KR102459681B1 - Etchant for cupper-based metat layer, manufacturing method of an array substrate for liquid crystal display using the same and an array substrate for liquid crystal display - Google Patents

Abstract

The present invention relates to (A) 15 to 25 wt% of hydrogen peroxide, (B) 0.01 to 1.0 wt% of a fluorine compound, (C) 0.05 to 3.0 wt% of an azole compound, (D) 0.5 to a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule to 5.0 wt%, (E) 0.05 to 5.0 wt% of an acid or salt containing sulfur, (F) 1.0 to 5.0 wt% of a polyalcohol-type surfactant, and an etchant composition for a copper-based metal film comprising the remaining amount of water, and using the same It provides a method of manufacturing an array substrate for a liquid crystal display device and an array substrate for a liquid crystal display device.

Description

An etchant composition for a copper-based metal film, a method for manufacturing an array substrate for a liquid crystal display using the same, and an array substrate for a liquid crystal display using the same ARRAY SUBSTRATE FOR LIQUID CRYSTAL DISPLAY}

The present invention relates to an etchant composition, a method for manufacturing an array substrate for a liquid crystal display using the same, and an array substrate for a liquid crystal display.

The process of forming a metal wiring on a substrate in a semiconductor device is usually composed of a metal film formation process by sputtering, etc., a photoresist formation process in a selective area by photoresist application, exposure and development, and an etching process, It includes a cleaning process before and after each unit process, and the like. Such an 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 etchant composition is used.

In such a semiconductor device, the resistance of metal wiring has recently emerged as a major concern. This is because resistance is a major factor inducing RC signal delay, and in particular, in the case of TFT-LCD (thin film transistor-liquid crystal display), an increase in panel size and realization of high resolution are key to technology development. Therefore, in order to realize the reduction of the RC signal delay, which is essential for the enlargement of the TFT-LCD, it is essential to develop a low-resistance material. Therefore, the gate and data metal wiring of a large display uses copper metal, which has low resistance and has no environmental problems compared to conventional aluminum and chromium wiring, and copper has low adhesion to the glass substrate and silicon insulating film and is diffused into the silicon film. Since there is a problem, titanium, molybdenum, etc. are used as the lower barrier metal.

However, copper-based etchant compositions known to date do not satisfy the performance required by users. For example, in the case of etching a multilayer metal film using a conventional copper film etching solution containing hydrogen peroxide and a fluorine-containing compound, as the concentration of dissolved metal ions increases, the etching rate of the copper layer by hydrogen peroxide and the molybdenum alloy by the fluorine-containing compound There is a problem in that there is a difference in the etching rate of the layers, and deformation of the interface at which the two metal layers are bonded occurs due to the influence of the electric effect, so that the etching characteristics are not good.

Korean Patent Application Laid-Open No. 10-2010-0090538 discloses an etchant composition for a copper-based metal film comprising hydrogen peroxide and a fluorine-containing compound. However, when the gate electrode and the first and second source/drain electrodes are batch etched using the etchant composition, damage to the glass substrate is caused by the fluorine-containing compound, so it cannot contain more than a certain amount of the fluorine-containing compound, and the glass When the damage to the substrate is minimized, there is a problem in that the amount of etching for the silicon-based active layer positioned under the first and second source/drain electrodes is insufficient, so that residues are generated.

Republic of Korea Patent Publication No. 10-2010-0090538

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

In addition to the copper-based metal thin film and thick film, the gate electrode, the first and second source/drain electrodes can be etched at once, and in particular, the first and second sources while minimizing damage to the glass substrate positioned under the gate electrode / An object of the present invention is to provide an etchant composition having excellent etching properties for the silicon-based active layer located under the drain electrode.

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

The present invention is

Based on the total weight of the composition, (A) 15 to 25% by weight of hydrogen peroxide, (B) 0.01 to 1.0% by weight of a fluorine compound, (C) 0.05 to 3.0% by weight of an azole compound, (D) having a nitrogen atom and a carboxyl group in one molecule An etchant composition for a copper-based metal film comprising 0.5 to 5.0% by weight of a water-soluble compound, (E) 0.05 to 5.0% by weight of an acid or salt containing sulfur, (F) 1.0 to 5.0% by weight of a polyalcohol-type surfactant, and the remainder of water provides

In addition, 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) a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,

At least one of step a) or step d) comprises laminating a copper-based metal film on the substrate, and etching using an etchant composition,

The etchant composition is, (A) 15 to 25% by weight of hydrogen peroxide, (B) 0.01 to 1.0% by weight of a fluorine compound, (C) 0.05 to 3.0% by weight of an azole compound, (D) Water-soluble having a nitrogen atom and a carboxyl group in one molecule A liquid crystal display comprising 0.5 to 5.0% by weight of the compound, (E) 0.05 to 5.0% by weight of an acid or salt containing sulfur, (F) 1.0 to 5.0% by weight of a polyalcohol-type surfactant, and the remainder of water A method of manufacturing an array substrate for use is provided.

In addition, the present invention,

It provides an array substrate for a liquid crystal display including at least one of a gate electrode, a source electrode, and a drain electrode etched using the etchant composition of the present invention.

The etchant composition of the present invention is capable of batch etching the gate electrode, the first and second source/drain electrodes, and minimizes damage to the glass substrate by including a fluorine compound and an acid or salt containing sulfur while minimizing damage to the lower barrier metal layer. It provides the effect of having excellent etching characteristics.

Therefore, the etchant composition may be usefully used for etching an array substrate for a liquid crystal display used for realization of a high resolution.

Hereinafter, the present invention will be described in more detail.

The present invention relates to the total weight of the composition, (A) 15 to 25% by weight of hydrogen peroxide, (B) 0.01 to 1.0% by weight of a fluorine compound, (C) 0.05 to 3.0% by weight of an azole compound, (D) a nitrogen atom in one molecule Copper-based metal containing 0.5 to 5.0% by weight of a water-soluble compound having a carboxyl group, (E) 0.05 to 5.0% by weight of an acid or salt containing sulfur, (F) 1.0 to 5.0% by weight of a polyalcohol-type surfactant, and the remainder of water It relates to a film etchant composition.

An object of the present invention is to provide an etchant composition capable of collectively etching a gate electrode and first and second source/drain electrodes, and in the case of such a batch etching, silicon positioned under the first and second source/drain electrodes Since it is necessary to etch the active layer of the series, the etchant composition used at this time contains a fluorine compound. However, the fluorine compound has a great effect on the glass substrate positioned under the gate electrode, and if the etching damage to the glass substrate is large, it is impossible to reuse it, so it is necessary to minimize the etching. In this case, the problem of etching damage to the glass substrate can be solved by minimizing the content of the fluorine compound, but the amount of etching for the active layer located under the first and second source/drain electrodes is insufficient, so cannot be unconditionally minimized.

The inventors of the present invention, when using an etchant composition containing a fluorine compound and an acid or salt containing sulfur together, sufficient etching of the active layer is possible even using a relatively small amount of the fluorine compound, and The present invention was completed by experimentally confirming that damage could be prevented.

The copper-based metal film includes copper (Cu) as a component of the film, and is a concept including a single film and a multilayer film having more than a double film. In more detail, the copper-based metal film may include a single film of copper or a copper alloy (Cu alloy); Or it is a concept including a multilayer film including one or more films selected from the copper film and the copper alloy film and one or more films selected from a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film, wherein the alloy film is a nitride film or an oxide film concept that includes

As the single film, the copper-based metal film has a copper (Cu) film or copper as a main component, and includes aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), and manganese. (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), at least one selected from tantalum (Ta) and tungsten (W) A copper alloy film containing a metal, etc. are mentioned.

Further, examples of the multilayer film include a double film such as a copper/molybdenum film, a copper/molybdenum alloy film, a copper alloy/molybdenum film, a copper alloy/molybdenum alloy film, or a molybdenum/copper/molybdenum triple film, a molybdenum alloy/copper/molybdenum alloy. A triple film, a molybdenum alloy/copper alloy/molybdenum alloy triple film, etc. are mentioned. The copper / molybdenum alloy film means comprising a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, and the copper alloy / molybdenum alloy film includes a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer. This means that the copper/titanium film includes a titanium layer and a copper layer formed on the titanium layer. In particular, the etchant composition of the present invention may be preferably used in the multilayer film exemplified above, and specifically may be more preferably used in a multilayer film consisting of a copper or copper alloy film and a molybdenum or molybdenum alloy film.

In addition, the molybdenum (Mo) alloy film includes, for example, one or more metals selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In); It means a layer made of an alloy of molybdenum.

Hereinafter, the components of the etchant composition of the present invention will be described in detail.

A) hydrogen peroxide (H ₂ O ₂ )

Hydrogen peroxide (H ₂ O ₂ ) included in the etchant composition of the present invention is a copper molybdenum film or a molybdenum alloy layer including a molybdenum layer and a copper layer formed on the molybdenum layer and a copper layer formed on the molybdenum alloy layer. It is a main oxidizing agent that affects the etching of a copper-based metal film, which is a copper molybdenum alloy film.

The hydrogen peroxide is included in an amount of 15 to 25.0 wt%, preferably 18.0 to 23.0 wt%, based on the total weight of the composition. When included in less than the above range, the etching rate for the copper-based metal film and the molybdenum-based metal film is slow, so it is difficult to perform sufficient etching. is reduced

B) Fluorine compounds

The fluorine compound refers to a compound capable of dissociating in water to generate F ions, and as an auxiliary oxidizing agent that affects the etching rate of the molybdenum alloy film, controls the etching rate of the molybdenum alloy film, and also controls the etching of the silicon-based layer.

The fluorine compound is not particularly limited as long as it is used in the art, but HF, NaF, NH ₄ F, NH ₄ BF ₄ , NH ₄ HF ₂ (ammonium bifluoride; ABF), KF, KHF ₂ , AlF _{3 ,} and HBF ₄ It is preferable that at least one selected from the group consisting of NH ₄ F, NH ₄ HF ₂ and the like are more preferable in terms of damage to the silicon-based lower layer.

The fluorine compound is included in an amount of 0.01 to 1.0% by weight, preferably 0.05 to 0.2% by weight, based on the total weight of the composition. When included in less than the above range, the etching rate of the molybdenum-based metal film and the metal oxide film is slowed, so that sufficient etching is difficult to be made. Therefore, undercut phenomenon or damage to the silicon-based lower layer is large.

C) azole compounds

The azole compound controls the etching rate of the copper-based metal layer and reduces the CD loss of the pattern, thereby increasing the margin in the process.

The azole compound includes a triazole-based compound; Aminotetrazole-based compound, pyrrole-based compound, pyrazol-based compound, imidazole-based compound, tetrazole-based compound, pentazole-based compound, oxazole It is preferably at least one selected from the group consisting of (oxazole)-based compounds, isoxazole-based compounds, diazole-based compounds, and isothiazole-based compounds.

The azole compound is included in an amount of 0.05 to 3.0 wt%, preferably 0.05 to 1.0 wt%, based on the total weight of the composition. When included below the above range, the amount of etch bias variation increases as the number of processing increases. When included in excess of the above-described range, there is a problem in that the etching rate for the metal layer is reduced or not etched.

D) Water-soluble compounds having a nitrogen atom and a carboxyl group in one molecule

The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule prevents the self-decomposition reaction of hydrogen peroxide that may occur during storage of the etchant composition, and prevents the etching characteristics of the etchant composition from changing when a large number of substrates are etched.

In general, in the case of an etchant composition using hydrogen peroxide, the storage period is not long due to the self-decomposition reaction of hydrogen peroxide, and in some cases, there is a risk that the storage container may explode. However, in the case of an etchant composition containing a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, the decomposition rate of hydrogen peroxide is reduced by nearly 10 times, which is advantageous in securing storage period and stability. In particular, when a large amount of copper ions remain in the etchant composition when the copper layer is etched, a passivation film may be formed and may not be etched any more. However, by adding a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, phenomenon can be prevented.

The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid ) and at least one selected from the group consisting of sarcosine, and among them, iminodiacetic acid is most preferred.

The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is included in an amount of 0.5 to 5.0 wt%, preferably 1.0 to 3.0 wt%, based on the total weight of the composition. When included below the above-mentioned range, the concentration of the etchant can be reduced, so that the etching may be non-uniform even at low copper ions. When the content exceeds the above-described range, there is a problem in that the etching rate for the molybdenum-titanium alloy film quality of the lower film is reduced and residues are generated.

E) acids or salts comprising sulfur

The sulfur-containing acid or salt etches the active layer together with the fluorine compound when the first and second source/drain electrodes are etched. In addition, it is a component that increases the etching rate of the copper film by controlling the oxidation potential of the copper surface. If the sulfur-containing acid or salt is not included, the etching rate is very low and the etching profile may be poor.

The acid or salt containing sulfur is ammonium sulfate, sulfamic acid, methanesulfonic acid, p-Toluenesulfonic acid, magnesium sulfate, and lithium sulfate. (Lithium sulfate) is preferably at least one selected from the group consisting of.

The acid or salt containing sulfur is included in an amount of 0.05 to 5.0% by weight, preferably 1.0 to 3.0% by weight, based on the total weight of the composition. When included below the above-mentioned range, the etching rate is very low, and an etch profile defect and process time loss may occur. When included in excess of the above range, the etching rate of the copper or copper alloy film is too fast or the taper angle is too high, which makes it vulnerable to poor step coverage, so it is difficult to apply a thick film.

F) Polyhydric Alcohol Type Surfactant

The polyalcohol-type surfactant serves to increase the uniformity of the etching by reducing the surface tension. In addition, the polyalcohol-type surfactant suppresses the activity of copper ions by surrounding copper ions dissolved in the etchant after etching the copper film, thereby suppressing the decomposition reaction of hydrogen peroxide. If the activity of copper ions is lowered in this way, the process can be performed stably while using the etchant. In particular, it functions to prevent heat generation of the etchant by the above mechanism.

At least one selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol may be used as the polyol alcohol-type surfactant, and preferably triethylene glycol may be used. have.

The polyalcohol-type surfactant is included in an amount of 1.0 to 5.0% by weight, preferably 1.5 to 3.0% by weight, based on the total weight of the composition. When included in less than the above-mentioned range, there may be problems in that the etching uniformity is lowered and the decomposition of hydrogen peroxide is accelerated. When included in excess of the above-mentioned range, there is a problem that a lot of bubbles are generated.

G) water

Water contained in the copper-based metal film etchant composition of the present invention is included in the remaining amount so that the total weight of the composition is 100% by weight. The water is not particularly limited, but deionized water is preferably used. In addition, as the water, it is more preferable to use deionized water having a specific resistance value of 18 MΩ·cm or more, which shows the degree of removal of ions in the water.

In addition, conventional additives may be further added in addition to the above-described components, and examples of the additive include a metal ion sequestrant and a corrosion inhibitor.

Each component used in the present invention can be prepared by a conventionally known method, and the etchant composition of the present invention preferably has a purity for semiconductor processing.

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

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) a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,

At least one of step a) or step d) comprises laminating a copper-based metal film on the substrate, and etching using an etchant composition,

The etchant composition is, (A) 15 to 25% by weight of hydrogen peroxide, (B) 0.01 to 1.0% by weight of a fluorine compound, (C) 0.05 to 3.0% by weight of an azole compound, (D) Water-soluble having a nitrogen atom and a carboxyl group in one molecule 0.5 to 5.0% by weight of the compound, (E) 0.05 to 5.0% by weight of an acid or salt containing sulfur, (F) 1.0 to 5.0% by weight of a polyalcohol-type surfactant, and the balance of water.

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

The present invention also provides an array substrate for a liquid crystal display including at least one of a gate wiring, a source electrode, and a drain electrode etched using the etchant composition.

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.

Examples 1 to 7 and Comparative Examples 1 to 3: Preparation of etchant composition

The etchant compositions of Examples 1 to 8 and Comparative Examples 1 to 12 were prepared according to the compositions and contents shown in Table 1 below.

[Table 1]

(Unit: % by weight)

ABF: ammonium bifluoride, NH ₄ HF ₂

ATZ: 5-aminotetrazole

IDA: iminodiacetic acid

TEG: triethylene glycol

AS: Ammonium Sulfate

SA: sulfamic acid

MSA: methanesulfonic acid

PTSA: para-toluenesulfonic acid

AN: ammonium nitrate

AP: Ammonium Phosphate

PA: phosphoric acid

DI: deionized water

Experimental Example: Evaluation of etching properties of etchant composition

The etching process was performed using the etchant compositions of Examples 1 to 8 and Comparative Examples 1 to 12, respectively.

Experimental equipment (model name: ETCHER (TFT), SEMES Co., Ltd.) of the spray-type etching method was used, and the temperature of the etchant composition during the etching process was about 32°C. The etching time may vary depending on the etching temperature, but in the LCD etching process, it was usually performed for about 100 to 200 seconds. The etching degree of the silicon-based film etched in the etching process was checked using a contact-type step measuring instrument (Dektak, 6M), and the cross-section of the profile of the copper-based metal film etched in the etching process was SEM (made by Hitachi, model name S-) 4700) was used.

For the silicon-based film used in the etching process, a glass substrate and an Acitvie layer, a 2,000 Å thin film substrate was used, and each substrate was etched by fixing it for 200 seconds, and the results are shown in Table 2 below.

[Table 2]

<Active layer etching evaluation criteria>

○: etching degree 310Å or more,

△: the degree of etching is 290 Å or more, less than 310 Å,

Х: The degree of etching is less than 290 Å

<Taper angle evaluation criteria>

○: a taper angle of 40° or more to 50° or less,

Х: Taper angle less than 40° or greater than 50°

Referring to Table 2, in the etching solution compositions of Examples 1 to 8 according to the present invention, it was confirmed that the amount of etching for the active layer selectively increased as the content of the acid or salt containing sulfur increased. In particular, when comparing the etchant composition of Examples 1 to 8 and Comparative Example 2 in which the remaining components except for the acid or salt containing sulfur are the same, the etching amount on the glass substrate is not significantly affected, but the active layer It can be seen that the amount of etching for the etchant is selectively increased.

In addition, (B) in the case of Comparative Example 3 containing less than 0.01% by weight of the fluorine compound, the etching amount for both the glass substrate and the active layer was significantly reduced, and in Comparative Example 4 containing more than 1.0% by weight, the glass It can be seen that damage to the substrate is excessively increased.

In addition, (E) in the case of Comparative Example 5 containing less than 0.05% by weight of an acid or salt containing sulfur, the effect of increasing the etching amount on the Active layer is insignificant, and Comparative Example 6 containing more than 5.0% by weight In the case of , it can be seen that the etching amount for the active layer is increased, but the taper angle characteristic is lowered.

In addition, in the case of Comparative Examples 7 to 12 containing an acid or salt other than (E) sulfur-containing acid or salt, it can be seen that the etching of the active layer is not affected at all.

Therefore, it can be confirmed that, when the etching solution composition of the copper-based metal film according to the present invention is used, there is an effect of selectively increasing only the etching amount for the active layer without damage to the glass substrate and deterioration of the taper angle characteristic.

Claims (10)

Based on the total weight of the composition, (A) hydrogen peroxide 18 to 23% by weight, (B) fluorine compound 0.01 to 1.0% by weight, (C) azole compound 0.05 to 3.0% by weight, (D) iminodiacetic acid (iminodiacetic acid) 0.5 to 5.0% by weight, (E) 0.05 to 5.0% by weight of an acid or salt containing sulfur, (F) 1.0 to 5.0% by weight of a polyalcohol-type surfactant, and the remainder of water,
Does not contain organic acids except for water-soluble compounds having a nitrogen atom and a carboxyl group in one molecule,
The acid or salt containing sulfur is ammonium sulfate, sulfamic acid, methanesulfonic acid, p-Toluenesulfonic acid, magnesium sulfate, and lithium sulfate. (Lithium sulfate) at least one type selected from the group consisting of a copper-based metal film and a silicon-based active layer batch etchant composition. The method of claim 1,
The fluorine compound is at least one selected from the group consisting of HF, NaF, NH ₄ F, NH ₄ BF ₄ , NH ₄ HF ₂ (ammonium bifluoride; ABF), KF, KHF ₂ , AlF _3, and HBF ₄ A batch etchant composition of a copper-based metal film and a silicon-based active layer. The method of claim 1,
The azole compound includes a triazole-based compound; Aminotetrazole-based compound, pyrrole-based compound, pyrazol-based compound, imidazole-based compound, tetrazole-based compound, pentazole-based compound, oxazole Copper-based metal film and silicon-based compound, characterized in that at least one selected from the group consisting of (oxazole)-based compounds, isoxazole-based compounds, diazole-based compounds and isothiazole-based compounds Batch etchant composition of the active layer. delete delete The method of claim 1,
The polyalcohol-type surfactant is at least one selected from the group consisting of glycerol, triethylene glycol and polyethylene glycol. A batch etchant composition for a copper-based metal film and a silicone-based active layer. The method of claim 1,
The copper-based metal film may include a single film of copper or a copper alloy; Or a copper-based metal film, characterized in that it is a multilayer film comprising one or more films selected from a copper film and a copper alloy film, and one or more films selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film, and A batch etchant composition of a silicone-based active layer. a) forming a gate electrode on the substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; and
e) a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
At least one of step a) or step d) comprises laminating a copper-based metal film on the substrate, and etching using an etchant composition,
The etchant composition, (A) hydrogen peroxide 18 to 23% by weight, (B) fluorine compound 0.01 to 1.0% by weight, (C) azole compound 0.05 to 3.0% by weight, (D) iminodiacetic acid (iminodiacetic acid) 0.5 to 5.0 % by weight, (E) 0.05 to 5.0% by weight of an acid or salt containing sulfur, (F) 1.0 to 5.0% by weight of a polyalcohol-type surfactant and the remainder of water, and water-soluble having a nitrogen atom and a carboxyl group in one molecule It is a batch etchant composition of a copper-based metal film and a silicon-based active layer that does not contain an organic acid except for a compound,
The sulfur-containing acid or salt is ammonium sulfate, sulfamic acid, methanesulfonic acid, p-Toluenesulfonic acid, magnesium sulfate, and lithium sulfate. (Lithium sulfate) A method of manufacturing an array substrate for a liquid crystal display, characterized in that at least one selected from the group consisting of. 9. The method of claim 8,
The method of manufacturing an array substrate for a liquid crystal display device, characterized in that the array substrate for a liquid crystal display device is a thin film transistor (TFT) array substrate. An array substrate for a liquid crystal display comprising at least one of a gate electrode, a source electrode, and a drain electrode etched using the etchant composition of any one of claims 1 to 3, 6 and 7.