KR101329824B1 - Manufacturing method of array substrate for liquid crystal display - Google Patents

Abstract

The present invention provides a method of manufacturing a TFT array substrate for a liquid crystal display device, comprising: forming a molybdenum-based metal / aluminum-based metal double layer on a substrate in a gate electrode forming step, followed by etching with an etchant composition to form a gate wiring; and Forming an indium oxide film in the step of forming the pixel electrode, and then etching the etching liquid composition to form the pixel electrode;

The etchant composition, based on the total weight of the composition, A) iron nitrate (Fe (NO ₃ ) ₃ ) 2 to 5% by weight, B) fluorine-containing compound 0.1 to 1% by weight, C) sulfuric acid (H ₂ SO ₄ ) 1 to 15 wt%, D) 0.1-5 wt% of tetrazole-based compound, and E) 74-96.8 wt% of water; An etchant composition of a molybdenum-based metal / aluminum-based metal double film and an indium oxide film; And a method for etching a molybdenum-based metal / aluminum-based metal double layer or indium oxide layer using the etchant composition.

Nitric oxide, molybdenum, aluminum, indium oxide, etchant composition

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing an array substrate for a liquid crystal display (LCD)

The present invention relates to a method of manufacturing an array substrate for a liquid crystal display, an etching solution composition of a molybdenum-based metal / aluminum-based metal double film and an indium oxide film, and etching of a molybdenum-based metal / aluminum- ≪ / RTI >

In the manufacture of a semiconductor device for driving a liquid crystal display device, a process of forming a metal wiring on a substrate is usually a process of forming a metal film by sputtering or the like, applying a photoresist, forming a photoresist in a selective region by exposure and development , And an etching process, and includes a cleaning process before and after the individual unit process. The etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask, and typically, dry etching using plasma or wet etching using an etching solution is used.

In the above-described semiconductor device, a metal commonly used as a wiring material of a TFT-LCD (Thin Film Transistor-Liquid Crystal Display) is aluminum (Al) or an aluminum alloy. Pure aluminum has a weak resistance to a chemical substance, (Mo), chromium (Cr), tungsten (W), tin (Sn) or the like on the aluminum or aluminum alloy layer A multilayer laminated structure can be applied.

By the way, in the case of the Mo / Al double layer, for example, when wet etching with a conventional aluminum etching solution mainly composed of phosphoric acid, the upper Mo layer is lower than the aluminum etching rate, so the upper Mo layer is the lower aluminum layer. It represents a poor profile that has a cross section protruding out of it. This poor profile results in poor step coverage in subsequent processes and increases the likelihood that the top layer is disconnected from the slope or the upper and lower metals are shorted.

Recently, in order to solve the above problems, Korean Patent No. 579511 includes nitric acid (HNO ₃ ), iron nitrate (Fe (NO ₃ ) ₃ ), perchloric acid (HClO ₄ ), and ammonium fluoride (NH ₄ F). A method of collectively etching molybdenum / aluminum bilayer using an etchant has been presented. However, when the molybdenum / aluminum double-layer substrate is etched with the etching solution, fine etching residues are left on the substrate, causing a leakage current during TFT On / Off driving, Screen distortion may occur. Further, if the indium oxide film is etched with the etchant, an indium oxide film residue remains.

In the art, an etching solution that does not generate fine etching residues is required in order to realize high image quality, and an indium oxide film used as a gate electrode and a molybdenum / aluminum double layer used as a gate wiring and a pixel electrode are used as an etchant to simplify the process. There is a need to develop an etchant that can be etched in a batch.

Accordingly, an object of the present invention is to provide a method for manufacturing a metal-aluminum-metal double-layered structure, which does not generate fine etching residues during etching of a molybdenum-based metal / aluminum-based metal double layer, does not generate residues when the indium oxide film is etched, And to provide an etchant composition capable of batch etching the indium oxide film.

The present invention also provides a method for etching a molybdenum-based metal / aluminum-based metal double layer and an indium oxide layer using the etchant composition.

Further, the present invention provides a method for manufacturing an array substrate for a liquid crystal display device, which comprises a step of etching the molybdenum-based metal / aluminum-based metal double film and / or the indium oxide film by using the above etching solution composition.

In order to achieve the above object,

A) iron oxide (Fe (NO ₃ ) ₃ ),

B) Fluorine compounds,

C) sulfuric acid (H ₂ SO ₄ )

D) tetrazole compound, and

E) It provides an etching liquid composition of the molybdenum-based metal / aluminum-based metal double film and the indium oxide film containing water.

Further, according to the present invention,

I) forming a molybdenum-based metal / aluminum-based metal double-layer on a substrate;

II) selectively leaving a photoreactive material on the molybdenum-based metal / aluminum-based metal double layer; And

III) A method of etching a molybdenum-based metal / aluminum-based metal double-layer film comprising the step of etching the molybdenum-based metal / aluminum-based metal double-layer film using the etching liquid composition of the present invention.

Further, according to the present invention,

I) forming an indium oxide film on a substrate;

II) selectively leaving a photoreactive material on the indium oxide film; And

III) etching the indium oxide film using the etching solution composition of the present invention.

Further, according to the present invention,

a) forming a gate wiring on the substrate;

b) forming a gate insulating layer on the substrate including the gate wiring;

c) forming a semiconductor layer on the gate insulating layer;

d) forming source and drain electrodes on the semiconductor layer; And

e) forming a pixel electrode connected to the drain electrode

The method comprising the steps of:

In the step a), a molybdenum-based metal / aluminum-based metal double layer is formed on the substrate, and the gate wiring is formed by etching with the etching solution composition of the present invention. In step e), an indium oxide film is formed, And forming a pixel electrode by etching with an etchant composition. The present invention also provides a method of manufacturing an array substrate for a liquid crystal display device.

When the molybdenum-based metal / aluminum-based metal double film or indium oxide film is etched using the etching liquid composition of the present invention, the aluminum-based metal / molybdenum-based metal double film does not generate fine etching residues, It retains the initial etch characteristics due to the minimized galvanic effect and exhibits excellent etch characteristics that do not leave etch residues even if the indium oxide film is etched with the same etchant. Therefore, when the visual liquid composition of the present invention is used for manufacturing an array substrate for a liquid crystal display device including a gate electrode formed of a molybdenum-based metal / aluminum-based metal double film and / or a pixel electrode formed of an indium oxide film, Not only the driving characteristics of the device can be improved, but also the molybdenum-based metal / aluminum-based metal double film and the indium oxide film can be collectively etched, thereby maximizing the process efficiency.

Hereinafter, the present invention will be described in detail.

The present invention, A) iron nitrate (Fe (NO ₃ ) ₃ ), B) fluorine-containing compound, C) sulfuric acid (H ₂ SO ₄ ),

D) a tetrazole-based compound, and E) a molybdenum-based metal / aluminum-based metal double film and an indium oxide film containing water.

In the present invention, the molybdenum-based metal and the aluminum-based metal are concepts including alloys thereof, and the indium oxide film is a concept including an indium zinc oxide film (IZO) or an indium tin oxide film (ITO).

In the etchant composition of the present invention, A) iron nitrate (Fe (NO ₃ ) ₃ ) is used as an oxidant for etching the molybdenum-based metal / aluminum-based metal double film constituting the gate wiring and the indium oxide film constituting the pixel electrode. The nitrate iron oxide is preferably contained in an amount of 2 to 5% by weight based on the total weight of the etching solution composition of the present invention. If less than 2% by weight of iron nitrate may not be enough etching due to lack of etching power, if more than 5% by weight is included in the etching rate for molybdenum-based metal is faster and for aluminum-based metal When the etching rate is slowed, the upper molybdenum may be over-etched when the molybdenum-based metal / aluminum-based metal double layer is etched to cause etching non-uniformity.

In the etching liquid composition of the present invention, the B) fluorine-containing compound accelerates the aluminum-based metal etching rate when etching the molybdenum-based metal / aluminum-based metal double layer, and the etching rate of the indium oxide layer when etching the indium oxide film. do.

The fluorinated compound is preferably contained in an amount of 0.1 to 1% by weight based on the total weight of the composition. When the fluorine-containing compound is contained in less than 0.1% by weight, the etching rate of the molybdenum-based metal / aluminum-based metal double layer and the indium oxide film is slowed, and when it exceeds 1% by weight, the molybdenum-based metal / aluminum-based metal double layer When etching, the aluminum-based metal etching rate may be too high to cause an upper molybdenum-based metal overhang, and when etching the indium oxide layer, an attack may be applied to the lower insulating layer of the indium oxide layer.

The fluorinated compound is preferably at least one selected from the group consisting of NH ₄ FHF, KFHF, NaFHF, KF and NaF, and more preferably NH ₄ FHF, but is not limited thereto.

In the etchant composition of the present invention, C) sulfuric acid (H ₂ SO ₄ ), when etching the molybdenum-based metal / aluminum-based metal double layer is accelerated its etching rate.

The sulfuric acid is preferably included 1 to 15% by weight based on the total weight of the composition. When sulfuric acid is included in less than 1% by weight, not only the etching rate of the molybdenum-based metal / aluminum-based metal double layer may be slowed, but also the etching residue of the molybdenum-based metal / aluminum-based metal double layer may occur. In this case, the molybdenum-based metal / aluminum-based metal double film etch rate is too fast to control the process time.

In the etching liquid composition of the present invention, the D) tetrazole-based compound functions to greatly increase the amount of the etchable substrate in etching the molybdenum-based metal / aluminum-based metal double layer substrate. Tapered etching of molybdenum-based metal / aluminum-based metal double layers modulates the galvanic effect so that the two metals are etched together as a single metal. The cumulative effect becomes a factor that changes the galvanic effect. In the etchant composition according to the present invention, the tetrazole-based compound has a galvanic effect due to the metal accumulated in the etchant as described above. By minimizing the change, the initial etching performance is maintained. In addition, the tetrazole-based compound chelates the molybdenum-based metal when etching the molybdenum-based metal / aluminum-based metal double-layer substrate to minimize the possibility of remaining of the residual film.

The tetrazole-based compound may be any compound having a tetrazole ring, for example, 5-aminotetrazole, 1-alkyl-5-aminotetrazole, 5- 5-hydroxy-tetrazole, 1-alkyl-5-hydroxy-tetrazole, tetrazol-5-thiol, 1-alkyl-tetrazole-5-thiol, or mixtures thereof, and the like, and more preferably 5-aminotetrazole (hereinafter referred to as “ATZ”). In alkyl-substituted tetrazole alkyl is preferably a C1 to C7 straight or branched chain alkyl group.

The tetrazole-based compound is preferably included 0.1 to 5% by weight relative to the total weight of the composition. When the tetrazole-based compound is included in less than 0.1% by weight, the galvanic effect cannot be controlled as the etching amount of the molybdenum-based metal / aluminum-based metal double layer substrate is increased, so that the etching rate becomes slow or difficult to etch. Molybdenum-based metal residual film may be left, and when the molybdenum-based metal / aluminum-based metal etching rate is too high, the control may be difficult.

In the etchant composition according to the present invention, the water is not particularly limited, but deionized water is preferable. More preferably, deionized water having a specific resistivity of 18 ㏁ / cm or more, which shows the degree of ions removed from the water, may be used. The water content is included in the range of 74 ~ 96.8% by weight based on the total weight of the composition and is adjusted according to the content of the other components.

The iron nitrate, fluorine-containing compound, sulfuric acid, and tetrazole-based compound used in the etching solution composition of the present invention can be produced by a conventionally known method, and preferably has a purity for a semiconductor process.

In the present invention, the etchant composition of the molybdenum-based metal / aluminum-based metal double layer and the indium oxide layer,

A) 2 to 5% by weight of iron oxide (Fe (NO ₃ ) ₃ )

B) 0.1 to 1% by weight of a fluorine compound,

C) sulfuric acid (H ₂ SO ₄ ) 1 to 15% by weight,

D) 0.1 to 5 wt% of a tetrazole compound, and

E) preferably comprises 74 to 96.8% by weight of water.

In addition, the etchant composition according to the present invention may further include any additives commonly used in the art for improving etching performance, for example, a surfactant, a metal ion sequestrant or a corrosion inhibitor. Surfactants decrease the surface tension and increase the uniformity of etching. As such a surfactant, a surfactant which is resistant to an etching solution and has compatibility with the surfactant is preferable. Examples thereof include any anionic, cationic, zwitterionic or nonionic surfactant. Further, a fluorine-based surfactant can be used as a surfactant. The additive is not limited thereto, and various other additives known in the art can be selected and added for better effect of the present invention.

The etchant composition according to the present invention can collectively etch a molybdenum-based metal / aluminum-based metal double film and indium oxide films such as indium zinc oxide (IZO) and indium tin oxide (ITO).

The etchant composition according to the present invention does not generate fine etching residues for the molybdenum-based metal / aluminum-based metal double film, and therefore has excellent etching properties and does not generate indium oxide film residue. Therefore, the defect caused by the residue of indium oxide film is minimized .

Further, according to the present invention,

I) forming a molybdenum-based metal / aluminum-based metal double-layer on a substrate;

II) selectively leaving a photoreactive material on the molybdenum-based metal / aluminum-based metal double layer; And

III) A method of etching a molybdenum-based metal / aluminum-based metal double-layer film comprising the step of etching the molybdenum-based metal / aluminum-based metal double-layer film using the etching liquid composition of the present invention.

Further, according to the present invention,

I) forming an indium oxide film on a substrate;

II) selectively leaving a photoreactive material on the indium oxide film; And

III) etching the indium oxide film using the etching solution composition of the present invention.

In the etching method of the present invention, the photoreactive material is preferably a conventional photoresist material, and may be selectively left by conventional exposure and development processes.

Further, according to the present invention,

a) forming a gate wiring on the substrate;

b) forming a gate insulating layer on the substrate including the gate wiring;

c) forming a semiconductor layer on the gate insulating layer;

d) forming source and drain electrodes on the semiconductor layer; And

e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

In the step (a), after forming a molybdenum-based metal / aluminum-based metal double layer on the substrate, the gate wiring is formed by etching with the etchant composition of the present invention, and in the step (e), after forming an indium oxide film, The present invention provides a method of manufacturing an array substrate for a liquid crystal display device, the pixel electrode being formed by etching with the etchant composition of the present invention.

In the method of manufacturing an array substrate for a liquid crystal display according to the present invention, the step a) may include: a1) depositing a molybdenum-based metal / aluminum-based metal double layer on a substrate using a vapor deposition method or a sputtering method; And a2) forming the gate wiring by patterning the molybdenum-based metal / aluminum-based metal double layer with the etching solution of the present invention. Here, the method of forming the molybdenum-based metal / aluminum-based metal double film on the substrate is not limited to the above-described ones.

In the method for manufacturing an array substrate for a liquid crystal display according to the present invention, in step (b), silicon nitride (SiN _x ) is deposited on a gate wiring formed on a substrate to form a gate insulating layer. Here, the material used in the formation of the gate insulating layer is not limited to silicon nitride (SiN _x ), but a material selected from various inorganic insulating materials including silicon oxide (SiO ₂ ) may be used to form the gate insulating layer have.

In the method for manufacturing an array substrate for a liquid crystal display according to the present invention, in the step c), a semiconductor layer is formed on the gate insulating layer by a chemical vapor deposition method (CVD). That is, an active layer and an ohmic contact layer are sequentially formed, and patterned through dry etching. Here, the active layer is generally formed of pure amorphous silicon (a-Si: H), and the ohmic surface layer is formed of amorphous silicon (n ⁺ a-Si: H) containing impurities. Chemical vapor deposition (CVD) may be used to form the active layer and the ohmic contact layer, but is not limited thereto.

In the method for manufacturing an array substrate for a liquid crystal display according to the present invention, the step d) includes the steps of: d1) forming source and drain electrodes on the semiconductor layer; And d2) forming an insulating layer on the source and drain electrodes. In the step d1), a metal film is deposited on the ohmic surface layer by sputtering, and the source electrode and the drain electrode are formed by etching with the etching solution of the present invention. Here, the method of forming the metal film on the substrate is not limited to the above examples. In step d2), an inorganic insulating group including silicon nitride (SiN _x ) and silicon oxide (SiO ₂ ) or a benzocyclobutene (BCB) and an acrylic resin (resin) are formed on the source electrode and the drain electrode. The insulating layer may be formed of a single layer or a double layer by selecting from a group of organic insulating materials. The material of the insulating layer is not limited to those illustrated above. Particularly, when the source and drain electrodes are made of the same material as the gate wiring, the etching composition can be applied to a process for forming source and drain electrodes.

In the method of manufacturing an array substrate for a liquid crystal display according to the present invention, the pixel electrode connected to the drain electrode is formed in step e). For example, a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO) is deposited by sputtering and etched using the etchant composition according to the present invention to form a pixel electrode. The method of depositing the indium oxide film is not limited to the sputtering method.

Further, in the method for manufacturing an array substrate for a liquid crystal display device, in the step (e) etching step using the etching solution composition according to the present invention, the attack to the data line including the drain electrode located under the pixel electrode can be minimized , It is possible to manufacture an array substrate for a liquid crystal display device which can improve the driving characteristics of the TFT-LCD and improve the productivity of the array substrate for a liquid crystal display device.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples, but may be variously modified and changed.

Example  1 to 10: Etchant  Preparation of the composition

Fe (NO ₃ ) ₃ , NH ₄ FHF, H ₂ SO ₄ , ATZ, a grade for semiconductor processing, was mixed as shown in Table 1 below, and the etching liquid composition was added by adding deionized water so that the total weight of the composition was 100% by weight. Was prepared.

Etchant composition (% by weight) Fe (NO _{3) 3} NH ₄ FHF H ₂ SO ₄ ATZ Deionized water Example 1 2.0 0.3 One 0.1 Balance Example 2 2.5 0.3 2 0.2 Balance Example 3 3.0 0.4 5 0.5 Balance Example 4 3.5 0.4 7 1.0 Balance Example 5 3.5 0.3 9 0.2 Balance Example 6 3.5 0.5 12 0.3 Balance Example 7 4.0 0.8 12 1.0 Balance Example 8 4.0 1.0 6 0.7 Balance Example 9 4.5 0.8 12 2.0 Balance Example 10 5.0 0.9 15 4.0 Balance

Comparative Example  One: Etchant  Preparation of the composition

3% by weight of Fe (NO ₃ ) ₃ , 0.4% by weight of NH ₄ FHF, 10% by weight of HNO ₃ , ₃ % by weight of HClO ₄ and a total of 100% by weight.

Comparative Example  2: Etchant  Preparation of the composition

5% by weight oxalic acid and 95% by weight deionized water.

Test Example  1: molybdenum / aluminum Double membrane  And indium Oxide film Etching  Property evaluation

A molybdenum / aluminum double film was sequentially deposited on the glass substrate by the sputtering method, and the indium oxide film was also deposited by the same method as above. Then, a photoresist of about 1 mu m or so was coated thereon, . The test piece was etched using the spraying method with the etching solutions of Examples 1 to 10 and Comparative Examples 1 and 2. Each of the test pieces etched in Examples 1 to 10 and Comparative Examples 1 and 2 was examined using a scanning electron microscope (SEM; Hitach, S-4700). The results are shown in Table 2 and FIGS. 1 to 4 Respectively.

The criteria for evaluation of etching properties of molybdenum / aluminum double film and indium oxide film are as follows.

- Etching characteristics of molybdenum / aluminum double film

?: No fine residue occurred,

X: Fine residue was generated.

- Etching Characteristics of Indium Oxide Film

O: no residue,

X: Residual occurred.

Etch characteristics Molybdenum / aluminum double layer Indium oxide film Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Example 5 ○ ○ Example 6 ○ ○ Example 7 ○ ○ Example 8 ○ ○ Example 9 ○ ○ Example 10 ○ ○ Comparative Example 1 × × Comparative Example 2 × ×

In the etchant composition of Comparative Example 1, a residue of a fine molybdenum oxide film was formed when the molybdenum / aluminum double layer was etched (see FIG. 3), and the etchant composition of Comparative Example 2 containing oxalic acid produced a residue of the indium oxide film ).

However, as shown in Table 2, residue (minute residue) was not generated when the molybdenum / aluminum double film and the indium oxide film were etched with the etching liquid compositions according to the present invention (Examples 1 to 10). This fact can be confirmed also in Fig. 1 (surface SEM image of the molybdenum / aluminum double film etched with the etching liquid composition of Example 1) and Fig. 2 (surface SEM image of the indium oxide film etched with the etching liquid composition of Example 1). Therefore, it can be seen that the etching solution of the present invention exhibits excellent etching properties for molybdenum / aluminum and indium oxide films.

1 is a scanning electron microscope (SEM) image of an entire surface of a molybdenum / aluminum double-layer film etched using the etchant composition according to Example 1 of the present invention,

2 is an electron micrograph of the surface of the indium oxide film etched using the etchant composition according to Example 1 of the present invention,

3 is a scanning electron microscope (SEM) image of an entire surface of a molybdenum / aluminum double-layer film etched using the etchant composition according to Comparative Example 1 of the present invention,

4 is an electron micrograph of the surface of the indium oxide film etched using the etchant composition according to Comparative Example 2 of the present invention.

Claims (15)

a) forming a gate wiring on the substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the semiconductor layer; And e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of: In the step (a), a molybdenum-based metal / aluminum-based metal double layer is formed on the substrate, and the gate wiring is formed by etching with the etching composition. In step (e), an indium oxide layer is formed, Thereby forming a pixel electrode, The etchant composition, based on the total weight of the composition, A) iron nitrate (Fe (NO ₃ ) ₃ ) 2 to 5% by weight, B) fluorine-containing compound 0.1 to 1% by weight, C) sulfuric acid (H ₂ SO ₄ ) 1 to 15% by weight, D) 0.1 to 5% by weight of tetrazole-based compound, and E) 74 to 96.8% by weight of water. The method according to claim 1, wherein the fluorinated compound is at least one selected from the group consisting of NH ₄ FHF, KFHF, NaFHF, KF, and NaF. The method according to claim 1, d) tetrazole-based compound is 5-aminotetrazole, 1-alkyl-5-aminotetrazole, 5-hydroxy-tetrazole, 1-alkyl-5-hydroxy-tetrazole, tetrazole- A method for producing an array substrate for a liquid crystal display device, characterized in that it is one kind or a mixture of two or more kinds selected from the group consisting of 5-thiol and 1-alkyl-tetrazol-5-thiol. The method of manufacturing an array substrate for a liquid crystal display device according to any one of claims 1 to 3, wherein the indium oxide film is an indium zinc oxide film (IZO) or an indium tin oxide film (ITO). The method of manufacturing an array substrate for a liquid crystal display according to any one of claims 1 to 3, wherein the array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate. A) iron oxide (Fe (NO ₃ ) ₃ ), B) Fluorine compounds, C) sulfuric acid (H ₂ SO ₄ ) D) tetrazole compound, and E) An etchant composition of a molybdenum-based metal / aluminum-based metal double membrane and indium oxide film containing water. The etchant composition of claim 6, wherein the fluorine-containing compound is at least one member selected from the group consisting of NH ₄ FHF, KFHF, NaFHF, KF, and NaF. . The etchant composition according to claim 7, wherein the fluorine-containing compound is NH ₄ HF. The method according to claim 6, d) tetrazole-based compound is 5-aminotetrazole, 1-alkyl-5-aminotetrazole, 5-hydroxy-tetrazole, 1-alkyl-5-hydroxy-tetrazole, tetrazole- An etching solution composition of a molybdenum-based metal / aluminum-based metal double film and an indium oxide film, which is selected from the group consisting of 5-thiol and 1-alkyl-tetrazol-5-thiol. The etchant composition according to claim 6, further comprising at least one additive selected from surfactants, metal ion sequestrants or corrosion inhibitors. The etchant composition of claim 6, wherein the indium oxide film is an indium zinc oxide film (IZO) or an indium tin oxide film (ITO). The method according to claim 6, based on the total weight of the composition, A) iron nitrate (Fe (NO ₃ ) ₃ ) 2 to 5% by weight, B) fluorine-containing compound 0.1 to 1% by weight, C) sulfuric acid (H ₂ SO ₄ ) 1 to 15 wt%, D) 0.1-5 wt% of tetrazole-based compound, and E) 74-96.8 wt% of water, wherein the etchant composition comprises molybdenum-based metal / aluminum-based metal double layer and indium oxide layer. I) forming a molybdenum-based metal / aluminum-based metal double-layer on a substrate; II) selectively leaving a photoreactive material on the molybdenum-based metal / aluminum-based metal double layer; And III) Etching the molybdenum-based metal / aluminum-based metal double film comprising the step of etching the molybdenum-based metal / aluminum-based metal double film using the etching liquid composition of any one of claims 6 to 12. I) forming an indium oxide film on a substrate; II) selectively leaving a photoreactive material on the indium oxide film; And III) An etching method of the indium oxide film comprising etching the indium oxide film using the etching solution composition of any one of claims 6 to 12. The etching method according to claim 13 or 14, wherein the photoreactive material is a photoresist material, which is selectively left by an exposure and development process.

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