JPH08211629A - Preprocessing liquid for development of radiation-sensitive resist, and preprocesssing method for development of radiation-sensitive resist - Google Patents

Abstract

PURPOSE: To suppress irregular development and to uniformly develop by using a liquid containing a water-soluble org. compd. and water for preprocessing for development of a radiation-sensitive resist. CONSTITUTION: This preprocessing liquid is used for the process before development of a radiation-sensitive resist containing a binder resin and a radiation- sensitive compd. and the liquid contains at least one kind of water-soluble org. compd. and water. The preprocessing liquid is obtd. by dissolving a water- soluble org. compd. in water. As for the water-soluble org. compd., for example, amine compds. such as diethyl amine, amide compds., alcohol compds., or ether compds. can be used. The amt. of the water-soluble org. compd. is usually determined in the range of 1-50wt.%, and preferably 5-2wt.%. As for the amino compd. used for the preprocessing liquid, dimethylamino ethanol, diethylamino ethanol, or dimethylformamide is especially preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing pretreatment solution and a developing pretreatment method used for developing a radiation sensitive resist used in the production of photo (radiation) lithography masks, semiconductor integrated circuits and the like. Is.

[0002]

2. Description of the Related Art Conventionally, when forming a pattern on a radiation-sensitive resist containing a binder resin and a radiation-sensitive compound, the resist is applied to a substrate, dried, and then exposed to actinic rays in a predetermined pattern. This has been done by dissolving the parts to be removed by spraying the developer onto the surface. However, when the developer is sprayed,
The resist surface is not instantly uniformly covered with the developing solution, and there is a time lag in supplying the developing solution depending on the position on the substrate surface.Therefore, the portion where the developing solution is supplied first and the portion where the developing solution is supplied later are provided. There is a drawback that the development becomes non-uniform and uneven development occurs.

[0003]

DISCLOSURE OF THE INVENTION The present invention was devised in view of the above situation, and its purpose is to develop unevenness in patterning a radiation-sensitive resist containing a binder resin and a radiation-sensitive compound. It is an object of the present invention to provide a pre-development treatment solution and a pre-development treatment method for suppressing development and performing uniform development.

[0004]

The object of the present invention is to provide at least one water-soluble organic compound used for pre-development treatment of a radiation-sensitive resist containing a binder resin and a radiation-sensitive compound. And a radiation-sensitive resist developing pretreatment liquid containing water and a radiation-sensitive resist containing a binder resin and a radiation-sensitive compound, which is treated with the pretreatment liquid before development. This is accomplished by a pre-development treatment method for radiation-sensitive resist.

The pretreatment liquid of the present invention can be obtained by dissolving a water-soluble organic compound in water. Examples of the water-soluble organic compound used in this pretreatment liquid include diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylethanolamine, methylethanolamine, ethyl. Diethanolamine, methyldiethanolamine, diethylaminoethanol, dimethylaminoethanol, propanolamine, isopropanolamine, methylpropanolamine, methylisopropanolamine, dimethylpropanolamine, dimethylisopropanolamine, ethylpropanolamine, ethylisopropanolamine,
Amine compounds such as diethylpropanolamine, diethylisopropanolamine, dibutylaminoethanol, pyrrolidine, pyrrole, pyridinemorpholine, N,
N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, pyrrolidone, N-methylpyrrolidone, N-vinylpyrrolidone, 3-pyrrolidino-1, Amide compounds such as 2-propanediol, valerolactam and caprolactam, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, n-pentanol, 2 -Methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-
2-butanol, 2,2-dimethyl-1-propanol, n-hexanol, cyclohexanol, 2,2-
Alcohol compounds such as dimethyl-1,3-propanediol, glycerin and tetrahydrofuran, acetone,
Methyl ethyl ketone, 4-hydroxy-4-methyl-2
-Ketone compounds such as pentanone, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tri Ether compounds such as ethylene glycol diethyl ether, triethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, polyethylene glycol, 1,4-dioxane and tetrahydrofuran, dimethyl sulfoxide, acetonitrile Although etc. can be used without limitation. Particularly, an amino compound or an amide compound is preferably used, and more preferably dimethylaminoethanol, diethylaminoethanol or dimethylformamide. These water-soluble organic compounds,
They can be used alone or in combination of two or more.

The amount of the water-soluble organic compound added is usually 1 to 50.
It is selected in the range of wt%, but is more preferably 5 to 20 wt%.

If necessary, a surfactant can be added to the pretreatment liquid of the present invention. Known surfactants can be used as the surfactant, and they are added within a range that does not impair the effect of the pretreatment.

The pretreatment liquid of the present invention is used before developing a radiation-sensitive resist containing a binder resin and a radiation-sensitive compound with a developer. As the treatment method, dipping of the resist in the pretreatment liquid, spraying or puddle of the pretreatment liquid on the resist surface can be used. The treatment time for treatment with the pretreatment liquid is not particularly limited as long as it is a time sufficient for the effect to appear, but usually 10 to 180 seconds is preferably used. If necessary, rinse may be performed using water after the treatment.

The radiation-sensitive resist in which the pretreatment liquid of the present invention is used is a resist containing a binder resin and a radiation-sensitive compound, and known ones are also included. The binder resin is not particularly limited, but the pretreatment liquid of the present invention is particularly effective for a resist using an alkali-soluble resin such as a novolac resin, polyhydroxystyrene or a derivative thereof, and a styrene-maleic anhydride copolymer.
The effect is particularly remarkable in the case of novolac resin. Examples of novolac resins include phenols, o-cresol,
m-cresol, p-cresol, 3-ethylpheno-
Alkylphenols such as 2,5-xylenol, 3,5-xylenol, 2-methoxyphenol, 4
-Alkoxy or aryloxyphenols such as methoxyphenol and 4-phenoxyphenol, 1,
3-dihydroxybenzene, 1,3-dihydroxy-2
-Polyhydroxybenzene such as methylbenzene, 1,2,3-trihydroxybenzene, 1,3,5-trihydroxybenzene, α-naphthol, β-naphthol,
Naphthol such as 3-methyl-α-naphthol, monomer components such as formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde,
Carbonyl compounds such as acetone, for example, hydrochloric acid,
It can be obtained by mixing and heating sulfuric acid, oxalic acid, etc. as a catalyst and polycondensing.

The radiation-sensitive compound is not particularly limited, but a 1,2-naphthoquinonediazide compound is highly effective. Examples of the 1,2-naphthoquinonediazide compound include 1,2-naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid ester or amide, and specifically, a hydroxyl group-containing compound. Compounds (polyhydroxyalkyl compounds such as glycerin and pentaerythritol, polyhydroxy aromatic compounds such as bisphenol A, gallic acid ester, quercetin, morin and polyhydroxybenzophenone, or dehydration condensation of phenols with aldehydes and / or ketones 1,2-naphthoquinonediazide-5-sulfonic acid ester or 1,2-naphthoquinonediazide-4-
Examples thereof include 1,2-naphthoquinonediazide-5-sulfonic acid amides and 1,2-naphthoquinonediazide-4-sulfonic acid amides of sulfonic acid esters or aromatic amines such as aniline and metaphenylenediamine.

The developer used for the development after the treatment with the pretreatment liquid of the present invention may be any developer which can optimally develop the resist used, and is not particularly limited, but the binder resin of the resist is alkaline. When the soluble resin and the radiation-sensitive compound are 1,2-naphthoquinonediazide compounds, an aqueous alkali solution is generally used. As the alkaline aqueous solution, an aqueous solution of an inorganic base such as potassium hydroxide or sodium hydroxide, an aqueous solution obtained by adding a weak acid such as phosphoric acid, boric acid or silicic acid, an aqueous solution of an organic base such as tetramethylammonium hydroxide or choline, etc. Is given as an example. If necessary, a water-soluble organic compound such as ethanol, dimethylformamide, diethylaminoethanol, diethanolamine, or a surfactant may be added to these alkaline aqueous solutions.

[0012]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 10 parts by weight of N, N-dimethylformamide was dissolved in 90 parts by weight of water to obtain a pretreatment liquid I. An electron beam resist (EBR-900, manufactured by Toray Industries, Inc., containing a novolac resin and a 1,2-naphthoquinonediazide compound) was spin-coated on a chrome blank so that the film thickness after drying was 5000 angstrom, and the temperature was 100 ° C. And dried for 10 minutes to obtain a resist-coated blank. The blank thus obtained was subjected to pattern exposure using an electron beam, then immersed in the pretreatment liquid I for 30 seconds and rinsed with water to perform pretreatment. When this pretreated blank was spray-developed for 90 seconds with an alkaline developer (DVL M-24 Toray Co., Ltd.), a uniform pattern having no unevenness could be obtained. Comparative Example 1 A resist-coated blank was obtained in the same manner as in Example 1. When this blank was spray-developed for 90 seconds with an alkaline developer (DVL M-24 Toray Co., Ltd.) without pretreatment, fine unevenness was generated on one surface, and a non-uniform pattern was formed.

Example 2 10 parts by weight of N, N-diethylaminoethanol was dissolved in 90 parts by weight of water to obtain a pretreatment liquid II. An electron beam resist (EBR-900, manufactured by Toray Industries, Inc., containing a novolac resin and a 1,2-naphthoquinonediazide compound) was spin-coated on a chrome blank so that the film thickness after drying was 5000 angstrom, and the temperature was 100 ° C. And dried for 10 minutes to obtain a resist-coated blank. The blank thus obtained was subjected to pattern exposure using an electron beam, then immersed in the pretreatment liquid II for 30 seconds and rinsed with water for pretreatment. This pre-treated blank was washed with an alkaline developer (DVL M-24 Toray Co., Ltd.)
When spray development was carried out for 0 seconds, a uniform pattern without any unevenness could be obtained.

Example 3 10 parts by weight of ethanol was dissolved in 90 parts by weight of water to obtain a pretreatment liquid III. Electron beam resist (E
BR-900, Toray Industries, Novolak resin and 1,2
-Including naphthoquinonediazide compound) is spin-coated so that the film thickness after drying is 5000 angstroms,
It was dried at 100 ° C. for 10 minutes to obtain a resist-coated blank. The blank thus obtained was subjected to pattern exposure using an electron beam, then immersed in the pretreatment liquid III for 30 seconds and rinsed with water for pretreatment. When this pretreated blank was spray-developed for 90 seconds with an alkaline developer (DVL M-24 Toray Co., Ltd.), a uniform pattern with almost no unevenness could be obtained.

Example 4 10 parts by weight of methyl ethyl ketone was dissolved in 90 parts by weight of water to obtain a pretreatment liquid IV. An electron beam resist (EBR-900, manufactured by Toray Industries, Inc., containing a novolac resin and a 1,2-naphthoquinonediazide compound) was spin-coated on a chrome blank so that the film thickness after drying was 5000 angstrom, and the temperature was 100 ° C. And dried for 10 minutes to obtain a resist-coated blank. The blank thus obtained was subjected to pattern exposure using an electron beam, then immersed in the pretreatment liquid IV for 30 seconds and rinsed with water for pretreatment. When this pretreated blank was spray-developed for 90 seconds with an alkaline developer (DVL M-24 Toray Co., Ltd.), a uniform pattern having no unevenness could be obtained.

[0017]

When developing the radiation sensitive resist containing the binder resin and the radiation sensitive compound, by treating the resist with the pre-development treatment solution of the present invention, it was possible to perform uniform development without unevenness.

Claims (8)

[Claims] 1. A radiation-sensitive material, which comprises at least one water-soluble organic compound and water, which is used for pre-development treatment of a radiation-sensitive resist containing a binder resin and a radiation-sensitive compound. Pretreatment liquid for resist development. 2. The water-soluble organic compound is an amino compound and / or
Alternatively, the pretreatment liquid for developing a radiation-sensitive resist according to claim 1, which is an amide compound. 3. The pretreatment liquid for developing a radiation-sensitive resist according to claim 1, wherein the radiation-sensitive compound is a 1,2-naphthoquinonediazide compound. 4. The development pretreatment liquid for a radiation-sensitive resist according to claim 1, wherein the binder resin is an alkali-soluble resin. 5. A pretreatment method for developing a radiation-sensitive resist, which comprises treating the radiation-sensitive resist containing a binder resin and a radiation-sensitive compound with a pretreatment liquid before developing. 6. The method for pretreatment for development of a radiation-sensitive resist according to claim 5, wherein the pretreatment liquid contains at least one water-soluble organic compound and water. 7. The method for pretreatment for development of a radiation-sensitive resist according to claim 5, wherein the radiation-sensitive compound is a 1,2-naphthoquinonediazide compound. 8. The pre-development treatment method for a radiation-sensitive resist according to claim 5, wherein the binder resin is an alkali-soluble resin.