JP2874520B2 - Cleaning solution and cleaning method for photoresist equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to a cleaning solution and a cleaning method for an apparatus using a photosensitive photoresist. More specifically, the present invention relates to a cleaning solution and a cleaning method for an apparatus using a photoresist composition obtained by dissolving a quinonediazide-based photosensitive compound and an alkali-soluble resin in an organic solvent.

[0002]

2. Description of the Related Art Semiconductor integrated circuits are becoming more and more integrated with each passing year, and dynamic random access memories (DRs) are being developed.
AM) as an example, full-scale production has been started at present with a storage capacity of 16 Mbits. Accordingly, the demand for photolithography technology, which is indispensable for the production of integrated circuits, is increasing year by year.
In a DRAM, a photolithography technique at a level of 0.5 μm is required. In such fine photolithography, the presence of fine particles in the photoresist appears as an image defect, resulting in a decrease in yield and a serious problem. For this reason, in the production of a photoresist, strict filtration control is performed to remove fine particles. However, immediately after the production, even if the photoresist does not contain fine particles at all, fine particles may be generated due to aging. In addition to manufacturing a photoresist free of fine particles, when there is a problem, it is necessary to wash the photoresist device and wash and remove fine particles adhering to the inside of the device. However, since the precipitated fine particles have low solubility and the like, there was no good cleaning agent capable of removing them.

Under these circumstances, conventionally, the precipitated fine particles are
-Methylpyrrolidine, N, N-dimethylacetamide and the like were dissolved and washed. However, although N-methylpyrrolidone and the like dissolve fine particles separated out of the system to some extent, they are found to generate fine particles when mixed with a photoresist solution under certain conditions. It was found to be a good solvent.

That is, after the line is washed with N-methylpyrrolidone or the like, if the cleaning solution is not sufficiently purged, the remaining cleaning solution and the photoresist solution may be mixed to generate fine particles. Further, it has been found that the generated minute amount of fine particles may serve as a nucleus for generation and the fine particles may proliferate. In particular, it is difficult to purge the cleaning liquid in a dead space portion such as a connection portion of a bellows pump, a filter, a pipe, and the like.

[0005]

SUMMARY OF THE INVENTION The present invention provides a good cleaning solution and a good cleaning method for an apparatus using a photoresist obtained by dissolving a quinonediazide-based photosensitive compound and an alkali-soluble resin in an organic solvent.

[0006]

SUMMARY OF THE INVENTION The gist of the present invention is a cleaning solution for an apparatus using a photoresist composition obtained by dissolving a quinonediazide-based photosensitive compound and an alkali-soluble resin in an organic solvent, wherein γ-butyrolactone is mainly used. A cleaning solution for a photoresist device, wherein the cleaning solution is a component. Another gist of the present invention is a method for cleaning an apparatus using a photoresist composition obtained by dissolving a quinonediazide-based photosensitive compound and an alkali-soluble resin in an organic solvent, wherein a cleaning liquid mainly containing γ-butyrolactone is used. Cleaning method of a photoresist device, characterized by washing by
Exists.

Hereinafter, the present invention will be described in more detail. The apparatus using or applying the cleaning liquid and the cleaning method of the present invention is an apparatus having a portion through which the photoresist liquid passes, and specifically, a photoresist is applied to a silicon wafer, a glass substrate, or the like. A spin coater for spin coating and the like can be given. More specifically, it is an apparatus provided with a line such as a pump, a pipe, and a filter for passing the photoresist solution from a bottle filled with the photoresist solution to a spinning unit for spin coating, and the cleaning solution and the cleaning of the present invention. The method corresponds to a cleaning liquid or a cleaning method for cleaning such a line.

The quinonediazide-based photosensitive compound to which the present invention is applied includes, for example, 1,2-benzoquinonediazide-4-sulfonic acid ester compound or amide compound, 1,2-naphthoquinonediazide-4-sulfonic acid ester compound or Examples include an amide compound, a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound, an amide compound, and the like. More specifically, methanol, a compound having an aliphatic hydroxyl group such as ethylene glycol,
And / or phenols such as phenol and cresol; bisphenols such as bisphenol-A;
4 ', 4 "-methylidene trisphenol, 4,4'-
[1- [4- [1- (4-hydroxyphenyl) -1-
Trisphenols such as methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″, 4 ″ ′ −
(1,4-phenylenedimethylidene) tetrakisphenols such as tetrakisphenol; pyrogallol derivatives such as pyrogallol and gallic acid ester; 2,3,4-trihydroxybenzophenone; and 2,3,4,4'-tetrahydroxybenzophenone Polyhydroxybenzophenones, 1,2-benzoquinonediazide-4-sulfonic acid ester compound of a compound having a hydroxyl group, such as a compound having a phenolic hydroxyl group such as a novolak resin described below, and 1,2-naphthoquinonediazide-4- Sulfonate compounds and 1,2-naphthoquinonediazide-5-sulfonic acid ester compounds are exemplified. or,
1,2-benzoquinonediazide-4-sulfonic acid amide compound, 1,2-naphthoquinonediazide of a compound having an aliphatic amino group such as ethylamine or butylamine or a compound having an aromatic amino group such as aniline or paraphenylenediamine And 4-sulfonic acid amide compounds and 1,2-naphthoquinonediazido-5-sulfonic acid amide compounds.

The alkali-soluble resin to which the present invention is applied generally includes a novolak resin and a polyvinylphenol resin. Examples of the novolak resin include phenols; alkylphenols such as o-cresol, m-cresol, p-cresol, 3-ethylphenol, 2,5-xylenol, 3,4-xylenol, and 3,5-xylenol; 2-methoxy Phenol, 4-
Alkoxyphenols such as methoxyphenol and 4-phenoxyphenol or aryloxyphenols; α-naphthol, β-naphthol, 3-methyl-α
-Naphthols which may be substituted with an alkyl group such as naphthol; phenolic hydroxyl groups such as polyhydroxybenzenes which may be substituted with an alkyl group such as resorcinol, 2-methylresorcinol, pyrogallol, 5-methylpyrogallol With formaldehyde, paraformaldehyde, acetaldehyde,
Aliphatic aldehydes such as paraaldehyde; aromatic aldehydes such as benzaldehyde; carbonyl compounds such as alkyl ketones such as acetone, for example, hydrochloric acid, sulfuric acid,
Examples include those produced by heating and polycondensing in the presence of an acidic catalyst such as oxalic acid. In addition, this polycondensation reaction can be performed in a solvent inert to the reaction of ethanol, ethyl cellosolve acetate, methyl 3-methoxypropionate, or the like, or without a solvent.

Examples of the polyvinyl phenol resin include a resin obtained by polymerizing 4-hydroxystyrene whose aromatic ring may be substituted with an alkyl group, a halogen, or the like as a main component. In this polyvinyl phenol resin, a part of hydroxyl groups may be substituted with an ester group or the like. As the organic solvent dissolving the quinonediazide-based photosensitive compound and the alkali-soluble resin, an organic solvent having solubility in the photosensitive compound and having a boiling point of 100 to 200 ° C. at normal pressure is used. Specifically, aliphatic carboxylic esters such as butyl acetate and amyl acetate, aliphatic ketones such as methyl isobutyl ketone, methyl amyl ketone, cyclopentanone and cyclohexanone, aliphatic ethers such as diethylene glycol dimethyl ether, methyl cellosolve Aliphatic ether esters such as acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate-3-methyl ethoxypropionate, and ethyl 3-ethoxypropionate; ethyl pyruvate Aliphatic ketone esters such as methyl lactate, ethyl lactate, etc .; aliphatic hydroxy ketones such as diacetone alcohol; Aliphatic ethers ketones such as emissions alcohol monomethyl ether, propylene glycol monomethyl ether, aliphatic ether alcohols such as ethyl cellosolve. These solvents may be used alone or as a mixture of two or more. The photoresist composition targeted by the present invention is obtained by dissolving the quinonediazide-based photosensitive compound and the alkali-soluble resin in an organic solvent, and contains any other known additives as long as the performance is not impaired. You may go out.

According to the present invention, in a device using such a photoresist, when there is a trouble of generation of fine particles,
Further, for the prevention, it is an essential condition that lines such as pumps, pipes, and filters through which the photoresist solution flows are washed with a washing solution containing γ-butyrolactone as a main component. γ-butyrolactone may be used alone or as a mixture with another solvent without departing from the spirit of the present invention.

Fine particles generated with the lapse of time from the above-described photoresist composition may have a particle diameter exceeding 1 mm attached to the entire surface of the pipe wall or the like in a severe case.
Such fine particles do not dissolve in the solvent used in preparing the photoresist composition, and N-methylpyrrolidone, N, N-dimethylacetamide and the like have been conventionally used. It was not satisfactory.

However, when a cleaning liquid containing γ-butyrolactone as a main component is used, fine particles adhering to a tube wall or the like can be removed satisfactorily, and moreover, the generation of fine particles due to mixing with a photoresist solution can be prevented. And good performance as a cleaning solution.

[0014]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Photoresist Preparation Example 1 Quinonediazide-based photosensitive compound synthesized from 2,3,4,4'-tetrahydroxybenzophenone (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (4 mol) in a conventional manner 262 g and 785 g of a novolak resin synthesized from m-cresol, p-cresol, 2,5-xylenol and folimarin in a conventional manner were stirred into 2800 g of methyl 3-methoxypropionate,
It was dissolved and filtered through a 0.1 μm filter to prepare a photoresist solution.

Photoresist Preparation Example 2 A quinonediazide system synthesized from 2,3,4,4'-tetrahydroxybenzophenone (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3 mol) in a conventional manner. 262 g of the photosensitive compound, 785 g of a novolak resin synthesized from m-cresol, p-cresol, 2,5-xylenol, and folimarin in a conventional manner were stirred and dissolved in 2800 g of ethyl cellosolve acetate, and filtered through a 0.1 μm filter. A photoresist solution was prepared.

REFERENCE EXAMPLE 1 The photoresist liquid of the photoresist preparation example 1 was applied to an inner diameter of 3 m.
m, and left in a dark room of a clean room at 23 ° C. for 2 weeks. As a result, particles adhered and precipitated all over the tube wall. Reference Example 2 The photoresist solution of Photoresist Preparation Example 2 was applied to an inner diameter of 3 m.
m, and left in a constant temperature bath at 50 ° C. for 2 weeks. As a result, particles were deposited on the entire surface of the tube wall.

Example 1 The photoresist solution in the tube where the particles of Reference Example 1 had been attached and deposited was drained, and γ-butyrolactone was passed through the tube. After 3 minutes, the attached matter was dissolved and removed. Comparative Examples 1-4 Instead of γ-butyrolactone, methyl 3-methoxypropionate (Comparative Example 1), ethyl lactate (Comparative Example 2), propylene glycol monomethyl ether acetate (Comparative Example 3) and ethyl cellosolve acetate (Comparative Example 4) Was carried out in the same manner as in Example 1 except that each was used, but in each case, even if the washing solution was passed for 30 minutes, the attached matter was not dissolved and removed.

Example 2 The photoresist solution in the tube where the particles of Reference Example 2 were deposited was drained, and γ-butyrolactone was passed through the tube. After 3 minutes, the deposit was dissolved and removed. Comparative Example 5 Washing was carried out in the same manner as in Example 2, except that ethyl cellosolve acetate was used instead of γ-butyrolactone.
Even if the washing solution was passed for 30 minutes, the attached matter was not dissolved and removed.

REFERENCE EXAMPLES 3-4 The photoresist solution (8 parts by volume) of the photoresist preparation example 2 and γ-butyrolactone (2 parts by volume) or N-methylpyrrolidone (2 parts by volume) were mixed. It was left in a dark place of a clean room for three days. Each composition was applied to a 5-inch silicon wafer, and the number of fine particles in the applied film was measured by a laser surface inspection device (LS-5000, manufactured by Hitachi Electronics Engineering Co., Ltd.). The number mixed with γ-butyrolactone (Reference Example 3) was as small as 9 pieces, but N-
The mixture of methylpyrrolidone (Reference Example 4) is 231
There was one and many. Further, when the mixture was visually observed, generation of fine particles was clearly observed in those mixed with N-methylpyrrolidone, but no generation of fine particles was observed in those mixed with γ-butyrolactone. .

[0020]

The cleaning liquid of the present invention is capable of satisfactorily cleaning fine particles precipitated in the passage of the photoresist composition and the like, and has a small amount of fine particles when mixed with the photoresist composition. It is useful as a cleaning solution for a photoresist device, and the use of the cleaning solution enables good cleaning.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C11D 1/00-19/00 G03F 7/26

Claims (3)

(57) [Claims] 1. A cleaning liquid for an apparatus using a photoresist composition obtained by dissolving a quinonediazide-based photosensitive compound and an alkali-soluble resin in an organic solvent, wherein the cleaning liquid contains γ-butyrolactone as a main component. . 2. A method for cleaning an apparatus using a photoresist composition obtained by dissolving a quinonediazide-based photosensitive compound and an alkali-soluble resin in an organic solvent, wherein the apparatus is cleaned with a cleaning liquid containing γ-butyrolactone as a main component. A method comprising: 3. A method for cleaning a flow path through which a photoresist composition obtained by dissolving a quinonediazide-based photosensitive compound and an alkali-soluble resin in an organic solvent passes, wherein the cleaning liquid containing γ-butyrolactone as a main component is applied to the flow path. A method comprising passing a liquid through a road.