TW202405131A - Etching composition and etching method thereof - Google Patents

Abstract

The present invention provides an etching solution composition, suitable for thick films, especially for etching transparent conductive oxides coating with thickness greater than 500Å or more, comprising 0.5-10wt% organic acid, 0.001-0.5wt% surfactant, 0.001-0.5wt% additive, and water. The etching solution composition provided by the present invention can effectively reduce the ITO residue remaining on the glass substrate, will not corrode the metal wires, and has the characteristics like low surface tension, low foaming, high defoaming, so that the present invention can improve the stability of the solution to prolong the service life.

Description

Etching liquid composition and etching method thereof

The present invention relates to an etching liquid composition for thick films, particularly for transparent conductive oxides with a film thickness greater than 500 angstroms (Å), and an etching method using the etching liquid composition.

Transparent Conductive Oxide (TCO) has a wide range of applications due to its good conductivity, extremely high visible light transmittance and infrared reflectivity. Among them, transparent conductive oxide doped with indium tin oxide (ITO) is commonly used in liquid crystal displays (LCD), electroluminescent displays (ELD), touch panels, solar cells and other fields. conductive material. In the commercial process, film formation methods such as sputtering are mainly used to first form a film on a substrate such as glass, and then the ITO film is etched through wet etching to obtain a patterned ITO film.

In recent years, with the development of large-size panels, displays require lower resistance-capacitance signal delay (RC delay) and lower aperture ratio. Therefore, the demand for wiring materials has gradually shifted to high conductivity and better electromigration capabilities. Good materials, in order to make the ITO film meet the above requirements, there are two commonly used methods. The first method is to increase the temperature during coating to crystallize the ITO film and obtain higher conductivity, but this method is easy When encountering problems in the subsequent etching stage, the main reason is that the crystallized ITO film has higher chemical resistance due to its denser molecular arrangement. Strong acids such as hydrochloric acid and nitric acid series are required for etching. When using these When strong acid is used for etching, it is also easy to cause corrosion to other metal wires, leading to concerns about wire breakage. The second method is to increase the thickness of the ITO film to increase the conductivity. In the past, the common ITO film thickness was about 400Å - 800Å. Recently, it has gradually changed to thick film ITO of 800Å - 1200Å. Although this method will not form a crystallized ITO film, due to the increase in film thickness and the time required for coating, Relatively elongated, the ITO film on the bottom layer is prone to semi-crystallization due to heat storage problems. As the amount of semi-crystalline ITO film increases, the resistance of the ITO film in this state will also increase, resulting in uneven etching and obvious ITO residue during the etching stage.

In the industry, the most common wet etching method for amorphous ITO films is etching with oxalic acid aqueous solution. When early ITO films were etched, in order to make thin line width lines etched more uniformly, surfactants were added to reduce the surface tension. Next, etching is performed. For example, Japanese Patent Application Laid-Open No. 7-141932 discloses an oxalic acid-based etching solution containing dodecylbenzene sulfonic acid series surfactants. However, the added surfactant will cause severe foaming problems. , and this result will make the substrate easy to float due to the accumulation of foam. In addition to causing poor etching accuracy, it is also easy to interfere with the optical sensor at the factory end, causing production troubles; a method is recorded in the patent document CN104388090A Oxalic acid-based etching solution containing oxalic acid, alkylphenol polyoxyethylene ether series surfactants, organic polybasic phosphoric acid and water. Adding organic polybasic phosphoric acid can improve the precipitation problem of indium oxalate, but it has strong corrosion ability and it is difficult to control the etching angle and etching time. , often causes corrosion of other metal wires during the etching process, making the operation difficult; the patent document CN107446582A describes an oxalic acid-based etching solution containing polyvinylpyrrolidone and naphthalene sulfonic acid condensate as surfactants. Although this type of formula is not good for oxidation The dissolution of indium is helpful, but since the naphthalene sulfonic acid condensate must be added to a certain concentration to significantly improve the dissolution effect of indium, and due to the characteristics of this type of compound, it is not easy to penetrate the PTFE film. This property can easily cause blockage in subsequent processes. The filter core will be blocked and the production capacity will be affected.

Although the prior art discloses an oxalic acid etching solution technology, it still has the following shortcomings in actual use:

1. Severe blistering and low processing accuracy The substrate cannot be firmly fixed due to bubbling problems and cannot fully contact the etching liquid, resulting in poor pattern etching accuracy. In addition, foaming foam can easily interfere with the detection of optical sensors, reducing detection accuracy and causing production problems.

2. It is difficult to control the etching effect and there are concerns about safety during operation. It is known that adding strong acids such as hydrochloric acid to oxalic acid-based etching solutions can improve the incomplete etching effect. However, due to its strong corrosion ability, it is difficult to control the etching effect and damage other metal wires, resulting in a reduction in yield. In addition, the risk to operators is high.

3. Insufficient stability and reduced service life It is known that the surfactants used in conventional etching solutions are prone to decay in acidic environments, resulting in insufficient stability of the etching solution and reduced service life.

Currently, as more and more high-resolution panel products begin to use thick-film ITO layers, therefore, how to produce an etching solution that can improve processing accuracy and reduce underlying ITO residues is an urgent goal for relevant technical personnel. .

In view of this, the purpose of the present invention is to provide an etching liquid composition suitable for etching transparent conductive oxide, which contains 0.5~10wt% organic acid, 0.001~0.5wt% surfactant, 0.001~0.5 wt% of additives, and balance water.

Another technical means of the present invention is that the organic acid contains a carboxyl group.

Another technical means of the present invention is that the organic acid can be selected from the group consisting of malic acid, malonic acid, adipic acid, succinic acid, tartaric acid, glutaric acid, glycolic acid, aspartic acid, itaconic acid, and glutaric acid. Amino acid, tricarboxylic acid, pimelic acid, suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid, fumaric acid, glutaconic acid, traumatic acid , muconic acid, aconitic acid, carballylic acid, tribasic acid, mellitic acid, isocitric acid, citric acid, lactic acid, gluconic acid, maleic acid, ascorbic acid, iminoacetic acid, oxalic acid, pyrolysis Gallic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentanoic acid Acid, palmitic acid, sulfamic acid, salicylic acid, p-toluenesulfonic acid, polystyrenesulfonic acid, 2-naphthalenesulfonic acid, polyethylenesulfonic acid, dodecylbenzenesulfonic acid, p-hydroxybenzenesulfonic acid, toluene sulfonic acid A mixture of one or more of nitrobenzene sulfonic acid and nitrobenzene sulfonic acid.

Another technical means of the present invention is that the surfactant can be selected from one or more of fatty acid salts, phosphate ester salts, naphthenate salts, fatty acid esters, polyoxyethylene alkyl ethers, and alkylammonium salts. the mix of.

Another technical means of the present invention is that the additive is selected from sulfonic acid compounds, and can be selected from alkyl disulfonic acid, potassium alkyl disulfonate, sodium alkyl sulfonate, ammonium alkyl sulfonate, alkyl benzene A mixture of one or more of sodium sulfonate, polynaphthalene formaldehyde sulfonic acid compound or salt thereof.

Another technical means of the present invention is that the remaining water is deionized water.

Another technical means of the present invention is that the transparent conductive oxide contains indium tin oxide or indium zinc oxide.

Another technical means of the present invention is that the transparent conductive oxide is microcrystalline or semi-crystalline.

Another object of the present invention is to provide an etching method that uses the etching liquid composition to etch a transparent conductive oxide.

Another technical means of the present invention is that the film thickness of the transparent conductive oxide is greater than 500 angstroms (Å), and the etching temperature is between 35°C and 50°C.

The beneficial effect of the present invention is that by selecting surfactants and additives with special functional groups, the etching liquid composition can effectively remove ITO residues on the bottom layer of thick film ITO and improve the accuracy of etching patterns. At the same time, the etching liquid composition The material has high stability and long service life, which can reduce etching costs.

The relevant patented features and technical content of the present invention will be clearly presented in the following detailed description of the preferred embodiments with reference to the drawings. Before proceeding to the detailed description, it should be noted that similar components are designated by the same numbers.

A preferred embodiment of the etching solution composition of the present invention is suitable for etching transparent conductive oxides, and contains 0.5~10wt% organic acid, 0.001~0.5wt% surfactant, and 0.001~0.5wt% additives. and remaining water. [ Organic acid ]

The organic acid is mainly used to provide etching effect, contains carboxyl groups, and can be selected from malic acid, malonic acid, adipic acid, succinic acid, tartaric acid, glutaric acid, glycolic acid, aspartic acid, itaconic acid, glutamine Acid, tricarboxylic acid, pimelic acid, suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid, fumaric acid, glutenedic acid, traumatic acid, Muconic acid, aconitic acid, carballylic acid, tribasic acid, mellitic acid, isocitric acid, citric acid, lactic acid, gluconic acid, maleic acid, ascorbic acid, iminoacetic acid, oxalic acid, pyrotoxic acid Gallic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid , palmitic acid, sulfamic acid, salicylic acid, p-toluenesulfonic acid, polystyrenesulfonic acid, 2-naphthalenesulfonic acid, polyethylenesulfonic acid, dodecylbenzenesulfonic acid, p-hydroxybenzenesulfonic acid, methyl One or more mixtures of sulfonic acid and nitrobenzene sulfonic acid.

Furthermore, the organic acid described in the present invention is preferably oxalic acid. The present invention only uses organic acids and does not add inorganic acids such as hydrochloric acid and nitric acid. In addition to effectively controlling the etching effect and not corroding the metal wires on the substrate, the invention can also improve the safety of operators during the etching process.

In some preferred embodiments, the organic acid of the present invention accounts for 0.5~10wt% of the etching composition. In some preferred embodiments, the organic acid of the present invention accounts for 1 to 5 wt% of the etching composition. In some preferred embodiments, the weight percentage of the organic acid in the etching composition can be 0.5%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3 %, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, 8%, 10%, etc. [ Surfactant ]

The main function of the surfactant is to effectively reduce the surface tension of the etching solution composition, increase penetration and wettability, and effectively improve defoaming properties. In addition, the surfactant is stable in acidic environments. The surfactant is not particularly limited and can be selected from one or a mixture of more than one of fatty acid salts, phosphate ester salts, naphthenate salts, fatty acid esters, polyoxyethylene alkyl ethers, and alkylammonium salts. Preferred are phosphate ester salts and polyoxyethylene alkyl ethers, and the best surfactant is phosphate ester salts.

In some preferred embodiments, the surfactant of the present invention accounts for 0.001~0.5wt% of the etching composition. In some preferred embodiments, the surfactant of the present invention accounts for 0.005~0.05wt% of the etching composition. In some preferred embodiments, the weight percentage of the surfactant in the etching composition can be 0.001%, 0.002%, 0.003%, 0.005%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.5%, etc. [ Additive ]

The main function of the additive is to react with microcrystalline and semi-crystalline indium oxide, thereby destroying the stability of the crystal, making it easier to be etched by organic acids, and effectively improving the etching residue removal effect for thick film ITO. The additive is selected from sulfonic acid compounds, and may be selected from alkyl disulfonic acid, potassium alkyl disulfonate, sodium alkyl sulfonate, ammonium alkyl sulfonate, sodium alkyl benzene sulfonate, and polynaphthalene formaldehyde sulfonate compounds. or a mixture of one or more of its salts. Preferred are alkyl ammonium sulfonates, polynaphthalene formaldehyde sulfonate compounds or salts thereof, and most preferably, alkyl ammonium sulfonate compounds can be used.

In some preferred embodiments, the additives described in the present invention account for 0.001~0.5wt% of the etching composition. In some preferred embodiments, the additives described in the present invention account for 0.005~0.05wt% of the etching composition. In some preferred embodiments, the weight percentage of the additive in the etching composition can be 0.001%, 0.002%, 0.003%, 0.005%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1% , 0.5%, etc. [ water ]

The etching liquid composition of the present invention contains water, which can be pure water or deionized water. Deionized water is preferably used as the solvent to eliminate the adverse effects of possible impurity ions in the water on the etching performance. The water content range can make the total weight of the etching liquid composition become 100 wt%. In some preferred embodiments, the water of the present invention accounts for more than 80wt% of the etching composition. [ Preparation of etching liquid composition ]

The etching liquid composition of the present invention can be prepared by mixing organic acids, surfactants, additives and water at room temperature using conventional methods until they are completely dissolved and uniform, and then filtered before being discharged. Wherein, the filtration step can be performed using a 0.1-1 μm filter, preferably a 0.5 μm filter. The etching liquid composition of the present invention can be prepared at normal temperature, normal pressure and simple stirring equipment. It does not require special preparation conditions and equipment, and can reduce production costs. [ Etching method ]

An ITO film is first formed on the glass substrate by sputtering. After exposure, development and other procedures, a resist coating pattern is formed. The glass substrate with the ITO film can be etched using the etching liquid composition of the present invention at a temperature of 35 to 50°C, preferably between 38 to 42°C. The etching time can be adjusted according to the film thickness of the ITO film. Since the etching rate of the etching solution composition of the present invention is about 10 Å/Second, the film thickness is 500 Å and 800 Å. For example, the required times are about 50~100 seconds and 80~160 seconds respectively. Generally speaking, the etching time is about 1~5 minutes. After etching is completed, subsequent cleaning and drying can be performed according to actual needs.

According to the above embodiments, actual examples and comparative examples are used to more specifically illustrate that the etching liquid composition of the present invention can effectively remove the underlying ITO residue after etching the transparent conductive oxide, making the substrate surface smooth. [ Examples and Comparative Examples ]

First, the etching liquid compositions of Examples 1 to 15 and the etching liquid compositions of Comparative Examples 1 to 7 were prepared. Regarding the organic acid in the etching liquid compositions of the Examples and Comparative Examples, oxalic acid was used, and the components of the other surfactants and additives are as shown in Table 1. Table 1 oxalic acid(%) Surfactant(%) Additive(%) water Example 1 3.4 Phosphate salt 0.01% Alkylammonium sulfonate compound 0.01% margin Example 2 3.4 Polyoxyethylene alkyl ether 0.01% Alkylammonium sulfonate compound 0.01% margin Example 3 3.4 fatty acid salts 0.01% Alkylammonium sulfonate compound 0.01% margin Example 4 3.4 Glyceryl fatty acid ester 0.01% Alkylammonium sulfonate compound 0.01% margin Example 5 3.4 Alkylammonium salt 0.01% Alkylammonium sulfonate compound 0.01% margin Example 6 3.4 Phosphate salt 0.01% Polynaphthalene formaldehyde sulfonate compound 0.01% margin Example 7 3.4 Polyoxyethylene alkyl ether 0.01% Polynaphthalene formaldehyde sulfonate compound 0.01% margin Example 8 3.4 fatty acid salts 0.01% Polynaphthalene formaldehyde sulfonate compound 0.01% margin Example 9 3.4 Glyceryl fatty acid ester 0.01% Polynaphthalene formaldehyde sulfonate compound 0.01% margin Example 10 3.4 Alkylammonium salt 0.01% Polynaphthalene formaldehyde sulfonate compound 0.01% margin Example 11 3.4 Phosphate salt 0.01% Alkyl sulfate compounds 0.01% margin Example 12 3.4 Polyoxyethylene alkyl ether 0.01% Alkyl sulfate compounds 0.01% margin Example 13 3.4 fatty acid salts 0.01% Alkyl sulfate compounds 0.01% margin Example 14 3.4 Glyceryl fatty acid ester 0.01% Alkyl sulfate compounds 0.01% margin Example 15 3.4 Alkylammonium salt 0.01% Alkyl sulfate compounds 0.01% margin Comparative example 1 3.4 Phosphate salt 0.01% - margin Comparative example 2 3.4 - - Alkylammonium sulfonate compound 0.01% margin Comparative example 3 3.4 Polyoxyethylene alkyl ether 0.01% - - margin Comparative example 4 3.4 - - Polynaphthalene formaldehyde sulfonate compound 0.01% margin Comparative example 5 3.4 Alkylammonium salt 0.01% - - margin Comparative example 6 3.4 - - Alkyl sulfate compounds 0.01% margin Comparative example 7 3.4 - - - - margin

According to the following test items and the evaluation criteria in Table 2, the surface tension, foaming properties, defoaming properties, ITO residue removal ability and chemical solution stability of the etching solution compositions of the Examples and Comparative Examples in Table 1 were evaluated. 1. Surface tension: Mix all the added ingredients evenly, then fix it at room temperature 25°C and measure it with a surface tension meter. 2. Foaming property: Place 100mL of etching solution composition in a 100mL quantitative bottle, shake it vertically several times, and measure the foam height. 3. Defoaming property: Place 100 mL of etching solution composition in a 100 mL quantitative bottle, shake vertically several times, and measure the foam height after stopping for 1 minute. 4. Stability: Mix all added ingredients evenly, then store at room temperature of 25°C, and measure changes in surface tension over time. 5. ITO residue removal ability test: The test piece for this test is a 1000 Å thick film ITO and has been etched at 40 degrees Celsius (over etching, O/E, indicating the percentage of the actual etching time exceeding the exact etching time) The test specifically carried out O/E 100% test, and used a scanning electron microscope (SEM) to observe the ITO residue after etching for evaluation. Table 2 Rating Surface tension(N/m) Foaming Defoaming property ITO residue removal ability Stability A 25~35 Foam height＜0.5cm Foam height＜0.5cm No residue >March B 35~45 Foam height 0.5~1.0cm Foam height 0.5~1.0cm There is a small amount of residue 1-2 months C 45 and above Foam height＞1.0cm Foam height＞1.0cm There is obvious residue <January

The results of relevant examples and comparative examples are shown in Table 3. table 3 -- Surface tension(N/m) Foaming Defoaming property ITO residue removal ability Stability Example 1 A A A A A Example 2 B B B A B Example 3 B B B A B Example 4 B B B A B Example 5 B B B A A Example 6 B A A A A Example 7 B B B A B Example 8 B B B A B Example 9 B B B A B Example 10 B B B A A Example 11 A A B B A Example 12 B B B B B Example 13 B B B B B Example 14 B B B B B Example 15 B B B B A Comparative example 1 A A A C A Comparative example 2 B C C A A Comparative example 3 B A A C B Comparative example 4 B C C B B Comparative example 5 B C C C B Comparative example 6 B C C C A Comparative example 7 C A A C A

Please refer to Figure 1, which is an SEM image of the etching liquid composition of Comparative Example 7 on an ITO film. The etching solution composition of Comparative Example 7 only uses oxalic acid without adding surfactants and additives. Although the foaming property, defoaming property, and stability tests are all evaluated as level A, the surface tension and ITO residue removal ability tests are only rated A. There is a C grade. It can be clearly seen from Figure 1 that due to incomplete etching of the ITO film, there is a large amount of residue on the surface of the substrate. Therefore, the surface of the substrate is obviously rough and uneven, which affects the accuracy of the etching pattern.

Regarding the etching liquid compositions of Comparative Examples 1, 3 and 5, in addition to oxalic acid, different surfactants were added respectively. Although Comparative Example 1 uses a surfactant of phosphate ester salt, which can make the overall etching solution composition test roughly rated A, the residue removal ability test evaluation is still only C, and the ITO residue cannot be effectively improved.

Regarding the etching liquid compositions of Comparative Examples 2, 4 and 6, in addition to oxalic acid, different additives were added respectively. Although Comparative Example 2 uses an alkyl ammonium sulfonate compound as an additive, the residue removal ability test evaluation of the etching liquid composition can be improved to level A, but in contrast, other test items are only evaluated as level B~C, and the overall etching performance Not ideal. Please also refer to Figure 2, which is an SEM image of the etching liquid composition of Comparative Example 6 on an ITO film. Comparative Example 6 is a commercially available etching solution composition product. Although it has high stability, the foaming property, defoaming property, and ITO residue removal ability test evaluations are all only grade C. It can be clearly seen that the underlying ITO film is not completely etched. As a result, there is a large amount of residue on the surface of the substrate, and the surface is rough and uneven as shown in Figure 1, which affects the processing accuracy.

It can be known from the above comparative examples 1 to 7 that simply using oxalic acid, oxalic acid combined with surfactants, or oxalic acid combined with additives can only improve the performance of some test items, cannot have excellent etching performance, and has obvious ITO residue.

In order to improve the above shortcomings, in addition to using oxalic acid, specific surfactants and additives are also added in embodiments of the present invention to improve etching performance. Please refer to FIG. 3 , which is an SEM image of the etching liquid composition on an ITO film according to Embodiment 1 of the present invention. Regarding the etching liquid composition of Example 1, a phosphate ester salt is selected as the surfactant and an alkyl ammonium sulfonate compound is used as an additive. Compared with the above comparative example, there is no ITO residue on the glass substrate, and the surface of the substrate is smooth, which improves the accuracy of the etching pattern. Since the selected surfactants and additives have acidic functional groups and can exist stably in an acidic environment, the etching liquid composition of the present invention has excellent etching effects. It can be seen from Examples 1 to 10 that selecting sulfonic acid compounds as additives and adding different surfactants can greatly improve the ITO residue removal ability and effectively and completely remove ITO residues.

Regarding the etching solution compositions of Examples 11 to 15, alkyl sulfate compounds are used as additives, and different surfactants are used. Although the overall test evaluation is maintained above level B, the ITO residual value removal effect is slightly inferior to An etching solution composition using a sulfonic acid compound.

It can be seen from the above description that the etching liquid composition and its etching method of the present invention indeed have the following effects:

1. Effectively remove ITO residues and improve processing accuracy The etching solution composition of the present invention uses surfactants and additives with acidic functional groups, which can effectively remove the semi-crystalline ITO residue produced during the thick film ITO production process, keep the substrate surface smooth, and improve the accuracy of the etching pattern. .

2. Excellent etching performance In addition to being able to effectively remove ITO residues, the etching solution composition of the present invention also has the characteristics of low surface tension, low foaming, and high defoaming. In addition, the process is simple and consumes less energy, and can be produced at nearly normal temperatures. , without the need for complicated process conditions or equipment, which can effectively reduce production costs.

3. Low risk and extended service life Since the etching solution composition of the present invention uses a weak acid and does not add strong acids such as hydrochloric acid, the safety of operators can be improved. In addition, surfactants and additives with acidic functional groups can also be combined with weak acids to improve the stability of the solution and extend its service life.

In summary, the etching solution composition of the present invention not only improves the ability to remove semi-crystalline ITO residues that occur in the thick-film ITO process, but also has the characteristics of low surface tension, low foaming, and high defoaming, and can help Improve patterning yield and increase accuracy. In addition, the etching liquid composition of the present invention has high stability, long storage life, higher error tolerance in the storage and preparation of raw materials and finished products, and can reduce etching costs.

However, the above are only preferred embodiments of the present invention, and should not be used to limit the scope of the present invention. That is, simple equivalent changes and modifications may be made based on the patent scope of the present invention and the description of the invention. All are still within the scope of the patent of this invention.

Figure 1 is an SEM image of the etching liquid composition of Comparative Example 7 on an ITO film; Figure 2 is an SEM image of the etching solution composition of Comparative Example 6 on an ITO film; and Figure 3 is an SEM image of the etching liquid composition on an ITO film according to Example 1 of the present invention.

Claims (10)

An etching liquid composition suitable for etching transparent conductive oxides, which contains 0.5~10wt% organic acid, 0.001~0.5wt% surfactant, 0.001~0.5wt% additives, and the balance water. The etching liquid composition according to claim 1, wherein the organic acid contains a carboxyl group. The etching liquid composition according to claim 2, wherein the organic acid can be selected from malic acid, malonic acid, adipic acid, succinic acid, tartaric acid, glutaric acid, glycolic acid, aspartic acid, itaconic acid, etc. Acid, glutamic acid, tricarboxylic acid, pimelic acid, suberic acid, sebacic acid, stearic acid, pyruvic acid, acetoacetic acid, glyoxylic acid, azelaic acid, fumaric acid, glutenedioic acid , Wound acid, muconic acid, aconitic acid, carballylic acid, tribasic acid, mellitic acid, isocitric acid, citric acid, lactic acid, gluconic acid, maleic acid, ascorbic acid, iminoacetic acid, Oxalic acid, pyrogallic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid , Pentadecanoic acid, palmitic acid, sulfamic acid, salicylic acid, p-toluenesulfonic acid, polystyrenesulfonic acid, 2-naphthalenesulfonic acid, polyethylenesulfonic acid, dodecylbenzenesulfonic acid, p-hydroxybenzenesulfonate A mixture of one or more of acid, methylsulfonic acid and nitrobenzenesulfonic acid. The etching liquid composition according to claim 1, wherein the surfactant can be selected from fatty acid salts, phosphate ester salts, naphthenate salts, fatty acid esters, polyoxyethylene alkyl ethers, and alkylammonium salts. A mixture of one or more. The etching liquid composition according to claim 1, wherein the additive is selected from sulfonic acid compounds, and may be selected from alkyl disulfonic acid, potassium alkyl disulfonate, sodium alkyl sulfonate, ammonium alkyl sulfonate, A mixture of one or more of sodium alkyl benzene sulfonate, polynaphthalene formaldehyde sulfonate compound or salt thereof. The etching liquid composition according to claim 1, wherein the remaining water is deionized water. The etching liquid composition according to claim 1, wherein the transparent conductive oxide contains indium tin oxide or indium zinc oxide. The etching liquid composition according to claim 7, wherein the transparent conductive oxide is microcrystalline or semi-crystalline. An etching method that uses the etching liquid composition described in any one of claims 1 to 8 to etch transparent conductive oxide. The etching method according to claim 9, wherein the film thickness of the transparent conductive oxide is greater than 500 angstroms (Å), and the etching temperature is between 35°C and 50°C.