JPH10120940A - Composition for bottom anti-reflective coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition capable of providing a bottom anti-reflective coating excellent in light absorbing ability and having high anti-reflective effect in resist pattern-forming process by compounding a specific light-absorbing agent with a specific compound having large light-absorbing action. SOLUTION: This composition comprises (A) a polymer comprising a recurring unit selected from recurring units of formulas I to III [R<1> is H, a 1-20C alkyl, etc.; R<2> and R<3> are each H, OH, etc.; X is a divalent group; P<1> and P<2> are each a 5-14C aromatic group; Y<1> and Y<2> are each an electron donating group or a halogen; (m) and (n) are each 0-3; Q is oxygen atom. CO, etc.] as a light-absorbing component and (B) a compound replaced with a group selected from methylol, an alkoxymethyl and an acyloxymethyl and selected from melamine derivatives, guanamine derivatives, glycoluryl derivatives and urea derivatives (e.g. hexamethylomelamine). The weight average molecular weight of the component A is preferably 3,000 to 200,000. The content of the component B is preferably 5-30wt.% based on total solid content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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 are semiconductor manufacturing processes such as IC,
Manufacturing of circuit boards such as liquid crystal and thermal head, 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 Coatin) is placed between the photoresist and the substrate.
g, 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. For the former, vacuum deposition equipment, CVD equipment,
While the latter requires equipment such as a sputtering apparatus, the latter is advantageous in that no special equipment is required, and many studies have been made. For example, a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorbing agent, and a maleic anhydride copolymer described in U.S. Pat. No. 5,294,680. Those comprising a reaction product of a diamine type light absorbing agent, those comprising a resin binder and a methylolmelamine-based thermal crosslinking agent described in JP-A-6-118631, and those comprising a carboxylic acid group and an epoxy group described in JP-A-6-118656. Low-molecular-weight absorbers made of an acrylic resin having a light-absorbing group in the same molecule, those made of methylolmelamine and a benzophenone-based light-absorbing agent described in JP-A-8-87115, and those of a polyvinyl alcohol resin described in JP-A-8-179509. And the like.

[0004] Physical properties desired as a material for an organic antireflection film include having a large absorbance against radiation,
Insoluble in the resist solvent (intermixing with the resist layer does not occur), there is no low molecular diffusion material from the antireflective coating composition to the overcoated resist during coating or heating and drying, compared to the resist Have a large dry etching rate, etc.
Proc. SPIE, Vol. 2195, 225-229 (1994).

[0005] However, the compounds described in the above patent publications do not satisfy all of these requirements, and improvements thereof have been desired. For example, conventional anti-reflective coatings do not have sufficient light absorption capacity of the binder and require additional use of a light absorbing agent. To prevent intermixing with the resist layer (interdiffusion), the anti-reflective coating has a heat-crosslinking function. However, since the cross-linking function was introduced independently of the light-absorbing group, there was a problem that an attempt to increase the cross-linking property caused a decrease in absorbance. Further, those containing a functional group such as a carboxylic acid group which enhances alkali permeability in the cross-linking system have a problem that when development is performed with an alkaline aqueous solution, the antireflection film swells and the resist pattern shape is deteriorated. .

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resist pattern forming process which is excellent in light absorption ability.
An object of the present invention is to provide a composition for an antireflection film capable of providing an antireflection film having a high antireflection effect. Another object of the present invention is to
An object of the present invention is to provide an antireflection film composition that can prevent mutual diffusion between a resist and an antireflection film composition during heating and drying, which is one step of a resist pattern formation process. It is another object of the present invention to provide a composition for an antireflection film which does not cause deterioration of the resist pattern shape. It is another object of the present invention to provide a composition for an anti-reflection film capable of providing an anti-reflection film having a higher dry etching rate than a resist. Still another object of the present invention is to provide a method for forming a resist pattern using the composition for an antireflection film.

[0007]

According to the present invention, (A)
A polymer having at least one type of repeating unit (a) selected from the group consisting of repeating units represented by the following general formulas (1), (2) and (3) as a light absorbing agent component; (B) a melamine derivative substituted with at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group;
There is provided a composition for an antireflection film, comprising: at least one compound (b) selected from the group consisting of a guanamine derivative, a glycoluril derivative and a urea derivative. A polymer comprising, as an agent component, at least one type of repeating unit (a) selected from the group consisting of repeating units represented by the following general formulas (1), (2) and (3); (C) at least two hydrogen atoms bonded to the aromatic ring are
At least one compound selected from the group consisting of a phenol derivative, a naphthol derivative and a hydroxyanthracene derivative, which is substituted by at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group ( c), and a method for forming a resist pattern characterized by using these antireflection film compositions. The objectives and advantages are achieved.

[0008]

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(In the above formula, R ¹ is a hydrogen atom, carbon number 1
Represents an alkyl group, a halogen atom, and a cyano group of -20;
R ² and R ³ are the same or different and are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,
X represents a divalent group; P ¹ represents —OH or —SH;
And P ² are the same or different and represent an aromatic group having 6 to 14 carbon atoms; Y ¹ and Y ² are the same or different and represent an electron donating group or a halogen atom; The same or different and represents an integer of 0 to 3, and when m and n are each 2 or 3, a plurality of Y ¹ and Y ² may be the same or different; , -CO-, a sulfur atom, -NR'- (where R 'represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a single bond or an alkylene group. )

The polymer having a repeating unit (a), which is a light-absorbing agent component of the composition for an antireflection film of the present invention, has a light-absorbing portion linked to the polymer side chain, so that the resist can be dried by heating. Since there is no diffused substance inside, and the light absorbing portion has a sufficiently large light absorption coefficient, the antireflection film has a high antireflection effect, and the content of cyclic carbon such as aromatic ring contained in the light absorbing portion ( (Weight fraction) is small, so that even if the addition amount of the light absorbing portion is increased for the purpose of further increasing the absorbance, the decrease in the dry etching rate is small. The compound (b) acts as a thermal crosslinking agent, and makes it possible to insolubilize a polymer having the repeating unit (a) in a solvent by heating. The compound (c) acts as a thermal crosslinking agent similarly to (b), but at the same time has a light absorbing structure, so that the antireflection ability of the antireflection film can be further enhanced. Hereinafter, the present invention will be described in detail, which will clarify other objects and advantages of the present invention.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the polymer which is a light absorbing agent component of the composition for an antireflection film of the present invention, R ^{1 of the} above general formulas (1), (2) and (3) representing the repeating unit (a) is used. Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, preferably a hydrogen atom, a methyl group, a chlorine atom,
It represents a bromine atom or a cyano group, more preferably a hydrogen atom or a methyl group. R ² and R ³ are the same or different and are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (the hydrocarbon group may be substituted by a halogen atom or an —OH group), An alkoxy group of -OH
Or -SH, preferably a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an -OH group.
Preferred examples of R ² and R ³ include 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,
Examples thereof include an n-lauryl group and an n-stearyl group. From the viewpoint of not reducing the dry etching rate, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
acyclic hydrocarbon groups having 1 to 6 carbon atoms such as n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-hydroxyethyl group, allyl group, 2, 3
-Dichloropropyl and 2,3-dibromopropyl are particularly preferred.

X represents a divalent linking group, preferably having a single bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms which may have a substituent or a substituent. An aralkylene group having 7 to 15 carbon atoms which may be present. Further, any of these groups may have -O-, -CO
-, - NH -, - CO 2 -, - CONH- and -SO ₂
At least one group selected from-is preferably 1
A divalent group formed by linking two or two groups is also preferable. Preferred specific examples include the following. -C ₆ H ₄ -CH ₂ -O- -C ₆ H ₄ -SO ₃ --C ₆ H ₄ -CH ₂ -NH- -C ₆ H ₄ -SO ₂ NH- -CONH-C ₆ H ₄ -CH _{2 -O- -CONH-C 6 H 4} -SO 3 - -CONH-C 6 H 4 -CH 2 -NH- -CONH-C 6 H 4 -SON 2 NH- -COO-C 6 H 4 -CH 2 —O——COO—C ₆ H ₄ —SO ₃ ——COO—C ₆ H ₄ —CH ₂ —NH——COO—C ₆ H ₄ —SO ₂ NH——CO ₂ CH ₂ CH ₂ CH (OH) CH ₂ O-

P ¹ and P ² are the same or different and each have 5 carbon atoms.
To 14 aromatic groups. The aromatic group can include a heteroatom in the aromatic ring. And the aromatic group is
Preferably, a 5- to 14-membered aromatic ring including a heteroaromatic ring is used as a basic skeleton. Specific examples of the aromatic ring include hydrocarbon aromatic rings such as benzene ring, naphthalene ring and anthracene ring; thiophene ring, furan ring, pyrrole ring, imidazoyl ring, isothiazoyl ring, pyrazoyl ring, isoxazoyl ring, indole ring, indazole Oxygen such as rings,
Heteroaromatic rings having nitrogen and sulfur atoms in the ring are mentioned. In the case of a heteroaromatic ring, those containing a sulfur atom such as a thiophene ring are preferred from the viewpoint of increasing the film refractive index. Particularly preferred aromatic groups are phenylene, naphthylene and anthrylene.

Y ¹ and Y ² are the same or different and represent an electron donating group, a chlorine atom, a bromine atom or an iodine atom.
The electron donating group is a group having a negative Hammett's substituent constant σ _p , and is preferably -OH, -OR ⁴ , -SR ⁴ ,
—NR ⁵ R ⁶ . Here, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom may be substituted by a halogen atom or —OH. R ⁵ and R ⁶ are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ and R ⁶ may be bonded to each other via —O— to form a cyclic structure containing a nitrogen atom.
Preferred specific examples of R ⁴ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-lauryl, n-butyl A stearyl group can be used. From the viewpoint of not lowering the dry etching rate, a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group,
acyclic hydrocarbon groups having 1 to 6 carbon atoms, such as n-hexyl group, allyl group, 2,3-dichloropropyl group, 2, 3
-Dibromopropyl groups are particularly preferred.

Preferred examples of R ⁵ and R ⁶ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl and n-butyl.
-Pentyl group, n-hexyl group, cyclohexyl group, n
-Octyl group, 2-ethylhexyl group, n-nonyl group,
Examples thereof include n-decyl group, n-lauryl group, n-stearyl group, allyl group and the like, among which methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl. And a t-butyl group are more preferred. Further, those in which —NR ⁶ R ⁷ is a morpholino group are also suitable. m
And n are the same or different and are integers from 0 to 3,
When m and n are each 2 or 3, a plurality of Y1 and Y2 may be the same or different. Q represents an oxygen atom, -CO-, a sulfur atom, -NR'-, a single bond, or an alkylene group. Here, R ′ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

The polymer containing the repeating unit represented by the general formulas (1) to (3), which is a light absorbing agent component of the composition for an antireflection film of the present invention, has a light absorbing property contained in the antireflection film. Since the group has a high absorbance, a large dry etching rate can be realized, and in particular, a compound into which a sulfur atom is introduced has a high refractive index and is particularly advantageous since it increases the light extinction coefficient of the film.

The polymer of the present invention has the general formula (1)
In addition to the repeating unit represented by (6), a repeating unit derived from a non-crosslinkable monomer can be contained by copolymerization, whereby fine adjustment of a dry etching rate, a reflectance, and the like can be performed. The following are mentioned as such a copolymerization monomer. For example, an addition-polymerizable polymer selected from acrylic acid, methacrylic acid, acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters, and the like. It is a compound having one saturated bond. Specifically, for example, acrylates, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate,
Amyl acrylate, cyclohexyl acrylate, ethyl hexyl 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 acrylates (eg, phenyl acrylate, hydroxyphenyl acrylate, etc.);

Methacrylic acid esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms)
Methacrylate (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl 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 methacrylates (eg,
Phenyl methacrylate, hydroxyphenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl groups having 1 to 10 carbon atoms, for example, methyl group, ethyl group, A propyl group, a butyl group, a t-butyl group, a heptyl group, an octyl group, a cyclohexyl group, a benzyl group, a hydroxyethyl group, a benzyl group, etc.), an N-arylacrylamide (as the aryl group, for example, a phenyl group, a tolyl group) A nitrophenyl group, a naphthyl group, a cyanophenyl group, a hydroxyphenyl group, a carboxyphenyl group, etc.), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms,
For example, there are a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, and the like. ), N, N-arylacrylamide (as the aryl group, 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-alkylmethacrylamide (an alkyl group having 1 to 10 carbon atoms)
Such as a methyl group, an ethyl group, a t-butyl group,
Examples include an ethylhexyl group, a hydroxyethyl group, and a cyclohexyl group. ), N-arylmethacrylamide (aryl groups include phenyl, hydroxyphenyl, carboxyphenyl, etc.), N, N-
Dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group and a butyl group), N, N
-Diaryl methacrylamide (as the aryl group,
And a phenyl group. ), N-hydroxyethyl-N
-Methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide and the like; allyl compounds such as allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, lauric acid) Allyl, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol and the like;

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-ethylbutyl 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 ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl 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,
Vinyl cyclohexyl carboxylate, 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, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluors Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc., hydroxystyrene (e.g., 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, etc.), carboxystyrene; crotonic esters such as alkyl crotonates (e.g.,
Dialkyl itaconate (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of maleic acid or fumaric acid (eg, dimethyl maleate) rate,
Dibutyl fumarate) or monoalkyl esters; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile,
Examples include methacrylonitrile and maleilenitrile. In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized with an addition-polymerizable monomer capable of giving a repeating unit represented by the above general formulas (1) to (6) may be used.

The proportion of the repeating unit (a) constituting the polymer, which is the light-absorbing agent component of the composition for an antireflection film of the present invention, is preferably at least 10% by weight, more preferably at least 10% by weight. ~ 99% by weight, more preferably 30%
９７97% by weight, most preferably 50-95% by weight. Hereinafter, specific examples of the polymer used in the composition of the present invention will be shown, but the present invention is not limited thereto.

[0022]

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[0023]

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[0024]

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The polymer (copolymer), which is a light absorber of the composition for an 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 above-mentioned polymer varies depending on the coating solvent used, the required solution viscosity, the required film shape, and the like.
0, preferably 2,000 to 300,000, more preferably 3,000 to 200,000.

Next, the compound (b) and the compound (c) contained in the composition for an antireflection film of the present invention will be described. Compound (b) is selected from the group consisting of a melamine derivative, a guanamine derivative, a glycoluril derivative and a urea derivative substituted with at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group. Selected. The number of the above groups contained in one molecule of the compound (b) is preferably 2 to 6, more preferably 5 or 6, in the case of a melamine derivative, and in the case of a glycoluril derivative, a guanamine derivative and a urea derivative, It is preferably 2 to 4, more preferably 3 or 4. Among the compounds (b), a methylol group-containing compound is obtained by reacting melamine, guanamine or urea with formalin in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia and tetraalkylammonium hydroxide. Is obtained by The alkoxymethyl group-containing compound can be obtained by heating the methylol group-containing compound in an 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 acyloyl chloride in the presence of a base catalyst.

Specific examples of compound (b) include hexamethylol melamine, hexamethoxymethyl melamine, and 1 to 5 of the methylol group of hexamethylol melamine.
A methoxymethylated compound or a mixture thereof, a melamine derivative such as hexamethoxyethylmelamine; one of the methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, or tetramethylolguanamine
A compound or a mixture thereof in which three or more are methoxymethylated, a guanamine derivative such as tetramethoxyethyl guanamine; a methylol group of tetramethylol urea, tetramethoxymethyl urea, or tetramethylol urea
A compound having three methoxymethylated compounds or a mixture thereof,
Urea derivatives such as tetramethoxyethyl urea; and other homopolymers or copolymers of N-methylolacrylamide, or homopolymers or copolymers in which some of the methylol groups are methoxymethylated. Compound (b) may be used alone or
More than one species can be used in combination.

Compound (c) is a phenol wherein at least two hydrogen atoms bonded to the aromatic ring are substituted by at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group. A compound selected from the group consisting of derivatives, naphthol derivatives and hydroxyanthracene derivatives. Thus, compound (c) contains two or more of the above groups per molecule. From the viewpoints of the thermal crosslinking property and storage stability of the composition for an antireflection film of the present invention, a compound in which all of the phenolic hydroxyl groups are completely substituted at positions 2 and 4 is preferable.

Of these preferred compounds (C), 2,4
The compound in which the substituent at the 2-position is a methylol group is prepared by using a phenol compound in which the 2- or 4-position of the phenolic hydroxyl group is unsubstituted, for example, phenol as a raw material, sodium hydroxide, potassium hydroxide, ammonia, It is obtained by reacting with formalin in the presence of a basic catalyst such as alkylammonium hydroxide. The compound (C), in which the substituent at the 2- or 4-position is an alkoxymethyl group, is also an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid and methanesulfonic acid in an alcohol. By heating in the presence of Similarly, the preferred compound (c), in which the substituent at the 2,4-position is an acyloxymethyl group, is obtained by acylating the methylol group-containing compound with an acylating agent in the presence of a basic catalyst. It is obtained by doing.

The starting compound for producing the compound (C) in which the phenolic hydroxyl group is completely substituted at the 2,4-positions is a phenolic compound, naphthol compound or the like, which is unsubstituted at the 2- or 4-position of the phenolic hydroxyl group. A hydroxyanthracene compound such as phenol, o
-, M-, p-cresol, 2.3-xylenol, 2.5-xylenol, 3.4-xylenol,
3.5-xylenol, bisphenols such as bisphenol-A, 4,4'-bishydroxybiphenyl, T
risP-PA (Honshu Chemical Industry Co., Ltd.), naphthol, dihydroxynaphthalene, hydroxyanthracene and the like can be mentioned.

Specific examples of the compound (c) include, for example, trimethylolphenol, tri (methoxymethyl) phenol, and one of the methylol groups of trimethylolphenol.
A compound in which one or two of the methylol groups of trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, and trimethylol-3-cresol are methoxymethylated; 6-
Dimethylol-4-cresol such as dimethylol-cresol tetramethylolbisphenol-A, tetramethoxymethylbisphenol-A A compound in which one to three methylol groups of tetramethylolbisphenol-A are methoxymethylated, tetramethylol-4,4′-bis Hydroxybiphenyl, tetramethoxymethyl-4,4'-
Hexamethylol derivative of bishydroxybiphenyl, TrisP-PA (trade name, product of Honshu Chemical Industry Co., Ltd.),
Hexamethoxymethyl form of TrisP-PA, Tris
1 to 5 of the methylol group of the hexamethylol form of P-PA
Examples include the compound methoxymethylated bishydroxymethylnaphthalenediol. Among such compounds, preferred are trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, hexamethylol of TrisP-PA, or those methylol groups having an alkoxymethyl group or a methylol group and an alkoxymethyl group. Is a phenol compound substituted with both. Further, the compound represented by the following general formula (4) is particularly effective as the compound (c) for the purpose of further increasing the absorbance of the antireflection film.

[0033]

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In the general formula (4), P ³ and P ⁴ are
The same or different, and represents a trivalent or tetravalent aromatic ring having 6 to 14 carbon atoms. The aromatic ring may contain a heteroatom and may be a 5-14 membered hydrocarbon aromatic or heteroaromatic ring. Y ¹ and Y ² are the same meanings as Y ¹ and Y ² in the general formula (1) to (3), preferably, I the same or ^{different, -OH, -OR 4, -SR 4} , -
NR ⁵ R ⁶ . Here, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom may be substituted by a halogen atom. R ⁵ and R ⁶ are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ and R ⁶ may be bonded to each other via —O— to form a cyclic structure containing a nitrogen atom. Multiple Es
Represents the same or different and represents at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group. The alkoxy in the alkoxymethyl group preferably has 1 to 4 carbon atoms, and more preferably a methoxy group and an ethoxy group. s and t
Are the same or different and are 1 or 2.

Specific examples of the compound represented by the general formula (4) include the following compounds.

[0036]

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The above compound can be synthesized from a phenol compound having a corresponding skeleton as a raw material in the same manner as in the compound (b).

The content of the compound (b) or (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. Compound (b) and compound (c) can be used in combination. When used together, the content of both is preferably 2 to 40% by weight in total.

The composition for an antireflection film of the present invention uses a polymer containing a repeating unit (a) as a structural unit contained therein as a light absorbing agent, so that diffusion into a resist during heating and drying is reduced. In addition, the light-absorbing portion of the polymer has a large and sufficient light-absorbing coefficient, so that the effect of preventing reflected light is high, and the content (weight fraction) of cyclic carbon such as an aromatic ring contained in the light-absorbing portion is high. Since it is small, even if the content of the polymer is increased to increase the absorbance and the ratio of the light absorbing portion is increased, the decrease in the dry etching rate is small.

Since the compound (b) or the compound (c) has a large light-absorbing effect, the introduction amount of aromatic cyclic carbon atoms in the polymer component (a) in the antireflection film material can be reduced, so that the compound (b) or the compound (c) is large. A dry etching rate can be realized.

The composition for an antireflection film of the present invention is prepared by using a light absorbing agent other than the above-mentioned polymer, an adhesion aid and a surfactant in combination, if necessary.

Examples of the light absorbing agent other than the above polymer include:
Commercially available light-absorbing agents described in “Technologies and Markets of Industrial Dyes” (CMC Publishing) and Dye Handbook (edited by the Society of Synthetic Organic Chemistry), for example, C.I. I. Disperse Yellow 1,
3, 4, 5, 7, 8, 13, 23, 31, 49, 50,
51, 54, 60, 64, 66, 68, 79, 82, 8
8, 90, 93, 102, 114 and 124; I.
Desperse Orange 1,5,13,2
5, 29, 30, 31, 44, 57, 72 and 73;
C. I. Disperse Red 1,5,7,1
3,17,19,43,50,54,58,65,7
2, 73, 88, 117, 137, 143, 199 and 210; I. Disperse Violet 4
3, C.I. I. Disperse Blue 96, C.I.
I. Fluorescent Brightening
Agent 112, 135 and 163, C.I. I. S
solventOrange2 and 45, C.I. I. Sol
vent Red 1,3,8,23,24,25,2
7 and 49, C.I. I. Pigment Green 1
0, C.I. I. Pigment Brown 2 or the like can be suitably used. These light-absorbing agents are usually the above-mentioned polymer 1 which is a light-absorbing component of the composition for an antireflection film of the present invention.
It can be blended in an amount of 50 parts by weight or less, preferably 30 parts by weight or less based on 00 parts by weight.

The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate or the resist and the antireflection film, and particularly preventing 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 Silanes such as -aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole Heterocyclic compounds such as, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, urazolethiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea and the like Urea or thiourea compounds.

These adhesion aids are usually used 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 above-mentioned polymer which is a light absorbing agent component of the composition for an antireflection film of the present invention. Is done.

In the present invention, a surfactant can be added to the composition for an antireflection film for the purpose of further improving the applicability of a striation and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as 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 trioleate, sorbitan tristearate Fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, Efutotsupu EF301, EF
303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101 , SC102, SC103, SC1
04, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP
No. 341 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid or methacrylic acid (co) polymerized polyflow No. 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. Among these surfactants, fluorine surfactants and silicon surfactants are particularly preferred. The amount of these surfactants to be added is generally 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition for an antireflection film.

These surfactants may be added alone or in some combination.

Solvents for dissolving the antireflective coating composition 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, and propylene glycol methyl. Ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone,
-Ethyl hydroxypropionate, 2-hydroxy-2
-Ethyl methyl propionate, Ethyl ethoxyacetate, Ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-ethoxypropionate, Pyrvin Methyl acid, ethyl pyruvate, ethyl acetate, butyl acetate and the like can be used. These organic solvents are used alone or in combination of two or more. Furthermore, N-methylformamide, N, N-dimethylformamide, N-
Methylacetamide, N, N-dimethylacetamide,
High-boiling solvents such as N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether can be used as a mixture.

Among these solvents, cyclopentanone, cyclohexanone, methyl 3-methoxypropionate,
-Ethyl ethoxypropionate is preferred because intermixing with the resist can be further prevented.

In the present invention, as the resist applied on the antireflection film, both negative and positive resists can be used. However, a positive resist comprising a novolak resin and 1,2-naphthoquinonediazidesulfonic acid ester, a photoacid Chemically amplified resist composed of a binder having a group capable of increasing the alkali dissolution rate by decomposing with a generator and an acid, or a low molecular compound capable of decomposing with an alkali-soluble binder, a photoacid generator and an acid to increase the alkali dissolution rate of the resist Chemically amplified resist composed of a compound, or a chemical amplification composed of a binder having a group that decomposes with a photoacid generator and an acid to increase the alkali dissolution rate and a low molecular compound that decomposes with an acid to increase the alkali dissolution rate of the resist Type resist, for example, F manufactured by Fuji Hunt Microelectronics i-620BC, include ARCH-2.

In the present invention, as a developer for a positive photoresist composition using the composition for an antireflection film, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, etc. Inorganic alkalis, ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine, 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.

Of these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred.

The composition for an anti-reflection film is spin-coated on a substrate (eg, a transparent substrate such as silicon / silicon dioxide coating, a glass substrate, an ITO substrate, etc.) used in the manufacture of precision integrated circuit devices. After baking by an appropriate coating method such as baking, the composition for an antireflection film is cured to form an antireflection film. Here, the thickness of the antireflection film is preferably 0.01 to 3.0 μm. 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, then exposing through a predetermined mask, developing, rinsing, and drying. If necessary, post-exposure heating (PEB: Post Exposure Ba)
ke) can also be performed.

[0053]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. Synthesis Example 1 4,4′-bis (diethylamino) benzophenone 3
After dissolving 2.4 g in 160 ml of methanol, 20 g of hydroxylamine hydrochloride was added. Aqueous sodium hydroxide solution (18 g of sodium hydroxide in 50 ml of distilled water)
Was dissolved therein, and the mixture was reacted under heating and reflux for 3 hours.
400 ml of distilled water was added to the reaction solution, and the precipitated crystals were collected by filtration. Yield 91% 6.8 g of the above crystals were treated with N, N-dimethylformamide 30.
After dissolving in chloromethylstyrene (3.1 g), 2.9 g of a 28% sodium methoxide solution was added.
Was added dropwise. After reacting at 50 ° C. for 4 hours, distilled water 50
ml was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. 63% yield. λ
max 341 nm (methanol)

Synthesis Example 2 After dissolving 21.4 g of 4,4′-dihydroxybenzophenone in 160 ml of methanol, 20 g of hydroxylamine hydrochloride was added. After dropwise adding an aqueous sodium hydroxide solution (18 g of sodium hydroxide dissolved in 50 ml of distilled water), the mixture was reacted under heating and refluxing for 3 hours. 400 ml of distilled water was added to the reaction solution, and the precipitated crystals were collected by filtration. Yield 72% 6.8 g of the above crystals were treated with N, N-dimethylformamide 30.
After dissolving in chloromethylstyrene (3.1 g), 2.9 g of a 28% sodium methoxide solution was added.
Was added dropwise. After reacting at 50 ° C. for 4 hours, distilled water 50
ml was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. 63% yield. λ
max 321 nm (methanol)

Synthesis Example 3 2,4-Diethyl-9H-thioxanthen-9-one 2
After dissolving 7.0 g in 240 ml of methanol, 6.9 g of hydroxylamine hydrochloride was added. Sodium hydroxide aqueous solution (4 g of sodium hydroxide and 30 ml of distilled water)
Was dissolved therein, and the mixture was reacted under heating and reflux for 3 hours.
400 ml of distilled water was added to the reaction solution, and the precipitated crystals were collected by filtration. Yield 59% 6.8 g of the above crystals were treated with N, N-dimethylformamide 30
After dissolving in chloromethylstyrene (3.1 g), 2.9 g of a 28% sodium methoxide solution was added.
Was added dropwise. After reacting at 50 ° C. for 4 hours, distilled water 50
ml was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. Yield 71%.

Synthesis Example 4 21.0 g of N-methyl-9-acridone was added to methanol 2
After dissolving in 40 ml, 6.9 g of hydroxylamine hydrochloride was added. An aqueous sodium hydroxide solution (4 g of sodium hydroxide dissolved in 30 ml of distilled water) was added dropwise, and the mixture was reacted under heating and reflux for 3 hours. Distilled water 40
0 ml was added, and the precipitated crystals were collected by filtration. Yield 47% 6.8 g of the above crystals were treated with N, N-dimethylformamide 30.
After dissolving in chloromethylstyrene (3.1 g), 2.9 g of a 28% sodium methoxide solution was added.
Was added dropwise. After reacting at 50 ° C. for 4 hours, distilled water 50
ml was added, and the precipitated crude crystals were collected by filtration. The crude crystals were recrystallized with ethanol-water. Yield 71%.

Synthesis Example 5 20.0 g of benzoin methyl ether was added to methanol 16
After dissolving in 0 ml, hydroxylamine hydrochloride 20
g was added. After dropwise addition of an aqueous sodium hydroxide solution (18 g of sodium hydroxide dissolved in 50 ml of distilled water),
The reaction was carried out under heating and refluxing for hours. 400 ml of distilled water in the reaction solution
Was added, and the precipitated crystals were collected by filtration. Yield 43
% 6.8 g of the above crystals were added to N, N-dimethylformamide 30.
After dissolving in chlorosulfonylstyrene 3.6.
g, then a 28% solution of sodium methoxide.
9 g was added dropwise. After reacting at 5 ° C for 6 hours, distilled water 5
0 ml was added, and the precipitated crude crystals were collected by filtration.
The crude crystals were recrystallized with ethanol-water. Yield 28%.

Synthesis Example 6 bis (4-hydroxy, 3,5-dihydroxymethylstyryl) ketone 4-hydroxybenzaldehyde 12
After adding 2 g and 30 g of acetone to 300 ml of methanol, 5 g of piperidine was added and 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. 50 g of the yellow crystals were added to methanol 2
After dissolving in 100 ml, sodium hydroxide aqueous solution (10
%) Was added. There formalin (37%
An aqueous solution (50 ml) 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 5
4%

Synthesis Example 7 14 g of the monomer obtained in Synthesis Example 1 and 6 g of methyl methacrylate were dissolved in 60 g of methanol, and nitrogen was passed through the reaction solution for 30 minutes. V-65 (product of Wako Pure Chemical Industries, Ltd.) as a polymerization initiator while maintaining the reaction solution at 65 ° C.
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 8 After dissolving 20 g of the monomer obtained in Synthesis Example 2 and 10 g of 2-hydroxyethyl acrylate in 60 g of methanol, nitrogen was passed through the reaction solution for 30 minutes. While maintaining the reaction solution at 65 ° C., 50 mg of V-65 (a product of Wako Pure Chemical Industries, Ltd.) was added three times every two hours as a polymerization initiator.
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 630 in terms of standard polystyrene.
It was 0.

Synthesis Example 9 10 g of the monomer obtained in Synthesis Example 3 above, 4 g of acrylonitrile and 6 g of methyl methacrylate were added to methanol 60
g, and then nitrogen was passed through 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 10 After dissolving 10 g of the monomer obtained in Synthesis Example 4 and 8 g of 2-hydroxypropyl acrylate in 60 g of methanol, nitrogen was passed through the reaction solution for 30 minutes. While maintaining the reaction solution at 65 ° C., 50 mg of V-65 (a product of Wako Pure Chemical Industries, Ltd.) was added three times every two hours as a polymerization initiator.
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 630 in terms of standard polystyrene.
It was 0.

Synthesis Example 11 After dissolving 11 g of the monomer obtained in Synthesis Example 5 and 9 g of methyl methacrylate in 60 g of methanol, nitrogen was passed through the reaction solution for 30 minutes. V-65 (product of Wako Pure Chemical Industries, Ltd.) as a polymerization initiator while maintaining the reaction solution at 65 ° C.
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 1 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 heated to 65 ° C. , And at the same time, nitrogen was passed through the reaction solution for 30 minutes. V-65 as a polymerization initiator (Wako Pure Chemical Industries, Ltd.)
Product) 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 9000 in terms of standard polystyrene.

Synthesis of Comparative Example 2 208 g of 9-hydroxymethylanthracene, 101 g of triethylamine and 1 g of hydroquinone were dissolved in 1 l 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.

Examples 1 to 5 18 g of the polymer light absorbing agent obtained in Synthesis Examples 7 to 11 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. 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.

Examples 6 to 10 In place of hexamethoxymethylolmelamine of Examples 1 to 5, 2.0 g of a hexamethylol derivative of TrisP-PA (obtained from Honshu Chemical Industry Co., Ltd.) was used. 2
In the same manner as in the above, antireflection coating solutions of Examples 3 and 4 were obtained.

Example 11 In place of hexamethoxymethylol melamine of Example 1, 2.0 g of bis (4-hydroxy, 3,5-dihydroxymethylstyryl) ketone was used in the same manner as in Examples 1-2. The antireflection coating solutions of Examples 3 and 4 were obtained. The antireflection coating solutions of Examples 1 to 11 were 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 is all 0.
It was adjusted to 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.

FHi-620 was used as a positive photoresist on the antireflection films of Examples 1, 6, 11 and Comparative Example 1.
BC (Fuji Hunt Electronics Technology Co., Ltd.)
Product) (resist film thickness 0.85 μm), and then a reduction projection exposure apparatus (NSR-2005i9 manufactured by Nikon Corporation).
After exposure using C), the film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute and dried for 30 seconds. Observing the resist pattern on the silicon wafer thus obtained with a scanning electron microscope,
The critical resolution and the film thickness dependence were investigated. 365 nm
Were also evaluated for membrane absorbance and dry etch rate. Where 3
The absorbance at 65 nm was measured by applying an antireflective coating composition on a quartz plate and drying by heating to form a film, which was measured with a spectrophotometer UV-240 manufactured by Shimadzu Corporation. The critical resolution means a critical resolution at an exposure amount for reproducing a 0.50 μm mask pattern at a film thickness of 0.85 μm. The film thickness dependence was evaluated by the ratio of the resolution at a resist film thickness of 0.85 μm to the resolution at a resist film thickness of 0.87 μm. The closer this value is to 1.0, the better. Dry etch speed is CSE-1110 manufactured by Japan Vacuum Engineering Co., Ltd.
It was measured under F4 / O2 conditions.

The results of the evaluation are shown in Table 1. As a result, the antireflection coating composition of the present invention has high film absorbance, improves the critical resolution of the photoresist, and reduces the film thickness dependence of the sensitivity caused by standing waves due to the reduction of reflected light from the substrate. It turns out that the etching rate is also sufficient. In Comparative Example 1, an undercut shape was observed at the lower part of the resist profile, whereas the example of the present invention was excellent in the resist profile without undercut or skirting.

[0071]

[Table 1]

After applying ARCH-2 (product of Fuji Hunt Electronics Technology Co., Ltd.) as a positive type photoresist for KrF excimer laser on the antireflection films of Examples 2 to 5, 7 to 10 and Comparative Example 2 (film) Thickness 0.
85 μm), reduction projection exposure apparatus (Nikon Corporation NSR
After exposure using -2005i9C), the substrate was treated at 110 ° C. for 60 seconds as post-exposure heating, 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 membrane absorbance at 248 nm and the dry etch rate were also evaluated. Here, the absorbance at 248 nm was measured by applying an antireflection film composition on a quartz plate and drying by heating to form a film, which was measured by a spectrophotometer UV-240 manufactured by Shimadzu Corporation. The limiting resolution is 0.5 at a film thickness of 0.85 μm.
It means the limit resolution at the exposure amount for reproducing the mask pattern of 0 μm. Dependence on film thickness: resist film thickness 0.85
It was evaluated by the ratio of the resolving power at μm to the resolving power at 0.87 μm in film thickness. The closer this value is to 1.0, the better. Dry etch speed is CSE- manufactured by Japan Vacuum Engineering Co., Ltd.
Measured according to 1110 under CF4 / O2 conditions.

Table 2 shows the results of the evaluation. Thus, the antireflection coating composition of the present invention has high film absorbance, improves the limit resolution of the photoresist, and reduces the thickness dependence of the sensitivity caused by the standing wave due to the reduction of the reflected light from the substrate, and in particular It can be seen that the dry etch speed is high and advantageous.

[0074]

[Table 2]

[0075]

According to the composition for an antireflection film of the present invention and the method of forming a resist pattern using the same, the interdiffusion between a resist and the composition for an antireflection film is reduced, and the resolution and the thickness of the resist depend. Excellent dry etching rate.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25/18 C08L 57/12 57/12 H01L 21/30 574

Claims (7)

[Claims] (A) at least one kind of repeating unit (a) selected from the group consisting of repeating units represented by the following general formulas (1), (2) and (3) as a light absorbing agent component: A melamine derivative, a guanamine derivative, a glycoluril derivative and a urea substituted by a polymer as a constituent component and (B) at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group; A composition for an antireflection film, comprising at least one compound (b) selected from the group consisting of derivatives. Embedded image (In the above formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom or a cyano group; R ² and R ³ are the same or different and represent a hydrogen atom,
0 hydrocarbon group, C1-C6 alkoxy group, -OH
X represents a divalent group; P ¹ and P ² are the same or different and represent an aromatic group having 5 to 14 carbon atoms; Y ¹ and Y ² are the same or different And m and n are the same or different and each represents an integer of 0 to 3, and when m and n are 2 or 3, respectively, a plurality of Y ¹ and Y ² may be the same or different; Q is an oxygen atom, -CO-, a sulfur atom, -NR'- (where R 'represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) , A single bond or an alkylene group. ) 2. The general formulas (1), (2) and (3)
In the above, X is a single bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms which may have a substituent, or an arylene group having 7 to 15 carbon atoms which may have a substituent. An aralkylene group, or any of these three groups,
O -, - CO -, - NH -, - CO 2 -, - CONH-
And a divalent group formed by linking at least one group selected from —SO ₂ —; and P ¹ and P ² are
Identical or different, a phenylene group, a naphthylene group or an anthrylene group; Y ¹ and Y ² are the same or different and are —OH, —OR ⁴ , —SR ⁴ , —NR ⁵ R ⁶ (here Wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms,
R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 2. The composition for an antireflection film according to claim 1. 3. A repeating unit (a) selected from the group consisting of repeating units represented by the general formulas (1), (2) and (3) as a light-absorbing agent component (A). And (C) at least two hydrogen atoms bonded to the aromatic ring are a methylol group,
At least one compound (c) selected from the group consisting of a phenol derivative, a naphthol derivative and a hydroxyanthracene derivative, substituted by at least one group selected from the group consisting of an alkoxymethyl group and an acyloxymethyl group; A composition for an antireflection film, comprising: 4. The general formulas (1), (2) and (3)
In the above, X is a single bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms which may have a substituent, or an arylene group having 7 to 15 carbon atoms which may have a substituent. An aralkylene group, or any of these three groups,
O -, - CO -, - NH -, - CO 2 -, - CONH-
And a divalent group formed by linking at least one group selected from —SO ₂ —; and P ¹ and P ² are
Identical or different, a phenylene group, a naphthylene group or an anthrylene group; Y ¹ and Y ² are the same or different and are —OH, —OR ⁴ , —SR ⁴ , —NR ⁵ R ⁶ (here Wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms,
R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The composition for an antireflection film according to claim 3, wherein 5. The composition for an antireflection film according to claim 3, wherein the compound (c) is represented by the following general formula (4). Embedded image (In the above formula, P ³ and P ⁴ are the same or different and represent a trivalent or tetravalent aromatic ring having 6 to 14 carbon atoms; Y ¹ and Y ² are each represented by the above general formula (1) to (3) Y ¹ and Y
Synonymous with ² ; a plurality of Es are the same or different and represent at least one group selected from the group consisting of a methylol group, an alkoxymethyl group and an acyloxymethyl group; Same or different, 1 or 2) 6. Y ¹ and Y ² are the same or different, and
OH, -OR ^4, -SR ^4, a -NR ⁵ R ⁶ (wherein
R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are the same or different and each have a hydrogen atom or 1 carbon atom.
Represents up to 20 hydrocarbon groups. The composition for an antireflection film according to claim 5, wherein 7. A method for forming a resist pattern, comprising using the composition for an antireflection film according to claim 1.