JPH07219240A - Removing liquid for positive type resist - Google Patents

Abstract

PURPOSE:To improve removing property and stability to removal and to suppress the corrosion of a metallic material such as Al or Cu by blending a compsn. for removing a resist made of a nitrogen-contg. org. hydroxy compd. with a carboxyl group-contg. org. compd. CONSTITUTION:A nitrogen-contg. org. hydroxy compd. or a blend of the org. hydroxy compd. as an effective component with an arom. hydroxy compd., a triazole compd., a water-soluble org. solvent or water is used as a compsn. for removal and blended with a carboxyl group-contg. org. compd. This org. compd. is org. carboxylic acid or its anhydride and a compd. having no hydroxyl group in each molecule. It is preferably formic acid, phthalic acid, benzoic acid or phthalic anhydride excellent in action of improving stability to removal and phthalic acid or phthalic anhydride is especially suitable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for use in the production of a novel positive resist stripping solution, more specifically, a semiconductor element such as IC or LSI or a liquid crystal panel element.
The present invention relates to a stripping solution for a positive resist, which has little deterioration in stripping property over time, is excellent in stripping stability, and has little corrosiveness to metal materials such as aluminum and copper.

[0002]

2. Description of the Related Art Semiconductor elements such as ICs and LSIs and liquid crystal panel elements are provided with a uniform photoresist on a conductive metal film such as aluminum, copper or aluminum alloy formed on a substrate or an insulating film such as a SiO ₂ film. After coating and exposing and developing it to form a resist pattern, the conductive metal film or insulating film is selectively etched using this pattern as a mask to form a fine circuit, and then an unnecessary resist layer is formed. It is manufactured by removing with a stripper.

As a stripping solution for removing the above resist, conventionally, a stripping solution comprising an alkylbenzene sulfonic acid having a total carbon number of 10 to 20 and a non-halogenated aromatic hydrocarbon solvent having a boiling point of 150 ° C. or more (JP-A-51-72503). Issue),
A stripping solution composed of dimethyl or diethyl sulfoxide and organic sulfone (JP-A-57-84456), a surface-active alkylaryl sulfonic acid having 10 to 20 carbon atoms, and a hydrotropic aromatic sulfone having 6 to 9 carbon atoms. Boiling point 150
A stripping solution composed of a non-halogenated aromatic hydrocarbon solvent having a temperature of ℃ or higher (US Pat. No. 4,165,294), an organic sulfonic acid and 1,2-dihydroxybenzene to which a polar or nonpolar organic solvent is added. The stripping solution (European Patent No. 0119,337) has been used.

However, the above-mentioned stripping solution does not have sufficient stripping ability to resist, and is exposed to high temperature, especially in the manufacturing process of semiconductor elements and liquid crystal panel elements, and is harsh such as strong acid solution or plasma during etching. Since it has low releasability with respect to a resist that has been altered by being exposed to a different chemical environment, it is not practical in some cases. Further, the stripping solution is not only corrosive to metals such as aluminum forming a conductive metal film, copper and aluminum alloys,
100 is a practical temperature for the peeling temperature of the resist film.
At a temperature of not lower than 0 ° C., the stripping solution has a large amount of volatilization, and the composition of the solution changes with time, so that a stable stripping solution cannot be maintained.

In recent years, a stripping solution which eliminates the above-mentioned drawbacks of the conventional stripping solution, has excellent anticorrosion properties, and has a high stripping property is disclosed in, for example, JP-A-4-350660.
As a stripping solution consisting of 2-imidazolidinone, dimethyl sulfoxide and a predetermined amount of a water-soluble organic amine, and an alkanolamine compound described in JP-A-5-281753.
It has been proposed as a release agent composed of a sulfone compound or a sulfoxide compound, and a hydroxy compound.

However, although the above-mentioned stripping solution is certainly improved in corrosion resistance and stripping property as compared with the conventional stripping solution, aluminum is used in the manufacturing process of semiconductor elements and liquid crystal panel elements in which microfabrication is progressing. Copper and aluminum alloys have come to be used, and even if they have a slight corrosiveness against these, problems such as disconnection occur, so there is a drawback that they are not sufficient from a practical level. is doing.

[0007]

In view of the current situation,
The present inventors have conducted extensive studies to improve the problems of the conventional positive resist stripping solutions, and as a result, by adding a carboxyl group-containing organic compound to a resist stripping composition consisting of a nitrogen-containing organic hydroxy compound. The present invention has been completed by finding that a peeling liquid having improved peeling property and peeling stability and less corrosiveness of metal materials such as aluminum, copper and aluminum alloy can be obtained.

That is, an object of the present invention is to provide a stripping solution for a positive resist which is less likely to corrode a metal forming a conductive metal layer.

Another object of the present invention is to provide a stripping solution which is excellent in stripping property and also in stripping stability.

[0010]

The present invention which achieves the above object relates to a positive resist stripping solution comprising a resist stripping composition comprising a nitrogen-containing organic hydroxy compound and a carboxyl group-containing organic compound. .

The stripping solution of the present invention will be described in detail below.

The resist stripping composition comprising a nitrogen-containing organic hydroxy compound of the present invention is a conventionally known nitrogen-containing organic hydroxy compound alone or a nitrogen-containing organic hydroxy compound as an active ingredient. , A triazole compound, a water-soluble organic solvent or at least one kind of water is contained in the resist stripping composition. The nitrogen-containing organic hydroxy compound which is an essential component of the resist stripping composition is not particularly limited as long as it is an organic hydroxy compound having a nitrogen atom in the molecule, and various compounds can be used. Specifically, monoethanolamine, N-hydroxyethylpiperazine, 1- (2-hydroxyethyl) -2-pyrrolidone, 1- (3-hydroxypropyl) -2-pyrrolidone, 4- (2-hydroxyethyl) morpholine. , N- (2-hydroxyethyl) phthalimide, 2- (2-hydroxyethyl) pyridine,
Hydroxylamine, 3- (1-pyrrolidyl) -1,2
-Propanediol, 2-piperidinemethanol, N-
Methyl-3-piperidinemethanol, 2-piperidine ethanol, N-methyl-3-hydroxypiperidine, N
-Methyl-4-piperidinol, 1-piperidine ethanol, ethylaminoethanol, dimethylaminoethanol, diethylaminoethanol, 2- (2-aminoethoxy) ethanol and the like can be mentioned. Of the nitrogen-containing organic hydroxy compounds, N-hydroxyalkyl-substituted amines and nitrogen-containing heterocyclic compounds are preferable,
Monoethanolamine is particularly suitable.

The water-soluble organic solvent to be added to the resist stripping composition comprising the nitrogen-containing organic hydroxy compound is not particularly limited as long as it is a water-soluble organic solvent. For example, N-methyl-2-pyrrolidone , Dimethyl imidazolidinone, dimethyl sulfoxide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether Ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. These water-soluble organic solvents may be used alone or in combination of two or more.

Water is an amount that does not corrode the metal forming the wiring material, and is 1 with respect to the total amount of the resist stripping composition.
Used in the range of up to 15% by weight.

Aromatic hydroxy compounds to be added to the resist stripping composition include cresol, xylenol, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol,
Salicyl alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p-aminophenol, m-
Aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid,
3,5-dihydroxybenzoic acid and the like,
These compounds may be used alone or in combination of two kinds. Of these, pyrocatechol, which is excellent in the action of improving peelability, is preferable.

Examples of the triazole compound include benzotriazole, o-tolyltriazole, m-
Examples thereof include tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole and the like. These compounds may be used alone or in combination of two or more kinds. Among them, benzotriazole, which has an excellent anticorrosive effect, is preferable.

The mixing ratio of the above components is such that (A) is a nitrogen-containing organic hydroxy compound, (B) is an aromatic hydroxy compound, (C) is a triazole compound, and (D) is a water-soluble organic solvent. In the case of a two-component system consisting of the component (A) and the component (B), the component (A) is blended in the proportion of 50 to 98% by weight and the component (B) in the proportion of 2 to 50% by weight, and the component (A) is added. In the case of a two-component system consisting of (C) or (D) component,
(A) component 20 to 80% by weight and (C) or (D) component 2
In the case of a three-component system comprising (A) component and (B) component or (D) component and (C) component, the component (A) is 50 to 97.8% by weight. % And (B)
2 to 40% by weight of component or (D) component and 0.2 of (C) component
It is blended in a ratio of 10 to 10% by weight, and the component (A) and the component (B)
In the case of a three-component system consisting of the component and the component (D), it is blended in a proportion of 50 to 93% by weight of the component (A), 2 to 40% by weight of the component (B) and 5 to 30% by weight of the component (D). , (A)
In the case of a four-component system consisting of the component, the component (B), the component (C) and the component (D), 50 to 92.8% by weight of the component (A), 2 to 40% by weight of the component (B) and (C). It is preferable to mix 0.2 to 10% by weight of component and 5 to 30% by weight of component (D).

The carboxyl group-containing organic compound which is a component of the stripping solution of the present invention means an organic carboxylic acid or an acid anhydride thereof, which does not have a hydroxyl group in the molecule. Specific examples of the carboxyl group-containing organic compound include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid,
Oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid, malic acid,
Examples thereof include citric acid, acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, etc., but are not limited to these, and any compound satisfying the above requirements may be used. The carboxyl group-containing organic compound may be used alone or in combination of two or more, and in selecting it, in consideration of compatibility with each component of the stripping solution,
It is selected appropriately. Preferred carboxyl group-containing organic compounds include formic acid, phthalic acid, benzoic acid and phthalic anhydride. These carboxylic acids are excellent in the action of improving peeling stability, and phthalic acid and phthalic anhydride are particularly preferable.

The carboxyl group-containing organic compound is contained in an amount of 0.05 to 10% by weight, preferably 0.1 to 0.1% by weight, based on the resist stripping composition comprising a nitrogen-containing organic hydroxy compound.
It is blended at a ratio of 6% by weight. This blend amount is 0.05
If it is less than 10% by weight, the effect of stabilizing the releasability is low and it is not practical, and if it exceeds 10% by weight, the releasability is lowered, which is not preferable. Practically, 0.1 to 6% by weight is suitable.

It goes without saying that well-known additives can be added in addition to the above components.

The positive resist stripper of the present invention is used by contacting it with a resist film formed on a substrate at a temperature of 60 to 130 ° C. The stripper has a small amount of volatilized components at the processing temperature and is stable over time, does not generate harmful substances to the element or the environment due to decomposition of the components, and is excellent in strippability of the resist film. ing.
The resist film is provided on a silicon wafer, a silicon dioxide, a gallium arsenide simple substance used for a liquid crystal display panel or a conductive metal film or an insulating film formed thereon.

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

[0023]

【Example】

Examples 1 to 11 Positive resist OFPR-800 on a silicon wafer
(Manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to give a dry film thickness of 1.35 μm, and prebaked in an oven. After resist patterning treatment on the silicon wafer,
(I) Sample (a) post-baked at 150 ° C. for 5 minutes, and (ii) Post-baked at 150 ° C. for 5 minutes, and then mixed acid CT (produced by Tokyo Ohka Kogyo Co., Ltd.), which is an etching solution of ceric ammonium nitrate system. Samples (b) in which the resist pattern was denatured by immersing the resist film in () were prepared to obtain resist films of the samples (a) and (b), respectively. Then, the samples (a) and (b) were immersed in a stripping solution shown in Table 1 at a liquid temperature of 80 ° C., taken out after 2 minutes, 5 minutes and 10 minutes, and the strippability was evaluated according to the following criteria. . ◎ ・ ・ ・ Peeling off in less than 2 minutes ○ ・ ・ ・ ・ ・ ・ Peeling in 2 to less than 5 minutes △ ・ ・ ・ Peeling in 5 to 10 minutes × ・ ・ ・ ・ No peeling after 10 minutes

The stripping solution subjected to the above-described stripping property evaluation was allowed to stand for 1 week while maintaining the solution temperature at 80 ° C., and then reused and the same stripping property evaluation as above was performed to examine the change with time of the stripping solution. . The results are shown in Table 1. In the evaluation, those in which the peelability did not change were evaluated as ◯, and those in which the peelability decreased were evaluated as x.

Separately, 10,000 on a silicon wafer
Å A thick aluminum pattern is formed and immersed in a 50% by weight aqueous solution of a stripping solution of each composition shown in Table 1 at 40 ° C. to determine the corrosion rate of the aluminum pattern by the immersion time (minutes).
Calculated from the corrosion amount of aluminum and aluminum (mÅ). The results obtained are shown in Table 1.

In the table, MEA is monoethanolamine, A
EE is 2- (2-aminoethoxy) ethanol, EAE
Is ethylaminoethanol, A is benzotriazole,
NMP represents N-methyl-2-pyrrolidone, DMSO represents dimethylsulfoxide, DEBE represents diethylene glycol monobutyl ether, and parentheses represent% by weight. Further, the compounding amounts of (E) and (F) are from (A) to
It is the amount based on the total amount of (D).

Comparative Examples 1 to 4 Using only the resist stripping composition consisting of the nitrogen-containing organic hydroxy compound used in the above examples, the same strippability evaluation as in the examples was carried out. The results are shown in Table 1 as a comparative example.

[0028]

[Table 1]

As is clear from the above table, the positive resist stripping solution prepared by blending the resist stripping composition comprising a nitrogen-containing organic hydroxy compound with a carboxy group-containing organic compound is excellent in strippability with respect to the resist film formed on the substrate. ,
In addition, the stability over time is good. Moreover, the corrosion rate for aluminum is low.

[0030]

The positive resist stripper of the present invention has excellent strippability and does not cause decomposition of the nitrogen-containing organic hydroxy compound due to heat. There is no change and the peeling stability is excellent. In particular, it has a remarkable effect of being able to easily peel off even a resist which has been exposed to a harsh chemical environment and which has been deteriorated, and does not corrode metal materials such as aluminum and copper. Can be suitably used for the production of

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hatsuko Tanaka, 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Tokyo Ohka Kogyo Co., Ltd. (72) Hisashi Nakayama 150, Nakamaruko, Nakahara-ku, Kawasaki, Kanagawa Prefecture Tokyo Oka Kogyo Co., Ltd.

Claims (6)

[Claims] 1. A positive resist stripping solution comprising a resist stripping composition comprising a nitrogen-containing organic hydroxy compound and a carboxyl group-containing organic compound. 2. A resist stripping composition comprising a nitrogen-containing organic hydroxy compound is a nitrogen-containing organic hydroxy compound, or a mixture of the compound and at least one of a water-soluble organic solvent, water and a compounding agent. The stripping solution for positive resist according to claim 1. 3. The stripping solution for positive resist according to claim 1, wherein the compounding agent is at least one of an aromatic hydroxy compound and a triazole compound. 4. The positive resist stripping composition according to claim 1, wherein the carboxyl group-containing organic compound is an organic carboxylic acid or an acid anhydride thereof and does not have a hydroxyl group in the molecule. liquid. 5. The organic compound containing a carboxyl group is formic acid,
At least one of phthalic acid, benzoic acid or phthalic anhydride
The positive resist stripper according to claim 4, which is a seed. 6. The content of the carboxyl group-containing organic compound is 0.05 to 10% by weight with respect to the resist stripping composition comprising a nitrogen-containing organic hydroxy compound. Item 4. The stripping solution for positive resist according to Item 4 or 5.