JPH0954442A - Photoresist remover composition and removing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a remover compsn. capable of easily removing residue of a photoresist at a low temp. in a short time and capable of superfine working without corroding a wiring material by specifying the mixing ratio among the components of a compsn. consisting of a specified alkanolamine, hydroxylamine or its deriv., sugar or sugar-alcohol and water. SOLUTION: This remover compsn. consists of 10-70wt.% alkanolamine, alkoxyamine or alkoxyalkanolamine represented by the formula R<1> R<2> - NCm H2m OR<3> , 1-40wt.% hydroxylamine or its deriv., 1-20wt.% sugar or sugar- alcohol and the balance water and preferably further contains 0.01-1.0wt.% surfactant. In the formula, each of R<1> and R<2> is H, 1-4C alkyl or hydroxyethyl, R<3> is H, 1-4C alkyl, hydroxyethyl, methoxyethyl or ethoxyethyl and (m) is an integer of 2-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stripping agent composition for stripping a photoresist layer in a semiconductor integrated circuit manufacturing process and a photoresist stripping method.

[0002]

2. Description of the Related Art In a semiconductor integrated circuit, a photoresist is coated on an inorganic substrate, a pattern is formed by exposure and development, and then the photoresist pattern is used as a mask to etch the inorganic substrate in a non-masked area to form a fine pattern. It is manufactured by a method of peeling the photoresist film from the inorganic substrate after forming a circuit, or a method of forming a fine circuit in the same manner and then ashing and peeling the remaining resist residue from the inorganic substrate. It

Conventionally, an acidic stripping agent and an alkaline stripping agent have been generally used as photoresist stripping solutions for these methods. As the acidic stripping agent, for example, a stripping agent comprising aryl sulfonic acids such as benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenols and a chlorine-based organic solvent (US Pat. No. 3,582,401)
No.), naphthalene and other aromatic hydrocarbons, phenols, and aryl sulfonic acids (Japanese Patent Laid-Open No. 62-35357). These acidic stripping agents have a weak stripping force and have a strong corrosive action on aluminum, copper, etc., which are often used as wiring materials for fine wiring processing, and are therefore not preferable for fine processing with severe dimensional accuracy in recent years. Further, since these acidic stripping solutions have low solubility in water, it is necessary to rinse with an organic solvent such as alcohol after stripping the photoresist, and then wash with water, which has a problem that the process becomes complicated. There is.

On the other hand, the alkaline stripping solution is a stripping agent consisting of an ethylene oxide adduct of an alkanolamine or polyalkylenepolyamine, a sulfone compound and a glycol monoalkyl ether (JP-A-62-49355).
No.), a release agent comprising dimethyl sulfoxide as a main component and a diethylene glycol monoalkyl ether and a nitrogen-containing organic hydroxy compound (JP-A-64-42653).
No.) and the like. However, the above-mentioned alkaline release agent exhibits alkalinity due to the dissociation of amine due to moisture absorbed during use, and exhibits alkalinity when washed with water without using an organic solvent such as alcohol after peeling. Further, the alkaline release agent has a strong corrosive effect on aluminum, copper, etc., which are often used as wiring materials for fine wiring processing, and is not preferable for processing ultrafine wiring, which has a severe dimensional accuracy in recent years. Further, the alkaline stripping agent requires rinsing with an organic solvent such as alcohol after stripping the photoresist, and has a problem that the process becomes complicated as in the case of the acidic stripping agent.

Further, in recent years, with the ultra-miniaturization in the wiring process, the etching conditions of the wiring material have become stricter, and the photoresist used tends to deteriorate, and the acid stripping solution or alkaline stripping solution described above has a releasability. Is weak,
There is a problem that the photoresist remains on the inorganic substrate. Therefore, a stripping agent which is an aqueous solution containing a nucleophilic amine such as hydroxylamine and an alkanolamine, and a chelating agent such as dihydroxybenzene for the purpose of stripping a resist residue which has been deteriorated by severe dry etching (JP-A-6- No. 266119).
However, the above-mentioned release agent has a weak anticorrosive effect for various wiring materials, and further requires an organic solvent such as alcohol to be used as a rinsing solution after the release, which causes a problem that the process becomes complicated. Therefore, in order to prevent the above problems, a peeling agent that can easily peel off a resist film, a resist layer, a resist residue, etc. and that does not corrode wiring materials is required. There is a demand for a simple stripping method that does not require an organic solvent such as alcohol as a liquid and uses only water as a rinse liquid.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the stripping agent in the prior art, and to apply a photoresist film coated on an inorganic substrate or a photo-resist coated on an inorganic substrate. The photoresist layer remaining after dry etching of the resist film or the photoresist residue remaining after ashing after dry etching can be easily peeled off at a low temperature in a short time, and the wiring material is not corroded at all. A photoresist stripper composition that can be microfabricated and that does not require the use of an organic solvent such as alcohol as a rinse liquid, can be rinsed only with water, and can be used to produce circuit wiring having a degree of composition Is to provide.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that alkanolamines, alkoxyalkylamines or alkoxyalkanolamines, and hydroxylamine or hydroxylamine derivatives. And a stripping composition comprising an aqueous solution containing saccharides or sugar alcohols, or a stripping composition containing a surfactant in the stripping composition described above, can be used as a photoresist at a low temperature at a low temperature in a manufacturing process of a semiconductor integrated circuit. It was found that it can be easily peeled off in a time, and further that the peeling agent composition has extremely excellent characteristics with non-corrosion that does not corrode wiring materials at all and convenience of work,
The present invention has been reached.

That is, the present invention has the general formula R ¹ R ² -NC _m
H _2m OR ³ (R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group, R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group,
Methoxyethyl group or ethoxyethyl group, m is 2-4
The integer) of alkanolamines, alkoxyamines or alkoxyalkanolamines
-70% by weight, 1 to 40% by weight of hydroxylamine or hydroxylamine derivatives, 1 to 20% by weight of sugars or sugar alcohols, and the balance being water, a photoresist stripping composition. Further, a photoresist stripper composition containing 0.01 to 1.0% by weight of a surfactant in the composition, and a photoresist stripping the photoresist using the stripper composition. It is a peeling method.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the general formula R ¹ R ²
An alkanolamine represented by —NC _m H _2m OR ³ ,
Examples of alkoxyalkylamines and alkoxyalkanolamines include ethanolamine and N
-Methylethanolamine, N, N-dimethylethanolamine, N-ethylethanolamine, N, N-diethylethanolamine, propanolamine, N-methylpropanolamine, N, N-dimethylpropanolamine, N-ethylpropanolamine, N, N-dimethylpropanolamine, 2-methoxyethylamine,
2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethoxy) propanol, 2-amino-1-propanol, 1-amino-2. -Propanol and the like. Among the above-mentioned alkanolamines, alkoxyalkylamines and alkoxyalkanolamines, ethanolamine, N-methylethanolamine, 2- (2-aminoethoxy) ethanol and the like are preferably used. The concentration range of these alkanolamines, alkoxyalkylamines and alkoxyalkanolamines is 20 to 70% by weight, preferably 30 to 60% by weight, based on the total solution. When the concentration of alkanolamines, alkoxyalkylamines, or alkoxyalkanolamines is lower than the range, the photoresist peeling speed is slow, and when it is higher than the range, corrosion of wiring materials is prevented. Can not.

Examples of the hydroxylamine and hydroxylamine derivatives used in the present invention include hydroxylamine, N-methylhydroxylamine and N-
Examples thereof include ethylhydroxylamine, N, N-diethylhydroxylamine, N, N-dipropylhydroxylamine, etc. Among them, hydroxylamine is preferably used. The concentration range of these hydroxylamine or hydroxylamine derivatives is 1 to 40% by weight,
It is preferably 5 to 30% by weight. If the hydroxylamine or hydroxylamine derivative is lower than the above concentration, the peeling rate of the resist residue is reduced, and if it is higher than the above concentration range, the corrosion of the wiring material proceeds.

The saccharides used in the present invention include:
In addition to sugars such as monosaccharides and polysaccharides, specifically, for example, glycerinaldehyde having 3 to 6 carbon atoms, threose, arabinose, xylose, ribose, cibrose, xylulose, glucose, mannose, galactose, tagatose, allose, altose, gulose. , Idose, talose, sorbose, psicose, fructose and the like.
As sugar alcohols, threitol, erythritol, adonitol, arabitol, xylitol,
Examples thereof include talitol, sorbitol, mannitol, iditol, dulcitol and the like. Of these, glucose, mannose, galactose, sorbitol, mannitol, xylitol and the like are preferable from the viewpoint of solubility or degradability. These sugars or sugar alcohols are used in a concentration range of 1 to 20% by weight, preferably 3 to 15% by weight in the total solution. If the sugar or sugar alcohol is lower than the above range, the corrosion of the wiring material cannot be sufficiently prevented. On the other hand, even if the concentration is higher than the range, there is no particular advantage and it is not economically advantageous.

As the surfactant used in the present invention, any cationic, anionic or nonionic surfactant can be used without any limitation, but the nonionic surfactant is most preferred. used. The concentration of these surfactants used is 0.01 to 1.0% by weight in the total solution. When the concentration of the surfactant is lower than the above concentration, the peeling speed is decreased, while when it is higher than the concentration range, there is no particular advantage and it is not economically advantageous.

The photoresist stripping agent of the present invention is a photoresist film coated on an inorganic substrate, or a photoresist layer remaining on a photoresist film coated on an inorganic substrate after dry etching, or ashing after dry etching. It is used when the photoresist film such as the remaining photoresist residue on the inorganic substrate is stripped, and when these stripping is performed, heating or ultrasonic waves can be appropriately used in combination. Examples of the inorganic substrate used in the present invention include semiconductor wiring materials such as silicon, polysilicon, silicon oxide film, aluminum, aluminum alloy, titanium, titanium-tungsten, titanium nitride, and tungsten, or gallium-arsenic, gallium-phosphorus, indium. -Compound semiconductors such as phosphorus, glass substrates for LCDs, etc. are used. The treatment method with the release agent according to the present invention is generally a dipping method, but other methods such as a spray method may be used. As a rinse after the treatment of the release agent according to the present invention, it is not necessary to use an organic solvent such as alcohol,
Rinsing with water is sufficient.

[0014]

Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

Examples 1 to 9 and Comparative Examples 1 to 4 FIG. 1 shows a cross section of a semiconductor device in which an aluminum wiring body 3 is formed by dry etching using the resist film 4 as a mask. In FIG. 1, a semiconductor device substrate 1 is covered with an oxide film 2, and a side wall protective film 5 is formed during dry etching. The semiconductor device of 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). Removability of the resist film 4 and the residue 5 and aluminum (Al)
Table 1 shows the results of evaluation of the corrosiveness of the wiring body 3. The criteria for judgment by SEM observation are as follows. (Peelability) A: Completely removed. Δ: Some residual material was observed. X: Most of them remained. (Corrosion) A: No corrosion was observed at all. Δ: Some corrosion was observed. X: Severe corrosion was recognized.

[0016]

[Table 1]

Examples 10 to 18 and Comparative Examples 5 to 8 FIG. 2 is a sectional view of the semiconductor device used in Example 1 in which resist ashing is performed using oxygen plasma and the resist film 4 of FIG. 1 is removed. Indicates. In FIG. 2, the residue (sidewall protective deposition film) 5 is not removed by oxygen-based plasma, and the upper side of the residue 5 is only deformed so as to open to the center of the aluminum wiring body 3. The semiconductor device after the resist ashing of FIG. 2 was immersed in a stripping agent having the composition shown in Table 2 for a predetermined time, rinsed with ultrapure water, dried, and observed with an electron microscope (SEM). It was Table 2 shows the evaluation results of the peelability of the residue 5 and the corrosiveness of the aluminum (Al) wiring body 3.

[0018]

[Table 2]

[0019]

EFFECTS OF THE INVENTION By using the photoresist stripper composition of the present invention, a photoresist film coated on an inorganic substrate or a photoresist remaining after dry etching a photoresist film coated on an inorganic substrate. Layers or photoresist residues remaining after ashing after dry etching can be easily peeled off at low temperature in a short time, at which time ultrafine processing is possible without corroding wiring materials. As a result, it is not necessary to use an organic solvent such as alcohol, and it is possible to rinse only with water, and it is possible to manufacture a highly accurate circuit wiring.

[Brief description of drawings]

FIG. 1 is a sectional view. Dry etching is performed using the resist film 4 as a mask.
The cross section of the semiconductor device which formed the aluminum wiring body 3 is shown.

2 is a cross-sectional view of the semiconductor device of FIG. 1 in which resist ashing is performed using oxygen plasma to remove the resist film 4. FIG.

[Explanation of symbols]

 1: Semiconductor device substrate 2: Oxide film 3: Aluminum wiring body 4: Resist film 5: Residue (sidewall protective deposition film)

Front Page Continuation (72) Inventor Hidetoshi Ikeda 182 Tayuhama, Niigata City, Niigata Prefecture Mitsubishi Gas Chemical Co., Ltd.

Claims (6)

[Claims] 1. A general formula, R ¹ R ² —NC _m H _2m OR ³ (R
¹ and R ² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyethyl group, R ³ is a hydrogen atom, having 1 to 4 carbon atoms
10 to 70% by weight of an alkanolamine, an alkoxyamine or an alkoxyalkanolamine represented by the alkyl group, hydroxyethyl group, methoxyethyl group or ethoxyethyl group, m is an integer of 2 to 4, hydroxylamine or 1-40% by weight of hydroxylamine derivatives, 1-20 sugars or sugar alcohols
A photoresist stripper composition, characterized in that it comprises wt% and the balance is water. 2. The photoresist stripper composition according to claim 1, which contains 0.01 to 1.0% by weight of a surfactant. 3. A photoresist stripping method, which comprises stripping a photoresist using the stripping agent composition according to claim 1. 4. The photoresist stripping method according to claim 3, wherein the photoresist film coated on the inorganic substrate is stripped. 5. The photoresist stripping method according to claim 3, wherein a mask is formed on the inorganic substrate by using a photoresist film, the non-mask region is dry-etched, and the masked photoresist layer is stripped. 6. A mask is formed on an inorganic substrate using a photoresist film, a non-masked region is dry-etched, the masked photoresist layer is further ashed, and the remaining photoresist remaining is peeled off. Item 4. The photoresist stripping method according to Item 3.