JPH11249311A - Composition for forming antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compsn. for forming an antireflection film having a high antireflection effect and no sublimability. SOLUTION: This compsn. contains a dye obtd. by reacting an anthracene deriv. represented by the formula with aldehydes, a resin and a solvent. In the formula, R<1> is a monovalent substituent, (n) is a number of 0-9, and in the case of 2<=n<=9, plural groups R<1> may be the same or different. Since the compsn. has a high antireflection effect and no sublimability, a resist pattern excellent in resolution, precision, etc., can be formed by using the compsn. in combination with a positive or negative resist, therefore the compsn. contributes particularly to the production of an integrated circuit having a high degree of integration.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a composition for forming an antireflection film. More specifically, the present invention relates to a composition for forming an antireflection film useful for forming an antireflection film suitable for fine processing in a lithography process using various types of radiation, particularly for manufacturing an integrated circuit device.

[0002]

2. Description of the Related Art In a method of manufacturing an integrated circuit device, a processing size in a lithography process is becoming finer in order to obtain a higher degree of integration. In this lithography process, a desired pattern is obtained by applying a resist composition onto a substrate, transferring a mask pattern by a reduction projection exposure apparatus (stepper), and developing with a suitable developer. However, a substrate such as aluminum, aluminum-silicon alloy, aluminum-silicon-copper alloy, polysilicon, or tungsten silicide having a high reflectivity used in this process reflects the irradiated radiation on the surface. As a result, halation occurs in the resist pattern, and a fine resist pattern cannot be accurately reproduced.

In order to solve this problem, there has been proposed a method of forming an antireflection film having a property of absorbing radiation reflected from the substrate under a resist film to be formed on the substrate. As such an antireflection film, first, vacuum deposition,
Inorganic films such as a titanium film, a titanium dioxide film, a titanium nitride film, a chromium oxide film, a carbon film and an α-silicon film formed by a method such as CVD and sputtering are known. Since these inorganic antireflection films have conductivity, they cannot be used for manufacturing integrated circuits, or special devices such as a vacuum deposition device, a CVD device, and a sputtering device are required for forming the antireflection film. And the like. In order to compensate for the drawbacks of the inorganic anti-reflection coating, for example, an organic anti-reflection coating comprising a polyamic acid (co) polymer or a polysulfone (co) polymer and a dye has been proposed (for example, Japanese Patent Application Laid-Open No. 59-1984). No. 93448). This antireflection film has no conductivity and can be applied on a substrate by dissolving in an appropriate solvent without using a special device, in the same manner as a resist.
However, the antireflection film composed of a polyamic acid (co) polymer or polysulfone (co) polymer and a dye has a problem that the dye is sublimated during baking, thereby contaminating the device.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for forming an antireflection film in which a dye does not sublime during baking, which is a conventional problem. Other objects and advantages of the present invention will become apparent from the following description.

[0005]

According to the present invention, the above objects and advantages of the present invention are as follows:

[0006]

Embedded image Wherein R ¹ is a monovalent substituent and n is a number from 0 to 9, provided that when n is 2 to 9, a plurality of R ¹ may be the same or different;

This is achieved by a composition for forming an antireflection film, characterized by containing a dye, a resin and a solvent which are reaction products of anthracenes and aldehydes represented by the formula:

Hereinafter, the present invention will be described in detail, which will clarify the objects, configurations, and effects of the present invention.

The dye used in the present invention has the formula (1)
Is a reaction product of an anthracene and an aldehyde, and mainly consists of an anthracene multimer.
The reaction is preferably carried out by heating the anthracene and the aldehyde in the presence of an acid catalyst. The anthracene represented by the formula 1 has a strong absorption band particularly in the far-infrared region, and thus has been expected as a dye for a resist material using far-infrared rays such as a KrF excimer laser in a lithography process. Because
It was difficult to use it as it was.

The present inventors have conducted intensive studies and as a result, those obtained by polymerizing the above-mentioned anthracenes with aldehydes have a strong absorption band in the far infrared region and have no sublimability. The present inventors have found that they can be used as dyes, and have reached the present invention. Furthermore, it is surprising that anthracenes, which were previously only soluble in a specific solvent, became soluble in a wide range of solvents by multimerization.

In the above formula (1), R ¹ is a monovalent substituent, and n is a number from 0 to 9. However, n is 2-9
In the formula, a plurality of R ¹ may be the same or different. Examples of the monovalent substituent represented by R ¹ include an alkyl group, an alkenyl group, a halogen group, a nitro group, an amino group,
Examples include a hydroxyl group, a phenyl group, an acyl group, a carboxyl group, a sulfonic acid group, and a mercapto group. As the alkyl group, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and as the alkenyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms is preferable. Preferred examples of the halogen atom include fluorine, chlorine and bromine. Preferred examples of the acyl group include an aliphatic or aromatic acyl group having 1 to 6 carbon atoms.

The anthracene used in the present invention includes, for example, anthracene; 1-methylanthracene,
2-methylanthracene, 9-methylanthracene, 9
-Ethyl anthracene, 9-vinyl anthracene, 9-
Propylanthracene, 9-isopropylanthracene, 9-butylanthracene, 9-isobutylanthracene, 9-isoamylanthracene, 1,3-dimethylanthracene, 1,4-dimethylanthracene, 1,5-
Dimethylanthracene, 2,3-dimethylanthracene, 2,6-dimethylanthracene, 2,7-dimethylanthracene, 2,9-dimethylanthracene, 3,9-dimethylanthracene, 9,10-dimethylanthracene, 9,10-diethyl Alkyl or alkenyl anthracenes such as anthracene; 1-chloroanthracene, 2-chloroanthracene, 9-chloroanthracene, 9-bromoanthracene, 1,4-dichloroanthracene, 1,5-dichloroanthracene, 1,6-di Chloranthracene, 1,7-dichloroanthracene, 1,8
Dichloroanthracene, 1,9-dichloroanthracene, 2,3-dichloroanthracene, 2,3-dibromoanthracene, 9,10-dichloroanthracene, 9,10
-Dibromoanthracene, 1,2,7-trichloroanthracene, 1,5,9-trichloroanthracene, 1,8,1
Halogen-substituted anthracene such as 0-trichloroanthracene, 1,9,10-trichloroanthracene, 2,9,10-trichloroanthracene; 1-nitroanthracene, 2-nitroanthracene, 9-nitroanthracene, 9,10-dinitroanthracene 1-aminoanthracene, 2-aminoanthracene, 2-dimethylaminoanthracene, 2-anilinoanthracene, 9-aminoanthracene, 9-methylaminoanthracene, 9-anilinoanthracene;
Anthracene amino-substituted products such as 1,4-diaminoanthracene and 9,10-dianilinoanthracene; 1-hydroxyanthracene, 2-hydroxyanthracene, 9-
Hydroxyanthracene, 10-methylanthranol, 10-phenylanthranol, 10-nitroanthranol, 2-amino-1-anthranol, 1-amino-2-anthranol, 1,2-dihydroxyanthracene, 1,4- Dihydroxyanthracene, 1,5-
Dihydroxyanthracene, 1,8-dihydroxyanthracene, 2,3-dihydroxyanthracene, 2,6-
Dihydroxyanthracene, 2,7-dihydroxyanthracene, 1,9-dihydroxyanthracene, 9,10
Anthracene hydroxy derivatives such as dihydroxyanthracene diacetate, 2,9-dihydroxyanthracene diacetate, 2,10-dihydroxyanthracene diacetate, 9,10-dihydroxyanthracene; anthracene-9-aldehyde, 1-acetylanthracene, 2-acetyl Acylanthracenes such as anthracene, 9-acetylanthracene, 9-benzoylanthracene, 10-nitroanthraphenone, 10-benzoylanthranol, 9,10-dibenzoylanthracene; anthracene-1-carboxylic acid, anthracene-2-carboxylic acid; Anthracene-9-carboxylic acid, anthracene-1,2-dicarboxylic acid, anthracene-1,3-dicarboxylic acid, anthracene-1,4-dicarboxylic acid, anthracene-1,5 Dicarboxylic acid, anthracene-1,9-dicarboxylic acid, anthracene-2,3
Anthracenecarboxylic acids such as dicarboxylic acid, anthracene-9,10-dicarboxylic acid; anthracene-1-
Anthracenesulfonic acids such as sulfonic acid, anthracene-2-sulfonic acid, anthracene-9-sulfonic acid, anthracene-1,5-disulfonic acid, anthracene-1,8-disulfonic acid, and anthracene-2,6-disulfonic acid; 2 And mercaptoanthracenes such as -mercaptoanthracene and 9-mercaptoanthracene. These can be used alone or in combination of two or more.

The aldehydes used in the present invention include, for example, saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde and propylaldehyde; unsaturated aliphatic aldehydes such as acrolein and methacrolein; and alicyclics such as furfural. Aliphatic aldehydes: benzaldehyde, naphthalaldehyde,
Examples thereof include aromatic aldehydes such as anthralaldehyde, and particularly preferred are formaldehyde and paraformaldehyde. These can be used alone or in combination of two or more.

The dye used in the present invention is produced by mixing the above-mentioned anthracenes and aldehydes and heating in the presence of an acid catalyst without a solvent or in a solvent. Examples of the acid catalyst used in producing the dye include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid; and carboxylic acids such as formic acid and oxalic acid.

The amount of the acid catalyst used in the production of the dye is variously selected depending on the kind of the acid to be used, but is usually 0.1 to 100 parts by weight of the anthracene.
001 to 10,000 parts by weight, preferably 0.01 to 10,000 parts by weight
It is 1,000 parts by weight. The dye is usually produced without a solvent, but a solvent may be used if necessary. Any solvent can be used as long as it does not inhibit the reaction. For example, solvents used for resins made from aldehydes such as phenol resins, melamine resins and amino resins can be used. If the acids used are liquids such as formic acid, they can be used as solvents.

The reaction temperature for producing the dye is usually 4
0 ° C to 200 ° C. The reaction time for producing the dye is variously selected depending on the reaction temperature, and is usually 30 minutes to 72 hours. The amount of the dye used in the present invention is variously selected depending on the type of the dye used,
Usually, 0.01 to 10,000 based on 100 parts by weight of the resin.
Parts by weight, preferably 0.1 to 5,000 parts by weight, more preferably 1 to 1,000 parts by weight.

The resin used in the present invention functions as a binder in the composition for forming an antireflection film of the present invention. Various synthetic resins can be used as the resin. Examples thereof include polyethylene, polypropylene, poly 1-butene, poly 1-pentene, poly 1-hexene, poly 1-heptene, poly 1-octene,
Poly 1-decene, poly 1-dodecene, poly 1-tetradecene, poly 1-hexadecene, poly 1-octadecene,
Α-olefin polymers such as polyvinylcycloalkane;
Α, β-unsaturated aldehyde polymers such as poly-1,4-pentadiene, poly-1,4-hexadiene, poly1,5-hexadiene, poly1,7-o-chloroacrolein;
Α, β-unsaturated ketone polymers such as polymethyl vinyl ketone, polyaromatic vinyl ketone, and polycyclic vinyl ketone; poly (meth) acrylic acid, salts of poly (meth) acrylic acid, esters of poly (meth) acrylic acid Polymers of α, β-unsaturated acid derivatives such as halides of poly (meth) acrylic acid; α, β-unsaturated acid anhydrides such as poly (meth) acrylic anhydride and polymaleic anhydride Polymers; unsaturated polybasic acid ester polymers such as polymethylene malonic acid diester and polyitaconic acid diester; diolefin acid ester polymers such as polysorbic acid ester and muconic acid ester; polyacrylic acid thioester;
Α, β-unsaturated acid thioester polymers such as methacrylic acid thioester and α-chloroacrylic acid thioester;
Polymers of acrylonitrile derivatives such as polyacrylonitrile and polymethacrylonitrile; polymers of acrylamide derivatives such as polyacrylamide and polymethacrylamide; styryl metal compound polymers; polyvinyloxy metal compounds; polyimines; polyphenylene oxide; Polyethers such as poly1.3-dioxolane, polyoxirane, polytetrahydrofuran and polytetrahydropyran; polysulfides; polysulfonamides; polypeptides; polyamides such as nylon 66 and nylon 1 to nylon 12; Polyesters such as aromatic polyesters, alicyclic polyesters, polycarbonates and alkyd resins; polyureas; polysulfones; polyazines; polyamines; polyaromatic ketones; Polybenzoimidazoles; polybenzoxazoles; polybenzothiazoles; polyaminotriazoles; polyoxadiazoles; polypyrazoles; polytetrazoles; polyquinoxalines; polytriazines; Polyquinolines; polyanthrazolines and the like. These can be used alone or in combination of two or more.

Further, the resin used in the present invention includes:
In order to prevent intermixing with a resist, a thermosetting resin which is cured by heating after application to a substrate and becomes insoluble in a solvent is also preferably used. Examples of these thermosetting resins include phenol resins, urea resins, melamine resins, amino resins, aromatic hydrocarbon resins, epoxy resins, alkyd resins, and the like. These can be used alone or in combination of two or more. Of these, alkyd resins are particularly preferably used.

The alkyd resin is a thermosetting polyester resin having a three-dimensional network structure, which can be produced using an acid component such as carboxylic acid or carboxylic anhydride and an alcohol component such as polyhydric alcohol as raw materials. Alkyd resin is
Widely used for paints and molding materials. Various alkyd resins can be produced by a combination of the acid component and the alcohol component.

The acid component used in producing the alkyd resin includes, for example, aliphatic carboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, tartaric acid and citric acid and acid anhydrides thereof. Aromatic carboxylic acids such as phthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, ethylene glycol bistrimellitate, glycerol tristrimellitate, tetrabromophthalic acid, and their acid anhydrides; methyl tetrahydro Alicyclic carboxylic acids such as phthalic acid, methylhexahydrophthalic acid, nadic acid, methylnadic acid, hexahydrophthalic acid, tetrahydrophthalic acid, trialkyltetrahydrophthalic acid, methylcyclohexenedicarboxylic acid, and head acid and their acid anhydrides Things etc. It is. These can be used alone or in combination of two or more.

The alcohol component used for producing the alkyd resin includes aliphatic polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol, dipentaerythritol and mannitol; hydroquinone, bis (3,5- Dimethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 2,
Polyhydric phenols such as 2-bis (4-hydroxyphenyl) propane; aromatic polyhydric alcohols such as bis (2-hydroxyethyl) terephthalate, 1,4-benzenedimethanol, and 1,4-benzenediethanol; No. These can be used alone or as a mixture of two or more.

When the alkyd resin constituting the composition for forming an antireflection film of the present invention is produced, an unsaturated monomer can be added for the purpose of improving coating properties, heat resistance and the like. Examples of such unsaturated monomers include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, 0-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, Substituted styrene compounds such as 0-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene, pt-butoxystyrene; vinyl carboxylate compounds such as vinyl acetate, vinyl propionate and vinyl caproate; (meth) Vinyl cyanide compounds such as acrylonitrile and α-chloroacrylonitrile; methyl (meth) acrylate, ethyl (meth) acrylate,
unsaturated carboxylic ester compounds such as n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, and glycidyl (meth) acrylate; ethylene glycol di (meth)
Unsaturated group-containing unsaturated carboxylic esters such as acrylate, propylene glycol di (meth) acrylate, vinyl (meth) acrylate and dimethylvinyl methacryloyloxymethylsilane; 2-chloroethyl vinyl ether, vinyl chloroacetate, allyl chloroacetate and the like Halogen-containing vinyl compounds; hydroxyl-containing vinyl compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and (meth) allyl alcohol;
Amide group-containing vinyl compounds such as (meth) acrylamide and crotonamide; carboxyl group-containing vinyl compounds such as 2-methacryloyloxyethylsuccinic acid and 2-methacryloyloxyethylmaleic acid; 1-vinylnaphthalene; Examples thereof include vinyl aryl compounds such as vinyl naphthalene, 9-vinyl anthracene, and 9-vinyl carbazole. These unsaturated monomers can be used alone or as a mixture of two or more kinds. The amount of the unsaturated monomers added is usually not more than 80% by weight, and preferably not more than the total weight of the acid component and the alcohol component. , 70% by weight or less.

In the production of the alkyd resin, various modifiers can be added for the purpose of improving mechanical properties, chemical resistance and the like. Examples of these denaturing agents include higher fatty acids such as stearic acid, palmitic acid, oleic acid, and ricinolenic acid; phenols such as phenol, phenylphenol, cyclohexylphenol, and t-butoxyphenol; abietic acid, levopimaric acid, and dextrapiate. Rosins such as malic acid and hydroabitic acid are exemplified. These can be used alone or in combination of two or more.

The alkyd resin is produced by mixing the above-mentioned acid component, alcohol component, and various additives and heating. The reaction temperature for producing the alkyd resin is usually from 80C to 300C. The reaction time for producing the alkyd resin is variously selected depending on the reaction temperature, and is usually 30 minutes to 72 hours. As the alkyd resin, a resin in which a dye having a reactive group capable of reacting with an acid component or an alcohol component as a component of the alkyd resin (hereinafter abbreviated as a reactive dye) may be used. .

The reactive dyes include, for example, 9-anthracenemethanol, 1,2,10-anthracentriol, 1,8,9-anthracentriol, 2,6-
Dihydroxyanthraquinone, anthralphine, 9-
Aromatic alcohols such as hydroxyphenanthrene, 1-naphthol, 2-naphthol and naphthalene diol;
9-anthracenecarboxylic acid, anthraquinone-2-carboxylic acid, phenanthrene-9-carboxylic acid, naphthaleneacetic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8 -Naphthalenedicarboxylic anhydride, 1,4,8,
Aromatic carboxylic acids such as 5-naphthalenetetracarboxylic anhydride and 1-fluorenecarboxylic acid; aromatic amines such as anthralmine and 2-aminonaphthalene; fluorenone oxime, anthracenylbenzylketoxime, methyl-α-naphthyl Aromatic oximes such as ketoxime; aromatic aldehydes such as 9-anthraldehyde; These can be used alone or in combination of two or more.

In producing the alkyd resin, an unsaturated monomer can be added for the purpose of improving the coating property, heat resistance and the like. Examples of such unsaturated monomers include the same unsaturated monomers that can be used in producing the alkyd resin described above. When the alkyd resin is produced, various modifiers can be added for the purpose of improving mechanical properties, chemical resistance and the like. These include, for example, those similar to the unsaturated monomers that can be used when producing the alkyd resin described above.

The above-mentioned alkyd resin is produced by mixing the above-mentioned acid component, alcohol component, reactive dye, and various additives and heating. The reaction temperature at this time is
Usually, it is 80 ° C to 300 ° C, and the reaction time is variously selected depending on the reaction temperature, but is usually 30 minutes to 72 hours.

As the solvent constituting the composition for forming an antireflection film of the present invention, a solvent capable of dissolving the antireflection film material, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol Ethylene glycol monoalkyl ethers such as monobutyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol dipropyl ether, Diethylene dialkyl ethers such as ethylene glycol dibutyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glutaric bottles methyl, other esters such as ethyl pyruvate; toluene,
Aromatic hydrocarbons such as xylene; methyl ethyl ketone;
Methyl n-amyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone,
Ketones such as heptanone and cyclohexanone; N-methylformamide, N, N-dimethylformamide, N
Amides such as -methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone are appropriately selected and used. Of these, preferred solvents include ethylene glycol monoethyl ether acetate, ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl n-amyl ketone, cyclohexanone, and the like. These solvents are used alone or in combination of two or more.

The compounding amount of the solvent is such that the solid concentration is 0.01 to
It is about 70% by weight, preferably 0.05 to 60% by weight, and more preferably 0.1 to 50% by weight. Various additives can be added to the composition for forming an antireflection film of the present invention as long as the desired effects of the present invention are not impaired.

The additives include a dye, a surfactant,
Curing agents and the like can be mentioned. Examples of the dye include oil-soluble dyes, disperse dyes, basic dyes, methine dyes, pyrazole dyes, imidazole dyes, hydroxyazo dyes, and the like; bixin derivatives, norbixin, stilbene, 4,4′-diamino Fluorescent whitening agents such as stilbene derivatives, coumarin derivatives, and pyrazoline derivatives; hydroxyazo dyes; ultraviolet absorbers such as tinuvin 234 (manufactured by Ciba Geigy); and ultraviolet absorbers such as tinuvin 1130 (manufactured by Ciba Geigy); And the like. The amount of the radiation absorbing compound to be blended is usually 100 parts by weight or less, preferably 50 parts by weight or less, per 100 parts by weight of the solid content of the composition for forming an antireflection film.

The surfactant has an action of improving the coating properties, striation, wettability, developability and the like. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. In addition to nonionic surfactants such as rates, commercially available products include, for example, organosiloxane polymers,
KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow No. 1 which is a (meth) acrylic acid-based (co) polymer.
75; 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo KK), F-Top EF101, EF204, EF303, and EF352 (trade name, manufactured by Tochem Products Co., Ltd.), MegaFac F171, F172, and F173 ( Product name, manufactured by Dainippon Ink and Chemicals, Inc.)
Florard FC430, FC431, FC135,
FC93 (trade name, manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S382, SC10
1, same SC102, same SC103, same SC104, same S
C105 and SC106 (trade name, manufactured by Asahi Glass Co., Ltd.). The amount of these surfactants is usually 15 parts by weight or less, and preferably 10 parts by weight or less, per 100 parts by weight of the solid content of the antireflection coating composition.

Examples of the curing agent include isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate; Epicoat 812, 81
5, 826, 828, 834, 836, 87
1, 1001, 1004, 1007, 100
9, 1031 (trade name: Yuka Shell Epoxy Co., Ltd.)
Manufactured), Araldite 6600, 6700, 680
0, 502, 6071, 6084, 6097,
6099 (trade name: Ciba-Geigy), DER33
1, 332, 333, 661, 644, 66
Epoxys such as 7 (trade name: manufactured by Dow); Cymel 30
0, 301, 303, 350, 370, 77
1, 325, 327, 703, 712, 70
1, 272, 202, My Court 506, 508
Melamine-based curing agents such as (trade name: manufactured by Mitsui Cyanamid Co., Ltd.), Cymel 1123, 1123-10, 1
128, My Court 102, 105, 106, 1
Benzoguanamine-based curing agents such as 30 (trade name: manufactured by Mitsui Cyanamid Co., Ltd.); Cymel 1170, 1172
(Trade name: manufactured by Mitsui Cyanamid Co., Ltd.) and the like. The amount of these curing agents is usually 5,000 parts by weight or less, preferably 1,000 parts by weight, per 100 parts by weight of the solid content of the antireflection coating composition.
0 parts by weight or less.

Further, as other additives, a storage stabilizer, an antifoaming agent, an adhesion aid and the like can be blended. The method for forming a resist pattern using the composition for forming an anti-reflection film of the present invention includes the following steps: 1) applying a composition for forming an anti-reflection film on a substrate, followed by baking to form an anti-reflection film;
2) a step of applying a resist composition on the antireflection film, followed by baking to form a resist film; 3) a step of irradiating the resist film with radiation through an exposure mask;
Developing and 5) etching the anti-reflection film.

First, a composition for forming an anti-reflection film is applied on a substrate to a predetermined thickness, for example, 100 to 5,000 angstroms by a method such as spin coating or casting coating roll coating. Next, baking is performed to thermally cure the antireflection coating composition. The baking temperature at this time is, for example, 90
About 350 ° C. Next, a resist is applied on the antireflection film so as to have a predetermined thickness, and prebaked to evaporate a solvent in the resist film to form a resist film. The pre-bake temperature at this time is appropriately adjusted depending on the type of the resist to be used and the like.
The temperature is about 0 ° C, preferably 50 to 150 ° C.

When a resist film is formed, each resist is placed in an appropriate solution at a solid content concentration of, for example, 5 to 50% by weight.
Then, the solution was filtered through a filter having a pore size of about 0 or 2 μm to prepare a solution, which was coated with, for example, a silicon wafer or aluminum by a method such as spin coating, casting coating, or roll coating. It is applied on an antireflection film of a substrate such as a wafer. In this case, it goes without saying that a commercially available resist solution can be used as it is.

Examples of the resist used for forming the resist pattern include a positive resist comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, a negative resist comprising an alkali-soluble resin and a radiation-sensitive cross-linking agent,
Positive or negative chemically amplified resists containing a radiation-sensitive acid generator can be used. Thereafter, the resist film is irradiated with radiation through an exposure mask (hereinafter referred to as “exposure”). Depending on the type of resist, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, molecular beam,
Appropriate radiation such as an ion beam can be used.
Among these radiations, far infrared rays are preferred, and KrF excimer laser (248 nm) and ArF excimer laser (193 nm) are particularly preferably used for the composition of the present invention.

Next, this is developed. Then wash,
By drying, a desired resist pattern is formed. During this step, baking may be performed after exposure and before development in order to improve resolution, pattern shape, developability, and the like. Finally, using the resist pattern as a mask, dry etching of the antireflection film is performed using gas plasma such as oxygen plasma to obtain a resist pattern for substrate processing.

Examples of the developer used for forming the resist pattern include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and di-n- Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo (5.4.0) -7-undecene, Examples thereof include an alkaline aqueous solution in which 1,5-diazabicyclo- (4.3.0) -5-nonane is dissolved. In addition, a proper amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant can be added to these developers.

[0039]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments at all unless it exceeds the gist. The types of resist used in each of the examples and comparative examples are as follows.

Type of resist Positive resist for KrF (KrF K2G, JS)
The performance evaluation of the composition for forming an anti-reflection film was performed in the following manner.

Evaluation of performance of antireflection film Sublimation test: A composition for forming an antireflection film was applied on a 4-inch silicon wafer, spin-coated, and baked on a hot plate at 90 ° C. for 1 minute to form a film. 0.1
A μm antireflection film was formed. Another silicon wafer was placed in parallel on the silicon wafer on which the anti-reflection film was formed at an interval of 1 cm, and then the silicon wafer on which the anti-reflection film was formed was baked at 200 ° C. for 2 minutes. The sublimability of the composition for forming an antireflection film was determined based on the presence or absence of a sublimate attached to the upper silicon wafer.

Resolution: A composition for forming an anti-reflection film is applied on a 4-inch silicon wafer substrate, spin-coated, and then placed on a hot plate at 90 ° C. for 1 minute at 200 ° C.
For 2 minutes to form an antireflection film having a thickness of 0.1 μm. After that, a resist having a thickness of 0.7 μm was formed on the antireflection film.
To form a resist film, and baked on a hot plate at 80 ° C. for 2 minutes. Then, a stepper NSR200 manufactured by Nikon Corporation is placed at the center of the hole pattern.
Using 5EX8A (wavelength: 248 nm), exposure was performed for an exposure time (hereinafter, referred to as “optimal exposure time”) for forming a line and space pattern having a width of 0.5 μm with a line width of 1: 1. Then, on a hot plate at 100 ° C., 2
After baking for 2 minutes, the resist pattern was formed using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, washed with water, and dried to form a resist pattern. The size of the smallest resolved resist pattern was measured using a scanning electron microscope.

Intermixing prevention effect: In the same manner as in the above-described evaluation of resolution, formation of an antireflection film and a resist film, pre-baking, exposure and development are performed, and the degree of footing of the resist film at the contact with the substrate is determined by scanning electron scanning. It was examined using a microscope.

Standing Wave Prevention Effect: In the same manner as in the evaluation of the resolution, formation of an antireflection film and a resist film, pre-baking, exposure and development are performed, and the presence or absence of a standing wave in the resist film is determined by using a scanning electron microscope. I checked. Etch rate: In the same manner as in the evaluation of the resolution, the formation of an antireflection film and a resist film, pre-baking, exposure and development are performed, and the rate of dry etching (pressure 15 Pa, RF power 300 W, etching gas oxygen) by oxygen plasma is measured. Then, the etching rate ratio between the antireflection film and the resist film (etching speed of the antireflection film / etching speed of the resist film) was determined.

Synthesis Example 1 A separable flask equipped with a thermometer and a condenser was charged with 20 parts of anthracene, 33 parts of 37% formalin and 12 parts of concentrated sulfuric acid, and reacted at 95 ° C. for 5 hours. After washing the precipitated crude dye with water, it was dissolved in 100 parts of 2-heptanone, and unreacted anthracene as an insoluble component was removed by filtration. 2-Heptanone was removed under reduced pressure to obtain Dye 1 (80% yield). As a result of H-NMR and GPC measurement, the obtained Dye 1 was an oligomer in which 3 to 5 anthracenes were linked by a methylene bond.

Polymerization Example 1 A separable flask equipped with a thermometer and a condenser was charged with 15 parts of cyclohexanedicarboxylic anhydride and 6 parts of glycerin.
And 9 parts of 9-anthracenemethanol at 200 ° C.
For 1 hour to obtain an alkyd resin (1).

Polymerization Example 2 Cyclohexanedicarboxylic anhydride 1 in Polymerization Example 1
An alkyd resin (2) was obtained by performing the same operation as in Polymerization Example 1 except that 5 parts was changed to 15 parts of phthalic anhydride.

Polymerization Example 3 A separable flask equipped with a thermometer and a condenser was charged with 15 parts of cyclohexanedicarboxylic anhydride and 9 parts of glycerin.
Then, the mixture was stirred at 200 ° C. for 1 hour to obtain an alkyd resin (3).

Polymerization Example 4 Cyclohexanedicarboxylic anhydride 1 in Polymerization Example 3
An alkyd resin (4) was obtained by performing the same operation as in Polymerization Example 3 except that 5 parts was changed to 15 parts of phthalic anhydride.

Examples 1 to 4 10 parts of the resin obtained in Polymerization Examples 1 to 4, 4 parts of the dye obtained in Synthesis Example 1, Nikarac N-2702 (manufactured by Sanwa Chemical Co., Ltd .: glycoluril curing agent) 5) 5 parts were dissolved in 81 parts of 2-heptanone and filtered through a membrane filter having a pore size of 0.2 µm to prepare an antireflection coating composition. Next, a resist pattern was formed and the performance of the antireflection film was evaluated as described above. Table 1 shows the evaluation results.

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[Table 1]

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The antireflection film formed by using the composition for forming an antireflection film of the present invention has a high antireflection effect and has no sublimation property, so that it cooperates with a positive resist and a negative resist. A resist pattern excellent in resolution, accuracy, and the like can be provided. Therefore, the antireflection coating composition of the present invention greatly contributes to the production of a highly integrated circuit.

Claims (1)

[Claims] [Claim 1] The following formula (1) Here, R ¹ is a monovalent substituent and n is a number from 0 to 9, provided that when n is 2 to 9, a plurality of R ¹ may be the same or different. A composition for forming an antireflection film, comprising a dye, a resin, and a solvent, which are reaction products of an anthracene and an aldehyde.