JPH02125259A - Resist composition - Google Patents

Abstract

PURPOSE:To improve the balance among sensitivity, resolution, etching resistance and preservable stability by incorporating an alkaline soluble compd. obtd. from a phenolic compd. contg. a specific compd. and an aldehyde compd. CONSTITUTION:This compsn. contains the alkaline soluble compd. obtd. from the phenolic compd. contg. at least 5wt.% compd. expressed by the formula I and the aldehyde compd. In the formula, R<1> denotes an alkenyl group or alkenyloxy group; R<2> denotes hydrogen, alkyl group, alkoxy group or halogen. The sensitivity is insufficient and the residual film rate falls drastically if the content of the compd. expressed by the formula I is below 5wt.%. The resist compsn. which is excellent in the balance among the sensitivity, resolution, etching resistance and preservable stability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a resist/composition for microfabrication of semiconductor elements, and more specifically, to a pattern forming material by irradiation with deep ultraviolet light, KrF excimer laser light, etc. It is related to.

(Prior art) When manufacturing semiconductor devices, a resist is applied to the surface of a silicon wafer to form a photoresist film, a latent image is formed by irradiation with light, and then a negative or positive image is formed by developing the latent image. Images are obtained using lithography technology.

However, with the increasing integration, density, and miniaturization of semiconductor devices such as IC, LSI, and VTS I,
The following techniques for forming fine patterns are required.

However, in the conventional method using normal photolithography using near ultraviolet or visible light, 1 μm
It is extremely difficult to form the following patterns with high accuracy. At the same time, the yield is significantly reduced, so the method using ordinary photolithography cannot be used to form patterns of 1 μm or less.

For this reason, instead of conventional photolithography that uses light (ultraviolet light with a wavelength of 350 to 450 μm), lithography techniques that use far ultraviolet light, KrF excimer laser light, etc., which have shorter wavelengths, are being researched.

There are a wide range of performance requirements for resist materials, which are the core of this lithography technology, including sensitivity, resolution, etching resistance, and storage stability, but the materials developed to date fully satisfy all of these performance requirements. Well then (
, there was a strong desire for improved performance.

For example, negative resists such as polyglycidyl methacrylate have a high degree of anger, but have poor resolution and dry etching resistance, and improvements are desired.

Further, although positive resists such as polymethyl methacrylate have good resolution, they have poor sensitivity and dry etching resistance, which poses a practical problem. Furthermore, when a novolac positive type photoresist used in conventional photolithography is exposed to deep ultraviolet rays, the resist itself absorbs too much light, making it impossible to form a good pattern.

Therefore, there was a strong desire to develop a new, well-balanced resist.

(Problems to be Solved by the Invention) The purpose of the present invention is to solve the above-mentioned drawbacks of the prior art, improve sensitivity,
Well-balanced resist properties such as resolution, etching resistance, storage stability, etc., especially short-wavelength deep ultraviolet rays,
The object of the present invention is to provide a resist material suitable for lithography using KrF excimer laser light.

(Means for Solving the Problem) This object of the present invention is achieved by the following (1) or (2).

(11-A resist composition comprising an alkali-soluble resin obtained from a phenol compound and an aldehyde compound containing at least 5% by weight of the compound represented by Formation (1).

R1, an alkenyl group or an alkenyloxy group R2, hydrogen, an alkyl group, an alkoxy group, or a halogen (2) A resist composition comprising the alkali-soluble resin described in (II) above and a photocrosslinking agent.

-The compound of formation (1) is: 2-vinylphenol, 3-vinylphenol.

4-vinylphenol, 2-methyl-4-vinylphenol, 2-ethyl-4-vinylphenol.

2-methoxy-4-vinylphenol, 2-chloro-3
-vinylphenol, 2-chloro-4-vinylphenol, 2-bromo-4-vinylphenol, 2-isopropenylphenol, 3-isopropenylphenol, 4
-isopropenylphenol, 2-methyl-4-isopropenylphenol, 3-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol.

2-Methoxy-4-isopropenylphenol.

2-chloro-4-isopropenylphenol, 2-(1
-propenyl)phenol, 3-(1-propenyl)phenol, 4-(1-propenyl)phenol, 2-methyl-4-(1-propenyl)phenol, 2-ethyl-4-(1-propenyl)phenol, 2 -Methoxy-
4-(1-propenyl)phenol, 3-methoxy-4
-(1-propenyl)phenol, 2-ethoxy-4-
(1 propenyl)phenol, 3-ethoxy-4-(1
-7'lovenyl)phenol, 2-chloro-4-(17
"ohenyl)phenol, 310 4-(1-propenyl)phenol, 2-bromo4-(1-7"robenyl)phenol, 3-7'bromo4-(1-propenyl)phenol, 2-(2- propenyl) phenol, 3
-(2-propenyl)phenol, 4-(2-propenyl)phenol, 2-methyl-4-(2-propenyl)
Phenol, 2-ethyl-4-(2-7"lovenyl)phenol, 2-methoxy-4-(2-7'lopenyl)phenol, 3-methoxy-4-(2-propenyl)phenol, 2-ethoxy-4 -(2-propenyl)phenol, 2-riO-4-(2propenyl)phenol,
2-(1-7" tenyl) phenol, 3-(1-7" tenyl) phenol.

Examples include 4-(1-butenyl)phenol, which may be used alone or in combination.

The compound of the above-format (1) can be co-condensed with phenol, cresol, xylenol, ethylphenol, dihydroxyphenol, trihydroxyphenol, etc., but only a small amount (5% by weight of both) of the phenolic compounds is required. If it is less than 5% by weight, the sensitivity will be insufficient and the residual film rate will drop significantly.

Common aldehydes include formaldehyde, acetaldehyde, and furfural, but other aldehydes may also be used.

The condensation reaction between the phenol compound and aldehydes can be carried out according to the conventional method described in "Phenol Resin" by Arata Murayama, Nikkan Kogyo Shinbunsha (Tokyo), etc.

The photosensitive compound used in the present invention is described in "Photosensitive Polymer J (1980)" by Gentabe Nagamatsu and Hideo Inui, published by Kodansha.
Tokyo), by DeForest [Photoresist J (19
75) 1-Azidopyrene, p-azidobenzophenone, including but not limited to those described in McGraw-Hill Incorporated (New York).

Monoazide compounds such as 4'-methoxy-4-azidodiphenylamine 4-azidobenzal-2'-methoxyacetophenone, 4-azido-4'-nitrophenylazohenzene, 44'-diazidohensiphenone, 4.4'- Diazidobenzomethane, 4,4'-diazidostilbene.

4.4'-diazidochalcone, 4.4'-diazidodiphenylsulfone, 3.4'-diazidodiphenylsulfone, 3.3'-diazidodiphenylsulfone, 2,6-
Di(4'-azidobenzal)cyclohexanone, 2.6
-Bisazide compounds such as di(4'-azidobenzal)4-methylcyclohexanone, azide compounds such as monosulfonyl azide compounds and bissulfonyl azide compounds, 1.4-'; (chloromethyl)benzene, 1.3-
Di(chloromethyl)benzene 25-di(chloromethyl)
Toluene, 3,5-di(chloromethyl)benzene, 2,
5-di(chloromethyl)-p-xylene.

3.5-di(chloromethyl)-p-xylene, 2゜3
．． 4-1-li(chloromethyl)toluene, 2,4.
5-tri(chloromethyl)l-luene, 1,4-di(chloromethyl)naphthalene, 1,4,5.8-tetra(chloromethyl)naphthalene, 4.4'-di(chloromethyl)diphenyl ether, 4. 4'-di(chloromethyl)diphenylmethane, 4.4'-di(chloromethyl)
Diphenylsulfide, 4,4'-di(chloromethyl)
Diphenylsulfone, 4,4'-bis(trichloromethyl)diphenyl ether.

4.4'-bis(trichloromethyl)diphenylmethane, 4.4'-bis(trichloromethyl)diphenyl sulfide, 4.4'-bis(trichloromethyl)diphenylsulfone, 1,4-di(bromomethyl)henzen,
■, 3-di(bromomethyl)benzene, 2,5-di(bromomethyl)toluene 13,5-di(bromomethyl)benzene, 2,5-di(bromomethyl)-p-xylene, 3
．． 5-di(bromomethyl)-p-xylene, 2,3.4
-1-li(bromomethyl)toluene, 2,4.5-1
-di(bromomethyl)toluene, 1,4-di(bromomethyl)naphthalene.

1.4,5.8-tetra(bromomethyl)naphthalene 4
．． 4'-di(bromomethyl)diphenyl ether 4.4
'--di(bromomethyl)diphenylmethane4.4'-
Di(bromomethyl)diphenyl sulfide, 4.4'-
Di(bromomethyl)diphenylsulfone, 4.4'-
Bis(tribromomethyl)diphenyl ether, 4.4
'-bis(tribromomethyl)diphenylmethane, 4.
4'-bis(tribromomethyl)diphenyl sulfide, 4.4'-bis(tribromomethyl)diphenyl sulfone.

Trichloroacetophenone, p-nitrotrichloroacetophenone, hexachlorodimethylsulfoxide,
Hexachlorodimethylsulfone, l-dichloromethylphenylsulfone.

Trichloromethyl-p-chlorophenylsulfone, trichloromethyl-p-nitrophenylsulfone, trichloroacetophenone, p-nitrotrichloroacetophenone, hexabromodimethylsulfoxide, hexabromodimethylsulfone, tribromomethylphenylsulfone, tribromo Methyl-p-bromophenylsulfone, tribromomethyl-p-nitrophenylsulfone, 2,4-bis(trichloromethyl)-6-methyl-5-)riazine, 2,4bis(dichloromethyl)
-6-Medi-S-triazine, 2,4-bis(tribromomethyl)-6-methyl-s-triazine, 2,4
halogenated alkyl group-containing compounds such as -bis(dibromomethyl)-6-methyl-5-)riazine, acetophenone, 2,2-dimethoxyacetophenone, 2,2-jethoxyacetophenone, 2-methoxy-2-phenylacetophenone, 2-methoxy-2-isobutylacetophenone, 4-diethylaminoacetophenone, benzophenone.

Carbonyl compounds such as dimethylaminobenzophenone, benzyl dibenzoylmethane, 1,4-dibenzoylmenzene, ], + 3.5-meliacryloylhexahydro-S
Triazine compounds such as triazine, azo compounds such as azobisisobutyronitrile, organic peroxides such as benzoyl peroxide 1 dibutyl peroxide, thioxanthone compounds such as 2-chlorothioxanthone, benzophenothiazine compounds, benzophenoxazine compounds, Examples include photopolymerization initiators such as imidazole compounds.

The blending amount of these photosensitive compounds is 0.1 to 50 parts by weight, preferably 3 to 50 parts by weight, per 100 parts by weight of the resin.
The amount is 30 parts by weight. If it is less than 0.1 part by weight, it is impossible to form a pattern, and if it exceeds 50 parts by weight, development residues are likely to occur.

The resist composition of the present invention is used by dissolving the above alkali-soluble resin or this resin and a photocrosslinking agent in a solvent. Examples of solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Examples include glycol ethers such as ethyl ether, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, and aromatic hydrocarbons such as toluene and xylene. These may be used alone, but two or more types may be used in combination.

Furthermore, a surfactant, a storage stabilizer, an aggravating agent, an anti-striation agent, etc. can be added to the resist composition of the present invention, if necessary.

As the developer for the resist composition of the present invention, an aqueous alkaline solution is used, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate ammonia, and primary amines such as ethylamide propylamine. tertiary amines such as diethylamine and dipropylamine, tertiary amines such as trimethylamine and triethylamine, alcohol amines such as diethylethanolamine and triethanolamine, tetramethylammonium hydroxide, trictylhydroxyethylammonium hydroxide , quaternary ammonium salts such as tetraethylammonium hydroxide, and the like.

Furthermore, if necessary, add methanol or
Appropriate amounts of water-soluble organic solvents such as ethanol, propatool, and ethylene glycol, surfactants, and resin dissolution inhibitors can be added.

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in the examples are based on weight unless otherwise specified.

Dog 3N? It 4-(2-propenyl)phenol, 100 parts of a resin consisting of phenol and formaldehyde with a molar ratio of 2:8 and 0.01 part of a fluorine-based surfactant are dissolved in 400 parts of cyclohexanone, A resist solution was prepared by filtering through a 1 μm microfilter.

The above resist solution was mixed with hexamethyldisilazane (HMDS).
) After applying it to the treated silicon wafer with a spinner,
A resist film having a thickness of 1.0 μm was formed by beta-rotating at 80° C. for 20 minutes. This wafer is exposed to far ultraviolet irradiation equipment PLA.
Exposure was performed using -521F (manufactured by Canon) and a test mask.

Next, the film was developed by dipping in a tetramethylammonium hydroxide aqueous solution at 23° C. for 1 minute to obtain a negative pattern.

When the patterned wafer was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

Resin 10 consisting of phenol and formaldehyde with a molar ratio of 4-vinylphenol and resorcinol of 4 to 6.
0 parts was dissolved in 400 parts of ethyl cellosolve acetate,
A resist solution was prepared by filtering through a 0.1 μm microfilter.

The above resist solution was applied to a HMDS-treated silicon wafer using a spinner, and then beta-baked for 20 minutes at 90°C.
A resist film with a thickness of 0.9 μm was formed. This wafer was exposed to light using an excimer laser device C2926 (manufactured by Hamamatsu Photonics) filled with krypton/fluorine gas and a test mask. Next, the film was developed by dipping in a tetramethylammonium hydroxide aqueous solution at 23°C for 1 minute to obtain a negative pattern.

When the patterned wafer was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

1 4-(2-propenyl)phenol, m-') 100 parts of a resin consisting of phenol and formaldehyde in a resol molar ratio of 3:7, 15 parts of 3,3'-diazide diphenyl sulfone, fluorine-based 0.04 parts of surfactant was dissolved in 400 parts of cyclohexanone and filtered through a 0.1 μm microfilter to prepare a resiston solution.

After applying the above resist solution to an HMDS-treated silicon wafer using a spinner, baking it at 85°C for 20 minutes,
A resist film with a thickness of 0.9 μm was formed. This wafer was exposed to light using an excimer laser device C2926 (manufactured by Hamamatsu Photonics) filled with krypton/fluorine gas and a test mask. Next, the film was developed by dipping in a tetramethylammonium hydroxide aqueous solution at 23° C. for 1 minute to obtain a negative pattern.

When the patterned wafer was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

Household goods 14114 4-isopropenylphenol, resin 1 consisting of phenol and formaldehyde with a molar ratio of phenol of 4 to 6
00 parts, 0.01 part of fluorosurfactant to 400 parts of ethyl cellosolve acetate 't? JM and filtered through a 0.1 μm microfilter to prepare a resist solution.

The above resist solution was applied to an HMDS-treated silicon wafer using a spinner, and then baked at 85°C for 20 minutes to form a resist layer with a thickness of 1.0 μm. This wafer was exposed to light using a far ultraviolet irradiation device PLA521F (manufactured by Canon) and a test mask. Next, at 23°C with a tetramethylammonium hydroxide aqueous solution,
The film was developed by dipping for 1 minute to obtain a negative pattern.

When the patterned wafer was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

Example 5 100 parts of the resin of Example 3 and 3,5-di(chloromethyl)
A resist solution was prepared by dissolving 15 parts of p-xylene in 450 parts of cyclohexanone and filtering through a 0.1 μm microfilter.

The above resist solution was applied to a HMDS-treated silicon wafer using a spinner, and then beta-baked for 20 minutes at 75°C.
A resist film with a thickness of 0.9 μm was formed. This wafer was exposed to light using a far ultraviolet irradiation device PLA521F and a test mask.

Next, the film was developed by dipping in an aqueous solution of tetramethylammonium hydroxide overnight at 23° C. for 1 minute to obtain a negative pattern.

When the patterned wafer was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

Household items (100 parts of the resin from Example 3, 5 parts of 2-methoxy-2-phenylacetophenone, fluorine T, and 0.04 parts of surfactant were dissolved in 400 parts of cyclohexanone, and filtered through a 0.1 μm microfilter. A resist solution was prepared by filtration.

After applying the above resist solution to an HMDS-treated silicon wafer using a spinner, baking it at 85°C for 20 minutes,
A resist film with a thickness of 0.9 μm was formed. This wafer was exposed to light using an excimer laser device C2926 (manufactured by Hamamatsu Photonics) filled with krypton/fluorine gas and a test mask. Next, the film was developed by dipping in a tetramethylammonium hydroxide aqueous solution at 23° C. for 1 minute to obtain a negative pattern.

When the wafer with the pattern formed thereon was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

100 parts of the resin of Example 3, 7 parts of 1,3.5-) lyacryloylhexahydro-5-) riazine, 1 part of fluorine direct surfactant, 400 parts of cyclohexanone, 0.1 μm A resist solution was prepared by filtration through a microfilter.

After applying the above resist solution to an HMDS-treated silicon wafer using a spinner, it was baked at 75°C for 20 minutes.
A resist film with a thickness of 1.0 μm was formed. This wafer was exposed to light using an excimer laser GL C2926 filled with krypton/fluorine gas and a test mask. Next, the film was developed by dipping in a tetramethylammonium hydroxide aqueous solution at 23° C. for 1 minute to obtain a negative pattern.

When the patterned wafer was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

Example 8 2-(2-propenyl)phenol, 100 parts of a resin consisting of m-cresol in a molar ratio of phenol and formaldehyde of 7:3, 15 parts of 4,4'-diazide diphenyl sulfone, fluorine-based surfactant 0.01 part of the agent was dissolved in 450 parts of cyclohexanone and filtered through a 0.1 μm microfilter to prepare a resist solution.

After applying the above resist solution to an HMDS-treated silicon wafer using a spinner, it was incubated at 80°C for 20 minutes.
A resist film with a thickness of 1.0 μm was formed. This wafer was exposed to light using an excimer laser device C2926 filled with krypton/fluorine gas and a test mask. Next, a negative pattern was obtained by immersion development in an aqueous solution of tetramethylammonium hydroxide overnight at 0.degree. C. for 1 minute.

When the patterned wafer was taken out and observed under an electron microscope, a high-contrast pattern was resolved.

This 924 (L) Novolac positive resist was applied to an HMDS-treated silicon wafer using a spinner, and then beta-coated at 85°C for 20 minutes to form a resist film with a thickness of 1.0 μm. This wafer was exposed to a deep ultraviolet irradiation device. Exposure was performed using PLA-521F and a test mask.Next, development was carried out using a tetramethylammonium hydroxide aqueous solution at 23° C. for 1 minute using the immersion method to obtain a positive pattern.

When the patterned wafer was taken out and observed under an electron microscope, only lines and spaces of 0.80 μm could be resolved, and the pattern was triangular in shape.

(Effects of the Invention) According to the present invention, a resist composition with an excellent balance of sensitivity, resolution, etching resistance, storage stability, etc. can be obtained. This material is particularly useful as a pattern forming material suitable for lithography using short wavelength light.

Claims (2)

[Claims] (1) At least 5 compounds represented by the general formula (I)
1. A resist composition comprising an alkali-soluble resin obtained from a phenol compound and an aldehyde compound containing % by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) R^1; Alkenyl group or alkenyloxy group R^2;
Hydrogen, alkyl group, alkoxy group or halogen (2) A resist composition comprising the alkali-soluble resin according to claim (1) and a photocrosslinking agent.