JPH1020511A - Composition for stripping photoresist and manufacture of semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain the stripping of the photoresist at low temperature near to room temperature by forming the photoresist stripping composition comprising a polar solvent and ethylenediamine or its hydrate. SOLUTION: The composition for stripping the photoresist is composed of the polar solvent and the ethylenediamine or its hydrate in a weight proportion of 10-99:1-90. The polar solvent is not specially limited but it is preferred that it is superior in compatibility to the photoresist and water solubility, because of easiness of treatment of waste water from a rinse process after stripping of the photoresist, and an aprotic polar solvent is especially desirable among polar solvents, and the ethylenediamine may be its hydrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photoresist stripping composition and a method for manufacturing a semiconductor device. More specifically, the present invention relates to a photoresist stripping composition which can be widely used for stripping various photoresists, such as a semiconductor circuit pattern manufacturing process, an integrated circuit pattern manufacturing process, a liquid crystal display manufacturing process, and the like. The present invention relates to a method for manufacturing a semiconductor device.

[0002]

2. Description of the Related Art In general, in the manufacture of a semiconductor device, a conductive layer is formed on a semiconductor substrate, a mask is formed on the conductive layer using a photoresist, and the conductive layer in a non-mask portion is etched to form a mask. The photoresist that has been removed is stripped from the conductive layer using a photoresist stripping composition.

[0003] Conventionally, such a photoresist is stripped.
Until now, various suitable organic or inorganic chemicals have been found and used. For example, practically, Japanese Unexamined Patent Publication No.
In 1950, a stripping solution comprising dimethyl sulfoxide (DMSO) and amino alcohols is proposed as an organic stripping agent. Also, Japanese Patent Application Laid-Open No. 4-350660
In the publication, a stripping solution comprising 1,3-dimethyl-2-imidazoricinone and DMSO is proposed.

[0004] However, even with these stripping solutions, resists that are difficult to strip may not be sufficiently stripped or may take a long time to be stripped.
In consideration of such a problem, a method of heating the stripping liquid to increase the strippability has been adopted. Therefore, investment of a heating device or the like is necessary, and solvent vapor of a stripping solution is generated due to high-temperature processing, the solvent composition ratio is easily changed during operation, and there is a possibility that the semiconductor device material is corroded during the resist stripping processing. There is.

[0005]

As described above, in the conventional stripping solution for photoresist, a facility for heating the stripping solution at a high temperature is required in order to enhance the strippability of the photoresist. Heating to a high temperature may generate a large amount of solvent vapor in the stripping solution, or cause fluctuations in the solvent composition ratio, thereby deteriorating the stripping performance of the photoresist.

SUMMARY OF THE INVENTION It is an object of the present invention to remove photoresist at a low temperature around room temperature, hardly generate a solvent vapor of the stripping solution, and have a versatile photoresist stripping composition that is less likely to change the solvent composition ratio during operation. It provides things.

Another object of the present invention is to provide a method of manufacturing a semiconductor device which does not require equipment for heating at a high temperature, does not corrode wiring materials of the semiconductor device, and is advantageous from fire safety. is there.

[0008]

The photoresist stripping composition of the present invention which achieves the above object comprises a polar solvent and ethylenediamine (hereinafter sometimes referred to as EDA) or ethylenediamine hydrate. Preferably, these proportions are such that the polar solvent is
9% by weight and 1 to 90% by weight of EDA or EDA hydrate.

The present invention includes the following preferred embodiments. a. The ethylene diamine hydrate is ethylene diamine monohydrate. b. The polar solvent is an aprotic polar solvent, and is preferably at least one selected from dimethyl sulfoxide, NN-dimethylformamide, N-methyl-2-pyrrolidone and NN-dimethylacetamide. c. The photoresist is a positive type resist, a negative type resist, or a positive / negative type resist, particularly preferably a positive type photoresist comprising a novolak phenol resin and naphthoquinonediazide.

In the method of manufacturing a semiconductor device according to the present invention, a conductive layer is formed on a semiconductor substrate, a mask is formed on the conductive layer by using a photoresist, and the conductive layer in a non-mask portion is etched. The mask-molded photoresist is separated from the conductive layer using the photoresist stripping composition. At this time, the mask-shaped photoresist is stripped as a stripping treatment condition. The process is preferably performed at a low temperature such as 5 to 50 ° C.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polar solvent used in the present invention is not particularly limited, but has an excellent affinity with a photoresist and a waste water treatment in a water washing step after the photoresist is removed. It is preferably water-soluble for simplicity, and among the polar solvents, an aprotic polar solvent is particularly preferred.

The polar solvent used in the present invention includes, for example, methanol, phenol, water and the like, and preferably used aprotic polar solvents include, for example, NN
-Dimethylformamide (DMF), NN-dimethylacetamide (DMAc), dimethylsulfoxide (D
MSO), N-methyl-2-pyrrolidone (NMP), 1
-3-dimethyl-2-imidazolidinone, N-aceto-
ε-caprolactam and the like, in particular, DMSO,
DMF, NMP and DMAc are preferably used.
In the practice of the present invention, two or more of these polar solvents may be used.

An important component constituting the photoresist stripping composition of the present invention is ethylenediamine (EDA), which may be a hydrate containing water such as a monohydrate. Of the alkylene diamines, propylene diamine and hexamethylene diamine show no releasability, and it is surprising that EDA and its hydrate show releasability. In the present invention, EDA and ED
A hydrate can be used in combination.

In the practice of the present invention, the above-mentioned polar solvent and the composition for stripping from ethylenediamine or ethylenediamine hydrate are contained in an amount within the range that hinders the effects of the present invention.
Other components can be appropriately added and used. For example,
In order to lower the surface tension or to prevent redeposition of the resist on the substrate, for example, anionic surfactants such as alkylbenzene sulfate, nonionic surfactants such as polyoxyethylene ether of alkylphenol, dodecyl. A surfactant such as an amphoteric surfactant such as diaminoethyl glycine hydrochloride and a cationic surfactant such as alkyl dimethylbenzyl ammonium chloride can be added.

Further, in the present invention, a stripping liquid auxiliary such as oxalic acid which moderates the corrosive action on the metal and sodium pyrophosphate which blocks the metal ion can be added.

Of the above photoresist stripping compositions,
The composition ratio of such EDA is preferably 10 to 50% by weight.
And more preferably 10 to 30% by weight. That is, if the proportion of EDA is less than 10% by weight, the peeling performance of the photoresist is low, and if it exceeds 50% by weight, the odor of EDA may cause a problem in workability.

In the photoresist stripping composition of the present invention, the polar solvent and EDA or EDA hydrate are preferably contained in a ratio of 10 to 99% by weight of the polar solvent and 1 to 90% by weight of the EDA or EDA hydrate. And more preferably 50 to 90% by weight of a polar solvent, and EDA or ED
A hydrate is 10 to 50% by weight. When the amount of EDA is small, as described above, the photoresist stripping performance is low, and when the amount is too large, the odor of EDA may cause a problem in workability.

The photoresist to which the stripping composition of the present invention is preferably applied includes a positive resist, a negative resist, and a positive / negative resist. Particularly effective is a novolak phenol resin and a naphthoquinone diazide. Is a positive photoresist.

In the practice of the present invention, the temperature for the photoresist stripping process is much lower than that of the conventional method. In the conventional stripping solution, about 80 to 120 ° C. was required.
-50 ° C, more preferably about 15-45 ° C, even more preferably about 20-40 ° C. Therefore, one of the other features of the present invention is that the stripping process can be performed at such a low temperature including room temperature when the mask-formed photoresist is stripped from the conductive layer.

The photoresist stripping composition of the present invention which can be applied to stripping at a low temperature in this manner is suitably used for the manufacture of semiconductor devices. The manufacture of such semiconductor devices
First, a conductive layer is formed on a semiconductor substrate, a mask is formed using a photoresist on the conductive layer, the conductive layer in a non-mask portion is etched, and then the photoresist stripping composition of the present invention is used. This is performed by peeling off the mask-formed photoresist from the conductive layer.

Here, the substrate and the conductive layer of the semiconductor device, the masking step, the etching, and the like can be the same as those used in the conventional semiconductor device manufacturing method.

In the present invention, in the process of manufacturing a semiconductor device, the stripping step can be reliably performed at a low temperature by using the above-described photoresist stripping composition.

The composition for removing a photoresist of the present invention is used for forming a circuit pattern of a semiconductor, forming a pattern of an integrated circuit (particularly for TAB), and forming a pattern of a transparent electrode of a liquid crystal display. Can be used for stripping the resist. Further, it can be used as a rinse after the resist is stripped.

The photoresist stripping composition of the present invention comprises:
Since the composition is basically a two-component system as described above, it is possible to regenerate and recover the stripping composition containing impurities by a simple operation such as distillation after a stripping step in the manufacture of a semiconductor device. That is, since the used stripping solution can be separated into the original components by distillation or the like and recovered, it can be circulated and reused in the semiconductor device manufacturing process, which is efficient. Also,
If necessary, a polar solvent which is a basic composition of the present invention and EDA
Alternatively, EDA hydrate can be similarly separated by distillation, regenerated, recovered, and reused.

[0025]

Next, an embodiment of the present invention will be described. In addition, the sample was adjusted as follows. That is, two types of commercially available positive photoresists (manufactured by Tokyo Ohka Kogyo Co., Ltd., [A] OFPR-800 (trade name), and [B]
TSMR-V3 (trade name)) is 100 mm x 100 m
m was applied to a glass plate at a thickness of about 3 μm and baked at 200 ° C. for 30 minutes. Next, use a diamond cutter with 20mm ×
They were cut to 20 mm and used for the peel test.

The state of peeling of the photoresist was visually observed, and the judgment of peeling was made as follows.

A: The resist was sufficiently peeled off and there was no residue. C: The resist was almost peeled off, but a residue was observed. C: It was difficult to remove the resist.

(Examples 1 to 10 and Comparative Examples 1 and 2) 30 ml of the stripping solution shown in Table 1 below was placed in a 100 ml test tube.
After keeping the temperature in an oil bath at 0 ° C. for 15 minutes or more, the sample was charged, and the peeling state after standing for 10 minutes was determined. Table 1 shows the results.

[0029]

[Table 1] (Example 11) A positive photoresist (manufactured by Tokyo Ohka Kogyo Co., Ltd., on a Si substrate on which a 2,000 Å ITO conductive film and a 4,000 Å mask material SiO ₂ were sequentially applied. OFPR-
800 (trade name) was applied so as to have a thickness of 1 μm, and then exposed by a mask and developed to form a positive photoresist mask.

Next, after removing the SiO ₂ mask material in the non-mask region by etching and removing most of the photoresist by ashing, the same DMS as in Example 1 was performed.
The substrate was treated with an O / EDA stripper at 40 ° C. for 10 minutes, and the photoresist remaining on the surface of the conductive layer was stripped to manufacture a semiconductor device. There was no resist residue, and sufficient peeling was performed.

[0031]

According to the present invention, a photoresist stripping composition which can be easily stripped at a low temperature around room temperature can be obtained, and it is possible to easily and surely strip a photoresist which has conventionally been difficult to strip. The present invention provides a composition for stripping a photoresist, the composition comprising:

In the method of manufacturing a semiconductor device using the photoresist stripping composition according to the present invention, a device for heating at a high temperature is not required, and the stripping composition is not heated at a high temperature. Since the cost is low and the solvent vapor of the stripping composition is hardly generated, the solvent composition ratio during the operation is hardly fluctuated, and in addition, it corrodes the substrate material of the semiconductor device, for example, the wiring material such as Al-Si-Cu. There are effects such as difficulty.

Claims (6)

[Claims] 1. A photoresist stripping composition comprising a polar solvent and ethylenediamine or ethylenediamine hydrate. 2. The polar solvent is 10 to 99% by weight, and the ethylenediamine or ethylenediamine hydrate is 1 to 9% by weight.
The photoresist stripping composition according to claim 1, wherein the composition is 0% by weight. 3. The photoresist stripping composition according to claim 1, wherein the ethylenediamine hydrate is ethylenediamine monohydrate. 4. The method according to claim 1, wherein the polar solvent is dimethyl sulfoxide, N.N-dimethylformamide, N-methyl-2-.
2. The method according to claim 1, wherein the compound is at least one selected from pyrrolidone and N.N-dimethylacetamide.
4. The composition for stripping a photoresist according to any one of items 1 to 3. 5. A method for forming a conductive layer on a semiconductor substrate, forming a mask on the conductive layer using a photoresist, etching the non-masked portion of the conductive layer, removing the mask-formed photoresist, A method for manufacturing a semiconductor device, comprising: stripping from the conductive layer using the photoresist stripping composition according to claim 1. 6. The method of manufacturing a semiconductor device according to claim 5, wherein a temperature of the mask-molded photoresist is 5 to 50 ° C.