KR20170065253A - Manufacturing method of an array substrate for liquid crystal display - Google Patents

Abstract

The present invention relates to a method of manufacturing an array substrate for a liquid crystal display, and more particularly, to a method of manufacturing an array substrate for a liquid crystal display, An alcohol type surfactant and a certain amount of water, and a method of manufacturing an array substrate for a liquid crystal display device using the etching composition.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an array substrate for a liquid crystal display

The present invention relates to a method of manufacturing an array substrate for a liquid crystal display, and more particularly, to an etching liquid composition for a copper-based metal film and a method of manufacturing an array substrate for a liquid crystal display using the etchant composition.

The process of forming a metal wiring on a substrate in a semiconductor device is usually composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and an etching process, And a cleaning process before and after the individual unit process. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.

A metal film in which aluminum or an alloy thereof and another metal are laminated is used as a wiring material for a gate and a source / drain electrode. Aluminum is inexpensive and has low resistance, but it is not chemically stable and causes a short-circuit with other conductive layer due to defects such as hillock in the post-process, or an insulating layer due to contact with the oxide layer Thereby causing a malfunction of the liquid crystal panel.

Taking this into consideration, multilayer films of a copper-based metal film such as a copper film and a molybdenum film, a copper film and a molybdenum alloy film, a copper alloy film and a molybdenum alloy film have been proposed as the wiring material for the gate and the source / drain electrodes. However, in order to etch the multi-layered film of the copper-based metal film, it is necessary to use two different kinds of etching solutions for etching each metal film.

In addition, the etching time of a conventional etching solution is slow, so that a process time is increased. As a result, the etching profile is defective when applied to a thick metal film having a thickness of about 5,000 ANGSTROM or more.

In addition, conventionally, as the number of films treated with the etching solution is increased, the inclination angle of the etching pattern is changed, and the etching profile is poor, such as a decrease in the straightness of etching.

Particularly, when the thick film is etched, if the taper angle is high, there is a problem that the step coverage is poor when the subsequent process is performed, thereby lowering the process precision and efficiency. Also, as the concentration of metal ions in the etching solution increases, the risk of explosion due to heat generation is greatly increased.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,

In the etching of the copper-based metal film, the etch rate is good, the etching profile is excellent due to the small amount of unilateral etching change depending on the number of treatments, and the etching temperature And to provide a composition.

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

In order to solve the problems of the prior art,

With respect to the total weight of the composition,

(A) 15 to 26% by weight of hydrogen peroxide,

(B) 0.01 to 3% by weight of a fluorine compound,

(C) 0.05 to 3% by weight of 5-methyl-1H-tetrazole,

(D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule,

(E) 0.1 to 5% by weight of sodium triphosphate,

(F) 1 to 5% by weight of a polyhydric alcohol type surfactant, and

(G) remaining amount of water. The present invention also provides an etching solution composition for a copper-based metal film.

In addition,

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:

The step a) includes forming a copper-based metal film on the substrate, and etching the copper-based metal film with the etchant composition of the present invention to form a gate wiring,

Wherein the step d) includes forming a copper-based metal film on the semiconductor layer and etching the copper-based metal film with the etchant composition of the present invention to form source and drain electrodes. Of the present invention.

The present invention also provides an array substrate for a liquid crystal display manufactured by the above manufacturing method.

When the copper-based metal film is etched with the etchant composition of the present invention, the etching rate and the etching profile are excellent, and the effect of reducing the unilateral etching change amount according to the number of treatments can be provided. In addition, by preventing the exothermic phenomenon caused by the increase of the metal ion concentration, the etching process can be stably and effectively performed even when the thick film having a thickness of 5,000 or more is etched.

The present invention relates to an etching liquid composition for a copper-based metal film and a method of manufacturing an array substrate for a liquid crystal display using the same.

The etchant composition of the present invention contains components such as hydrogen peroxide, a fluorine compound, 5-methyl-1H-tetrazole and sodium triphosphate in a certain amount, so that the amount of change in side etch (S / E) , It is possible to prevent the exothermic phenomenon due to the increase of the metal ion concentration, and thus it is possible to provide particularly effective and stable characteristics when etching the thick film.

The present invention relates to a composition,

(A) 15 to 26% by weight of hydrogen peroxide,

(B) 0.01 to 3% by weight of a fluorine compound,

(C) 0.05 to 3% by weight of 5-methyl-1H-tetrazole,

(D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule,

(E) 0.1 to 5% by weight of sodium triphosphate,

(F) 1 to 5% by weight of a polyhydric alcohol type surfactant, and

(G) remaining amount of water. The present invention also relates to an etchant composition for a copper-based metal film.

The copper-based metal film includes copper (Cu) as a constituent component of the film, and is a concept including a multilayer film of a single film and a double film or more. More specifically, the copper-based metal film is a single film of copper or a copper alloy (Cu alloy); Or a multilayer film comprising at least one film selected from the copper film and the copper alloy film and at least one film selected from a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film. Here, the alloy film is a concept including a nitride film or an oxide film.

In particular, the copper-based metal film may be a thick film having a thickness of 5,000 Å or more.

The copper-based metal film is not particularly limited, but specific examples of the single film include a copper (Cu) film or copper as a main component, and may include neodymium (Nd), tantalum (Ta), indium (In), palladium (Pd), niobium A copper alloy film containing at least one metal selected from nickel (Ni), nickel (Ni), chromium (Cr), magnesium (Mg), tungsten (W), protactinium (Pa) and titanium .

Examples of the multilayer film include a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum film, a copper alloy / molybdenum alloy film, and a copper / titanium film.

The copper / molybdenum film includes a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper / molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, The copper alloy / molybdenum alloy film means that the copper / titanium film includes a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper / titanium film includes a titanium layer and a copper layer formed on the titanium layer.

The molybdenum alloy layer may include at least one metal selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), indium ≪ / RTI >

In particular, the etchant composition of the present invention can be preferably applied to a multilayer film made of a copper or copper alloy film and a molybdenum or molybdenum alloy film.

That is, the etchant composition of the present invention can collectively etch multilayer films made of a copper or copper alloy film and a molybdenum or molybdenum alloy film as an example.

Hereinafter, each component constituting the etchant composition of the present invention will be described.

(A) hydrogen peroxide

Hydrogen peroxide (H ₂ O ₂ ) contained in the etchant composition of the present invention is a component used as a main oxidizing agent and affects the etching rate of the copper-based metal film.

The hydrogen peroxide is contained in an amount of 15 to 26% by weight based on the total weight of the composition, more preferably 18 to 24% by weight. If the content of the hydrogen peroxide is less than 15 wt%, etching may not be performed on a single film of the copper-based metal film or a multilayer film composed of the single film and the molybdenum or molybdenum alloy film, and the etching rate may be slowed have. On the other hand, if it exceeds 26 wt%, the stability of the exotherm due to the increase of the copper ion may be largely lowered, and the etching speed may be entirely accelerated, which may make it difficult to control the process.

(B) Fluorine compound

The fluorine compound contained in the etchant composition of the present invention means a compound capable of dissociating into water or the like and capable of providing fluorine ion (F ^- ). The fluorine compound is a co-oxidizing agent that affects the etching rate of the molybdenum-based film when the copper-based metal film containing molybdenum or molybdenum alloy is etched, and the molybdenum-based film may preferably be a molybdenum alloy film.

The fluorine compound used in the present invention is not particularly limited as long as it is a compound which can be dissociated into a fluorine ion or a polyatomic fluorine ion in a solution.

Specific examples include hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH ₄ F), ammonium fluoride (NH ₄ F ₂ ), fluoroborate (NH ₄ BF ₄ ) Ammonium hydrogen fluoride (NH ₄ FHF), It may be preferable to use at least one selected from potassium fluoride (KF), potassium fluoride (KHF ₂ ), aluminum fluoride (AlF ₃ ) and tetrafluoroboric acid (HBF ₄ ). More preferably, ammonium fluoride (NH ₄ F ₂ ) can be used.

The fluorine compound is included in an amount of 0.01 to 3% by weight based on the total weight of the etching solution composition, more preferably 0.05 to 1% by weight. If the content of the fluorine compound is less than 0.01% by weight, the etching rate of the molybdenum alloy film may become slow and residue may be generated. On the other hand, if it exceeds 3 wt%, the etching performance of the molybdenum alloy film is improved, but the undercut phenomenon or etching damage of the lower layer (n + a-Si: H, a-Si: G) may occur because the etching rate is too fast.

(C) 5- methyl -1H- Tetrazole

The 5-methyl-1H-tetrazole contained in the etchant composition of the present invention controls the etch rate of the copper-based metal film and reduces the CD loss of the pattern, Height. Also, it reduces the fluctuation of the etch profile according to the number of processes, thereby enhancing the process margin.

The 5-methyl-1H-tetrazole is contained in an amount of 0.05 to 3% by weight based on the total weight of the composition, more preferably 0.1 to 1.0% by weight. When the content of the 5-methyl-1H-tetrazole is less than 0.05% by weight, the etching profile may vary depending on the overexcitation angle and the number of treatments. On the other hand, if it exceeds 3% by weight, the etching time of copper may be excessively slowed, resulting in a process time loss.

(D) a water-soluble compound 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 contained in the etching solution composition of the present invention serves to prevent the etching property from being changed when a large number of substrates are etched. In addition, it prevents self-decomposition reaction of hydrogen peroxide which may occur during storage of the etching solution composition.

Generally, in the case of the etching solution composition containing hydrogen peroxide, the storage period is shortened due to the self-decomposition of hydrogen peroxide during storage, and the container explosion is also a risk factor.

However, when a water-soluble compound having a nitrogen atom and a carboxyl group is included in the molecule, the decomposition rate of the hydrogen peroxide solution is reduced to about 10 times, which is advantageous for securing the storage period and stability. Particularly in the case of the copper layer, If a large amount of copper ions remain in the etchant composition, a passivation film may be formed and then oxidized to black, and then etched. However, when such a compound is included, such phenomenon can be prevented.

Specific examples of the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule include alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid nitrilotriacetic acid and sarcosine, and at least one selected therefrom can be used. Preferable examples include iminodiacetic acid.

The water-soluble compound having a nitrogen atom and a carboxyl group in the molecule is contained in an amount of 0.5 to 5% by weight based on the total weight of the composition, more preferably 1 to 3% by weight. When the content is less than 0.5% by weight, a passivation film is formed after etching a large amount of about 500 or more substrates, and it is difficult to obtain a sufficient process margin. On the other hand, if it is more than 5 wt%, the etching rate of the molybdenum-based metal film such as molybdenum or molybdenum-containing metal film is slowed, so that the residual problem of the molybdenum or molybdenum alloy film may occur during etching of the copper-based metal film containing molybdenum.

(E) Sodium triphosphate

The sodium triphosphate (Na ₅ P ₃ O ₁₀ ) contained in the etchant composition of the present invention acts to etch copper at a good rate and reduces the side etch variation and the exothermic phenomenon depending on the copper ion concentration . If the etchant composition of the present invention does not include sodium triphosphate, the etch rate of copper is slowed, which leads to process time loss. In addition, there is a fear that the uneven etching fluctuation amount depending on the copper ion concentration increases and a heat generation phenomenon occurs, resulting in poor etching profile and increased risk in the process.

The sodium triphosphate is contained in an amount of 0.1 to 5% by weight based on the total weight of the composition, more preferably 0.5 to 3% by weight. When the content is less than 0.1 wt%, the copper etching rate is slowed, and the unilateral etching variation is increased as the copper ion concentration is increased. On the other hand, if it exceeds 5% by weight, the etching rate of the copper film becomes excessively high, which makes it difficult to control, and there is a fear that the unilateral etching variation due to the increase in copper ion concentration increases.

(F) Polyhydric alcohol type  Surfactants

The polyhydric alcohol type surfactant contained in the etchant composition of the present invention lowers the surface tension and increases the uniformity of the etching. In addition, the copper or copper alloy film is etched, and the copper ions dissolved in the etching solution are enclosed to inhibit the activity of copper ions, thereby suppressing the decomposition reaction of hydrogen peroxide. When the activity of the copper ion is lowered by using the polyhydric alcohol type surfactant, the process can be performed stably while using the etching solution.

Specific examples of the polyhydric alcohol surfactant include glycerol, triethylene glycol, and polyethylene glycol. One or more of these surfactants can be selected from the polyhydric alcohol surfactants. Among these, triethylene glycol is more preferable.

The polyhydric alcohol type surfactant is contained in an amount of 1 to 5 wt%, more preferably 1.5 to 3 wt%, based on the total weight of the composition. If the content is less than 1% by weight, etching uniformity may be lowered, and decomposition of hydrogen peroxide may be accelerated. On the other hand, if it exceeds 5% by weight, there is a disadvantage that much foam is generated.

(G) Water

The water contained in the etchant composition of the present invention is not particularly limited, but it is preferable to use deionized water for semiconductor processing, and it is preferable to use deionized water having a specific resistance value of 18 M? / Cm or more desirable.

The water is contained in a balance such that the total weight of the composition is 100% by weight.

The etchant composition for a copper-based metal film of the present invention may further comprise at least one selected from the above-mentioned components, an etchant, a sequestering agent, a corrosion inhibitor, a pH adjuster, and other additives not limited thereto . The above additives can 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 for a copper-based metal film of the present invention preferably has purity for semiconductor processing, and each component can be manufactured by a conventionally known method.

In addition,

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:

The step a) includes forming a copper-based metal film on the substrate, and etching the copper-based metal film with the etchant composition of the present invention to form a gate wiring,

Wherein the step d) includes forming a copper-based metal film on the semiconductor layer and etching the copper-based metal film with the etchant composition of the present invention to form source and drain electrodes. Of the present invention.

The copper-based metal film includes copper as a constituent component of the film, and in particular, the copper-based metal film may be a thick film having a thickness of 5,000 Å or more.

The copper-based metal film is a concept that includes a single film and a multilayer film of a double film or more. More specifically, the copper-based metal film is a single film of copper or a copper alloy (Cu alloy); Or a multilayer film comprising at least one film selected from the copper film and the copper alloy film and at least one film selected from a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film. Here, the alloy film is a concept including a nitride film or an oxide film.

The copper-based metal film is not particularly limited, and specific examples of the single film include a copper (Cu) film; (Nd), Ta, In, Pd, Nb, Ni, Cr, Mg, and W, A copper alloy film containing at least one metal selected from the group consisting of platinum actin (Pa) and titanium (Ti); And the like.

Examples of the multilayer film include a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum film, a copper alloy / molybdenum alloy film, and a copper / titanium film.

The copper / molybdenum film includes a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper / molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, The copper alloy / molybdenum alloy film means that the copper / titanium film includes a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper / titanium film includes a titanium layer and a copper layer formed on the titanium layer.

The molybdenum alloy layer may be formed of, for example, molybdenum as a main component and may include at least one selected from the group consisting of Nd, Ta, In, Pd, Nb, Ni, Cr, Mg), tungsten (W), protactinium (Pa), titanium (Ti), and the like.

Particularly, in the present invention, a multilayer film made of a copper or copper alloy film and a molybdenum or molybdenum alloy film is preferably used as the copper-based metal film.

That is, the etchant composition of the present invention can collectively etch multilayer films made of a copper or copper alloy film and a molybdenum or molybdenum alloy film as an example.

In addition, the array substrate for a 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 manufactured by the above manufacturing method.

The array substrate for a liquid crystal display may include gate wirings and / or source and drain electrodes etched using the etchant composition of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.

< Example  And Comparative Example > Etchant  Preparation of composition

6 kg of the etching solution compositions of Examples 1 to 6 and Comparative Examples 1 to 4 containing water in the residual amount were respectively prepared in the compositions and contents shown in Table 1 below.

       (weight%) division H ₂ O ₂ ABF 5-MTZ IDA STPP NHP TEG Example 1 20 0.1 0.2 2.0 0.5 2.0 Example 2 20 0.1 0.2 2.5 0.5 2.0 Example 3 23 0.1 0.5 2.0 1.0 2.0 Example 4 23 0.1 0.5 2.5 2.0 2.0 Implementation 5 20 0.1 0.2 2.0 0.1 2.0 Example 6 20 0.1 0.2 2.0 5 2.0 Comparative Example 1 20 0.1 0.2 2.0 0.5 2.0 Comparative Example 2 23 0.1 0.2 2.5 0.05 2.0 Comparative Example 3 23 0.1 0.2 2.0 6.0 2.0 Comparative Example 4 23 0.1 0.2 2.5 2.0

week)

ABF: Ammonium bifluoride

5-MTZ: 5-Methyl-1H-tetrazole

IDA: Iminodiacetic acid

STPP: Sodium triphosphate

NHP: Sodium phosphate

TEG: Triethyleneglycol

< Experimental Example > Etchant  Performance testing of the composition

In the performance tests of the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4, a thin film substrate on which Cu / Mo-Ti 5,000 / 100 Å was deposited as a copper-based metal film on a glass (SiO ₂ ) substrate was used as a sample , And a photoresist having a predetermined pattern was formed on the substrate through a photolithography process. The performance test was carried out as follows.

Experimental Example  One. Etching  Profile test

The etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into an experimental apparatus (model name: ETCHER (TFT), manufactured by SEMES) of a spray-type etch system, and the temperature of the etchant composition was set at about 33 ° C Respectively. The total etch time may vary depending on the etch temperature, but is typically about 50 to 80 seconds in the LCD etch process.

After the substrate was put and spraying was started, when the etching time was reached for 50 to 80 seconds, the substrate was taken out, washed with deionized water, and dried using a hot air dryer. After cleaning and drying, the substrate was cut and its cross-section was measured by using an electron-scanning microscope (SEM: Model S-4700, Hitachi). The results are shown in Table 2 below.

<Evaluation Criteria>

○: Good

△: Normal

Х: Poor

Unetch: No etching

Experimental Example  2. Depending on the number of processed products Unilateral etching (side etch) change and Taper  Angle test

The etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into an experimental apparatus (model name: ETCHER (TFT), manufactured by SEMES) of a spray-type etch system, and the temperature of the etchant composition was set at about 33 ° C Respectively. The total etch time may vary depending on the etch temperature, but is typically about 50 to 80 seconds in the LCD etch process.

After the substrate was put and spraying was started, when the etching time was reached for 50 to 80 seconds, the substrate was taken out, washed with deionized water, and dried using a hot air dryer. After cleaning and drying, the substrate was cut and its cross-section was measured by using an electron-scanning microscope (SEM: Model S-4700, Hitachi). The results are shown in Table 2 below.

The etching of the copper-based metal film in the etching process was performed by using SEM (Hitachi, Model S-4700).

The side etch refers to the distance between the tip of the photoresist and the bottom metal measured after etching. When the unilateral etching amount is changed, the signal transmission speed may change during TFT driving, and unevenness may occur. Therefore, it is preferable to minimize the unilateral etching variation amount. In this test, the etchant composition satisfying the condition that the unilateral etching change amount is within ± 0.1 μm is determined to be continuously usable in the etching process.

Also, the taper angle refers to the slope of the copper (Cu) slope. If the taper angle is too high, it is important to maintain the proper taper angle because cracking due to poor step coverage occurs in the subsequent film deposition. Typically, when the initial taper angle is increased by more than 15 ° or more than 70 °, the defect rate may increase in the next process, and the used etching composition is replaced with a new etching composition. In this test, when the condition that the taper angle change amount according to the Cu ion concentration is within ± 12 ° is satisfied, the etching composition was determined to be able to continue to be used in the etching process and the experiment was conducted.

Experimental Example  3. Depending on the number of processing Etchant  Heating temperature test of composition

The etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into an experimental apparatus (model name: ETCHER (TFT), manufactured by SEMES) of a spray-type etch system, and the temperature of the etchant composition was set at about 33 ° C Respectively. The total etch time may vary depending on the etch temperature, but is typically about 50 to 80 seconds in the LCD etch process.

The substrate temperature was measured at a concentration of copper ion concentration of 7,000 ppm in the etchant composition, and the results are shown in Table 2 below.

Experimental Example  4. Residue  Measure

The etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into an experimental apparatus (model name: ETCHER (TFT), manufactured by SEMES) of a spray-type etch system, and the temperature of the etchant composition was set at about 33 ° C Respectively. The total etch time may vary depending on the etch temperature, but is typically about 50 to 80 seconds in the LCD etch process.

After the substrate was injected and spraying was started, when the etching time had elapsed for 50 to 80 seconds, the substrate was taken out, washed with deionized water, dried using a hot air drying apparatus, and photoresist was removed using a photoresist stripper. After cleaning and drying, the residue, which is a phenomenon in which the metal film was not etched, was measured using a scanning electron microscope (SEM; model name: S-4700, manufactured by Hitachi) Respectively.

<Evaluation Criteria>

No residue: X

Residual occurrence: Yes

division Etching
profile Number of processing
(300ppm - > 7,000ppm)
One side etching change amount (탆) Number of processing
(300ppm - > 7,000ppm)
Taper angle change (°) 7,000 ppm
Upon input
Temperature (℃) Residue Example 1 ○ 0.10 9 30 X Example 2 ○ 0.10 10 30 X Example 3 ○ 0.08 9 30 X Example 4 ○ 0.09 10 30 X Example 5 ○ 0.10 12 35 X Example 6 ○ 0.10 12 30 X Comparative Example 1 △ 0.15 20 50 X Comparative Example 2 ○ 0.30 25 47 ○ Comparative Example 3 ○ 0.27 25 30 X Comparative Example 4 Х 0.8 40 60 ○

As can be seen from the results of Table 2, all the etching solution compositions of Examples 1 to 6 exhibited good etching characteristics. In detail, when the copper based metal film was etched using the etching solution compositions of Examples 1 to 6, the etching profile and the straightness were excellent, and Mo and Ti residues did not occur. Also, it was confirmed that the condition of the unilateral etching change amount according to the number of treatments was ± 0.1 μm. It was confirmed that the temperature after dissolving the copper ion in the concentration of 7,000 ppm was also stable at about 35 캜.

On the other hand, in the case of the etching solution composition containing no sodium triphosphate (Comparative Example 1, Comparative Example 4), the etching rate was too slow and the etching profile was poor. In addition, the condition of unilateral etching change of ± 0.1 μm was not satisfied, and the temperature at 7,000 ppm of copper ion rapidly rose to 50 ° C. and 60 ° C., respectively.

In particular, the composition of Comparative Example 1 contains sodium phosphate, which is a single phosphate, but it can be confirmed that the evaluation result is not excellent.

In the case of Comparative Example 3 in which the content of sodium triphosphate exceeded the range of the present invention, stable results were obtained at 30 ° C in the evaluation of the exothermic temperature, but the etching rate was too fast and the evaluation result of unilateral etching change was poor.

Claims (9)

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:
The step a) includes forming a copper-based metal film on a substrate, and etching the copper-based metal film with an etchant composition for a copper-based metal film to form a gate wiring, wherein the step d) Forming a metal film, and etching the copper-based metal film with an etchant composition for a copper-based metal film to form source and drain electrodes,
The etchant composition for a copper-based metal film according to claim 1,
(A) 15 to 26% by weight of hydrogen peroxide, (B) 0.01 to 3% by weight of a fluorine compound, (C) 0.05 to 3% by weight of 5-methyl-1H-tetrazole, (D) (F) a water-soluble compound in an amount of 0.5 to 5% by weight, (E) 0.1 to 5% by weight of sodium triphosphate, (F) 1 to 5% by weight of a polyhydric alcohol type surfactant, Wherein the method comprises the steps of: The method according to claim 1,
Wherein the array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate. An array substrate for a liquid crystal display manufactured by the manufacturing method of claim 1 or 2. With respect to the total weight of the composition,
(A) 15 to 26% by weight of hydrogen peroxide,
(B) 0.01 to 3% by weight of a fluorine compound,
(C) 0.05 to 3% by weight of 5-methyl-1H-tetrazole,
(D) 0.5 to 5% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule,
(E) 0.1 to 5% by weight of sodium triphosphate,
(F) 1 to 5% by weight of a polyhydric alcohol type surfactant, and
(G) residual water in the etching solution. The method of claim 4,
The copper-based metal film may be a single film of copper or a copper alloy; Or at least one film selected from the copper film and the copper alloy film and at least one film selected from a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film, characterized in that the film is a multi- Composition. The method of claim 4,
The fluorine compound is selected from the group consisting of hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH ₄ F), ammonium fluoride (NH ₄ F ₂ ), fluoroborate (NH ₄ BF ₄ ) Ammonium hydrogen fluoride (NH ₄ FHF), Wherein at least one selected from potassium fluoride (KF), potassium fluoride (KHF ₂ ), aluminum fluoride (AlF ₃ ) and tetrafluoroboric acid (HBF ₄ ) is used. The method of claim 4,
The water-soluble compound having a nitrogen atom and a carboxyl group in the above-mentioned molecule may be selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid ) And sarcosine. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt; The method of claim 4,
Wherein the polyhydric alcohol type surfactant is at least one selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol. The method of claim 4,
Wherein the copper-based metal film has a thickness of 5,000 ANGSTROM or more.