KR20050008410A - compound of photoresist strip solution preventing of corrosion about a copper wire - Google Patents

Abstract

PURPOSE: Provided is a photoresist stripper composition, which has excellent capability of stripping cured or degenerated photoresist and prevents corrosion of copper lines, and thus contributes to manufacture high-quality and highly integrated LCDs and semiconductor devices. CONSTITUTION: The photoresist stripper composition comprises 10-70 wt% of an amine compound, 3-70 wt% of an organic solvent and 0.1-5 wt% of ascorbic acid as anti-corrosive agent. The amine compound is one or two selected from the group consisting of monoethanol amine, diethyleneglycol amine, isopropanol amine, N-methylethanol amine, dimethylethanol amine and 2-£2-((dimethylamino)epoxy)ethanol|. The organic solvent is one or two selected from the group consisting of tetrahydrofurfuryl alcohol, tetrahydro-3-furanmethanol, ethylcarbitol, butylcarbitol, N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

Description

Compound of photoresist strip solution preventing of corrosion about a copper wire}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist stripper composition which prevents corrosion on copper wiring, and more particularly, to image forming apparatuses such as liquid crystal displays (LCDs), flat panel displays (PDPs), organic ELs, and microcircuits for semiconductors. The present invention relates to a stripper composition (Stripper) for preventing corrosion of copper strips from a stripper composition for removing a photoresist cured or deteriorated by etching, ion implantation, or the like.

Copper wiring has superior electrical conductivity and less resistance than aluminum wiring, so that the wiring can be miniaturized and highly integrated while maintaining a constant carrier current. Therefore, the use metal layer can be reduced, and production cost can be reduced and high performance can be realized. In addition, the copper wiring has an advantage that the reliability of the device can be increased by excellent electroplating characteristics. In recent years, the implementation of copper wiring processes has been considered in the related image realization apparatus and semiconductor processing industry.

However, in the case of a stripper composition which is applied to mass production for the existing aluminum wiring, for example, a stripper composition composed of monoethanolamine, butyl carbitol, 1-methyl-2-pyrrolidone (Comparative Example 1) Corrosion may be so severe that problems may arise when used as a stripper for copper wiring.

The addition of additives such as Cathecol, Pyrogallol and Benzotriazole, which are used as corrosion inhibitors in some stripper compositions, is not only effective as a corrosion inhibitor for copper but also a peeling force. Can lead to a decrease. In addition, even when the secondary amine is used as in the previously disclosed Korean Patent Publication No. 2003-0030399, the inhibitory effect on copper corrosion is not sufficient, and there is a problem of lowering the peeling force.

The present invention has been invented to solve the above problems, a photoresist that is cured or deteriorated by etching, ion implantation, etc. in an image forming apparatus such as a liquid crystal display, a flat panel display, an organic EL, and a semiconductor fine circuit forming process. The purpose of the present invention is to provide a peeling liquid composition which is excellent in removing the corrosion resistance and particularly free of corrosion on copper wiring.

1 is a view showing the results of evaluating the corrosion of the copper for 3 hours at 70 ℃ according to the corrosion evaluation method for the copper of the example in the composition of Example 3 and Comparative Examples 1 and 5. And,

2 is a view showing a result of evaluating the corrosion of copper according to the deionized water content for 5 minutes at 70 ℃ according to the copper corrosion evaluation method in the deionized water rinse step of the composition of Example 3 and Comparative Example 1.

The present invention for achieving such an object,

(1) 10 to 70% by weight of an amine compound, (2) 3 to 70% by weight of an organic solvent, and 0.1 to 5% by weight of (3) ascorbic acid, which is a corrosion inhibitor, to provide a photoresist stripper composition. do.

Any of the amine compounds of the above (1) may be used as long as they are commonly used. Examples thereof include monoethanolamine, diethylene glycol amine, isopropanolamine, N-methylethanolamine, dimethylethanolamine, 2- [2- (dimethylamino) epoxy) ethanol], and the like. You may mix and use it.

The organic solvent of (2) includes one to two to 30% by weight of one selected from the group consisting of tetrahydrofurfuryl alcohol, tetrahydro-3-furan methanol, ethyl carbitol, butyl carbitol, 20 to 70% by weight of one or two selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetrahydrofurfuryl alcohol, tetrahydro-3-furanmethanol.

Ascorbic acid in the present invention is excellent in the corrosion protection effect against copper even when added in a small amount.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Preparation Example 1

15% by weight of monoethanolamine, 35% by weight of butylcarbitol, 30% by weight of N-methylpyrrolidone, 20% by weight of tetrahydrofurfuryl alcohol, 0.5% by weight of ascorbic acid were completely dissolved at room temperature and mixed uniformly. Stir until until the peeling liquid composition is prepared.

Preparation Examples 2 to 8, Comparative Examples 1 to 5

Compositions were prepared in the same manner as in Production Example 1, except that the compositions of each composition were as shown in Table 1.

Example

1. Evaluation of Peel Force on Photoresist Film

After applying DONGWOO FINECHEM's SLP-H2O I-line resist on a 4-inch silicon wafer with a thickness of 1 micrometer (µm) according to a conventional method, the hot plate should be 150 to 1 in order to increase the peeling efficiency. Baking for a time to form a photoresist film.

In addition, each peeling liquid composition prepared according to the Example and the comparative example was left to stand in a 70 degreeC constant temperature water tank for 30 minutes or more, and the temperature of the liquid was made uniform.

After cutting the wafer baked at 150 ° C. for 1 hour to a size of 1 cm in width and left for 30 minutes in a 70 ° C. constant temperature water bath, the temperature of the resist film was completely removed by immersion in a stripping solution having a uniform temperature. The peeling capacity was divided into 10 grades, and the removal was quick as R 10 and the removal was shown as R 1 in Table 1.

2. Corrosion evaluation for copper

20 g of each stripper composition prepared according to Examples and Comparative Examples after cutting a copper foil having a purity of 99.98% of purity commercially available from Aldrich Co., Ltd. to a length of 5 mm for corrosion evaluation on copper. Incubated in a 70 ° C. hot-air-dried oven for 3 hours, and the concentration of the eluted copper was measured by Hewlett Packard's Inductive Coupled Plasma Mass Spectrometer (HPP) HP-7500s. Dividing the degree into 10 grades, C 10 is a case where a lot of dissolution and severe corrosion is C 10, and a case where little corrosion is hardly generated due to C 1 is shown in <Table 1>.

Table 1 Composition and evaluation results of photoresist stripper composition

As shown in Table 1, the peeling force and the corrosion evaluation result for copper, the compositions of Examples 1 to 8 using tetrahydrofurfuryl alcohol and ascorbic acid are excellent in terms of peeling force as well as no corrosion to copper.

Comparing Comparative Example 2 and Example 1, it can be seen that the corrosion to copper was significantly reduced by adding a small amount of ascorbic acid. In Comparative Examples 3 to 4, in which benzotriazole or catechol was added to Comparative Example 1, corrosion to copper was reduced a little, but not enough. In addition, when secondary amine is used as in Comparative Example 5 (Example of Special 2003-0030399), not only the inhibitory effect on copper is insufficient, but also the peeling force is lowered.

Figure 1 shows the comparison of the results obtained by measuring the amount of copper elution by performing corrosion evaluation at 70 ° C. for 3 hours with the compositions of Example 3 and Comparative Examples 1 and 5 in Table 1.

3. Copper Corrosion Evaluation in Deionized Water Rinse Process

In order to evaluate the copper corrosion generated in the rinse process of deionized water, 20 g of a solution in which 30%, 60%, 70%, 80%, and 90% of deionized water was added to the stripper composition of Example 3 and Comparative Example 1 was prepared. After cutting Aldrich's copper foil to a length of 5mm, leaving it in a 70 ℃ hot air drying oven for 5 minutes, the concentration of the eluted copper was measured by Hewlett Packard's inductive coupling mass spectrometer HP-7500s. Is shown in FIG.

As shown in FIG. 2, the amount of copper eluted in the state of 100% organic solution is 7 times higher than that of Example 3, and maintains a high eluted state even in a state in which deionized water is mixed.

As described above, the photoresist stripper composition according to the present invention is not only excellent in the ability to remove the cured or deteriorated photoresist (Photoresist), but also provides a stripper composition (Stripper) with little corrosion to copper wiring. It is expected to contribute to high performance and high integration of display devices and semiconductors.

Although the preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, the present invention is not limited thereto and may be improved or modified by those skilled in the art within the scope of the technical idea of the present invention.

Claims (4)

A photoresist stripper composition comprising an amine compound as a first component, an organic solvent as a second component, and ascorbic acid as a corrosion inhibitor as a third component. The photoresist stripper composition according to claim 1, comprising 0.1 to 5% by weight of ascorbic acid. The method according to claim 1, wherein the organic solvent comprises one to two selected from the group consisting of tetrahydrofurfuryl alcohol, tetrahydro-3-furanmethanol, 3 to 30% by weight, ethyl carbitol, butyl carbitol, A photoresist stripper composition comprising 20 to 70% by weight of one to two selected from the group consisting of N-methyl-2-pyrrolidone and N, N-dimethylacetamide. The method of claim 1, wherein the amine compound is selected from the group consisting of monoethanolamine, diethylene glycol amine, isopropanolamine, N-methylethanolamine, dimethylethanolamine, 2- [2- (dimethylamino) epoxy) ethanol] A photoresist stripper composition comprising one to two weight loss of 10 to 70% by weight.