JPH1184686A - Resist removing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily peel a residual photoresist at a low temp. in a short time, to enable ultrafine processing while completely preventing corrosion of a wiring material during peeling, and to produce a circuit wiring of high accuracy by preparing a removing agent from a quaternary ammonium hydroxide, water-soluble amine and alkylpyrrolidone. SOLUTION: The removing agent is prepared from a quaternary ammonium hydroxide, water-soluble amine and alkylpyrrolidone. As for the quaternary ammonium hydroxide, tetramethylammonium hydroxide, trimethyl(2- hydroxyethyl)ammonium hydroxide, etc., are used, and its concn. is preferably 0.1 to 15 wt.% of the whole soln. As for the water-soluble amine, alkanol amines, polyamines and nucleophllic amines are used and its concn. is 1 to 90 wt.% of the whole soln., preferably 5 to 70 wt.%. As for the alkylpyrrolidone, N-methylpyrrolidone is preferably used, and its concn. is 10 to 90 wt.% of the whole soln., preferably 20 to 70 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resist stripping composition. In particular, the present invention relates to a photoresist stripping composition used in a wiring process of a semiconductor integrated circuit or a liquid crystal display device.

[0002]

2. Description of the Related Art In a semiconductor integrated circuit, a photoresist is applied on an inorganic substrate, a pattern is formed by exposure and development, and then the inorganic substrate in a non-mask region is etched using the photoresist pattern as a mask. After the circuit is formed, the photoresist is manufactured by a method of peeling the photoresist from the inorganic substrate. The photoresist remaining on the inorganic substrate is stripped directly by a stripping agent, or after the organic component is gasified and removed by ashing (ashing step), the remaining photoresist residue is stripped with a stripping agent. It is removed by a method or the like.
The object from which the photoresist stripping agent is stripped is a photoresist film applied on the inorganic substrate, a photoresist layer remaining after dry etching on the photoresist film applied on the inorganic substrate, or ashing after dry etching. This is the remaining photoresist residue. These photoresist films, photoresist layers, and photoresist residues are hereinafter collectively referred to as photoresist residues. Conventionally, as a photoresist stripping agent used in the above method, an acidic stripping agent and an alkaline stripping agent are generally used. Examples of the acidic release agent include release agents comprising arylsulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, and xylenesulfonic acid, phenols, and chlorine-based organic solvents (US Pat. No. 3,584,401).
), A release agent comprising aromatic hydrocarbons such as naphthalene, phenols, and arylsulfonic acids (JP-A-62-35357). These acidic peeling agents have a weak peeling force and a strong corrosive effect on aluminum and the like, which are frequently used in wiring materials, and therefore are not preferable for fine processing in which dimensional accuracy (design rule) is severe in recent years. In addition, these acidic strippers have low solubility in water, so it is necessary to rinse the photoresist with an organic solvent such as alcohol after stripping, and then wash with water, which has a problem that the process becomes complicated. I have. On the other hand, examples of the alkaline release agent include a release agent comprising an ethylene oxide adduct of an alkanolamine or a polyalkylene polyamine, a sulfone compound and a glycol monoalkyl ether (JP-A-62-49355), dimethyl sulfoxide as a main component, diethylene glycol Release agents comprising a monoalkyl ether and a nitrogen-containing organic hydroxy compound (JP-A-64-42653).
The above-mentioned alkaline stripping agent has a higher stripping force against photoresist residues and the like than the acidic stripping agent, and also suppresses a corrosive effect on wiring materials and the like. However, in recent microfabrication techniques, since the etching conditions for wiring materials are becoming increasingly severe, the quality of the used photoresist tends to be more severe. For this reason, the conventional alkaline release agent has insufficient release properties, and there is a problem that photoresist residues and the like remain on the inorganic substrate. At the same time, since the wiring width is narrower, it is necessary to further reduce the damage to the wiring in the peeling step, but from this viewpoint, the performance of the conventional alkaline release agent is insufficient. Further, since the conventional alkaline release agent needs to be used at a high temperature of 80 ° C. or more, generation of vapor and mist is large,
It is not preferable in terms of work environment. In order to solve such problems, alkanolamines or alkoxyamines or alkoxyalkanolamines, glycol monoalkyl ethers, sugars or sugar alcohols,
Release agent comprising quaternary ammonium hydroxide and water (JP-A-8-262746) and release agent comprising alkanolamines or alkoxyamines or alkoxyalkanolamines, acid amides, sugars or sugar alcohols and water ( Japanese Unexamined Patent Publication No. Hei 8-202051) has been proposed, but the removal of photoresist residues and the like is still insufficient, and a stripping solution with less damage to inorganic substrates such as wiring materials has been demanded. Further, as for the peeling conditions relating to the simplification of the operation, there is a demand for lowering the peeling temperature and shortening the peeling time.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the above-mentioned stripping agents in the prior art, and to provide a photoresist film coated on an inorganic substrate or a photoresist film coated on an inorganic substrate. A photoresist layer remaining after dry etching of a resist film, or a photoresist residue remaining after ashing after dry etching can be easily peeled off at a low temperature and in a short time. An object of the present invention is to provide a photoresist stripping composition which can be processed and can produce high-precision circuit wiring.

[0004]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a resist stripping composition comprising a quaternary ammonium hydroxide, a water-soluble amine and alkylpyrrolidone. A resist or a resist removing agent composition to which an anticorrosive agent is added can easily remove a photoresist residue or the like in a wiring step of a semiconductor integrated circuit at a low temperature and in a short time. The present inventors have found that the present invention has extremely excellent properties with non-corrosiveness that does not corrode the material at all and simplicity of operation, and reached the present invention.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The quaternary ammonium hydroxide used in the present invention includes, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium Hydroxide, dimethyldiethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, triethyl (2-hydroxyethyl) ammonium hydroxide and the like. Among these quaternary ammonium hydroxides, tetramethylammonium hydroxide (TMAH) and trimethyl (2-hydroxyethyl) ammonium hydroxide are particularly preferred. The concentration range of these quaternary ammonium hydroxides is preferably from 0.1 to 15% by weight, more preferably from 0.5 to 5% by weight in the total solution.

The water-soluble amine used in the present invention includes alkanolamine, polyamine and nucleophilic amine. The alkanolamine used in the present invention includes, for example, ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N
-Ethylethanolamine, N, N-diethylethanol-
Luamine, propanolamine, N-methylpropano-
Ruamine, N, N-dimethylpropanolamine, 2-
(2-aminoethoxy) ethanol, 2-amino-1-
And propanol and 1-amino-2-propanol. Examples of the polyamine used in the present invention include diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and N of these diamines.
-Alkyl-substituted diamines, and polyvalent amines such as 1,2,3-triaminopropane, tris (2-aminoethyl) amine and tetra (aminomethyl) methane;
Examples thereof include polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, heptaethyleneoctamine, nonaneethylenedecamine, hexamethylenetetramine, and bis (3-aminoethyl) amine. Examples of the nucleophilic amine used in the present invention include hydrazine, N.P. N-dimethylhydrazine, hydroxylamine, diethylhydroxylamine and the like can be mentioned. The concentration range of the above-mentioned alkanolamine, polyamine and nucleophilic amine is 1 to 90% by weight in the whole solution.
And preferably 5 to 70% by weight.

The alkylpyrrolidone used in the present invention includes N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone,
N-octylpyrrolidone, etc. Among these N-alkylpyrrolidones, N-methylpyrrolidone is particularly preferred. The concentration range of the alkylpyrrolidone used in the present invention is 10 to 90% by weight, preferably 20 to 70% by weight in the total solution.

An anticorrosive is added to the photoresist stripping agent of the present invention, if necessary, for the purpose of protecting the inorganic substrate from corrosion. Examples of the anticorrosive used in the present invention include glyceraldehyde, threose, arabinose, xylose, ribose, ribulose, xylulose, glucose, mannose, galactose, tagatose, allose, altrose, gulose, idose, talose,
Examples thereof include sugars such as sorbose, psicose, and fructose, and sugar alcohols such as threitol, erythritol, adonitol, arabitol, xylitol, talitol, sorbitol, mannitol, iditol, and dulcitol. Among these sugars and sugar alcohols, glucose, mannose, galactose, sorbitol, mannitol and xylitol are particularly preferred. Further, catechol, pyrocatechol, anthrani-
, O-hydroxyaniline, 1,2-hydroxycyclohexane, gallic acid, gallic acid ester and the like. The concentration range of these anticorrosives is 0.1 to 15% by weight, preferably 0.5 to 10% by weight.

When stripping the photoresist residue or the like with the photoresist stripping agent of the present invention, heating at room temperature or higher, ultrasonic waves or the like can be used in combination as necessary.
The treatment method using the photoresist stripping agent of the present invention is generally a dipping method, but other methods such as a spray method may be used. As the rinsing liquid after the treatment with the photoresist stripping agent of the present invention, an organic solvent such as alcohol may be used, or only ultrapure water may be used. There is no problem with using a mixture with water. Examples of the inorganic substrate used in the manufacture of the semiconductor integrated circuit or the liquid crystal display device of the present invention include a-silicon, polysilicon, a silicon oxide film, a silicon nitride film, aluminum, an aluminum alloy, titanium, titanium-tungsten, titanium nitride, Tungsten, tantalum, tantalum oxide, tantalum alloy,
Semiconductor wiring material such as chromium, chromium oxide, chromium alloy, ITO (indium-tin oxide), single crystal silicon, or compound semiconductor such as gallium-arsenic, gallium-phosphorus, indium-phosphorus, and glass for LCD Substrates and the like can be mentioned. Silicon, which is particularly susceptible to corrosion by the conventional alkaline stripper in the inorganic substrate, a
-Corrosion by the photoresist stripping composition of the present invention is not observed on silicon, polysilicon, aluminum, aluminum alloy, and titanium, and it can be suitably used.

[0010]

Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by these examples. FIG. 1 shows a cross section of a semiconductor device in which an aluminum wiring body 3 is formed by performing dry etching using a photoresist film 4 as a mask. In FIG. 1, a semiconductor device substrate 1 is covered with an oxide film 2,
Further, the sidewall protective deposition film 5 is formed at the time of dry etching.

Examples 1 to 12 The semiconductor device shown in FIG. 1 was immersed in a release agent having the composition shown in Table 1 for a predetermined time, rinsed with ultrapure water, dried, and observed with an electron microscope (SEM). The peeled state of the photoresist film 4 and the sidewall protective deposition film 5 and aluminum (Al)
Table 1 shows the results of the evaluation of the corrosion state of the wiring body 3.
Shown in The evaluation criteria based on SEM observation are as follows. This evaluation criterion was also used in Examples and Comparative Examples described below.

Comparative Examples 1 to 8 The semiconductor device shown in FIG. 1 was immersed in a release agent having the composition shown in Table 2 for a predetermined time, rinsed with ultrapure water, dried, and observed with an electron microscope (SEM). The peeled state of the photoresist film 4 and the sidewall protective deposition film 5 and aluminum (Al)
Table 2 shows the results of the evaluation of the corrosion state of the wiring body 3.
Shown in

Embodiments 13 to 24 FIG. 2 is a cross-sectional view of the semiconductor device used in Embodiment 1 in which ashing is performed using oxygen plasma and the photoresist film 4 in FIG. 1 is removed. In FIG. 2, the sidewall protective deposition film 5 is not removed by the oxygen-based plasma, and the upper side of the sidewall protective deposition film 5 is merely deformed so as to open to the center of the aluminum wiring body 3. The semiconductor device after the ashing shown in FIG. 2 was immersed in a release agent having a composition shown in Table 3 for a predetermined time, rinsed with ultrapure water, dried, and observed with an electron microscope (SEM). Sidewall protective deposition film 5
Table 3 shows the results of evaluating the peeling state of the aluminum alloy and the corrosion state of the aluminum (Al) wiring body 3.

Comparative Examples 9 to 16 The semiconductor device after the ashing shown in FIG. 2 was immersed in a release agent having the composition shown in Table 4 for a predetermined time, rinsed with ultrapure water, dried, and then subjected to an electron microscope (SEM). ) Was observed. Table 4 shows the results of evaluating the peeling state of the sidewall protective deposition film 5 and the corrosion state of the aluminum (Al) wiring body 3.

Examples 25 to 36 Table 5 shows a-silicon films formed on silicon wafers.
After being immersed in a release agent having the composition shown in Table 1 for a predetermined period of time, it was rinsed with ultrapure water and dried, and the corrosion state of a-silicon was evaluated.

Comparative Examples 17 to 24 Table 6 shows a-silicon formed on a silicon wafer.
After being immersed in a release agent having the composition shown in Table 1 for a predetermined period of time, it was rinsed with ultrapure water and dried, and the result of evaluation of the corrosion state of a-silicon was shown in Table 6.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

EFFECTS OF THE INVENTION By using the photoresist stripping composition of the present invention, a photoresist layer applied to an inorganic substrate or a photoresist layer remaining after dry etching of a photoresist film applied to an inorganic substrate After dry etching, ashing can be performed to remove the remaining photoresist residue and the like easily at a low temperature and in a short time. At that time, ultra-fine processing can be performed without corroding the wiring material, and high-precision circuit wiring is manufactured. it can.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a semiconductor device in which an aluminum wiring body is formed by performing dry etching using a photoresist film as a mask.

FIG. 2 is a cross-sectional view of a semiconductor device in which dry etching is performed using a photoresist film as a mask, and a semiconductor device in which an aluminum wiring body is formed is subjected to resist ashing using oxygen plasma.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Semiconductor device substrate 2 Oxide film 3 Aluminum wiring body 4 Photoresist film 5 Sidewall protective deposition film

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Tetsuo Aoyama 182, Tayuhama Shinwari, Niigata City, Niigata Pref.

Claims (5)

[Claims] 1. A resist stripping composition comprising a quaternary ammonium hydroxide, a water-soluble amine, and an alkylpyrrolidone. 2. A resist stripping composition comprising a quaternary ammonium hydroxide, a water-soluble amine, an alkylpyrrolidone, and an anticorrosive. 3. The resist stripping composition according to claim 1, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide or 2-hydroxyethyltrimethylammonium. 4. The resist stripping composition according to claim 1, wherein the water-soluble amine is at least one selected from the group consisting of alkanolamines, polyamines and nucleophilic amines. 5. The resist stripping composition according to claim 1, wherein the alkylpyrrolidone is N-methylpyrrolidone.