JP2003005384A - Photoresist remover composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a safe and simple remover composition having excellent performance to remove photoresist residue generated in dry etching of a transparent electrically conductive film in a step for producing LCD and not containing an organic solvent. SOLUTION: The remover comprises: an aqueous solution containing an aliphatic polycarboxylic acid; an aqueous solution containing an aliphatic polycarboxylic acid and an anionic surfactant; and an aqueous solution containing an aliphatic polycarboxylic acid, an anionic surfactant and a phosphoric acid type chelating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist stripper composition for removing photoresist residues generated during dry etching of a transparent conductive film used in the manufacture of liquid crystal displays (LCD). .

[0002]

2. Description of the Related Art In recent years, liquid crystal displays (LCDs) are CRTs.
With thin, lightweight, and low power consumption as a weapon,
It continues to make rapid progress in the fields of PCs, monitors, and personal digital assistants. Under such circumstances, high-definition displays, which are technically difficult to realize with CRTs, are attracting attention as an LCD market. In a high-definition display, the size of the picture element, which is the structural unit of the screen, is smaller. It is required to narrow the gap between a certain ITO and each wiring. The dry etching method is generally considered to be advantageous for processing these thin films from the viewpoint of processing accuracy and yield.In the liquid crystal industry, the dry etching method is widely adopted for processing semiconductor layers, metal layers, and insulating films. ing. In the dry etching process, a wiring material, an insulating film, etc. are formed on the substrate by sputtering, CVD, etc., and a photoresist is applied on the film, exposed, and developed to form a pattern. This is a process of forming an insulating film and a wiring pattern by dry etching using a reactive gas with a photoresist as a mask. After this patterning, ashing is performed, the photoresist used as the mask is removed by ashing, and further,
A general process is to remove the remaining resist residue with a stripping solution. The resist residue generated by such dry etching causes the photoresist to be physically and chemically damaged during the dry etching.
Since it forms a reaction product with the wiring material, dry etching gas, etc., it is extremely unlikely to be peeled off as compared with a normal photoresist. In order to remove the photoresist residue generated during dry etching as described above, one containing a fluorine compound (JP-A-7-201794) and one containing a quaternary ammonium hydroxide (JP-A-8-201794) -262746 gazette) has been proposed, but none of them can completely remove the photoresist residue after ITO dry etching, there is no attack on the wiring material and the insulating film, and the photoresist residue is completely peeled off. There is a demand for a stripper that can be used.

[0003]

DISCLOSURE OF THE INVENTION The present invention is excellent in the removability of photoresist residues generated during dry etching of a transparent conductive film in the LCD manufacturing process,
Another object of the present invention is to provide a safe and simple release agent composition containing no organic solvent.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous solution containing an aliphatic polycarboxylic acid, an aliphatic polycarboxylic acid and an anionic surfactant are contained. Aqueous solution, as well as aliphatic polycarboxylic acid, anionic surfactant and phosphoric acid type chelating agent
The inventors have found that a release agent composed of an aqueous solution containing a coating agent has an excellent effect of removing a photoresist residue generated during dry etching of a transparent conductive film, and completed the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the aliphatic polycarboxylic acid used in the present invention include oxalic acid, malonic acid, succinic acid, maleic acid, adipic acid, tartaric acid, malic acid and citric acid. The concentration of the aliphatic polycarboxylic acid is 0.
It is used in the range of 1 to 15% by weight, but if the concentration is lower than 0.1% by weight, the removability of photoresist residue becomes poor, and
If it is more than 10% by weight, corrosion of the transparent conductive material becomes severe, which is not preferable.

Examples of the anionic surfactant used in the present invention include fatty acid salts, higher alcohol sulfuric acid ester salts, liquid fatty acid sulfuric acid ester salts, sulfuric acid salts of aliphatic amines and aliphatic amides, and aliphatic alcohols. Examples thereof include anionic surfactants such as lurate ester salts, sulfonic acids of dibasic fatty acid esters, fatty acid amide sulfonates, and alkylallyl sulfonates. The concentration of the anionic surfactant is in the range of 0.001 to 1% by weight. When it is 0.001% by weight or less, the removability of the photoresist residue is poor, and when it is 1% by weight or more, the removability of the photoresist residue is low. It does not improve and it is not a good idea.

On the other hand, the phosphoric acid type chelate used in the present invention
Examples of the agent include methyldiphosphonic acid, aminotrismethylenephosphonic acid, ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, ethylaminobismethylene. Phosphonic acid, dodecylaminobismethylenephosphonic acid,
Nitrilotrismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, hexanediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 1,2-propanediaminetetramethylenephosphonic acid Phosphonic acid-based chelating agents having one or more, ammonium salts thereof, organic amine salts, alkali metal salts, and the like are mentioned. One having a nitrogen atom is oxidized to form an N-oxide. Examples of condensed phosphoric acids include metaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, tripolyphosphoric acid, ammonium salts, metal salts and organic amine salts thereof. Any of the above chelating agents can be used, but more preferably those having two or more phosphonic acid groups in the molecule, and more preferably those having 2 to 6 phosphonic acid groups in the molecule. To be Specifically, 1,2-propanediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid and the like are preferable, and particularly preferable is 1,
2-propanediaminetetramethylenephosphonic acid and ethylenediaminetetrakismethylenephosphonic acid. The chelating agents used in the present invention may be used alone or in combination of two or more kinds, and may be used in an appropriate combination. In addition, the above
The concentration of the coating agent is usually 0.001 to 5% by weight, preferably 0.005 to 3% by weight, based on the total liquid.

The stripping composition of the present invention is intended to remove photoresist residues after dry etching, and is basically used in the form of an aqueous solution. The photoresist residue that is the subject of the present invention is a transparent conductive film used in the manufacture of LCDs. Specifically, indium tin oxide (ITO) is generally used. It is a photoresist residue generated during dry etching of oxides, zinc oxides and the like. The temperature at which the release agent composition of the present invention is used is room temperature to 90 ° C, and the release time is about
It takes about 1 to 30 minutes. According to the present invention, water is sufficient for the rinse after the treatment with the above-mentioned release agent, and it is not necessary to use an organic solvent.

[0009]

【Example】

Example 1 ITO4 was sputtered on the insulating film SiNx2,
FIG. 1 shows the state of the substrate on which the photoresist has been removed by performing dry etching using oxygen as a mask and ashing with oxygen plasma. As a result of observing the substrate of FIG. 1 with an electron microscope (SEM), the photoresist residue 3 remained on the ITO 4 and the SiNx 2. Using the substrate shown in FIG. 1, using a stripping agent that is an aqueous solution containing 3% by weight of oxalic acid at 50 ° C. for 15 minutes, soaking in the stripping agent, rinsing with water, and then drying. Then, as a result of SEM observation, as shown in FIG.
It was completely removed.

Example 2 Using the substrate used in Example 1, 3% by weight of oxalic acid, and polyoxyethylene alkylphenyl ether sulfate anion type anionic surfactant Hitenol NE-0.
5 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was soaked in a release agent which was an aqueous solution containing 0.01% by weight at 50 ° C. for 10 minutes,
After rinsing with water and drying, SEM observation was performed. As a result, the photoresist residue was completely removed.

Example 3 Using the substrate used in Example 1, 3% by weight of oxalic acid and polyoxyethylene alkylphenyl ether sulfate anionic surfactant Hitenol NE-05 (Daiichi Kogyo Seiyaku Co., Ltd.) Co., Ltd.) in 0.01% by weight and 0.01% by weight of ethylenediaminetetrakismethylenephosphonic acid in a release agent, which is an aqueous solution, is immersed at 50 ° C for 5 minutes, rinsed with water, and dried SEM. Observed. As a result, the photoresist residue was completely removed.

Examples 4 to 9 and Comparative Examples 1 to 2 The substrates used in Example 1 were used, treated with the release agent shown in Table 1, rinsed with water, and then observed by SEM. The results were shown. The criteria for the peelability of the SEM observation were according to the following criteria. A: The photoresist residue was completely removed. X: Most of the photoresist residue remained.

[0014]

Comparative Example 3 Using the same substrate as in Example 1, 1.0 wt% of ammonium fluoride, 70 wt% of dimethylsulfoxide, and a balance of water were immersed in a release agent at 23 ° C. for 15 minutes, and then, After rinsing with water and drying, SEM observation was performed. As a result, most of the photoresist residue remained.

Comparative Example 4 Using the same substrate as in Example 1, using a release agent having 0.3% by weight of tetramethylammonium hydroxide, 5.0% by weight of sorbitol and the balance being water, 23 ° C. for 15 minutes. After immersing, it was rinsed with water, dried, and observed by SEM. As a result, most of the photoresist residue remained.

[0016]

By using the photoresist remover composition of the present invention, the photoresist residue generated during dry etching of the transparent conductive film can be completely removed, and the wiring material and the insulating film are not corroded.

[Brief description of drawings]

FIG. 1 is a state diagram of a substrate after removing a photoresist by sputtering ITO on an insulating film, using a photoresist as a mask, performing dry etching, and performing ashing with oxygen plasma.

FIG. 2 is a state diagram after immersing the substrate shown in FIG. 1 in a stripping agent which is an aqueous solution containing 3% by weight of oxalic acid, rinsing with water, and drying.

[Explanation of symbols]

1: Substrate 2: SiNx 3: Photoresist residue
4: ITO

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kuki Abe             Niigata City Niigata City Tayuhama Niiwari 182 Mitsubishi Mitsubishi             Gas Chemical Co., Ltd. Niigata Research Center (72) Inventor Tetsuo Aoyama             Niigata City Niigata City Tayuhama Niiwari 182 Mitsubishi Mitsubishi             Gas Chemical Co., Ltd. Niigata Research Center F-term (reference) 2H096 AA27 AA28 HA23 LA03                 4J038 RA02 RA05 RA09 RA12 RA17                 5F043 AA40 BB28 CC16 DD12 GG10                 5F046 MA02

Claims (4)

[Claims] 1. A photoresist remover composition comprising an aqueous solution containing an aliphatic polycarboxylic acid, which is used for removing photoresist residues generated during dry etching of a transparent conductive film. 2. The photoresist stripper composition according to claim 1, wherein the transparent conductive film is indium tin oxide. 3. The photoresist stripper composition according to claim 1, further comprising an anionic surfactant. 4. The photoresist stripper composition according to claim 1, further comprising a phosphoric acid-based chelating agent.