KR102269325B1 - Etching solution composition for molybdenum-containing layer and manufacturing method of an array substrate for liquid crystal display using the same - Google Patents

Abstract

The present invention relates to an etchant composition for a molybdenum-containing metal film, and more particularly, to an etchant composition for a molybdenum-containing metal film comprising hydrogen peroxide, a fluorine compound, an azole compound, a sulfonic acid, an organic (per) acid and/or an organic acid salt, and water; It relates to a method of manufacturing an array substrate for a liquid crystal display using the same.

Description

Etch composition of molybdenum-containing metal film and manufacturing method of array substrate for liquid crystal display using the same

The present invention relates to an etchant composition for a molybdenum (Mo)-containing metal film and a method for manufacturing an array substrate for a liquid crystal display using the same.

As we enter the information age in earnest, the field of display that processes and displays a large amount of information has developed rapidly, and various flat panel displays have been developed and are in the spotlight.

Examples of such a flat panel display device include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), and an organic light emitting device (Organic Light). Emitting Diodes (OLED), etc., and in particular, liquid crystal display devices are attracting attention because of their characteristics that provide clear images according to excellent resolution, consume less electricity, and make the display screen thin.

A single film of a molybdenum alloy film and an indium oxide film or a multilayer film of a molybdenum alloy film and an indium oxide film is used for a pixel electrode of a liquid crystal display device such as a TFT-LCD. The pixel electrode is generally laminated on a substrate through a method such as sputtering, a photoresist is uniformly applied thereon, and then light is irradiated through a mask engraved with a pattern, and then a photoresist of a desired pattern is formed through development. Next, the pattern is transferred to the metal film under the photoresist by dry or wet etching, and then the unnecessary photoresist is removed by a stripping process, and is completed through a series of lithography processes.

When the molybdenum alloy film and the indium oxide film are etched with the same etchant, the manufacturing process can be simplified, but in general, the molybdenum alloy film has excellent chemical resistance, so wet etching is not easy. There is a problem that the molybdenum alloy film cannot be etched with an oxalic acid-based etchant for this purpose.

As a prior art, Korean Patent Laid-Open Publication No. 10-2014-0025817 discloses 5 to 25% by weight of hydrogen peroxide; 0.1 to 2 wt% of a fluorine compound; 0.001 to 2% by weight of a compound having a sulfonic acid group; 0.1 to 2% by weight of a corrosion inhibitor; 0.01 to 1% by weight of an auxiliary oxidizing agent; Disclosed is an etchant composition for a multilayer of a molybdenum alloy film, an indium oxide film or a molybdenum alloy film and an indium oxide film containing water such that the water stabilizer is 0.1 to 5% by weight and the total weight of the composition is 100% by weight. However, the composition has disadvantages in that the etching rate for the molybdenum alloy film and the indium oxide film is not sufficient, and partial over-etching and the formation of the upper Mo-Ti tip cannot be suppressed.

Republic of Korea Patent Publication No. 10-2014-0025817

The present invention has been devised to solve the above problems,

There is no residue and tip generation in etching a single film of molybdenum (Mo) or a molybdenum alloy, or a multilayer film including the single film and the metal oxide film, and the etchant composition exhibits excellent etching characteristics with an etch profile aims to provide

Another object of the present invention is to provide a method for manufacturing an array substrate for a liquid crystal display using the etchant composition.

The present invention is

with respect to the total weight of the composition,

15 to 25% by weight of hydrogen peroxide (A);

0.1 to 2 wt% of a fluorine compound (B);

0.1 to 1 wt% of an azole compound (C);

0.3 to 1% by weight of sulfonic acid (D);

0.01 to 3% by weight of at least one compound (E) selected from organic (per)acids and organic acid salts; and

It provides an etchant composition for a molybdenum (Mo)-containing metal film, characterized in that it contains the remaining amount of water (F).

Also, 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; In the method of manufacturing an array substrate for a liquid crystal display comprising:

Step e) comprises forming a molybdenum (Mo)-containing metal film on a substrate and etching the molybdenum-containing metal film with the etchant composition of the present invention to form a pixel electrode. A manufacturing method is provided.

The molybdenum (Mo)-containing metal film etchant composition of the present invention includes hydrogen peroxide, a fluorine compound, an azole-based compound, a sulfonic acid, an organic (per) acid and/or an organic acid salt, and water to etch a molybdenum (Mo)-containing metal film. Therefore, it is possible to provide an etchant composition having no residue, uniform, excellent etch profile, and etching characteristics without the occurrence of a tip of the metal film.

In addition, the present invention may provide a method of manufacturing an array substrate for a liquid crystal display using the etchant composition.

The present inventors have prepared an etchant composition that has excellent etching properties for a molybdenum (Mo)-containing metal film, does not cause residue and re-adsorption, and has excellent etching control so that a tip or over-etching does not occur. As a result, the present invention was completed as an etchant composition containing hydrogen peroxide, a fluorine compound, an azole compound, a sulfonic acid, an organic (per) acid, and/or an organic acid salt.

The present invention is

with respect to the total weight of the composition,

15 to 25% by weight of hydrogen peroxide (A);

0.1 to 2 wt% of a fluorine compound (B);

0.1 to 1 wt% of an azole compound (C);

0.3 to 1% by weight of sulfonic acid (D);

0.01 to 3% by weight of at least one compound (E) selected from organic (per)acids and organic acid salts; and

It relates to an etchant composition for a molybdenum (Mo)-containing metal film, characterized in that it contains the remaining amount of water (F).

The molybdenum (Mo)-containing metal film includes molybdenum (Mo) as a component of the film, and is a concept including a single film and a multilayer film having more than a double film. The molybdenum (Mo)-containing metal layer may be a single layer of molybdenum (Mo) or a molybdenum alloy (Mo alloy), or a multilayer layer including the single layer and a metal oxide layer, but is not limited thereto.

Hereinafter, each component constituting the etchant composition of the molybdenum (Mo)-containing metal film of the present invention will be described. However, the present invention is not limited to these components.

(A) hydrogen peroxide

_{Hydrogen peroxide (H 2} O ₂ ) contained in the etchant composition of the molybdenum (Mo)-containing metal film of the present invention is a component used as a main oxidizing agent, and affects the etching rate of the molybdenum-containing metal film.

The hydrogen peroxide (H ₂ O ₂ ) is preferably included in an amount of 15 to 25 wt%, more preferably 18 to 23 wt%, based on the total weight of the etchant composition of the molybdenum (Mo)-containing thin film. When the hydrogen peroxide is contained in an amount of less than 15% by weight, it may cause a decrease in the etching rate of the molybdenum-containing metal layer, and thus sufficient etching may not be performed. On the other hand, when included in an amount exceeding 25% by weight, the stability of the etchant may decrease as the concentration of hydrogen peroxide becomes excessively high, and over-etching may cause problems in the subsequent process, which is not preferable.

(B) fluorine compounds

The fluorine compound included in the etchant composition of the molybdenum (Mo)-containing metal film of the present invention is a compound capable of providing ^{fluoride ions (F − ) by dissociating in water or the like.} The fluorine compound is a dissociating agent that affects the etching rate of the molybdenum-containing metal layer, and serves to control the etching rate of the molybdenum-containing metal layer.

The fluorine compound is not particularly limited as long as it is used in the art, but as a specific example, hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH ₄ F), borate fluoride (NH ₄ BF ₄ ), hydrogen fluoride At least one selected from ammonium (NH ₄ FHF), potassium fluoride (KF), potassium hydrogen fluoride (KHF ₂ ), aluminum fluoride (AlF ₃ ), and tetrafluoroboric acid (HBF ₄ ) may be used, and In terms of preventing damage to silicon dioxide (SiO ₂ ), etc., ammonium fluoride (NH ₄ F) without -HF group may be more preferable.

The fluorine compound is preferably included in an amount of 0.1 to 2 wt%, more preferably 0.5 to 1.5 wt%, based on the total weight of the etchant composition of the molybdenum (Mo)-containing metal film of the present invention. When the content of the fluorine compound is less than 0.1 wt%, the etching rate of the molybdenum-containing metal film is lowered, and when it exceeds 2 wt%, the etching performance of the molybdenum-containing metal film is improved, but etching damage of the silicon (Si)-based lower layer (damage) may appear large.

(C) azole compound

The azole-based compound included in the etchant composition of the molybdenum (Mo)-containing metal film of the present invention serves to control the etching rate of data lines such as copper that come into contact with the molybdenum-containing metal film and the metal oxide film.

The azole-based compound is not particularly limited as long as it is used in the art, but as a specific example, pyrrole-based, pyrazole-based, imidazole-based, triazole-based, tetrazole )-based, pentaazole-based, oxazole-based, isoxazole-based, diazole-based and isodiazole-based compounds, and the like, are listed. or two or more of them may be used together. Among them, a triazole-based compound is more preferable, and as a specific example, benzotriazole may be more preferable.

The azole-based compound is included in an amount of 0.1 to 1 wt%, more preferably 0.2 to 0.8 wt%, based on the total weight of the etchant composition of the molybdenum (Mo)-containing metal film of the present invention. When the azole-based compound is included in an amount of less than 0.1 wt%, the etching rate for wiring such as copper increases and the attack prevention effect is reduced. When the azole-based compound is included in an amount exceeding 1 wt%, the molybdenum (Mo)-containing metal film and the metal oxide film The etching rate may decrease, which may cause problems such as a long process time.

(D) sulfonic acid

The sulfonic acid (D) contained in the etchant composition of the molybdenum (Mo)-containing metal film of the present invention has an acidity similar to that of sulfuric acid, and is much stronger than that of carboxylic acids such as acetic acid, so by adjusting the pH of the etchant By increasing the activity of hydrogen peroxide, it plays a role in controlling the etching of the molybdenum-containing metal film, and minimizes the change rate of side etch when the number of sheets is processed.

The sulfonic acid may be included in an amount of 0.3 to 1% by weight, preferably 0.5 to 0.8% by weight, based on the total weight of the etchant composition of the molybdenum (Mo)-containing metal film of the present invention. When the content of the sulfonic acid is less than 0.3 wt %, the etching rate is lowered, and the effect of the change rate of the number of treatment sheets is not affected. On the other hand, when it is included in an amount exceeding 1 wt %, the etch rate becomes excessively high, resulting in pattern loss.

(E) organic (per) acids and from organic acid one or more compounds selected

The organic (per)acid and / or organic acid salt contained in the etchant composition of the molybdenum (Mo)-containing metal film of the present invention is a molybdenum-containing metal film, that is, a single film of molybdenum (Mo) or a molybdenum alloy (Mo alloy), or the single It acts as an oxidation regulator of a multilayer film composed of a film and a metal oxide film. As used above, the organic (per) acid means an organic acid, an organic per acid, or both.

In etching the multilayer film, the molybdenum (Mo)-containing metal film has a tip or undercut shape due to the difference in etching rate between the molybdenum or molybdenum alloy film and the metal oxide film. The organic (per)acid and/or organic acid salt serves to prevent these tips or undercuts from being formed.

The organic (per) acid and/or organic acid salt included in the etchant composition of the present invention may be understood as an organic (per) acid and/or a salt thereof, and as a specific example of the organic (per) acid, peracetic acid (peracetic Acid) , perbenzoic acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid acid), pentanoic acid, and oxalic acid, and the like, but are not limited thereto, and at least one selected therefrom may be used.

The organic acid salt may be at least one selected from the above-described potassium salt, sodium salt, and ammonium salt of the organic (per)acid, but is not limited thereto.

The at least one compound (E) selected from the organic (per)acid and organic acid salt may be included in an amount of 0.01 to 3% by weight based on the total weight of the etchant composition of the molybdenum (Mo)-containing metal film of the present invention, more preferably 0.01 to 1% by weight, more preferably 0.05 to 0.7% by weight may be included. When the content of organic (per)acid and/or organic acid salt is less than 0.01 wt%, it is impossible to control the etching rate of the metal oxide film, and when it exceeds 3 wt%, the etching rate is significantly slowed down, the process progresses, and excellent etching effect hard to get

(F) water

The water contained in the etchant composition of the molybdenum (Mo)-containing metal film of the present invention is not particularly limited, but it is preferable to use deionized water for semiconductor processing, and the specific resistance value showing the degree of ion removal in the water is 18 ㏁ / cm It is more preferable to use more than deionized water.

The water is included in the remaining amount such that the total weight of the etchant composition of the molybdenum (Mo)-containing metal film of the present invention is 100% by weight.

The molybdenum (Mo)-containing metal film etchant composition of the present invention contains, in addition to the above-mentioned components, at least one selected from an etch control agent, a surfactant, a metal ion sequestrant, a corrosion inhibitor, a pH adjuster, and other additives, but not limited thereto. may additionally include. The additive may be selected from additives commonly used in the art in order to further improve the effects of the present invention within the scope of the present invention.

The etchant composition of the molybdenum (Mo)-containing metal film of the present invention preferably has a purity for a semiconductor process, and each component can be prepared by a commonly known method.

The molybdenum (Mo)-containing metal film to which the etching solution composition of the molybdenum (Mo)-containing metal film of the present invention is applied includes molybdenum (Mo) as a component of the film, and a single film of molybdenum (Mo) or a molybdenum alloy, or the single film and a multilayer film composed of a film and a metal oxide film, but is not limited thereto.

The molybdenum-containing metal film is not particularly limited, but as a specific example, a molybdenum (Mo) film, molybdenum as a main component, neodinium (Nd), tantalum (Ta), indium (In), 1 selected from copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni), chromium (Cr), magnesium (Mg), tungsten (W), protactinium (Pa) and titanium (Ti), etc. a single film such as a molybdenum alloy film containing more than one kind of metal; a multilayer film composed of the single film and the metal oxide film; and the like. The metal oxide film contains a ternary or quaternary oxide composed of a combination of AxByCzO (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, y, z≥0). As the constituted film, it can be used as a pixel electrode. Specific examples of the metal oxide film include indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), or indium zinc oxide gallium (IGZO), but is not limited thereto.

As a more specific example of the multilayer film, indium oxide film / molybdenum (Mo) or indium oxide film / double film such as molybdenum alloy (molybdenum alloy), indium oxide film / molybdenum (Mo) / indium oxide film or indium oxide film / molybdenum alloy / indium oxide film, etc. of a triple membrane, and the like, but is not limited thereto.

Also, the present invention

(1) forming a molybdenum (Mo)-containing metal film on a substrate;

(2) selectively leaving a photoreactive material on the molybdenum-containing metal film; and

(3) It relates to an etching method of a molybdenum-containing metal film comprising the step of etching the molybdenum-containing metal film using the molybdenum-containing metal film etchant 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 a conventional exposure and development process.

Also, 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 an oxide semiconductor layer on the gate insulating layer;

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

e) forming a pixel electrode connected to the drain electrode; In the method of manufacturing an array substrate for a liquid crystal display comprising:

Step e) comprises forming a molybdenum (Mo)-containing metal film on a substrate and etching the molybdenum-containing metal film with the etchant composition of the present invention to form a pixel electrode. A manufacturing method is provided.

The array substrate for the liquid crystal display may be a thin film transistor (TFT) array substrate.

The molybdenum-containing metal film may be a single film of molybdenum (Mo) or a molybdenum alloy, or a multilayer film composed of the single film and a metal oxide film, and the molybdenum alloy has molybdenum (Mo) as a main component, and neodymium (Nd) , tantalum (Ta), indium (In), 1 selected from copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni), chromium (Cr), magnesium (Mg), tungsten (W), protactinium (Pa) and titanium (Ti), etc. It may be in the form of an alloy including more than one type of metal.

Specific examples of the metal oxide film may include indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), or indium zinc oxide gallium (IGZO), but is not limited thereto.

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, and may be variously modified and changed. The scope of the present invention will be determined by the spirit of the claims to be described later.

< Example and comparative example > etchant Preparation of the composition

6 kg of the etchant compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared with the composition and content shown in Table 1 below, respectively.

(weight%) division hydrogen peroxide preservative Fluorinated compounds Compounds containing sulfonic acid groups oxidation regulator water Example 1 18 BTA 0.3 AF 0.5 MSA 0.7 AA 0.1 remaining amount Example 2 18 BTA 0.3 AF 0.5 MSA 0.7 GA 0.1 remaining amount Example 3 20 BTA 0.5 AF 0.7 MSA 0.5 AA 0.3 remaining amount Example 4 20 BTA 0.5 AF 0.7 MSA 0.5 GA 0.3 remaining amount Example 5 23 BTA 0.8 AF 1.0 MSA 0.8 AA 0.5 remaining amount Example 6 18 BTA 0.5 AF 1.0 MSA 0.7 CA 0.2 remaining amount Example 7 20 BTA 0.5 AF 1.0 MSA 0.7 MA 0.2 remaining amount Example 8 20 BTA 0.8 AF 0.7 MSA 1.0 CA 0.5 remaining amount Example 9 23 BTA 0.8 AF 0.7 MSA 1.0 MA 0.5 remaining amount Comparative Example 1 18 BTA 0.3 AF 0.5 MSA 0.7 - - remaining amount Comparative Example 2 20 BTA 0.5 AF 0.7 MSA 0.5 AA 3.2 remaining amount Comparative Example 3 23 BTA 0.8 AF 1.0 MSA 0.8 - - remaining amount Comparative Example 4 23 BTA 0.8 AF 1.0 MSA 0.8 AA 5.0 remaining amount Comparative Example 5 20 BTA 0.5 AF 1.0 MSA 0.8 GA 3.5 remaining amount Comparative Example 6 18 BTA 0.5 AF 1.0 MSA 0.8 MA 4.0 remaining amount

week)

BTA: benzotriazole

AF: Ammonium Fluoride

MSA: methanesulfonic acid

AA: ammonium acetate

GA: Glycolic acid

CA: citric acid

MA: malonic acid

< Experimental example > etchant Performance testing of the composition

Depositing an insulating film on a substrate (SiO ₂ ), and depositing a molybdenum-titanium alloy film, indium tin oxide film (a-ITO) or Mo-Ti/a-ITO (100/400 Å) film thereon with a diamond knife A specimen was prepared by cutting it to 500 X 600 mm using

Using the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 6, performance tests were performed as follows.

Experimental example One. residue Measure

Each of the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 6 was put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), SEMES), and the temperature was set to 35 ° C. When the temperature reached 35±0.1° C., the etching process of the specimen was performed. The total etching time may vary depending on the etching temperature, but the molybdenum-based metal film (Mo-Ti alloy film), metal oxide film (a-ITO film), and Mo-Ti/a-ITO (100/400 Å) film are used for LCD etching. The process proceeded for about 80 to 100 seconds normally.

After inserting the substrate and starting spraying, when the etching time of 100 seconds is over, it is taken out, washed with deionized water, dried using a hot air dryer, and the photoresist is removed using a photoresist stripper (PR stripper). After washing and drying, using a scanning electron microscope (SEM; model name: S-4700, manufactured by HITACHI), the residue, which is a phenomenon in which molybdenum (Mo) is not etched on the part not covered with the photoresist, is measured, and the following Evaluated as a reference, the results are shown in Table 2 below.

<Residue Evaluation Criteria>

No residue: X

Residue generation: O

Experimental example 2. Mo - Ti /a-ITO double membrane Tip occurrence evaluation

Each of the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 6 was put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), SEMES), and the temperature was set to 35 ° C. When the temperature reached 35±0.1° C., the etching process of the specimen was performed. The total etching time may vary depending on the etching temperature, but the Mo-Ti/a-ITO (100/400 Å) film was generally performed for about 80 to 100 seconds in the LCD etching process.

After inserting the substrate and starting spraying, when the etching time of 100 seconds is over, it is taken out, washed with deionized water, and dried using a hot air dryer. After washing and drying, the substrate was cut and the cross-section was measured using a scanning electron microscope (SEM; model name: S-4700, manufactured by HITACHI).

Experimental example 3. unilateral etching (Side Etch) change amount measurement

Each of the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 6 was put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), SEMES), and the temperature was set to 35 ° C. When the temperature reached 35±0.1° C., the etching process of the specimen was performed. The total etching time may vary depending on the etching temperature, but the molybdenum-based metal film (Mo-Ti alloy film), metal oxide film (a-ITO film), and Mo-Ti/a-ITO (100/400 Å) film are used for LCD etching. The process proceeded for about 80 to 100 seconds normally.

After inserting the substrate and starting spraying, when the etching time of 100 seconds is over, it is taken out, washed with deionized water, and dried using a hot air dryer. After washing and drying, the substrate was cut and the cross-section was measured using a scanning electron microscope (SEM; model name: S-4700, manufactured by HITACHI).

<Evaluation criteria>

0.01 μm or less: good

division Molybdenum Titanium
alloy film residue indium tin oxide film
residue generation Double membrane Mo-Ti tips
Occurrence One-sided etching change Example 1 x x x 0.01㎛ Example 2 X X X 0.01㎛ Example 3 X X X 0.01㎛ Example 4 X X X 0.01㎛ Example 5 X X X 0.01㎛ Example 6 x x x 0.01㎛ Example 7 X X X 0.01㎛ Example 8 X X X 0.01㎛ Example 9 X X X 0.01㎛ Comparative Example 1 X X O 0.17㎛ Comparative Example 2 X O X 0.19㎛ Comparative Example 3 X X O 0.15㎛ Comparative Example 4 X O X 0.20㎛ Comparative Example 5 X O X 0.20㎛ Comparative Example 6 X O X 0.15㎛

As described in Table 2, it can be confirmed that the etchant compositions of Examples 1 to 9 not only do not generate residues, but also do not generate tips by exhibiting good properties in side etch. there was.

In more detail, when the Mo-Ti / a-ITO metal film was etched using the etchant composition of Example 5, a tip of the double film did not occur, and the number of treatments was evaluated from 0 to 2000 ppm and measured by SEM. As a result, it was found that the change in side etching was 0.01 μm, which was improved compared to 0.20 μm in Comparative Example 5 including an excess of oxidation regulator.

Referring to Table 2, the compositions of Examples 1 to 9 according to the present invention did not leave a residue around the pattern after the etching process, it was confirmed that the molybdenum titanium tip does not occur. On the other hand, in the compositions of Comparative Examples 1 and 3, molybdenum titanium tips were generated, and in the compositions of Comparative Examples 2, 4, 5, and 6, it was confirmed that residues were generated in the indium tin oxide film.

The above results show that when etching a molybdenum-titanium alloy film and a metal oxide film used as an electrode of a TFT-LCD display, when the etchant composition of the present invention is used, the double film residue and the tip characteristics of the double film are excellent, resulting in a TFT-LCD display profile It shows that this can be improved.

Claims (11)

with respect to the total weight of the composition,
15 to 25% by weight of hydrogen peroxide (A);
0.1 to 2 wt% of a fluorine compound (B);
0.1 to 1 wt% of an azole compound (C);
0.3 to 1% by weight of sulfonic acid (D);
0.1 to 0.5% by weight of at least one compound (E) selected from organic (per)acids and organic acid salts; and the remaining amount of water (F),
An etchant composition for a molybdenum (Mo)-containing metal film, characterized in that it can etch a single film made of molybdenum or a molybdenum alloy and a multilayer film made of a metal oxide film. delete The method according to claim 1,
The metal oxide film is a molybdenum (Mo) containing metal film, characterized in that at least one selected from indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO) and indium gallium zinc oxide (IGZO) etchant composition. The method according to claim 1,
The multilayer film composed of the single film and the metal oxide film is an indium oxide film / molybdenum, an indium oxide film / molybdenum alloy, an indium oxide film / molybdenum / indium oxide film, or an indium oxide film / molybdenum alloy / indium oxide film Molybdenum (Mo) containing metal, characterized in that The etchant composition of the membrane. The method according to claim 1,
The molybdenum alloy is molybdenum (Mo), neodymium (Nd), tantalum (Ta), indium (In), copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni), chromium (Cr) , magnesium (Mg), tungsten (W), protactinium (Pa) and titanium (Ti), characterized in that it comprises at least one selected from the molybdenum (Mo)-containing metal film etchant composition. The method according to claim 1,
The fluorine compound is hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH ₄ F), borate fluoride (NH ₄ BF ₄ ), ammonium hydrogen fluoride (NH ₄ FHF), Potassium fluoride (KF), potassium hydrogen fluoride (KHF ₂ ), aluminum fluoride (AlF ₃ ) and tetrafluoroboric acid (HBF ₄ ) Etch solution composition for a molybdenum (Mo)-containing metal film, characterized in that at least one selected from the group consisting of. The method according to claim 1,
The azole-based compound is a pyrrole-based, pyrazole-based, imidazole-based, triazole-based, tetrazole-based, pentaazole-based, oxazole-based compound )-based, isoxazole-based, diazole-based and isodiazole-based compounds, characterized in that at least one selected from the molybdenum (Mo)-containing metal film etchant composition. The method according to claim 1,
The organic (per) acid is peracetic acid, perbenzoic acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid , glycolic acid (glycolic acid), malonic acid (malonic acid), pentanoic acid (pentanoic acid) and at least one selected from oxalic acid (oxalic acid),
The organic acid salt is an etchant composition for a molybdenum (Mo)-containing metal film, characterized in that at least one selected from potassium salt, sodium salt and ammonium salt of the organic (per) acid. a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming an oxide semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the oxide semiconductor layer; and
e) forming a pixel electrode connected to the drain electrode; In the method of manufacturing an array substrate for a liquid crystal display comprising:
Step e) comprises forming a multilayer film consisting of a single film and a metal oxide film made of molybdenum or a molybdenum alloy on a substrate, and etching with the etchant composition of the molybdenum-containing metal film of claim 1 to form a pixel electrode. A method of manufacturing an array substrate for a liquid crystal display, characterized in that. 10. The method of claim 9,
The method of manufacturing an array substrate for a liquid crystal display, characterized in that the array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate. An array substrate for a liquid crystal display device manufactured by the manufacturing method of any one of claims 9 to 10.