JP3406055B2 - Stripper for positive resist - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist stripping solution, and more specifically, a positive stripping resist with high releasability, which is preferably used for manufacturing semiconductor elements such as IC and LSI or liquid crystal panel elements. Regarding the stripper.

[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.

In recent years, a stripping solution having a high stripping property, which eliminates the above-mentioned drawbacks of the stripping solution, is disclosed in, for example, JP-A-4-350.
No. 660 discloses a stripping solution comprising 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide and a predetermined amount of a water-soluble organic amine, and JP-A-4-289866 discloses a stripping solution comprising a hydroxyamine and an alkanolamine. However, JP-A-5-281753 proposes an alkanolamine compound, a sulfone compound or a sulfoxide compound, and an aromatic hydroxy compound.

However, although the above-mentioned stripping solution certainly shows an improvement in stripping property as compared with the conventional stripping solution, it is important to improve the yield in the production of semiconductor elements and liquid crystal panel elements, and the stripping property is high. There is a strong demand for higher ones, and conventional stripping solutions have not yet been sufficient from a practical level.

[0007]

In view of the current situation,
The inventors of the present invention have conducted extensive studies to improve the problems of the conventional positive resist stripping solution, and as a result, the positive resist stripping solution containing N, N-diethylhydroxylamine has excellent strippability. The inventors have found that and completed the present invention.

That is, the object of the present invention is to provide a stripping solution for a positive resist which is excellent in stripping property.

[0009]

Means for Solving the Problems The present invention which achieves the above-mentioned object is to provide N, N-diethylhydroxylamine and aminoacetate.
Rucol compound, triazole compound and aromatic
The present invention relates to a positive resist stripping solution containing a compounding agent comprising a hydroxy compound .

The stripping solution of the present invention will be described in detail below.
The stripping solution of the present invention contains N, N-diethylhydroxylamine , an aminoalcohol compound, and a toluene solution .
Composed of riazole compound and aromatic hydroxy compound
It is essential to contain a compounding agent .

In addition to the above components, a water-soluble organic solvent, water or a carboxyl group-containing organic compound may be mentioned.
Examples of the amino alcohol compound include monoethanolamine, ethylaminoethanol, dimethylaminoethanol, diethylaminoethanol, 2- (2-aminoethoxy) ethanol, and the like. Even when these are used alone, two or more kinds are used. You may mix and use. Of these amino alcohol compounds, monoethanolamine is particularly preferably used.

The water-soluble organic solvent is not particularly limited as long as it is a water-soluble organic solvent.
-Methyl-2-pyrrolidone, dimethylimidazolidinone, 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 monoethyl ether Propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether Ether, and dipropylene glycol monobutyl ether. These water-soluble organic solvents may be used alone or in combination of two or more.

Aromatic hydroxy compounds 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,
Examples thereof include 5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid, and these compounds may be used alone or in combination of two or more 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.

As the carboxyl group-containing organic compound,
An organic carboxylic acid or an acid anhydride thereof, which is a compound having no hydroxyl group in the molecule, for example, 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, citric acid
, Acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, salicylic acid and the like can be mentioned, but the invention is not limited thereto and any compound satisfying the above-mentioned requirements may be used. The above-mentioned carboxyl group-containing organic compounds are used alone or in combination of two or more, and in selecting them, they are appropriately selected in consideration of compatibility with each component of the stripping solution. Preferred carboxyl group-containing organic compounds include formic acid, phthalic acid, benzoic acid, phthalic anhydride, and salicylic acid, and these carboxyl group-containing organic compounds are excellent in improving the peeling stability, particularly phthalic acid,
Phthalic anhydride and salicylic acid are preferred.

The stripping solution of the present invention is mixed in proportions such that (A) is N, N-diethylhydroxylamine, (B) is an amino alcohol compound, (C) is an aromatic hydroxy compound, and
When (D) is a triazole compound, (E) is a water-soluble organic solvent, and (F) is water,

[0017] (i) (A) component and the (B) component and (C) formed
If four-component system consisting of partial and component (D), (A) component 10 to 40% by weight, (B) component 50 to 70 wt%,
Component (C) 5 to 60% by weight, and component (D) 0.2 to 1
0% by weight;

( Ii ) (A) component, (B) component and (C)
In the case of a five-component system consisting of the component, the component (D) and the component (E) or (F), the component (A) is 5 to 30% by weight, and the component (B) is 5
0 to 80% by weight, (C) component 5 to 20% by weight, (D) component 0.2 to 10% by weight, and (E) or (F) component 5
30% by weight;

( Iii ) In the case of a six-component system consisting of (A) component, (B) component, (C) component, (D) component, (E) component and (F) component, (A) component 10 to 40 weight%,
(B) component 20 to 70% by weight, (C) component 5 to 15% by weight, (D) component 0.2 to 10% by weight, (E) component 5 to 4
It is preferable to mix them in proportions of 0% by weight and 5 to 30% by weight of the component (F).

In the above blending ratio, if the blending amount of the component (A) deviates from the range, peelability and peeling stability are deteriorated, which is not preferable.

The above-mentioned carboxyl group-containing organic compound is contained in an amount of 0.05 to 1 with respect to the total amount of the resist stripping composition.
It is preferably blended in a proportion of 0% by weight.

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 stripping solution had a small amount of volatilized components at the processing temperature, was stable over time, and was excellent in stripping property of the resist film.

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

[0024]

[Examples] Examples 1 to 6 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, (ii) Sample (b) post-baked at 170 ° C. for 5 minutes, and (iii) Post-baked at 150 ° C. for 5 minutes, and then nitric acid second A sample (c) in which the resist pattern was altered by immersing it in a mixed acid CT (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a cerium-ammonium-based etching solution, was prepared, and each of the samples (a), (b) and (c) A resist film was obtained. Then sample (a),
(B) and (c) 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

In the table, MEA is monoethanolamine, AEE is 2- (2-aminoethoxy) ethanol,
EAE is ethylaminoethanol, A is benzotriazole, DEBE is diethylene glycol monobutyl ether, NMP is N-methyl-2-pyrrolidone, P is pyrocatechol, F is phthalic acid, and S is salicylic acid. Show. Further, the blending amount of (G) is the amount with respect to the total amount of (A) to (F).

Comparative Examples 1 to 4 Using only the resist stripping composition containing an amino alcohol compound as a main component used in the above examples, the same strippability evaluation as in the examples was performed. The results are shown in Table 1 as a comparative example.

[0027]

[Table 1]

As is apparent from the above table, the positive resist stripper containing N, N-diethylhydroxylamine as an essential component has excellent strippability with respect to the resist film formed on the substrate, and its stability with time. Is good.

[0029]

EFFECTS OF THE INVENTION The stripper for positive resist of the present invention is excellent in strippability, and in particular, it can easily strip even a resist which has been altered by being exposed to a harsh physical or chemical environment.
It can be suitably used for manufacturing semiconductor elements, liquid crystal panel elements, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hatsuko Tanaka, 150 Nakamaruko, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Tokyo Ohka Kogyo Co., Ltd. (72) Hisashi Nakayama 150, Nakamaruko, Nakahara-ku, Kawasaki City, Kanagawa Prefecture (56) References JP-A-6-73562 (JP, A) JP-A-6-116755 (JP, A) JP-A-5-45894 (JP, A) JP-A-5-281753 (JP, A) A) JP-A-5-259066 (JP, A) JP-A-6-266119 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/42 H01L 21/027

Claims (2)

(57) [Claims] 1. N, N-diethylhydroxylamine ,
Amino alcohol compounds, triazole compounds and
And a stripping solution for a positive resist, which contains a compounding agent comprising an aromatic hydroxy compound . 2. A water-soluble organic solvent, water and carbon
At least one selected from organic compounds containing a xyl group
The stripping solution for positive resist according to claim 1 , wherein the stripping solution is contained .