JP2001222112A - Positive resist laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist laminated body adaptable to exposure in the far ultraviolet region, having high resolving power, capable of forming a resist pattern nearly free from line waving and residue on development in a fine pattern of <=0.2 μm, processable at a high temperature in a short time and excellent also in suitability to production. SOLUTION: The positive resist laminated body comprises a two-layer resist having 1st and 2nd resist layers in this order on a substrate. The 1st resist layer contains a polymer containing specified repeating units and the 2nd resist layer contains a polymer having specified repeating units and a compound which generates an acid when irradiated with active light or radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive-type silicone-containing photosensitive composition for exposure to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, and synchrotron radiation. Specifically, in the process of manufacturing semiconductors such as ICs, for example, when manufacturing circuit boards, etc., it is a positive type silicone for microfabrication which provides a particularly high resolution and sensitivity, a rectangular solid resist, and has a wide process tolerance. Containing photosensitive composition. The positive silicone-containing photosensitive composition of the present invention can be used in the following steps. For example, a semiconductor wafer, or glass, ceramics, on a substrate such as a metal or on which an antireflection layer or an organic film is provided and then applied to a thickness of 0.01 to 3 μm by a spin coating method or a roller coating method. You. Thereafter, the film is heated and dried, and a circuit pattern or the like is baked through an exposure mask by irradiation with actinic rays or the like, and developed to obtain a positive image. Further, the substrate can be processed in a pattern by etching using the positive image as a mask. Typical application fields include a semiconductor manufacturing process such as an IC, a circuit board manufacturing such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art The resolution limit of conventional single-layer resists has become evident with the increasing integration of LSIs. By forming resists in multiple layers instead of single layers, thick and fine high-profile ratio patterns can be formed. Methods of forming have been proposed.
That is, a thick organic polymer film is formed on the first layer, a thin resist material layer is formed on the second layer thereon, and then the second resist material is irradiated with high energy rays and developed. The first organic polymer is anisotropically etched by oxygen plasma etching (O ₂ RIE) using the resulting pattern as a mask to obtain a pattern having a high rectangular shape (phosphorus, solid state technology). Vol. 24, p. 73 (1981)).

In this case, the second resist layer is made of O ₂ -RIE
Silicon-containing polymers are usually used because they must be highly resistant. In particular, vinyl polymerization type polymers having a silicon atom in the side chain have been widely studied from the viewpoint of heat resistance and ease of synthesis. For example, JP-A-2-29
No. 3850, No. 10-282678, U.S. Pat.
Nos. 6071 and the like. The first resist layer is made of a novolak resin or the like in order to impart adhesion and film forming properties to the substrate, high dry etching resistance, immiscibility with the second resist layer, high light absorption characteristics at the exposure wavelength, and the like. Is generally and widely used. However, this method has poor adhesion to the second resist layer containing the silicon-containing polymer, and therefore, particularly when used in fine lines / spaces of 0.2 μm or less, line undulations are likely to occur, and furthermore, the pattern collapses. There was a problem that was easy to cause. Further, in the first resist layer containing the novolak resin, it is necessary to perform a high-temperature treatment for a long time, and there is a problem that the suitability for production is extremely low in the production of semiconductor devices and the like. If the high-temperature treatment is performed in a short time, the solidification of the first resist layer becomes insufficient, and a phenomenon (intermix) of mixing with the second resist layer occurs, and as a result, there is also a problem that a pattern with a large development residue is formed. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive resist laminate having a high resolving power capable of coping with exposure in the far ultraviolet region in the manufacture of semiconductor devices. Another object of the invention is to provide a
An object of the present invention is to provide a positive resist laminate which provides a resist pattern with less line waviness in the following fine lines / spaces. Another object of the present invention is to provide a positive resist laminate having a small amount of development residue, particularly in a fine line / space of 0.2 μm or less. Another object of the present invention is to provide a positive resist laminate having high manufacturing suitability.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies while paying attention to the above characteristics, and as a result, have completed the present invention. That is, the object of the present invention can be achieved by the following configurations. In a two-layer resist having a first resist layer on a substrate and a second resist layer thereon, the first resist layer comprises (a-1) a polymer containing a repeating unit represented by the following general formula (1). Wherein the second resist layer comprises (b) a repeating unit represented by the following general formula (4):
A polymer having at least one repeating unit of the general formulas (5a) and (5b), or the following general formula (4)
And a polymer having at least one of the repeating units represented by the general formulas (5a) and (5b) and the repeating unit represented by the general formula (6); A positive resist laminate comprising: a compound that generates an acid upon irradiation with radiation.

[0006]

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In the formula (1), Y ¹ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, L ¹ and L ² each represent a divalent linking group, and J has a substituent. Represents a phenyl group, a naphthyl group, an anthryl group, or a phenanthryl group which may be substituted. b and c are each independently 0 or 1
Represents

[0008]

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In the formula (4), R ^{2 to} R ⁴ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group. n represents 0 or 1.

[0010]

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In the formula (5a), Y ² has the same meaning as Y ¹ . L
Represents a single bond or a divalent linking group. Q represents a group capable of decomposing with an acid to generate a carboxylic acid.

[0012]

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In the formula (5b), X ¹ and X ² each independently represent a group selected from an oxygen atom, a sulfur atom, —NH— and —NHSO ₂ —. L ¹¹ and L ¹² each independently represent a single bond or a divalent linking group. A ² is a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ⁵ , -CO-NH
—R ⁶ represents an alkyl group which may have a substituent, an alkoxy group, or —COOQ. (R ⁵ and R ⁶ each independently represent an alkyl group which may have a substituent.) Q represents a group capable of decomposing with an acid to generate a carboxylic acid.

[0014]

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In the formula (6), Z represents an oxygen atom or NR ⁷
Represents R ⁷ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁸ . R
⁸ represents an alkyl group or a trihalomethyl group.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments. The positive resist laminate of the present invention comprises a first resist layer containing a polymer having a repeating unit of the general formula (1) as the component (a-1) and a general resist (4) as the component (b). A polymer having at least one of the repeating units represented by the general formulas (5a) and (5b), or a repeating unit represented by the general formula (4), and the repeating units represented by the general formulas (5a) and (5b) And a second resist layer containing a polymer containing a repeating unit represented by the general formula (6). In order to achieve the object of the present invention to a higher degree, in the polymer (a-1) contained in the first resist layer, the content of the repeating unit represented by the general formula (1) is 20 to 99% by weight. Is preferably 30 to 98% by weight, and particularly preferably 40 to 95% by weight.

In the general formula (1), Y ¹ is a hydrogen atom,
An alkyl group having 1 to 3 carbon atoms, a cyano group, a halogen atom (Cl, B, I, etc.), more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom, a methyl group It is. L ¹ represents a divalent linking group, and is preferably an alkylene group, an arylene group, or an aralkylene group. These groups may have a substituent. Examples of the substituent include a halogen atom such as Cl, Br, and F, a —CN group, a —OH group, an amino group, and a group having 1 carbon atom.
An alkyl group having 4 to 4, a cycloalkyl group having 3 to 8 carbon atoms,
Examples thereof include an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 14 carbon atoms.
L ¹ is more preferably an alkylene group having 1 to 8 carbon atoms which may have a substituent, a phenylene group, or a carbon atom having 7 carbon atoms.
-10 aralkylene groups, and an alkylene group having 2 to 6 carbon atoms which may have a substituent, and a phenylenine group are particularly preferable. L ² represents a divalent linking group, -COO-, -O
CO -, - O -, - CON (R 1 1) -, - N (R 11) C
^{O -, - N (R 11} ) -, - NH-CO-NH -, - OC
OO-. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. More preferably, L ² is -CO
O -, - OCO -, - O -, - N (R 11) CO -, - N
(R ¹¹ ) —. b and c each independently represent 0 or 1. J represents a phenyl group, a naphthyl group, an anthryl group, or a phenanthryl group, and may have a substituent. Examples of the substituent include those described above as the substituent for L ^1. Preferred specific examples are an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a cycloalkyl having 4 to 7 carbon atoms. Group, -OH group, amino group, phenyl group, phenoxy group and the like. J is preferably a phenyl group, a naphthyl group or an anthryl group which may have a substituent, and particularly preferably a naphthyl group which may have a substituent.

The polymer (a-1) contained in the first resist layer preferably further contains a repeating unit represented by the general formula (2) in order to achieve a higher purpose.

[0019]

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In the general formula (2), Y ³ has the same meaning as Y ¹ , L ³ represents a divalent linking group, and has the same meaning as L ¹ . L
³ is more preferably an alkylene group having 1 to 8 carbon atoms which may have a substituent, a phenylene group, or a
An aralkylene group having 10 and an alkylene group having 2 to 6 carbon atoms which may have a substituent, and a phenylene group are particularly preferable. In the polymer (a-1) contained in the first resist layer, the content of the repeating unit represented by the general formula (2) is preferably 1 to 80% by weight, and more preferably 2 to 70% by weight.
Is more preferable, and particularly preferably 5 to 60% by weight.

In the first resist layer, in order to achieve a higher purpose, (a-2) activated by an acid,
A thermal crosslinking agent capable of reacting with a polymer containing a repeating unit represented by the general formula (2) to form a crosslinked structure (also referred to as a “thermal crosslinking agent”); (A thermal acid generator). As the thermal cross-linking agent, known ones can be widely used. For example, melamine compounds substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, a benzoguanamine compound, and glycoluril Compounds or urea compounds are preferred. Examples of the alkoxymethyl group include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl and the like. Examples of the acyloxymethyl group include acetyloxymethyl and the like. The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups contained in these compounds is
In the case of melamine, the number is 2 to 6, preferably 5 to 6, and in the case of a glycoluril compound or a benzoguanamine compound, the number is 2 to 4, preferably 3 to 4. In the case of a urea compound, the number is 3 to 4. Among these, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, and tetramethoxymethylglycoluril compounds are most preferable from the viewpoints of thermal crosslinkability and storage stability.

All of the above methylol group-containing compounds can be 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. 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 an acid anhydride or an acid halide in the presence of a base catalyst. The content of the thermal crosslinking agent in the composition of the present invention is 2 to 50% by weight, preferably 5 to 30% by weight in terms of solid content.

As the thermal acid generator, the temperature at which the acid starts to be generated is preferably from 150 to 220 ° C., more preferably from 170 to 200 ° C., and a sulfonic acid ester compound or a diaryliodonium salt is preferably used. The sulfonic acid ester compound preferably has 3 to 3 carbon atoms.
20 organic sulfonic acid esters, specifically 2-
Sulfonic acid esters of secondary alcohols such as propanol, 2-butanol, 2-pentanol and cyclohexanol are preferred. Examples of the diaryliodonium salt compound include salts of a diaryliodonium cation and an organic sulfonic acid anion, SbF ₆ anion, PF ₆ anion or AsF ₆ anion. Here, the anion of an organic sulfonic acid is preferable as the anion. Specific examples of the diaryliodonium salt compound include the following compounds.

[0024]

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[0025]

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[0026]

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[0027]

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Among these, salts of diaryliodonium and organic sulfonic acid are preferred from the viewpoints of stability and solvent solubility. Among them, the aryl group has 1 to 12 carbon atoms.
A salt of a diaryliodonium cation having a straight-chain or branched alkyl group or an alkoxy group having 1 to 12 carbon atoms as a substituent with an organic sulfonic acid anion is preferred from the viewpoint of safety. Here, as a linear or branched alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, i-butyl group, t-butyl group, n-amyl group, i-amyl group, t-
Amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, propoxy And butoxy groups. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Examples of the organic sulfonic acid anion include trifluoromethanesulfonate, methanesulfonate, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms on the aryl group. Examples of the group are the same as those described above.) Or an arylsulfonate which may have a halogen atom as a substituent is preferable from the viewpoint of solvent solubility. Examples of the aryl group include the same as those described above. These thermal acid generators can be used alone or in combination of two or more. The above-mentioned thermal acid generator is usually blended at a ratio of usually 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight in terms of solid content, based on 100 parts by weight of the resist composition of the first resist layer. You.

The polymer (a-1) used in the present invention is:
In addition to the repeating units represented by the general formulas (1) and (2),
Copolymers containing other repeating units for the purpose of improving film forming properties, adhesion, developability and the like may be used. Examples of the monomer corresponding to such another repeating unit include, for example, an addition-polymerizable monomer selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Compounds having one saturated bond are exemplified.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters such as alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group , Cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl) Groups, etc.), N-hydroxyethyl-N-methylacrylamide, N-2-
Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cycloethyl) Groups, etc.), N, N-dialkyl methacrylamide (alkyl groups include ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-methyl methacrylamide and the like;

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

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl 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, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters; acrylic acid, methacrylic acid, crotonic acid , Itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like. In addition,
Any addition-polymerizable unsaturated compound copolymerizable with the above-mentioned various repeating units may be used.

The weight-average molecular weight of the polymer (a-1) used in the present invention is not particularly limited, but may be different from that of the component (a-2) with the thermal crosslinking agent and the component (a-3) with the thermal acid generator. From the viewpoints of solubility, organic solvent properties, film forming properties, and the like, it is preferably 1,000 to 1,000,000, and more preferably 2 to 100,000.
000 to 100,000 is preferred. (A-1) used in the present invention
Specific examples of the polymer include the following,
It is not limited to these. The number attached to the arc is the mole fraction.

[0039]

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[0040]

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[0041]

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The first resist layer used in the present invention includes:
(A-1) a polymer described above, (a-2) a thermal crosslinking agent,
(A-3) In addition to the thermal acid generator, other polymers may be added in order to improve film forming properties, heat resistance, dry etching resistance, and the like. Preferred examples of such polymers include novolak phenolic resins, specifically phenolaldehyde resins, o-cresol formaldehyde resins, p-cresol formaldehyde resins, xylenol formaldehyde resins, or co-condensates thereof. . Further, as described in JP-A-50-125806, phenol or cresol substituted with an alkyl group having 3 to 8 carbon atoms, such as t-butylphenol aldehyde resin, together with the phenol resin as described above. A condensate with formaldehyde may be used in combination. Also, a polymer having a phenolic hydroxy group-containing monomer such as N- (4-hydroxyphenyl) methacrylamide as a copolymer component, p-hydroxystyrene, o-hydroxystyrene, m-isopropenylphenol, p-isopropenylphenol And the like, or a homo- or copolymerized polymer, or a polymer in which these polymers are partially etherified or partially esterified can also be used.

The photosensitive composition of the present invention may be added, if necessary, to JP-A-4-122938 and JP-A-2-27595.
An aromatic polyhydroxy compound described in JP-A Nos. 5 and 4-230754 may be added. The photosensitive composition of the present invention may contain an organic basic compound.

In the composition of the present invention, the components (a-1) and (a-
Solvents for dissolving 2) and (a-3), methyl ethyl ketone, ketones such as cyclohexanone, ethylene glycol monomethyl ether, alcohol ethers such as ethylene glycol monoethyl ether, dioxane,
Ethers such as ethylene glycol dimethyl ether,
Methyl cellosolve acetate, cellosolve esters such as ethyl cellosolve acetate, butyl acetate, methyl lactate, fatty acid esters such as ethyl lactate, halogenated hydrocarbons such as 1,1,2-trichloroethylene, dimethylacetamide, N-methylpyrrolidone, Highly polar solvents such as dimethylformamide and dimethylsulfoxide can be exemplified. These solvents can be used alone or as a mixture of a plurality of solvents.

The composition of the present invention may optionally contain a dye, a plasticizer, an adhesion aid, a surfactant and the like. Specific examples include methyl violet,
Dyes such as crystal violet and malachite green, stearic acid, acetal resin, phenoxy resin,
There are plasticizers such as alkyd resins and epoxy resins, adhesion aids such as hexamethyldisilazane and chloromethylsilane, and surfactants such as nonylphenoxypoly (ethyleneoxy) ethanol and octylphenoxypoly (ethyleneoxy) ethanol. In particular, in the case of a dye, a dye containing an alkali-soluble group such as an aromatic hydroxyl group or a carboxylic acid group in the molecule, such as glutamine, is particularly preferably used.

Next, the polymer of the component (b) used in the second resist layer will be described. In the repeating structural unit (4), R ^{2 to} R ⁴ each independently represent a group selected from an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, and a trialkylsilyloxy group. The alkyl group has 1 carbon atom.
A linear or branched alkyl group having 10 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. A methyl group, an ethyl group, an n-propyl group, and an i-propyl group are more preferable. , N-butyl group, i-butyl group, s-butyl group and t-butyl group. Examples of the haloalkyl group include a chloromethyl group, a bromomethyl group, and an iodomethyl group. The alkoxy group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butoxy group, an i-butoxy group. And s-butoxy and t-butoxy groups, and particularly preferred are methoxy and ethoxy groups. The alkyl group of the trialkylsilyl group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
Examples thereof include an n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group, and among them, the most preferred is a methyl group.
The alkyl group of the trialkylsilyloxy group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, An i-butyl group, an s-butyl group, and a t-butyl group are the most preferable, and among them, a methyl group is most preferable. n represents 0 or 1.

The following are specific examples of the repeating unit represented by the general formula (4), but the present invention is not limited to these specific examples.

[0048]

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In the repeating unit (5a), Y ² is Y ¹
Is synonymous with L represents a single bond or a divalent linking group. Q represents a group capable of decomposing with an acid to generate a carboxylic acid. Specific examples of Q include a t-butyl group, t
A tertiary alkyl group such as an amyl group, an isobornyl group, 1-
1-alkoxyethyl groups such as ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxymethyl group, 1
An alkoxymethyl group such as an ethoxymethyl group, a tetrahydropyranyl group, a tetrahydrofurfuryl group, a trialkylsilyl group, a 3-oxocyclohexyl group, a 2-methyl-adamantyl group, a mevalonic lactone residue,
(Γ-butyrolactonyloxycarbonyl) -2-propyl group and the like.

In the repeating unit (5b), X ¹ and X ²
Is independently an oxygen atom, a sulfur atom, -NH-,-
Represents a group selected from NHSO ₂ —. L ¹¹ and L ¹² each independently represent a single bond or a divalent linking group. L above
Examples of the divalent linking group for ¹¹ and L ¹² include an alkylene group, a substituted alkylene group, an ether group, a thioether group,
Examples thereof include a single group selected from the group consisting of a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups.
Examples of the alkylene group and substituted alkylene group in L ¹¹ and L ¹² include groups represented by the following formulas. -[C (R _a ) (R _b )] _r-wherein R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

A ² represents a hydrogen atom, a cyano group, a hydroxyl group, -C
^{OOH, -COOR 5, -CO-NH} -R 6, which may have a substituent alkyl group, an alkoxy group, or -CO
Represents OQ. (R ⁵ and R ⁶ each independently represent an alkyl group which may have a substituent.) As the alkyl group in A ² , R ⁵ and R ⁶ , a linear or linear alkyl group having 1 to 10 carbon atoms may be used. A branched alkyl group is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. A methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group is more preferable. i-butyl group, s-butyl group and t-butyl group. Similarly, the alkoxy group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group,
-Butoxy group, i-butoxy group, s-butoxy group, t-
Butoxy groups are particularly preferred, with methoxy and ethoxy being particularly preferred. Q represents a group capable of decomposing with an acid to generate a carboxylic acid. Similarly, Q is the same group as Q in the repeating unit (5a). Specific examples of the repeating unit represented by the general formula (5a) include the following, but the present invention is not limited to these specific examples.

[0052]

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[0053]

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Specific examples of the repeating unit represented by the above general formula (5b) include the following, but the present invention is not limited to these specific examples.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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In the repeating unit (6), Z represents an oxygen atom or NR ⁷ . R ⁷ is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂
It represents a -R ^8. R ⁸ represents an alkyl group or a trihalomethyl group. As the alkyl group for R ⁸ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
More preferably a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group. Specific examples of the repeating unit represented by the general formula (6) include the following, but the present invention is not limited to these specific examples.

[0062]

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[0063]

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The repeating unit represented by the general formula (4) of the component (b) used in the second resist layer of the present invention,
In the acid-decomposable polymer having at least one repeating unit of the general formulas (5a) and (5b), the repeating unit represented by the general formula (4) and the repeating units represented by the general formulas (5a) and (5)
b) the content of at least one repeating unit is
It can be appropriately set in consideration of the resist performance such as oxygen plasma etching resistance of the resist, substrate adhesion and the like, sensitivity, profile, resolution and the like. The content of the repeating unit represented by the general formula (4) is 10 to 90 mol%, preferably 15 to 70 mol%, more preferably 20 to 5 mol%.
0 mol%. Also, the repeating units (5a) and (5b)
Has a content of at least one repeating unit of 10
To 90 mol%, preferably 20 to 80 mol%, and more preferably 25 to 50 mol%.

Further, the repeating unit represented by the general formula (4) used in the second resist layer of the present invention and the general formula (5)
In the acid-decomposable polymer further containing a repeating unit represented by the general formula (6) in at least one of the repeating units a) and (5b), from the same viewpoint as described above, the content of the repeating unit is reduced. It can be set appropriately. The content of the repeating unit represented by the general formula (4) is 10 to 90.
Mol%, preferably 15 to 70 mol%, more preferably 20 to 50 mol%. The content of at least one of the repeating units (5a) and (5b) is 5 to 50 mol%, preferably 10 to 50 mol%.
４０40 mol%. The content of the repeating unit (6) is 1
0-90 mol%, preferably 15-70 mol%,
More preferably, it is 20 to 60 mol%.

The weight-average molecular weight of the acid-decomposable polymer of the component (b) is not particularly limited, but may be determined from the viewpoint of compatibility with other components, solubility in organic solvents, film-forming properties, resist performance, and the like. , 1000 to 1,000,000, and 2
000 to 100,000 is preferred. Specific examples of the polymer of the component (b) contained in the second resist layer of the present invention are shown below, but the invention is not limited thereto.

[0067]

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[0068]

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[0069]

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The component (c) used in the present invention is a compound which decomposes upon irradiation with actinic rays or radiation to generate an acid. Photo-initiators for photo-cationic polymerization, photo-initiators for photo-radical polymerization, photo-decolorants for dyes, photo-discolorants, or compounds that generate acids by known light used in micro-resist and the like, and mixtures thereof Can be appropriately selected and used. For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts, organic halogen compounds, organic metal / organic halogen compounds, and photoacid generators having an O-nitrobenzyl-type protecting group And disulfone compounds which generate sulfonic acid upon photolysis typified by an agent, iminosulfonate and the like. Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used. U.S. Pat.No. 3,779,778
And compounds capable of generating an acid by light described in EP 126,712 and the like can also be used.

Among these, diazodisulfone compounds, substituted or unsubstituted diaryliodonium or triarylsulfonium salts, and the like, from the viewpoints of acid generation efficiency by exposure, appropriate diffusion of acid, and stability in resist, among others.
In particular, a substituted or unsubstituted aryl sulfonate, camphor sulfonate and the like are preferable.

The composition of the present invention may contain an organic basic compound. This is preferable because the storage stability is improved and the line width change due to PED is reduced. Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0073]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
An aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² are bonded to each other to form a ring; It may be formed.

[0075]

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In the above formula (E), R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ are the same or different and represent an alkyl group having 1 to 6 carbon atoms.

Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples are substituted or unsubstituted guanidine,
Substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted Pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, etc. Is mentioned. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is. Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine,
-Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridici, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-virazoline,
Examples include, but are not limited to, N-aminomorpholine, N- (2-aminoethyl) morpholine, and the like.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is the photosensitive resin composition (excluding the solvent) 1
The amount is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 00 parts by weight. If the amount is less than 0.001 part by weight, the above effects cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

The positive photoresist composition of the present invention may further contain, if necessary, a phenolic OH group which promotes solubility in a surfactant, a dye, a pigment, a plasticizer, a photosensitizer and a developer. Compounds having two or more compounds can be contained.

Suitable surfactants include, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate ,
Sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan Non-ionic surfactants such as monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, F-top EF301, EF303,
EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MegaFac F1
71, F173 (manufactured by Dainippon Ink Co., Ltd.), Florado FC430, FC431 (manufactured by Sumitomo 3M Limited),
Asahi Guard AG710, Surflon S-382, SC
101, SC102, SC103, SC104, SC1
05, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

These surfactants may be added alone or in some combination. A preferable addition amount is 100 parts of the composition (excluding the solvent).
0.0005 to 0.01 parts by weight with respect to parts by weight.

Examples of the developing solution for the second resist layer used in the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and the like.
Primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and tetraamines Quaternary such as methylammonium hydroxide and tetraethylammonium hydroxide
Aqueous solutions of alkalis such as quaternary ammonium salts, cyclic amines such as pyrrole and piperidine can be used.
Further, an appropriate amount of an alcohol, a surfactant, an aromatic hydroxyl group-containing compound, or the like can be added to the aqueous solution of the above-mentioned alkalis. Among them, it is particularly preferable to use tetramethylammonium hydroxide.

In the positive resist laminate of the present invention, a first resist layer is formed on a substrate. The formation of this layer is performed by dissolving the compound contained in the first resist layer in an appropriate solvent, and applying the resulting solution by a spin coat method, a spray method, or the like. The thickness of the first resist layer is preferably from 0.1 to 2.0 μm, more preferably from 0.2 to 1.5 μm, and particularly preferably from 0.25 to 1.2 μm. If it is thinner than 0.1 μm,
It is not preferable from the viewpoints of antireflection and dry etching resistance, and if it is thicker than 2.0 μm, the aspect ratio becomes too high, and there is a problem that the formed fine pattern is easily collapsed, which is also not preferable.

Next, a second resist layer is formed.
Before that, it is preferable to heat-treat the first resist layer. The temperature of the heat treatment is preferably 150 to 250 ° C, more preferably 170 to 240 ° C, and 180 to 2 ° C.
30 ° C. is particularly preferred. When the temperature is lower than 150 ° C., when the second resist layer is applied, intermixing with the first resist layer is apt to occur, and when the temperature is higher than 250 ° C., the polymer in the first resist is easily decomposed and deteriorated. Absent. This heat treatment can be performed using a device such as a hot plate or a hot oven.
The time of the heat treatment varies depending on the heat treatment temperature, but in the case of the heat treatment at 180 to 230 ° C., 10 seconds to 10 seconds.
It is preferably set in the range of 00 seconds, more preferably 2 seconds.
0 to 600 seconds is preferred. If the time is shorter than 10 seconds, thermal curing is insufficient and intermixing with the second resist layer is apt to occur. If the time is longer than 1000 seconds, the number of substrates to be processed decreases, which is not preferable.

Next, a second resist layer is formed on the first resist layer, which can be performed in the same manner as the formation of the first resist layer. The thickness of the second resist layer is set to 0.1.
It is preferably from 0.3 to 0.6 μm, more preferably from 0.04 to 0.5 μm, particularly preferably from 0.04 to 0.5 μm.
5 to 0.45 μm. If the thickness is less than 0.03 μm, the pattern transferability to the first resist layer is poor, or a pinhole of the coating film is generated. If the thickness is more than 0.6 μm, the lithography performance is inferior.

The obtained two-layer resist is then subjected to a pattern forming step. As a first step, a pattern forming process is first performed on the second layer of the resist composition film. The mask is adjusted as required, and high-energy rays are irradiated through the mask, so that the resist composition in the irradiated portion is made soluble in an aqueous alkaline solution, and developed with an aqueous alkaline solution to form a pattern. Next, dry etching is performed as a second step. This operation is performed by oxygen plasma etching using the pattern of the film of the resist composition as a mask to form a fine pattern having a high aspect ratio. The etching of the organic polymer film by the oxygen plasma etching is exactly the same technique as the plasma etching used when the resist film is peeled off after the etching of the substrate is completed by the conventional photoetching operation. This operation can be performed by, for example, a cylindrical plasma etching apparatus using oxygen as a reactive gas, that is, an etching gas.
A gas such as a sulfurous acid gas may be mixed with oxygen gas.

[0087]

[Examples] Hereinafter, Synthesis Examples, Examples and Comparative Examples are shown, but the present invention is not limited to the following Examples.

Synthesis Example 1 (Synthesis of P-2) Polymer Synthesis After dissolving 19.2 g of benzyl methacrylate and 3.2 g of 2-hydroxyethyl methacrylate in 100 g of DMF, the reaction solution was heated to 65 ° C., and simultaneously Nitrogen was flowed through for 30 minutes. 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 liter of distilled water. GPC analysis of the obtained polymer showed that the weight average molecular weight was 8,200 in terms of standard polystyrene.

Synthesis Example 2 (Synthesis of P-11) Monomer Synthesis 14.2 g of glycidyl methacrylate, 21.8 g of 3-hydroxy-7-methoxy-2-naphthoic acid and 0.5 g of methoxyhydroquinone were added to 60 ml of acetone. Thereafter, 10.1 g of triethylamine was added dropwise. 70
After the reaction at 4 ° C. for 4 hours, 0.5 liter of distilled water was added and collected by decantation. The product was produced by silica gel column chromatography. The yield is 80
%Met. Polymer Synthesis After dissolving 20.2 g of the above monomer and 1.6 g of 2-hydroxyethyl methacrylate in 60 g of DMF, the reaction solution was heated to 65 ° C., and simultaneously, nitrogen was flowed into the reaction solution for 30 minutes. As a polymerization initiator, 35 mg of V-65 (a product of Wako Pure Chemical Industries, Ltd.) was added three times every two hours. The reaction product was recovered as a powder by reprecipitation in 1 liter of distilled water. When GPC analysis of the obtained polymer was performed,
The weight average molecular weight was 9,100 in terms of standard polystyrene.

Synthesis Example 3 (Synthesis of Resin 9) 10.4 g of trimethylallylsilane, 9.8 g of maleic anhydride, and 5.3 g of t-butyl acrylate were dried in TH.
After adding to 34 g of F, the mixture was heated to 65 ° C. under a nitrogen stream. When the reaction temperature becomes stable, initiator V- manufactured by Wako Pure Chemical Industries, Ltd.
65 was added at 10 mol% of the total number of moles of the monomer, and the reaction was started. After reacting for 6 hours, the reaction mixture is
After diluting twice with HF, throw it into a large amount of hexane,
A white powder was deposited. Next, in order to reduce residual monomers and low molecular components, the precipitated powder was dissolved in acetone, and hexane was added little by little to precipitate a polymer. The precipitated polymer was washed with hexane / acetone (8/2) and dried under reduced pressure to obtain a resin (9). As a result of GPC measurement, the molecular weight of the obtained resin (9) was 5600 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1000 or less was 4% by area ratio of GPC. Resins (1) to (16) were obtained in the same manner as above.

Example 1 (1) Formation of First Resist Layer Component (a-1): Compound Example P-2 (weight average molecular weight = 8200) 5.0 g Component (a-2): 0.35 g of hexamethylolmelamine Component (a-3): 0.125 g of di (t-amyl) phenyliodonium-2,4,6-triisopropylsulfonate is dissolved in 28 g of methoxypropyl acetate, and the resulting solution is passed through a 0.1 μm-diameter membrane filter. After fine filtration, a first resist composition was obtained. This composition was applied to a silicon wafer using a coater CDS-650 manufactured by Canon Inc. and heated at 110 ° C. for 90 seconds to form a film having a thickness of 0.62 μm
m was obtained. This was further heated at 200 ° C. for 90 seconds to obtain a first resist layer having a thickness of 0.48 μm.

(2) Formation of Second Resist Layer Component (b): Resin (1) 0.9 g Component (c): triphenylsulfonium-2,4,6-triisopropylpropylsulfonate 0.05 g 1,8-diazabicyclo [5.4.0] -7-undecene (0.006 g) was dissolved in methoxypropyl acetate (9 g), and the obtained solution was subjected to microfiltration with a 0.1 μm-diameter membrane filter to obtain a second resist composition. On the first resist layer, a second resist layer is similarly applied,
By heating at 90 ° C. for 90 seconds, a second resist layer having a thickness of 0.20 μm was obtained.

The wafer obtained in this manner was manufactured by Canon Kr.
An F excimer laser stepper FPA3000EX5 was loaded with a resolving power mask and exposed while changing the exposure amount. Thereafter, the film was heated in a clean room at 120 ° C. for 90 seconds, developed with a tetrahydroammonium hydroxide developer solution (2.38%) for 60 seconds, rinsed with distilled water and dried to obtain a pattern (upper layer pattern). The pattern was observed with a scanning electron microscope. Further, the wafer having the upper layer pattern was etched (dry-developed) using a parallel plate reactive ion etching apparatus manufactured by ULVAC to form a pattern in the lower layer. Etching gas is oxygen, pressure is 20 mTorr, applied power is 100 mW / c.
m ² , and the etching time was 15 minutes. The formed resist pattern was observed with a scanning electron microscope.

The following methods were used to evaluate the resolving power, line pattern undulation, and development residue. (1) Resolution: When the exposure amount was obtained when a 0.18 μm line / space of the mask was reproduced, the evaluation was made at the minimum dimension at which the line / space was separated and resolved in the lower layer. (2) Line pattern undulation: 0.18μ of the above mask
The deviation of the line from the straight line in the length direction of 20 m of the m line was evaluated by an average value measured at arbitrary 20 points. (3) Development residue: Visual evaluation of the degree of occurrence (electron microscope)
did. A five-point scale of 5 (significantly small) to 1 (significantly large) was given. The result of Example 1 shows that the resolution is 0.145 μm.
m, the undulation of the line pattern was 0.007 μm, and the development residue was as good as Level 1.

Examples 2 to 15 The components (a-1), (a-2), and (a-
3) In place of the components (b) and (c) of the second resist layer, the components (a-1), (a-2), (a-3), (b) and (c) shown in Table 1 are used. )
Was used in the same amount as in Example 1, exposed, developed, and etched in the same manner as in Example 1. The resultant was observed with a scanning electron microscope and evaluated in the same manner as in Example 1. Table 2 shows the results. Comparative Examples 1-3 Components (a-1), (a-2), (a-3) of the first resist layer of Example 1
, Instead of using FHi-028DD (resist for i-line manufactured by FUJIFILM Aurin Co.), high-temperature heating conditions were 200 ° C./90 seconds, 200 ° C./10 minutes, 200 ° C./60 minutes, respectively.
Exposure, development, and etching treatment were performed in the same manner as in Example 1, except that the amount was changed to minutes, and the resultant was observed with a scanning electron microscope, and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0096]

[Table 1]

[0097]

[Table 2]

Examples 16 to 25 The components (a-1), (a-2), and (a-
3) In place of the components (b) and (c) of the second resist layer, the components (a-1), (a-2), (a-3), (b) and (c) shown in Table 3 are used. )
Was used in the same amount as in Example 1, and the Kr manufactured by Canon of Example 1 was used.
The FPA3000EX5 F excimer laser stepper was replaced with an ArF excimer laser stepper 9300 manufactured by ICI.
Exposure, development and etching were carried out in the same manner as in Example 1 except that the above was changed to, and they were observed with a scanning electron microscope. Table 4 shows the results. Comparative Examples 4 to 6 Except that the KrF excimer laser stepper FPA3000EX5 manufactured by Canon of Comparative Examples 1 to 3 was changed to an ArF excimer laser stepper 9300 manufactured by ICI, exposure and development and etching were performed in the same manner as Comparative Examples 1 to 3, respectively. Was observed with a scanning electron microscope and evaluated in Example 1.
The same was done. Table 4 shows the results.

[0099]

[Table 3]

[0100]

[Table 4]

The following is clear from the evaluation results of Examples 1 to 15 and Comparative Examples 1 to 3 and the evaluation results of Examples 16 to 25 and Comparative Examples 4 to 6. That is, the resist laminate of the example is solidified by a high-temperature treatment for a short time of 90 seconds, and can form a resist pattern having high resolution and little line waviness and development residue. on the other hand,
In the case of the comparative example in which the conventional i-line resist is used for the first resist layer, the resolution is low, the line waviness is large, and the amount of development residue is large in the same short-time high-temperature treatment as in the example.
The long-term high-temperature treatment reduces the resolution, line waviness, and development residue, but is inferior to the performance of the examples, and the long-term treatment greatly reduces the suitability for production.

[0102]

The positive resist laminate of the present invention can cope with exposure in the far ultraviolet region and has a high resolution. Also,
A resist pattern with less line waviness and development residue in a fine pattern of 0.2 μm or less can be formed. Further, high-temperature treatment can be performed in a short time, and the suitability for production is excellent. Therefore, the composition of the present invention is very suitably used for mass production of semiconductor substrates having ultrafine circuits.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 5F046 C08L 33/04 C08L 33/04 35/00 35/00 43/04 43 / 04 G03F 7/004 501 G03F 7/004 501 7/075 511 7/075 511 7/26 511 7/26 511 H01L 21/027 H01L 21/30 502R 573 F term (reference) 2H025 AA02 AA03 AA04 AB16 AC04 AC08 AD03 BE00 BE07 BE10 BF02 BF30 BG00 CB10 CB43 CC17 CC20 DA29 FA41 2H096 AA25 BA11 GA08 GA37 HA01 HA11 KA03 KA06 4J002 BG021 BH021 BQ001 FD206 FD207 GP03 4J011 QA01 QA03 QA37 QA39 UA01 SA77SAA01SA77 BA04Q BA72P BC53Q CA04 CA05 CA06 JA38 5F046 NA05 NA18

Claims (3)

[Claims] 1. A two-layer resist having a first resist layer on a substrate and a second resist layer on the first resist layer,
The resist layer contains (a-1) a polymer containing a repeating unit represented by the following general formula (1), and the second resist layer contains (b) a repeating unit represented by the following general formula (4). ,
A polymer having at least one repeating unit of the general formulas (5a) and (5b), or the following general formula (4)
And (c) an actinic ray or a polymer having at least one of the repeating units represented by the general formulas (5a) and (5b) and the repeating unit represented by the general formula (6). A positive resist laminate comprising: a compound that generates an acid upon irradiation with radiation. Embedded image In the formula (1), Y ¹ represents a hydrogen atom, an alkyl group, a cyano group,
Or a halogen atom, L ¹ and L ² each represent a divalent linking group, and J represents a phenyl group, a naphthyl group, an anthryl group, or a phenanthryl group which may have a substituent. b and c each independently represent 0 or 1. Embedded image In the formula (4), R ^{2 to} R ⁴ each independently represent an alkyl group,
Represents a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, or a trialkylsilyloxy group. n represents 0 or 1. Embedded image In the formula (5a), Y ² has the same meaning as Y ¹ . L represents a single bond or a divalent linking group. Q represents a group capable of decomposing with an acid to generate a carboxylic acid. Embedded image In the formula (5b), X ¹ and X ² each independently represent a group selected from an oxygen atom, a sulfur atom, —NH—, and —NHSO ₂ —. L ¹¹ and L ¹² each independently represent a single bond or a divalent linking group. A ² represents a hydrogen atom, a cyano group, a hydroxyl group,
^{-COOH, -COOR 5, -CO-NH} -R 6, alkyl group which may have a substituent, an alkoxy group, or -
Represents COOQ. (R ⁵ and R ⁶ each independently represent an alkyl group which may have a substituent.) Q represents a group capable of decomposing with an acid to generate a carboxylic acid. Embedded image In the formula (6), Z represents an oxygen atom or N—R ⁷ . R ⁷ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁸ . R ⁸ represents an alkyl group or a trihalomethyl group. 2. The first resist layer contains (a-1) a polymer containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2); Second
The resist layer is represented by (b) a polymer having a repeating unit represented by the following general formula (4) and at least one repeating unit of the general formulas (5a) and (5b), or a resist represented by the general formula (4) And the general formulas (5a) and (5
b) containing at least one of the repeating units and a polymer having a repeating unit represented by the general formula (6), and (c) a compound capable of generating an acid upon irradiation with actinic rays or radiation. The positive resist laminate according to claim 1, wherein: Embedded image In the formula (1), Y ¹ represents a hydrogen atom, an alkyl group, a cyano group,
Or a halogen atom, L ¹ and L ² each represent a divalent linking group, and J represents a phenyl group, a naphthyl group, an anthryl group, or a phenanthryl group which may have a substituent. b and c each independently represent 0 or 1. Embedded image In the formula (4), R ^{2 to} R ⁴ each independently represent an alkyl group,
Represents a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, or a trialkylsilyloxy group. n represents 0 or 1. Embedded image In the formula (5a), Y ² has the same meaning as Y ¹ . L represents a single bond or a divalent linking group. Q represents a group capable of decomposing with an acid to generate a carboxylic acid. Embedded image In the formula (5b), X ¹ and X ² each independently represent a group selected from an oxygen atom, a sulfur atom, —NH—, and —NHSO ₂ —. L ¹¹ and L ¹² each independently represent a single bond or a divalent linking group. A ² represents a hydrogen atom, a cyano group, a hydroxyl group,
^{-COOH, -COOR 5, -CO-NH} -R 6, alkyl group which may have a substituent, an alkoxy group, or -
Represents COOQ. (R ⁵ and R ⁶ each independently represent an alkyl group which may have a substituent.) Q represents a group capable of decomposing with an acid to generate a carboxylic acid. Embedded image In the formula (6), Z represents an oxygen atom or N—R ⁷ . R ⁷ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁸ . R ⁸ represents an alkyl group or a trihalomethyl group. Embedded image In the formula (2), Y ³ has the same meaning as Y ¹ , and L ³ represents a divalent linking group. 3. A thermal crosslinking agent, wherein the first resist layer is activated by (a-2) an acid and reacts with a polymer containing a repeating unit of the general formula (2) to form a crosslinked structure; The positive resist laminate according to claim 2, further comprising (a-3) a compound that generates an acid by heat.