JP2001201854A - Positive radiation sensitive composition and resist pattern producing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high sensitivity positive radiation sensitive composition having such resolution as to attain sub-quarter micron patterning. SOLUTION: The positive radiation sensitive composition contains a polymer containing a structural unit of formula 1 (where X is a halogen or a cyano; and T is an organic group having at least one terpenoid skeleton) or formula 2 (where Y is H, methyl, halogen or cyano; and R is a 1-10C hydrocarbon or hydroxyl) and an acid generating agent which generates an acid when irradiated. A resist pattern is produced using the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive radiation-sensitive composition used for producing semiconductor integrated circuits, lithography masks and the like.

[0002]

2. Description of the Related Art In recent years, in fields such as the manufacture of semiconductor circuits and lithography masks, patterns have been miniaturized with an increase in the degree of integration. In order to realize this, a higher resolution resist material has been required, and it has become necessary to process a sub-quarter micron pattern of 0.25 μm or less with high sensitivity. Further, it is difficult to perform such fine processing with a conventional lithography using a light source having a relatively long wavelength, and lithography using far ultraviolet rays, vacuum ultraviolet rays, X-rays and electron beams having a shorter wavelength. Are being studied, and a resist corresponding to such a light source is required.

In recent years, in order to cope with such a light source, a chemically amplified resist has been actively studied as a known resist material having high sensitivity and high resolution characteristics. A chemically amplified resist is a resist having a mechanism in which an acid is generated in an exposed portion by the action of a photoacid generator, and the solubility of the exposed portion is changed by the catalytic action of the acid. Conventionally, among such chemically amplified resists, those exhibiting relatively good resist performance include those in which an alkali-affinity group in an alkali-soluble resin is a tertiary ester group such as a t-butyl group, a t-butoxycarbonyl group, an acetal. Resins protected with acid-decomposable groups such as groups are used.

[0004]

However, the resolution and the sensitivity are in a contradictory relationship, and there is a drawback that the sensitivity is not sufficient to obtain a resolution for processing a sub-quarter micron pattern.

[0005]

That is, the present invention comprises a polymer containing a structural unit represented by the following general formula (1) or (2) and an acid generator which generates an acid upon irradiation with radiation. And a method for producing a resist pattern using the composition.

[0006]

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(X represents a halogen atom or a cyano group. T represents an organic group having at least one terpenoid skeleton.)

[0008]

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(Y represents a hydrogen atom, a methyl group, a halogen atom or a cyano group. R represents a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention have studied a polymer for a chemically amplified resist capable of obtaining high resolution and high sensitivity. As a result, by using a polymer containing a specific acrylate-based monomer unit, high sensitivity can be obtained. It was found that a pattern having a good rectangular cross section could be obtained.

The positive radiation-sensitive composition of the present invention contains a polymer containing a structural unit represented by the general formula (1) or (2).

[0012]

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[0013]

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X in the general formula (1) represents a halogen atom or a cyano group, and among them, a chlorine atom is preferable. By introducing such a substituent on the α-carbon, the main chain is easily cut by exposure. As a result, the molecular weight of the polymer is reduced in the exposed area, and a high-contrast image is obtained. Further, the effect of these α-position substituents is as follows.
This is particularly noticeable when a high-energy radiation source such as radiation or vacuum ultraviolet light is used.

T in the general formula (1) is an organic group having at least one terpenoid skeleton. Examples of the compound having a terpenoid skeleton include α-pinene, β-pinene, caren, camphor, terpinolene, terpinene, limonene, rosin, and the like. Since these terpenoid skeletons have a ring structure, they have resistance to dry etching.

Specific examples of the structural unit represented by the general formula (1) are shown below, but the present invention is not limited thereto.

[0017]

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In the general formula (2), Y is a hydrogen atom, a methyl group,
Represents a halogen atom or a cyano group. Among them, Y is preferably a methyl group, a halogen atom or a cyano group, and among them, a halogen atom and a cyano group are more preferably used. Most preferred is a chlorine atom.

The menthyl derivative group in the ester portion of the general formula (2) is easily eliminated by the acid generated from the photoacid generator, and the carboxyl group which is an alkali-soluble group is regenerated. Further, since the menthyl derivative group has a ring structure, it has resistance to dry etching.

In the general formula (2), R represents a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group.

As a photosensitive material having a terpenoid skeleton or a menthyl derivative group represented by the general formulas (1) and (2), a resist described in JP-A-8-82925 is known. On the other hand, the present invention achieves higher sensitivity than the invention described in the above-mentioned publication by introducing a specific substituent on the α-carbon and setting the bonding position of the menthyl derivative group to a specific site.

The polymer used in the present invention has the general formula (1)
Alternatively, a polymer containing only the structural unit represented by the general formula (2) may be used, but a copolymer containing other monomer units may be used as long as the characteristics as a chemically amplified resist are not impaired. . Other monomer structures include acrylic acid,
Methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-
Butyl acrylate, t-butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methyl α-chloroacrylate, ethyl α-chloroacrylate, hydroxyethyl α- Chloroacrylate, isopropyl α-chloroacrylate,
n-butyl α-chloroacrylate, t-butyl α-chloroacrylate, methyl α-cyanoacrylate, ethyl α-cyanoacrylate, hydroxyethyl α-cyanoacrylate, isopropyl α-cyanoacrylate, n-butyl α-cyanoacrylate, Styrene, p
-Hydroxystyrene, α-methylstyrene, α-methyl-p-hydroxystyrene, maleic acid, maleic anhydride, crotonic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, acrylonitrile, methacrylonitrile, crotonnitrile, maleic Examples thereof include nitrile, fumalonitrile, metaconitrile, citraconitrile, itaconitrile, acrylamide, methacrylamide, crotonamide, maleamide, fumaramid, mesaconamide, citraconamide, itaconamide, vinylaniline, vinylpyrrolidone, and vinylimidazole. When the other monomer structure has an acidic functional group, it may include a monomer unit having a structure in which a hydrogen atom of the acidic functional group is substituted with an acid-decomposable group. Specific examples of the acid-decomposable group include methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzylthiomethyl, phenacyl, bromophenacyl, methoxy Phenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxy Benzyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, t-butoxycarbonylmethyl, propenyl, 1-methyl Xyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl Group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonyl Ethyl group,
1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t
-Butoxycarbonylethyl group, isopropyl group, s-
Butyl group, t-butyl group, 1,1-dimethylbutyl group,
Trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, t-butyldimethylsilyl, methyldi-t-butylsilyl, tri-t- Butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl Group, valeryl group, pivaloyl group, isovaleryl group, lauryloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group,
Glutaryl, adipoyl, piperoyl, suberoyl, azelaoil, sebacoil, acryloyl, propyloyl, methacryloyl, crotonoyl, oleoyl, maleoyl, fumaroyl, mesaconoyl, benzoyl, phthaloyl, isophthaloyl Group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, mesyl group, cyclopropyl group, cyclopentyl group , Cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl, 3-butane Mote tiger tetrahydropyranyl group, 4-
Methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-
Examples thereof include 1,1-dioxide.

Further, the polymer of the present invention may contain the following ring structure in the main chain for improving dry etching resistance and the like.

[0024]

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The weight average molecular weight of the polymer containing a structural unit represented by the general formula (1) or (2) used in the present invention is 500 in terms of polystyrene measured by GPC.
0 to 1,000,000, preferably 6,000 to 10,000
0, more preferably 7000 to 50,000.

The positive radiation-sensitive composition of the present invention contains an acid generator which generates an acid upon irradiation with radiation. This enables a pattern to be formed by a chemical amplification mechanism in addition to the main chain cleavage, and a high-sensitivity, high-resolution pattern can be obtained. The acid generator used here may be any as long as the polymer can be made alkali-soluble by the generated acid. Examples thereof include an onium salt, a halogen-containing compound, a diazoketone compound, a diazomethane compound, a sulfone compound, a sulfonate compound, and a sulfonimide compound.

Specific examples of onium salts include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, oxonium salts and the like. Preferred onium salts include diphenyliodonium triflate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate And the like.

Specific examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2-naphthyl-4,6. -Bis (trichloromethyl)
-S-triazine and the like.

Specific examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound. Preferred diazoketone compounds are 1,2-naphthoquinonediazido-4-sulfonic acid and 2,2,3,4,4 '
Esters with tetrahydroxybenzophenone, 1,
2-naphthoquinonediazide-4-sulfonic acid and 1,1,
Examples thereof include esters with 1-tris (4-hydroxyphenyl) ethane.

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane,
Bis (phenylsulfonyl) diazomethane, bis (p-
Tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p
-Toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane and the like.

Specific examples of the sulfone compound include β
-Ketosulfone compounds, β-sulfonylsulfone compounds and the like. Preferred compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone,
Bis (phenylsulfonyl) methane and the like can be mentioned.

Examples of the sulfonic acid ester compound include:
Examples thereof include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol trimesylate, and nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate.

Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, and N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(Trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6
-Oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthyldicarboximide, N- (campanylsulfonyloxy) succinimide, N- (campanylsulfonyloxy)
Phthalimide, N- (campanylsulfonyloxy)
Diphenylmaleimide, N- (campanylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (campanylsulfonyloxy) -7-oxabicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N
-(Campanylsulfonyloxy) bicyclo [2.
2.1] Heptane-5,6-oxy-2,3-dicarboximide, N- (campanylsulfonyloxy)
Naphthyl dicarboximide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N-
(4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N
-(4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthyldicarboximide, N- (2
-Trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 -Trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N-
(2-trifluoromethylphenylsulfonyloxy)
Naphthyl dicarboximide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-
Fluorophenylsulfonyloxy) phthalimide, N
-(4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy)
Bicyclo [2.2.1] heptane-5,6-oxy-
Examples thereof include 2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboximide and the like.

These acid generators can be used alone or in combination of two or more. The amount of the acid generator to be added is generally 0.01 to 50% by weight, more preferably 0.1 to 10% by weight, based on the polymer. 0.01% by weight
If the amount is less than 50%, the pattern cannot be formed.
If the amount is larger than the above, affinity with the developing solution is lowered, and poor development occurs.

A dissolution inhibitor can be added to the positive radiation-sensitive composition of the present invention. The dissolution inhibitor has a group that is decomposed by the action of an acid and becomes alkali-soluble. The dissolution inhibitor, when added to the composition, has the effect of reducing the rate of alkali dissolution of the composition until it is affected by an acid, and the alkali-soluble group is decomposed by the action of an acid, thereby reducing the composition. A compound that has the effect of increasing the alkali dissolution rate of a substance. As the dissolution inhibitor, for example, a compound containing an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, and a sulfoxy group, in which a hydrogen atom of the acidic functional group is substituted with an acid-decomposable group, can be used. Compounds having an acidic functional group used herein include hydroquinone, catechol,
Bisphenol A, hydroxyphenylacetic acid, 4-hydroxybenzenesulfonic acid and the like can be mentioned as examples. Examples of the acid leaving group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group,
Methoxyethoxymethyl group, benzyloxymethyl group,
Benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, promobenzyl group, nitro Benzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, t-butoxycarbonylmethyl Group, propenyl group, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1 -Phenoxy Butyl, 1-phenylthioethyl, 1,1-diphenoxyethyl, 1-benzyloxyethyl, 1-benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1,1- Diphenylethyl group, 1-methoxycarbonylethyl group,
1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t
-Butoxycarbonylethyl group, isopropyl group, s-
Butyl group, t-butyl group, 1,1-dimethylbutyl group,
Trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, t-butyldimethylsilyl, methyldi-t-butylsilyl, tri-t- Butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl Group, valeryl group, pivaloyl group, isovaleryl group, lauryloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group,
Glutaryl, adipoyl, piperoyl, suberoyl, azelaoil, sebacoil, acryloyl, propyloyl, methacryloyl, crotonoyl, oleoyl, maleoyl, fumaroyl, mesaconoyl, benzoyl, phthaloyl, isophthaloyl Group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, mesyl group, cyclopropyl group, cyclopentyl group , Cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiofuranyl, 3-butane Mote tiger tetrahydropyranyl group, 4-
Methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-terolahydrothiophene-
1,1-dioxide and the like can be mentioned.

As the dissolution inhibitor used in the present invention, a high molecular compound can also be used. As the polymer dissolution inhibitor, those in which a hydrogen atom of a hydroxyl group or a carboxyl group of a polymer having a hydroxy group or a carboxyl group is substituted by the above-described acid-decomposable group are used. Specific examples of the polymer having a hydroxyl group or a carboxyl group include hydroxystyrene, α-methylhydroxystyrene, α-chlorohydroxystyrene, vinylbenzoic acid,
At least one polymer of monomers having a polymerizable double bond such as carboxymethylstyrene, carboxymethoxystyrene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and cinnamic acid, and novolak resin Representative examples include condensation polymers. Specific examples of the acid-decomposable group include the aforementioned acid-decomposable groups.

The dissolution inhibitor is used in an amount of 0 to 150 parts by weight, preferably 5 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the polymer containing the structural unit represented by the general formula (1) or (2). 5 to 50 parts by weight.

If necessary, additives such as a surfactant, a sensitizer, a stabilizer, an antifoaming agent and an acid diffusion inhibitor can be added to the positive radiation-sensitive composition of the present invention.

The positive radiation-sensitive composition of the present invention can be obtained by dissolving the above components in a solvent. The amount of the solvent used is not particularly limited, but is adjusted so that the solid content is 5 to 35% by weight. Preferred solvents used are ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, methyl butyrate, methyl benzoate, methyl lactate, ethyl lactate, ethyl pyruvate, methyl β-isobutyrate, methyl 3-methoxypropionate, -Ethyl ethoxypropionate, esters such as γ-butyrolactone, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve esters such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol Propylene glycol esters such as monoethyl ether acetate, 1,2-dimethoxyethane, 1,2
-Diethoxyethane, tetrahydrofuran, ethers such as anisole, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, cyclohexanone, ketones such as isophorone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane and the like Solvents selected from aprotic polar solvents, or composite solvents thereof.

The positive-type radiation-sensitive composition of the present invention is applied on a substrate to be processed, dried, and usually used as a thin film having a thickness of 0.2 μm to 2 μm. The thin film is subjected to pattern exposure using radiation such as ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams, X-rays, etc., followed by baking and development after exposure to obtain a fine pattern. In particular, the effect is large in the case of pattern exposure using an electron beam or X-ray, and the effect is more remarkable in the case of using an electron beam.

The development of the radiation-sensitive composition of the present invention can be carried out using a known developer. Examples include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, and tetramethylammonium hydroxide. And aqueous solutions containing one or more quaternary ammoniums such as choline and choline.

[0042]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The weight average molecular weight in this example is a GPC (gel permeation chromatography) measurement value in terms of polystyrene.

Example 1 Using azobisisobutyronitrile as an initiator, 6,6
2-Trimethyl-bicyclo [3,1,1] -2-heptyl-α-chloroacrylic acid in tetrahydrofuran
Polymerization was performed at 0 ° C. to obtain a polymer represented by the following chemical formula (3) (weight average molecular weight: 15,000). 3 g of this polymer and 150 mg of triphenylsulfonium triflate were dissolved in propylene glycol monomethyl ether acetate.
The mixture was filtered through a 1 μm filter to obtain a resist composition.

[0044]

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The obtained resist composition was spin-coated on a silicon wafer and heated at 90 ° C. for 2 minutes to obtain a 0.5 μm-thick resist film. The resist film was irradiated with an electron beam in a pattern at an acceleration voltage of 20 kV using an electron beam exposure apparatus, heated at 90 ° C. for 3 minutes, and then developed with an aqueous solution of tetramethylammonium hydroxide.
At an exposure of 4.0 μC / cm ² , a pattern of 0.24 μm was obtained.

Example 2 Instead of the polymer represented by the chemical formula (3) used in Example 1, a copolymer represented by the following chemical formula (4) (weight average molecular weight: 9
000), a resist film was obtained in the same manner as in Example 1, and the film was developed by irradiation with an electron beam. 3.7 μC / c
At an exposure of m ² , a pattern of 0.22 μm was obtained.

[0047]

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Example 3 Instead of the polymer represented by the chemical formula (3) used in Example 1, a polymer represented by the following chemical formula (5) (weight average molecular weight: 12
000), a resist film was obtained in the same manner as in Example 1, and the film was developed by irradiation with an electron beam. 3.8 μC / c
With an exposure of m ² , a pattern of 0.23 μm was obtained.

[0049]

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Example 4 Instead of the polymer represented by the chemical formula (3) used in Example 1, a copolymer represented by the following chemical formula (6) (weight average molecular weight: 1)
A resist film was obtained in the same manner as in Example 1 except that the method (2000) was used, and the resist film was irradiated with an electron beam and developed. 3.1 μC /
A pattern of 0.22 μm was obtained with an exposure amount of cm ² .

[0051]

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Example 5 Instead of the polymer represented by the chemical formula (3) used in Example 1, a copolymer represented by the following chemical formula (7) (weight average molecular weight: 1) was used.
A resist film was obtained in the same manner as in Example 1 except that (5000) was used, and the film was developed by irradiation with an electron beam. 3.5 μC /
A pattern of 0.23 μm was obtained with an exposure amount of cm ² .

[0053]

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Example 6 Instead of the polymer represented by the chemical formula (3) used in Example 1, a copolymer represented by the following chemical formula (8) (weight average molecule 21
000), a resist film was obtained in the same manner as in Example 1, and the film was developed by irradiation with an electron beam. 3.2 μC / c
With a light exposure of m ² , a pattern of 0.23 μm was obtained.

[0055]

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Example 7 The same experiment as in Example 3 was performed except that an i-line stepper was used as an exposure device. 0.3 at an exposure of 33 mJ / cm ² .
A pattern of 35 μm was obtained.

Comparative Example 1 Poly (t-butyl-α-chloroacrylate) was used in place of the polymer represented by the chemical formula (3) used in Example 1.
Example 1 except that (weight average molecular weight 21,000) was used.
A resist film was obtained in the same manner as described above, and was irradiated with an electron beam and developed. A pattern of 0.33 μm was obtained at an exposure amount of 6.0 μC / cm ^{2, and} the characteristics were not sufficient in terms of sensitivity and resolution.

Comparative Example 2 A copolymer represented by the following chemical formula (9) (weight average molecular weight: 1) was used instead of the polymer represented by the chemical formula (3) used in Example 1.
8000), and a resist film was obtained and evaluated in the same manner as in Example 1. A pattern of 0.28 μm was obtained at an exposure dose of 5.5 μC / cm ^{2, and} the characteristics were not sufficient in terms of sensitivity and resolution.

[0059]

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Comparative Example 3 The same as Example 1 except that a copolymer represented by the following chemical formula (10) (weight average molecular weight: 17000) was used instead of the polymer represented by the chemical formula (3) used in Example 1. A resist film was obtained and irradiated with an electron beam for development. 20 μC /
No pattern was obtained at an exposure dose of cm ² .

[0061]

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[0062]

[Table 1]

[0063]

[Table 2]

[0064]

As described above, the positive-type radiation-sensitive composition of the present invention contains a polymer containing a specific acrylate monomer unit and an acid generator that generates an acid upon irradiation with radiation. By using a positive radiation-sensitive composition, it has become possible to obtain a composition with high resolution and high sensitivity.

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[Procedure amendment]

[Submission date] January 17, 2001 (2001.1.1)
7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

The polymer used in the present invention has the general formula (1)
Alternatively, a polymer containing only the structural unit represented by the general formula (2) may be used, but a copolymer containing other monomer units may be used as long as the characteristics as a chemically amplified resist are not impaired. . Other monomer structures include acrylic acid,
Methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, isopropyl acrylate, n-
Butyl acrylate, t-butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, methyl α-chloroacrylate, ethyl α-chloroacrylate, hydroxyethyl α- Chloroacrylate, isopropyl α-chloroacrylate,
n-butyl α-chloroacrylate, t-butyl α-chloroacrylate, methyl α-cyanoacrylate, ethyl α-cyanoacrylate, hydroxyethyl α-cyanoacrylate, isopropyl α-cyanoacrylate, n-butyl α-cyanoacrylate, Styrene, p
-Hydroxystyrene, α-methylstyrene, α-methyl-p-hydroxystyrene, maleic acid, maleic anhydride, crotonic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, itaconic anhydride, acrylonitrile, methacrylonitrile , Crotonnitrile, maleinitrile, fumaronitrile, methaconitrile, citraconitrile, itaconnitrile, acrylamide, methacrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, vinylaniline, vinylpyrrolidone, vinylimidazole, etc. be able to. When the other monomer structure has an acidic functional group, it may include a monomer unit having a structure in which a hydrogen atom of the acidic functional group is substituted with an acid-decomposable group. Specific examples of the acid-decomposable group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group,
Benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, Promobenzyl group,
Nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, t-butoxycarbonyl Methyl group, propenyl group, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1 , 1-diphenylethyl group, 1-methoxycarbonyl Group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonyl ethyl group, 1-
Isopropoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, isopropyl group, s-butyl group, t-butyl group,
1,1-dimethylbutyl group, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, methyldiisopropylsilyl group, triisopropylsilyl group,
t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t -Butoxycarbonyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group,
Malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoil group, acryloyl group, propyloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, benzoyl Group,
Phthaloyl group, isophthaloyl group, terephthaloyl group,
Naphthoyl group, toluoyl group, hydroatropoyl group,
Atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, mesyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, 4-methoxycyclohexyl group, tetrahydropyranyl Group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3
-Tetrahydrothiophene-1,1-dioxide and the like.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, and N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(Trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6
- oxy-2,3-dicarboxylic imide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxyl imide, N- (Kanfu § over sulfonyloxy) succinimide, N- (Kanfu § over sulfonyloxy) phthalimide, N- ( Kanfu § over sulfonyloxy) diphenyl maleimide, N- (Kanfu § over sulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic imide, N- (Kanfu § over sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5
Ene-2,3-dicarboxylic imide, N- (Kanfu §
Over sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylic imide, N
- (Kanfu § over sulfonyloxy) naphthyl dicarboxyl imides, N-(4-methylphenyl sulfonyloxy) succinimide, N-(4-methylphenyl sulfonyloxy) phthalimide, N-(4-methylphenyl-sulfonyloxy) diphenyl maleimide, N- (4-
Methylphenylsulfonyloxy) bicyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7
-Oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide,
N- (4-methylphenylsulfonyloxy) naphthyldicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2
-Trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N
-(2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxyl Imide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N-
(4-Fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2. 1] Hept-5
-Ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboximide and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AA02 AB16 AD03 BE00 BE07 BE10 BF02 BF09 BG00 FA17 4J002 BG071 BG081 EB106 EN136 EQ016 EV296 EW176 GP03

Claims (5)

[Claims] 1. A positive radiation-sensitive composition comprising a polymer containing a structural unit represented by the following general formula (1) and an acid generator that generates an acid upon irradiation with radiation. Embedded image (X represents a halogen atom or a cyano group. T represents an organic group having at least one terpenoid skeleton.) 2. A positive radiation-sensitive composition comprising a polymer containing a structural unit represented by the following general formula (2) and an acid generator that generates an acid upon irradiation with radiation. Embedded image (Y represents a hydrogen atom, a methyl group, a halogen atom or a cyano group. R represents a hydrocarbon group having 1 to 10 carbon atoms or a hydroxyl group.) 3. The positive radiation-sensitive composition according to claim 2, wherein Y in the general formula (2) is a halogen atom or a cyano group. 4. A method for producing a pattern wherein the positive-type radiation-sensitive composition according to claim 1 or 2 is applied onto a substrate to be processed, dried, exposed and developed. 5. The method according to claim 4, wherein the exposure is performed by an electron beam.