adding a low-molecular-weight light absorber to the polyvinyl alcohol resin described in the publication.

[0004] Physical properties desired as a material for an organic antireflection film include having a large absorbance against radiation,
Insoluble in resist solvent (intermixing with resist layer does not occur), no low molecular diffusion material from anti-reflective coating material into overcoated resist during coating or heating and drying, larger than resist May have a dry etching rate, etc.
oc. SPIE, Vol. 2195, 225-229 (1994).

[0005] However, the compounds described in the above-mentioned patent publications do not satisfy all of these requirements, and improvements thereof have been desired. For example, in the conventional antireflection films, the light absorbing ability of the binder is not sufficient, and it is necessary to separately increase the amount of the light absorbing agent. Also, in order to prevent intermixing with the resist layer, it is necessary to introduce a thermal crosslinkable function into the antireflection film, and since the thermal crosslinkable function was introduced independently of the light-absorbing group, it was attempted to increase the crosslinkability. There is a problem that the absorbance decreases. Further, when the crosslinking system contains a functional group that enhances alkali permeability such as a carboxylic acid group, the development of an alkaline aqueous solution causes a problem that the antireflection film swells and the resist pattern shape is deteriorated. there were.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an excellent anti-reflection effect, no intermixing with a resist layer, an excellent resist pattern, and a high dry etching rate as compared with a resist. Another object of the present invention is to provide a composition for an antireflection film material which does not cause a decrease in absorbance or swelling of the antireflection film due to development, and a method for forming a resist pattern using the same.

[0007]

The above object of the present invention is attained by the following constitutions. (1) (a) a polymer compound having a repeating unit represented by the following general formula (1), and (b) a methylol group,
A composition for an antireflection film material, comprising a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one group selected from an alkoxymethyl group and an acyloxymethyl group.

[0008]

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In the formula (1), R¹Is a hydrogen atom, a methyl group,
A chlorine atom, a bromine atom or a cyano group, X is a divalent linking group,
P is an (n + 1) -valent aromatic ring group having 6 to 14 carbon atoms or
5-membered to 14-membered heteroaromatic ring group, Y is electron donating
A group, Z is a monovalent organic group, n represents an integer of 0 to 3, and n is
In the case of two or more, Y may be the same or different. (2) In the general formula (1), X is a single bond, -O-,
Alkylene group, arylene group, aralkylene group, -CO
_Two-E-, -CONH-E-, -OE-, -CO-E
-, -SO_Two-E- (E is a carbon which may have a substituent
Represents a divalent aromatic ring group having 6 to 14 prime numbers. )
All of which have -CO _Two-, -CO
NH-, -O-, -CO-, -SO_TwoHaving one or more
P may be a (n + 1) -valent phenylene group, naph
Selected from Tylene, Anthrylene, and Thiophene
Y is -OH, -OR^Four, -SR^Four, -N (R
^Five) (R⁶A linking group (R^FourIs carbon number 1-2
Represents zero hydrocarbon groups; ^Five, R⁶Is the same
May be different, a hydrogen atom, a carbon having 1 to 20 carbons
Represents a hydride group. (1).
3. The composition for an antireflection film material according to item 1.

(3) (a) a polymer compound having a repeating unit represented by the general formula (1) described in the above (1),
And (c) an antireflection film containing a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted by at least two groups selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. Material composition. (4) In the general formula (1), Y is -OH, -O
R ⁴ , -N (R ⁵ ) (R ⁶ ), -S (R ⁴ ) (R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are the same or different. Hydrogen atom, carbon number 1 to
Represents 20 hydrocarbon groups. The composition for an antireflection film material according to the above (3), which is a group selected from the group consisting of: (5) The above (3) or (4), wherein the component (c) is a compound represented by the following general formula (2).
3. The composition for an antireflection film material according to item 1.

General formula (2)

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In the formula (2), Y has the same meaning as Y in the formula (1), and P is a trivalent or tetravalent aromatic ring group having 6 to 14 carbon atoms or a 5- to 14-membered heteroaromatic ring. Represents B may be the same or different and represents at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, and m represents an integer of 1-2. (6) In the general formula (2), Y is -OH, -O
R ⁴ , —N (R ⁵ ) (R ⁶ ) or —S (R ⁴ ) (R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are the same or different. Hydrogen atom, carbon number 1
Represents up to 20 hydrocarbon groups. The composition for an antireflection film material according to the above (5), wherein (7) The composition for an anti-reflective coating material according to any one of the above (1) to (6) is applied on a substrate, baked to cure the anti-reflective film, and then formed into a pattern thereon. A method for forming a resist pattern, comprising forming a photoresist layer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The composition for an antireflection film material of the present invention
Represented by the general formula (1) as the component (a) contained in
Polymer compounds having repeating units
It works. In the general formula (1), R¹Is hydrogen
Atom, methyl group, chlorine atom, bromine atom, cyano group
You. X represents a divalent linking group. X is preferably a single bond,
-O-, alkylene group, arylene group, aralkylene
Group, -CO_Two-E-, -CONH-E-, -OE-,
-CO-E-, -SO_Two-E-, and -CO_Two
-, -CONH-, -O-, -CO-, -SO_Two-One
You may have more than one. Provided that E has a substituent
A divalent aromatic ring group having 6 to 14 carbon atoms (Benze
Ring, naphthalene ring, anthracene ring, etc.). here
The arylene group includes phenylene group, naphthylene
And anthrylene groups. Aralkylene group and
So, -C₆H_Four-CH_Two-, -C_TenH ₆-CH
_Two-, -C₁₄H₈-CH_Two-And the like.

P represents an (n + 1) -valent aromatic ring group having 6 to 14 carbon atoms or a 5- to 14-membered heteroaromatic ring group. Examples of the aromatic ring include a benzene ring, a naphthalene ring and an anthracene ring. Examples of the heteroaromatic ring include a thiophene ring, a furan ring, a pyrrole ring, an imidazoyl ring, an isothiazoyl ring, a pyrazoyl ring, an isoxazoyl ring, an indole ring, and a five-membered ring having a sulfur atom in the ring such as an indazole ring. Examples thereof include a 14-membered heteroaromatic ring, and among them, those containing a sulfur atom such as a thiophene ring are preferable because the film refractive index can be increased.

Y represents an electron donating group. The electron donating group refers to a group having a negative Hammett's substituent constant σp. Y is preferably ^{-OH, -OR 4, -SR 4,} -N
(R ⁵ ) and (R ⁶ ). However, R ⁴ has 1 to 1 carbon atoms.
Represents 20 hydrocarbon groups. R ⁴ is a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group,
n-hexyl group, cyclohexyl group, n-octyl group,
2-ethylhexyl group, n-nonyl group, n-decyl group,
An n-lauryl group or an n-stearyl group is preferable, and a methyl group because it does not lower the dry etching rate,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group n-pentyl group, n
Particularly preferred are non-cyclic hydrocarbon groups having 1 to 6 carbon atoms such as hexyl group, 2-hydroxyethyl group, allyl group, 2,3-dichloropropyl group and 2,3-dibromopropyl group. R ⁴ does not necessarily have to be the same, and a plurality of different ones may be mixed.

R ⁵ and R ⁶ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. As R ⁵ and R ⁶ , a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group and a t-butyl group are preferable, and —N (R ⁵ )
Those in which (R ⁶ ) is a morpholino group are also suitable.

Z represents a monovalent organic group, preferably -CO _2- , -CONH-, -O-, -CO-, -S
An alkyl group which may have one or more O ₂ — and an aromatic ring group having 6 to 14 carbon atoms (the same specific examples as described above are mentioned). n represents an integer of 0 to 3, and when n is 2 or more, Y may be the same or different.

The repeating unit represented by the general formula (I) of the present invention can be copolymerized with a non-crosslinkable monomer, whereby fine adjustment of the dry etching rate, the reflectance and the like can be performed. The following are mentioned as such a copolymerization monomer. For example, it has one addition-polymerizable unsaturated bond selected from acrylates, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, and the like. Compound.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (for example, phenyl acrylate, hydroxyphenyl acrylate) Such);

Methacrylic acid esters such as alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl Methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (eg, phenyl methacrylate, hydroxyphenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, wherein the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group as the aryl group) , A carboxyphenyl group, etc.), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms,
For example, methyl group, ethyl group, butyl group, isobutyl group,
Examples include an ethylhexyl group and a cyclohexyl group. ),
N, N-arylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N
-Acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (where the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cycloethyl) Group), N-arylmethacrylamide (the aryl group is a phenyl group,
Examples include a hydroxyphenyl group and a carboxyphenyl group. ), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, and a butyl group), N, N-diarylmethacrylamide (an aryl group includes a phenyl group, and the like), and N-. Hydroxyethyl-N-methylmethacrylamide, N-methyl-
N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ether (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chloride) Phenyl ether, vinyl 2,4
-Dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene,
Benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, Dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3- Trifluoromethylstyrene, etc.), hydroxystyrene (for example, 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-hydroxy-3-methylstyrene) , 4-hydroxy-3,5-dimethylstyrene, 4-hydroxy-3-methoxystyrene, 4-hydroxy-3- (2-hydroxybenzyl)
Styrene), carboxystyrene;

Crotonic esters, such as alkyl crotonates (eg butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.);

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.) or monoalkyl esters;

Acrylic acid, methacrylic acid, crotonic acid,
Examples include itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile, and the like.

In addition, any addition-polymerizable unsaturated compound copolymerizable with the repeating unit represented by the formula (I) may be used.

The content ratio of the repeating unit represented by the general formula (I) to the other copolymer component in the polymer light-absorbing agent is preferably 1: 9 to 9: 1 in terms of molar ratio, more preferably 2: 8.
~ 8: 2, more preferably 2.5: 7.5 to 7.5:
2.5.

The content of the repeating unit represented by the general formula (I) contained in the polymer light absorbing agent of the present invention is 10 to 99% by weight, preferably 30 to 97% by weight, more preferably 50 to 95% by weight. is there.

Hereinafter, specific examples of the polymer compound having a repeating unit represented by the general formula (I) are shown, but the invention is not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The polymer compound of the present invention may be a random copolymer, a block copolymer, a graft copolymer or any structure. The polymer compound forming the antireflection film of the present invention can be synthesized by a method such as radical polymerization, anionic polymerization, or cationic polymerization. Various forms such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization are possible.

The molecular weight of the polymer compound forming the antireflection film of the present invention varies depending on the coating solvent used, the required solution viscosity, the required film shape, and the like. 2000
300,000, more preferably 3000 to 20,000
0.

In the composition for an antireflection coating material of the present invention, the component (a) is substituted with at least one substituent selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group. The melamine compound, guanamine compound, glycoluril compound or urea compound is used to crosslink the polymer light absorbing agent of the component (a) by heating to suppress intermixing with the overcoated photoresist. The content of at least one group among methylol group, alkoxymethyl group and acyloxymethyl group in these compounds is 2 to 6 in the case of melamine, glycoluril, guanamine,
The number of urea compounds is 2 to 4, preferably 5 to 6 for melamine, and 3 to 4 for glycoluril, guanamine and urea compounds.

All of these methylol group-containing compounds are obtained by reacting melamine, glycoluril, guanamine or urea with formalin in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide and the like. Obtained by Further, the alkoxymethyl group-containing compound is a compound containing a methylol group-containing compound in alcohol with hydrochloric acid, sulfuric acid, nitric acid,
It is obtained by heating in the presence of an acid catalyst such as methanesulfonic acid. The acyloxymethyl group-containing compound can be obtained by mixing and stirring the methylol group-containing compound with the acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compounds having the above substituents will be described. Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, and 1 to 5 of the methylol group of hexamethylol melamine.
Examples thereof include a compound or a mixture thereof in which methoxymethylation is performed, a compound in which 1 to 5 methylol groups of hexamethoxyethylmelamine, hexaacyloxymethylmelamine, and hexamethylolmelamine are acyloxymethylated or a mixture thereof. As the guanamine compound, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 3 methylol groups of tetramethylolguanamine are methoxymethylated or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylolguanamine, A compound in which 1 to 3 methylol groups are acyloxymethylated, a mixture thereof, and the like.

Examples of the glycoluril compound include tetramethylolglycoluril, tetramethoxymethylglycoluril, a compound in which one to three methylol groups of tetramethylolglycoluril are methoxymethylated or a mixture thereof, and a methylol group of tetramethylolglycoluril. Or a mixture thereof in which 1 to 3 are acyloxymethylated, or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which one to three methylol groups of tetramethylol urea are methoxymethylated or a mixture thereof, and tetramethoxyethyl urea.

The content of the component (b) in the composition for an antireflective coating material of the present invention is 2 to 50% by weight, preferably 5 to 30% by weight, based on the total solid content.

Next, in the composition for an antireflection film material of the present invention, at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group, which is contained as the component (c) together with the component (a) The phenolic compound, the naphthol compound or the hydroxyanthracene compound substituted with the compound suppresses the intermixing between the component (a) and the overcoated photoresist by thermal crosslinking similarly to the case of the component (b), and further comprises an antireflective coating composition. To further increase the absorbance of

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the component (c) is required to be at least two per molecule. From the viewpoint of thermal crosslinkability and storage stability, two of the phenolic OH groups are required. Compounds in which all of the 4- and 4-positions are substituted are preferred. The naphthol compound and the hydroxyanthracene compound serving as the skeleton are OH
Those in which the 2-position of the group is unsubstituted are preferred. The 3- or 5-position of the phenol compound serving as a skeleton may be unsubstituted or may have a substituent. The naphthol compound serving as the skeleton may be unsubstituted or may have a substituent other than the 2-position of the OH group.

These methylol group-containing compounds use, as a raw material, a phenolic OH group-containing compound in which the 2- or 4-position of the phenolic OH group is a hydrogen atom, and use this compound as sodium hydroxide, potassium hydroxide, ammonia, or tetraalkyl. It is obtained by reacting with formalin in the presence of a basic catalyst such as ammonium hydroxide. Further, the alkoxymethyl group-containing compound can be obtained by heating the above-mentioned methylol group-containing compound in alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, and methanesulfonic acid. The acyloxymethyl group-containing compound is obtained by reacting the methylol group-containing compound with an acyl chloride in the presence of a basic catalyst.

Examples of the skeleton compound include a phenolic compound in which the 2- or 4-position of the phenolic OH group is unsubstituted, naphthol, a hydroxyanthracene compound such as phenol, o-, m-, p-cresol, 2,3-xylenol, , 5-xylenol, 3,4-xylenol,
Bisphenols such as 3,5-xylenol and bisphenol-A, 4,4′-bishydroxybiphenyl,
TrisP-PA (a product of Honshu Chemical Industry Co., Ltd.), dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

Specific examples of the component (c) include trimethylolphenol, tri (methoxymethyl) phenol, a compound in which one or two methylol groups of trimethylolphenol are methoxymethylated, and trimethylol-
A compound in which one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol and trimethylol-3-cresol are methoxymethylated, dimethylol cresol such as 2,6-dimethylol-4-cresol, Tetramethylol bisphenol-A, tetramethoxymethylbisphenol-A A compound in which 1 to 3 methylol groups of tetramethylolbisphenol-A have been methoxymethylated, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4, 4 '
-Bishydroxybiphenyl, hexamethylol form of TrisP-PA, hexamethoxymethyl form of TrisP-PA, 1 to 3 of hexamethylol form of TrisP-PA
Compounds in which five methylol groups are methoxymethylated, such as bishydroxymethylnaphthalenediol. Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene. As the acyloxymethyl group-containing compound, for example, a compound in which the methylol group of the methylol group-containing compound is partially or entirely acyloxymethylated is exemplified.

Preferred among these compounds are trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, Tris
Hexamethylol of P-PA (product of Honshu Chemical Industry Co., Ltd.) or those methylol groups are alkoxymethyl groups,
And a phenol compound substituted with both a methylol group and an alkoxymethyl group.

The component (c) particularly effective for increasing the absorbance is a compound represented by the above formula (2). In the general formula (2), Y has the same meaning as Y in the general formula (1),
Y is preferably _{-OH, -OCH 3, -N (R} 5) (R
^6), - SR is ^{4 (wherein, R 4, R 5, R} 6 are as defined above). m represents an integer of 1 to 2. P is preferably a trivalent or tetravalent phenylene group, a naphthylene group, an anthrylene group, a thiophene group, B is a methylol group,
It represents at least one group selected from an alkoxymethyl group and an acyloxymethyl group. The alkoxy group is preferably one having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. As the acyloxymethyl group, an acetoxymethyl group is particularly preferable.

The compound of the general formula (2) can be synthesized from a phenol compound having a corresponding skeleton as a raw material in the same manner as the component (b).

The content of the component (c) in the composition for an antireflection film of the present invention is 2 to 50% by weight, preferably 5 to 30% by weight based on the total solid content.

The copolymer forming the antireflection film of the present invention may further contain a light absorbing agent, an adhesion aid and a surfactant, if necessary.

Further light absorbing agents include, for example, commercially available light absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and Dye Handbook (edited by Organic Synthetic Chemistry Association), for example, C.I.
I. Disperse Yellow 1,3,4
5,7,8,13,23,31,49,50,51,5
4,60,64,66,68,79,82,88,9
0, 93, 102, 114 and 124, C.I. I. D is
perse Orange1,5,13,25,29,
30, 31, 44, 57, 72 and 73, C.I. I. Di
sperse Red 1,5,7,13,17,1
9, 43, 50, 54, 58, 65, 72, 73, 8
8, 117, 137, 143, 199 and 210;
I. Disperse Violet 43, C.I. I.
Disperse Blue 96, C.I. I. Fluor
escent Brightening Agent 1
12, 135 and 163, C.I. I. Solvent O
renge2 and 45, C.I. I. Solvent Re
d 1, 3, 8, 23, 24, 25, 27 and 49;
C. I. Pigment Green 10, C.I. I.
Pigment Brown 2 or the like can be suitably used. The light absorbing agent is usually used in the composition 10
It is blended in an amount of 50 parts by weight or less, preferably 30 parts by weight or less based on 0 parts by weight.

The adhesion aid is mainly added to improve the adhesion between the substrate or the resist and the composition for the antireflection film material, and particularly to prevent the resist from peeling off in the etching step. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenylsilane. Alkoxysilanes such as enyltriethoxysilane, silazane such as hexamethyldisilazane, N, N'-bis (trimethylsilin) urea, dimethyltrimethylsilylamine and trimethylsilylimidazole, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ
Silanes such as glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, urazole thiouracil, mercaptoimidazole, mercapto Examples include a heterocyclic compound such as pyrimidine, a urea such as 1,1-dimethylurea and 1,3-dimethylurea, and a thiourea compound. These adhesion aids are usually added in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the composition for an antireflection film material.

The composition for an anti-reflective coating material of the present invention is used in order to further improve the coating properties of a striation and the like.
Surfactants can be included. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and polyoxyethylene nonyl. Polyoxyethylene alkyl allyl ethers such as phenol ether, polyoxyethylene
Polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate,
Sorbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tristearate;
1, EF303, EF352 (manufactured by Shin-Akita Chemical Co., Ltd.),
MegaFuck F171, F173 (Dainippon Ink Co., Ltd.)
), Florado FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, S
C104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.)
Such as fluorine-based surfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow Nos. 7
5, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. Among these surfactants, fluorine surfactants and silicon surfactants are particularly preferred.
These surfactants may be added alone, or
It can also be added in several combinations. The amount of these surfactants is usually 2 parts by weight or less per 100 parts by weight of the solid content in the composition for an antireflection film material of the present invention,
It is preferably at most 1 part by weight.

Solvents for dissolving the composition for an antireflective coating material of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl 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, ethyl acetate, Butyl acetate and the like can be used. These organic solvents alone,
Alternatively, they are used in combination of two or more. Furthermore, N-
Methylformamide, N, N-dimethylformamide,
High-boiling solvents such as N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether can be used as a mixture. Among these solvents, cyclopentanone, cyclohexanone, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate are preferred because intermixing with the resist can be further prevented.

In the present invention, as the resist applied on the antireflection film made of the composition of the present invention, both negative and positive resists can be used.
Positive resist composed of naphthoquinonediazide sulfonic acid ester, chemically amplified resist composed of a photoacid generator and a binder having a group capable of decomposing by acid to increase the alkali dissolution rate, or alkali-soluble binder and photoacid generator and acid Chemically amplified resist composed of a low molecular weight compound that decomposes and increases the alkali dissolution rate of the resist, or a binder having a group that decomposes with a photoacid generator and an acid to increase the alkali dissolution rate and a binder that decomposes with an acid to form a resist There is a chemically amplified resist composed of a low molecular compound that increases the alkali dissolution rate. For example, there is FHi-620 manufactured by Fuji Hunt Microelectronics.
BC and ARCH-2.

Examples of the developing solution for the positive photoresist composition using the composition for an antireflection film material of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia and the like. Inorganic alkalis, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanolamine and the like Aqueous solutions of alkali amines such as alcohol amines, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine can be used. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a zonion may be added to an aqueous solution of the above alkalis. Preferred among these developers are quaternary ammonium salts, and more preferred are tetramethylammonium hydroxide and choline.

Next, a method of forming a resist pattern according to the present invention will be described. A substrate (eg, a transparent substrate such as a silicon / silicon dioxide cover, a glass substrate, an ITO substrate, etc.) used for manufacturing a precision integrated circuit device will be described. ) Spinner on,
The composition for an antireflection film material is applied and baked and cured by an appropriate application method such as a coater to form an antireflection film. Here, the thickness of the antireflection film is 0.01 to 3.
0 μm is preferred. The conditions for baking after application are 80 to 250 ° C. for 1 to 120 minutes. Thereafter, a good resist can be obtained by applying a photoresist, exposing through a predetermined mask, developing, rinsing and drying. Heat after exposure if necessary (PEB: Po
stExposure Bake) can also be performed.

By using the polymer light-absorbing agent having a repeating unit represented by the general formula (1) of the present invention, the light-absorbing group contained in the anti-reflection film can have high absorbance and
A large dry etching rate can be realized because the amount of the aromatic cyclic carbon atoms introduced is suppressed. The composition for an anti-reflection coating material of the present invention has no light diffusion part in the resist at the time of heating and drying because the light absorbing part is connected to the polymer resin side chain, and the light absorbing part has a sufficiently large absorption coefficient. It has an excellent anti-reflection effect because it has, and the content (weight fraction) of cyclic carbon such as aromatic ring contained in the light absorbing part is small,
Even if the amount of the light-absorbing portion is increased to increase the absorbance, the decrease in the dry etching rate is small.

[0065]

EXAMPLES Examples of the present invention will be described below, but the content of the present invention is not limited to these examples.

Synthesis Example 1 To 214 g of acetoacetoxyethyl methacrylate (a product of Nippon Synthetic Chemical Industry Co., Ltd.) was added 600 ml of methanol, and then 122 g of 4-hydroxybenzaldehyde and 10 g of methanesulfonic acid were added. After reacting at 60 ° C. for 4 hours, 1 liter of distilled water was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. Yield 74%, λmax 338 nm (methanol).

[0067]

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Synthesis Example 2 214 g of acetoacetoxyethyl methacrylate (a product of Nippon Synthetic Chemical Industry Co., Ltd.) was added to 600 ml of methanol, and then 152 g of 3-methoxy-4-hydroxybenzaldehyde and 5 g of piperidine were added. 4 at 60 ° C
After reacting for an hour, 1 liter of distilled water was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. Yield 83%, λmax 358 nm (methanol).

[0069]

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Synthesis Example 3 (bis (4-hydroxy, 3,5
-Dihydroxymethylstyryl) ketone 122 g of 4-hydroxybenzaldehyde, acetone 3
After 0 g was added to 300 ml of methanol, 5 g of piperidine was added and the mixture was stirred at 70 ° C. for 4 hours. By slowly adding 1000 ml of distilled water to the reaction solution, yellow crystals of bis (4-hydroxystyryl) ketone were obtained. After dissolving 50 g of these yellow crystals in 200 ml of methanol, 100 ml of an aqueous sodium hydroxide solution (10%)
Was added. There formalin (37% aqueous solution) 50m
1 was added dropwise over 30 minutes (so that the reaction solution temperature did not rise to 40 ° C. or higher). After stirring the reaction solution for 10 hours, it was neutralized with acetic acid, and the precipitated yellow powder was collected by filtration. The crude crystals were recrystallized from methanol. Yield 54%.

[0071]

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Synthesis Example 4 (Synthesis of Specific Example (1)) After 14 g of the methacrylic monomer obtained in Synthesis Example 1 and 6 g of methyl methacrylate were dissolved in 60 g of methanol, nitrogen was removed from the reaction solution for 30 minutes. While maintaining the reaction solution at 65 ° C, V-65 was used as a polymerization initiator.
(Product of Wako Pure Chemical Industries, Ltd.) 50 mg was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 L of distilled water. GPC analysis of the obtained polymer showed that the weight average molecular weight was 4,300 in terms of standard polystyrene.

Synthesis Example 5 (Synthesis of Specific Example (2)) After dissolving 20 g of the methacrylic monomer obtained in Synthesis Example 2 and 8 g of 2-hydroxyethyl acrylate in 60 g of methanol, nitrogen was added to the reaction solution for 30 minutes. I did. While maintaining the reaction solution at 65 ° C, V-65 was used as a polymerization initiator.
(Product of Wako Pure Chemical Industries, Ltd.) 50 mg was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 L of distilled water. The obtained polymer was subjected to a GPC analysis and was found to have a weight average molecular weight, converted into that of standard polystyrene, of 6,300.

Synthesis of Resin of Comparative Example 1 After dissolving 18 g of 4 '-(3-methyl-4-methoxycinnamoyl) phenyl acrylate, 4.5 g of methacrylic acid and 9 g of glycidyl methacrylate in 60 g of DMF, the reaction solution was treated with 65 g of DMF. C., and at the same time, nitrogen was passed through the reaction solution for 30 minutes. As a polymerization initiator, 50 mg of V-65 (a product of Wako Pure Chemical Industries, Ltd.) was added three times every two hours.
The reaction product was recovered as a powder by reprecipitation in 1 L of distilled water. GPC analysis of the obtained polymer showed that the weight average molecular weight was 900 in terms of standard polystyrene.
It was 0.

[0075]

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Examples 1 and 2 and Comparative Example 1 18 g of the polymer light absorbing agent obtained in Synthesis Examples 4 and 5 and 2 g of hexamethoxymethylolmelamine were dissolved in ethoxyethyl propionate to form a 10% solution, and the pore diameter was 0.10 μm. Was filtered using a Teflon microfilter to prepare an antireflection coating solution. In Comparative Example 1, an antireflection coating solution was prepared in the same manner as in Examples 1 and 2, except that 20 g of the resin of Comparative Example 1 was used instead of the polymer light absorbing agents of Examples 1 and 2.

Examples 3 and 4 An antireflection coating solution was obtained in the same manner as in Examples 1 and 2, except that 2.0 g of tetramethylol bisphenol A was used instead of hexamethoxymethylol melamine of Examples 1 and 2.

Examples 5 to 6 In the same manner as in Examples 1 and 2 except that 2.0 g of bis (4-hydroxy-3,5-dihydroxymethylstyryl) ketone was used instead of hexamethoxymethylolmelamine of Examples 1 and 2. Thus, an antireflection coating solution was obtained.

(Evaluation Test) Examples 1 to 6 and Comparative Example 1
Was filtered using a Teflon microfilter having a pore size of 0.10 μm, and then applied to a silicon wafer using a spinner. Heating was performed at 170 ° C. for 3 minutes on a vacuum contact hot plate to form an antireflection film. The thickness of the antireflection film was all set to 0.17 μm. Then, these antireflection films were immersed in a coating solvent used for the resist, for example, γ-butyrolactone or ethoxyethyl propionate, and were confirmed to be insoluble in the solvent.

After applying FHi-620BC (a product of Fuji Hunt Electronics Technology Co., Ltd.) as a positive photoresist on the obtained anti-reflection film (resist film thickness 0.85 μm), a reduction projection exposure apparatus (Nikon Corporation) After exposure using NSR-2005i9C)
It was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute and dried for 30 seconds. The resist pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the critical resolution and the film thickness dependency were examined. The film absorbance at 365 nm and the dry etch rate were also evaluated.

Here, the film absorbance at 365 nm was measured on a quartz plate.
Apply an anti-reflective coating composition to the film, heat and dry to form a film,
It was measured by Shimadzu Corporation spectrophotometer UV-240.
Measured. The limit resolution is 0.85 μm
0.50μm mask exposure pattern
Means the maximum resolution. Film thickness dependence is resist film thickness
Sensitivity at 0.85 μm and thickness at 0.87 μm
It was evaluated by the sensitivity ratio. The closer this value is to 1.0, the better
Good. Dry etch speed is CS manufactured by Japan Vacuum Engineering Co., Ltd.
CF by E-1110_Four/ O _TwoWas measured under the following conditions.
Table 1 shows the results of the evaluation.

[0082]

[Table 1]

From these results, it is clear that the composition for an antireflection film material of the present invention has a high film absorbance, is excellent in the limit resolution of a photoresist, and has a film thickness dependence of a sensitivity caused by a standing wave due to a reduction in reflected light from a substrate. It can be seen that the dry etching rate is sufficient. In Comparative Example 1, an undercut shape was observed at the lower portion of the resist profile, whereas in Examples 1 to 6, the resist profile was excellent without undercut or skirting.

Synthesis Example 9 After adding 214 g of acetoacetoxyethyl methacrylate (a product of Nippon Synthetic Chemical Industry Co., Ltd.) to 600 ml of methanol, 206 g of 9-anthraldehyde and 5 g of piperidine were added. After reacting at 60 ° C. for 4 hours, 1 liter of distilled water was added, and the precipitated crude crystals were collected by filtration.
The crude crystals were recrystallized with ethanol-water. Yield 85%.

[0085]

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Synthesis Example 10 After adding 214 g of acetoacetoxyethyl methacrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) to 600 ml of methanol, 5-hydroxy-2-naphthaldehyde 17 was added.
3 g and 5 g of piperidine were added. After reacting at 60 ° C. for 4 hours, 1 liter of distilled water was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. Yield 85%.

[0087]

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Synthesis Example 11 (Synthesis of Specific Example (13)) After dissolving 4 g of the methacrylic monomer and 12 g of methyl methacrylate obtained in Synthesis Example 9 in 60 g of DMF, the reaction solution was heated to 65 ° C. and reacted simultaneously. Nitrogen was passed through the liquid for 30 minutes. V-6 as a polymerization initiator
5 (product of Wako Pure Chemical Industries, Ltd.) was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 L of distilled water. GPC analysis of the obtained polymer showed a weight average molecular weight of 4,000 in terms of standard polystyrene.

Synthesis Example 12 (Synthesis of Specific Example (10)) After dissolving 4 g of the methacrylic monomer, 8 g of ethyl methacrylate and 4 g of acrylonitrile obtained in Synthesis Example 10 in 60 g of DMF, the reaction solution was heated to 65 ° C. At the same time, nitrogen was passed through the reaction solution for 30 minutes. V-6 as a polymerization initiator
5 (product of Wako Pure Chemical Industries, Ltd.) was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 L of distilled water. GPC analysis of the obtained polymer showed a weight average molecular weight of 4,000 in terms of standard polystyrene.

Synthesis of Resin of Comparative Example 2 208 g of 9-hydroxymethylanthracene, 101 g of triethylamine and 1 g of hydroquinone were dissolved in 1 liter of DMF. 90 g of acryloyl chloride was added dropwise thereto over 2 hours so that the temperature of the reaction solution did not exceed 30 ° C. 2 L of distilled water was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. Yield 75%. After dissolving 7 g of the obtained acrylic monomer and 12 g of methyl acrylate in 60 g of DMF, the reaction solution was heated to 65 ° C., and nitrogen was simultaneously passed through the reaction solution for 30 minutes. V-65 as a polymerization initiator (product of Wako Pure Chemical Industries, Ltd.)
50 mg was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 L of distilled water. GPC analysis of the obtained polymer showed a weight average molecular weight of 4,000 in terms of standard polystyrene.

[0091]

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Examples 7 to 8 and Comparative Example 2 18 g of the polymer light absorbing agent obtained in Synthesis Examples 11 to 12 and 2 g of hexamethoxymethylolmelamine were dissolved in ethoxyethyl propionate to form a 10% solution, and the pore size was 0.10 μm.
Then, filtration was performed using a Teflon microfilter made of m to prepare an antireflection film solution. This was applied on a silicon wafer using a spinner. Heating was performed at 170 ° C. for 3 minutes on a vacuum contact hot plate to form an antireflection film. Comparative Example 2 is different from the polymer light absorbing agents of Examples 7 and 8 described above,
Using 20 g of the resin of Comparative Example 2, an antireflection coating solution was prepared in the same manner as in Examples 7 and 8 above.

Examples 9 to 10 Instead of hexamethoxymethylol melamine of Examples 7 and 8, 2.0 g of a hexamethylol derivative of TrisP-PA (a product of Honshu Chemical Industry Co., Ltd.) was used. Similarly, an antireflection coating solution was obtained.

(Evaluation Test) The antireflection coating solutions of Examples 7 to 10 and Comparative Example 2 were filtered using a Teflon microfilter having a pore diameter of 0.10 μm, and then applied to a silicon wafer using a spinner. . Heating was performed at 170 ° C. for 3 minutes on a vacuum contact hot plate to form an antireflection film.

The thickness of each of the antireflection films was 0.17 μm.
m. Next, these antireflection films were immersed in a coating solvent used for the resist, for example, γ-butyrolactone or ethoxyethyl propionate, and were confirmed to be insoluble in the solvent. ARCH as a positive photoresist for KrF excimer laser on the obtained antireflection film
-2 (Fuji Hunt Electronics Technology Co., Ltd.)
Product) (film thickness 0.85 μm), exposure using a reduced projection exposure apparatus (NSR-2005i9C, manufactured by Nikon Corporation), post-exposure heating at 110 ° C. for 60 seconds, and 2.38 % Of tetramethylammonium hydroxide aqueous solution for 1 minute and dried for 30 seconds. The resist pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the critical resolution and the film thickness dependency were examined. The film absorbance at 248 nm and the dry etch rate were also evaluated.

Here, the absorbance at 248 nm was measured on a quartz plate.
An anti-reflective coating composition is applied and dried by heating to form a film.
By using Shimadzu Corporation spectrophotometer UV-240
It was measured. The limit resolution is 0.85 μm
0.50μm mask exposure pattern
Means the maximum resolution. Film thickness dependence is resist film thickness
Resolution at 0.85μm and thickness at 0.87μm
It was evaluated by the ratio of the resolving power. As this value approaches 1.0,
Which is preferable. Dry etch speed is manufactured by Japan Vacuum Engineering Co., Ltd.
CF by CSE-1110_Four/ O _TwoUnder the conditions of
Was. Table 2 shows the results of the evaluation.

[0097]

[Table 2]

From these results, it is clear that the composition for an antireflection coating material of the present invention has a high film absorbance, is excellent in the limit resolution of a photoresist, and has a dependency on the film thickness of the sensitivity caused by the standing wave due to the reduction of the reflected light from the substrate. It can be seen that it has been reduced.

[0099]

As described above, according to the present invention, an excellent antireflection effect, no intermixing with a resist layer occurs, an excellent resist pattern can be obtained, and a high dry etching rate as compared with a resist can be obtained. It is possible to provide a composition for an antireflection film material that does not cause a decrease in absorbance or swelling of the antireflection film due to development, and a method for forming a resist pattern using the same.

Claims (7)

[Claims] (1) a polymer compound having a repeating unit represented by the following general formula (1), and (b) at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A composition for an antireflection film material, comprising a substituted melamine compound, a guanamine compound, a glycoluril compound or a urea compound. Embedded image In the formula (1), R ¹ is a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or a cyano group, X is a divalent linking group, and P is C 6
~ 14 (n + 1) -valent aromatic ring groups or 5-membered rings ~ 14
A membered heteroaromatic group, Y is an electron donating group, Z is a monovalent organic group, n is an integer of 0 to 3, and when n is 2 or more,
May be the same or different. 2. In the general formula (1), X is a single bond,-
O-, an alkylene group, an arylene group, an aralkylene group,
_{-CO 2 -E -, - CONH-} E -, - O-E -, - C
_{O-E -, - SO 2} -E- (E represents a divalent aromatic ring group which may be several 6 to 14 carbon substituted.) A linking group selected from, In any case, -CO _2- ,
-CONH -, - O -, - CO -, - SO 2 - may have one or more, P is (n + 1) valent phenylene group, naphthylene group, anthrylene group, selected from thiophene group group in it, Y is -OH, -OR ^4, -SR ^4,
-N (R ⁵⁾ linking group selected from (R ⁶⁾ (R ⁴ represents 1-20 hydrocarbon group having a carbon number, R ^5, R ⁶ may be different even in the same, Hydrogen atom, carbon number 1-2
Represents 0 hydrocarbon groups. 2. The composition for an antireflective coating material according to claim 1, wherein 3. A compound selected from (a) a polymer compound having a repeating unit represented by the general formula (1) according to claim 1, and (c) a methylol group, an alkoxymethyl group, or an acyloxymethyl group. A composition for an anti-reflective coating material, comprising a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted by at least two groups with at least two groups. 4. In the general formula (1), Y is -OH,-
OR ⁴ , -N (R ⁵ ) (R ⁶ ), -S (R ⁴ ) (R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are different even if they are the same. Hydrogen atom, carbon number 1
Represents up to 20 hydrocarbon groups. 4. The composition for an anti-reflective coating material according to claim 3, which is a group selected from the group consisting of: 5. The composition according to claim 3, wherein the component (c) is a compound represented by the following general formula (2).
3. The composition for an antireflection film material according to item 1. General formula (2) In the formula (2), Y has the same meaning as Y in the general formula (1), and P is a trivalent or tetravalent aromatic ring group having 6 to 14 carbon atoms or 5
Represents a 14-membered heteroaromatic ring. B may be the same or different and represents at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, and m represents an integer of 1-2. 6. In the general formula (2), Y is -OH,-
OR^Four, -N (R^Five) (R⁶) Or -S (R^Four) (R^Four
Represents a hydrocarbon group having 1 to 20 carbon atoms; ^Five, R⁶Is
Same or different, hydrogen atom, carbon number
Represents 1 to 20 hydrocarbon groups. )
The composition for an antireflection film material according to claim 5, wherein 7. The composition for an anti-reflective coating material according to claim 1, applied to a substrate, baked to cure the anti-reflective coating, and then patterned in a photolithographic manner. A method for forming a resist pattern, comprising forming a resist layer.