KR102310096B1 - Manufacturing method of an array substrate for liquid crystal display - Google Patents

Abstract

The present invention relates to a method for manufacturing an array substrate for a liquid crystal display, and more particularly, hydrogen peroxide, a fluorine compound, 5-methyl-1H-tetrazole, a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, sodium triphosphate, polyvalent An etchant composition for a copper-based metal film containing an alcohol-type surfactant and a predetermined amount of water, and a method of manufacturing an array substrate for a liquid crystal display using the etchant composition.

Description

Manufacturing method of 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 etchant composition for a copper-based metal film and a method for 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, etc., a photoresist forming 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. The etching process refers to a process of leaving a metal film in a selective area using a photoresist as a mask, and typically dry etching using plasma or wet etching using an etchant composition is used.

Conventionally, as a wiring material for gate and source/drain electrodes, a metal film in which aluminum or an alloy thereof and another metal are laminated has been used. Aluminum has a low price and low resistance, but has poor chemical resistance and short circuits with other conductive layers due to defects such as hillocks in the post-processing process, or the insulation layer by contact with the oxide layer. It causes malfunction of the liquid crystal panel, such as forming.

In consideration of this point, multilayer films of copper-based metal films such as a copper film and a molybdenum film, a copper film and a molybdenum alloy film, and a copper alloy film and a molybdenum alloy film have been proposed as wiring materials for the gate and source/drain electrodes. However, in order to etch the multilayer film of the copper-based metal film, there is a disadvantage in that two different types of etchants for etching each metal film must be used.

In addition, since the conventional etchant has a slow etching rate, a process time is increased. Accordingly, when applied to a thick metal film having a thickness of about 5,000 Å or more, an etch profile defect occurs.

In addition, conventionally, as the number of layers treated with the etchant accumulates, the etch pattern inclination angle changes, and the etching profile is poor, such as poor etch straightness, and thus the use period of the etchant could not be prolonged.

In particular, when the thick film is etched, if the taper angle is high, there is a problem in that the step coverage defect occurs during the subsequent process, thereby lowering the process precision and efficiency. In addition, when the concentration of metal ions in the etchant increases, the risk of explosion due to heat is greatly increased, so a solution is required.

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

In etching a copper-based metal film, the etching rate is good, the etching profile is excellent because the amount of change in one-sided etching according to the number of treatment is small, and the etchant that can secure stability by preventing heat generation and temperature increase due to an increase in the concentration of metal ions It aims to provide a composition.

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.

In order to solve the problems of the prior art, the present invention

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) provides an etchant composition for a copper-based metal film, characterized in that it contains the remaining amount of water.

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

Step d) comprises 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. It provides a manufacturing method of

In addition, the present invention 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, an etch rate and an etch profile are excellent, and an effect of a small unilateral etch change according to the number of treatment can be provided. In addition, by preventing an exothermic phenomenon caused by an increase in metal ion concentration, it is possible to stably and effectively perform the etching process even when etching a thick film having a thickness of 5,000 Å or more.

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

As the etchant composition of the present invention contains components such as hydrogen peroxide, fluorine compound, 5-methyl-1H-tetrazole and sodium triphosphate in a certain amount, the amount of side etch (S/E) change according to the number of treatment sheets is small. , it is possible to prevent heat generation caused by an increase in the concentration of metal ions, so that it is possible to provide particularly effective and stable properties when etching a thick film.

The present invention, 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) relates to an etchant composition for a copper-based metal film, characterized in that it contains the remaining amount of water.

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); Alternatively, 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. 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 film thickness of 5,000 Å or more.

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

Further, 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, a double film such as a copper/titanium film, or a triple film.

The copper / molybdenum film means comprising 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 including 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.

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

In particular, the etchant composition of the present invention can be preferably applied to a multi-layer film consisting of a copper or copper alloy film and a molybdenum or molybdenum alloy film.

That is, the etchant composition of the present invention may etch a multilayer film including 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 ) included 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 layer.

The hydrogen peroxide is characterized in that it is included in an amount of 15 to 26% by weight, more preferably in an amount of 18 to 24% by weight, based on the total weight of the composition. If the content of the hydrogen peroxide is less than 15% by weight, the etching may not be performed by causing a decrease in the etching power of the single film of the copper-based metal film, or the multilayer film made of the single film and the molybdenum or molybdenum alloy film, and the etching rate may be slow have. On the other hand, when it exceeds 26 wt %, thermal stability due to an increase in copper ions may be greatly reduced, and the overall etching rate may be increased, making it difficult to control the process.

(B) Fluorine compounds

The fluorine compound included in the etchant composition of the present invention means a compound capable of ^{dissociating in water or the like to provide fluorine ions (F − ).} The fluorine compound is an auxiliary oxidizing agent that affects the etching rate of the molybdenum-based film when etching the copper-based metal film including molybdenum or a molybdenum alloy, and the molybdenum-based film may be preferably a molybdenum alloy film.

As the fluorine compound, a compound commonly used in the art is used, and if it is a compound that can be dissociated into a fluorine ion or a polyatomic fluorine ion in a solution, the type is not particularly limited.

Specific examples include hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH ₄ F), ammonium bifluoride (NH ₄ F ₂ ), borate fluoride (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 hydrogen fluoride (KHF ₂ ), aluminum fluoride (AlF ₃ ), and tetrafluoroboric acid (HBF _{4 ).} More preferably, ammonium bifluoride (NH ₄ F ₂ ) may be used.

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

(C) 5- methyl -1H- tetrazole

5-Methyl-1H-tetrazole included in the etchant composition of the present invention controls the etching rate of the copper-based metal layer and reduces the CD loss of the pattern to increase the margin on the process height plays a role. In addition, it serves to increase the margin in the process by reducing the variation of the etch profile (etch profile) according to the number of treatments.

The 5-methyl-1H-tetrazole is characterized in that it is included in an amount of 0.05 to 3% by weight based on the total weight of the composition, and more preferably in an amount of 0.1 to 1.0% by weight. When the content of 5-methyl-1H-tetrazole is less than 0.05 wt %, over-etching and etch profile variation according to the number of treatment sheets may be greatly changed. On the other hand, when it exceeds 3 wt %, the etching rate of copper is excessively slow, and thus process time loss may occur.

(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 included in the etchant composition of the present invention serves to prevent the etching characteristics from changing when a large number of substrates are etched. In addition, it prevents the self-decomposition reaction of hydrogen peroxide that may occur during storage of the etchant composition.

In general, in the case of an etchant composition containing hydrogen peroxide, the storage period is shortened due to the self-decomposition of hydrogen peroxide during storage, and there is also a risk of container explosion.

However, when a water-soluble compound having a nitrogen atom and a carboxyl group is included in one molecule, the decomposition rate of the hydrogen peroxide solution is reduced by nearly 10 times, which is advantageous for securing storage period and stability. In particular, in the case of a copper layer, When a large amount of copper ions remain in the etchant composition, a passivation layer is formed to be oxidized to black, and then there are many cases in which etching is not performed. However, when the compound is included, this phenomenon can be prevented.

Specific examples of the water-soluble compound having a nitrogen atom and a carboxyl group in one molecule include alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid ( and nitrilotriacetic acid) and sarcosine, and at least one selected from these may be used. Preferably, iminodiacetic acid is mentioned.

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

(E) sodium triphosphate

_{Sodium triphosphate (Na 5} P ₃ O ₁₀ ) contained in the etchant composition of the present invention serves to etch copper at an excellent rate, and reduces side etch variation and heat generation according to copper ion concentration serves to make When the etchant composition of the present invention does not contain sodium triphosphate, the etching rate of copper is slowed, resulting in loss of process time. In addition, there is a possibility that the variation of one-sided etching according to the copper ion concentration increases, and heat generation occurs, so that the etching profile is deteriorated and there is a risk of increasing the risk in the process.

The sodium triphosphate is characterized in that it is included in an amount of 0.1 to 5% by weight based on the total weight of the composition, and more preferably in an amount of 0.5 to 3% by weight. When the content is less than 0.1% by weight, the copper etching rate is slowed, the amount of unilateral etching variation is increased according to the increase in the concentration of copper ions, and the effect of suppressing the exothermic phenomenon is insignificant. On the other hand, when it exceeds 5 wt %, the etching rate of the copper film is too fast to control, and there is a fear that the variation in one-sided etching may increase due to an increase in the concentration of copper ions.

(F) polyhydric alcohol Surfactants

The polyalcohol-type surfactant included in the etchant composition of the present invention serves to increase the uniformity of the etching by reducing the surface tension. In addition, after etching the copper or copper alloy film, the copper ions dissolved in the etchant are wrapped around the copper ions to suppress the activity of the copper ions, thereby suppressing the decomposition reaction of hydrogen peroxide. If the activity of copper ions is lowered by using the polyalcohol-type surfactant as described above, the process can be stably performed while the etchant is used.

Specific examples of the polyhydric alcohol-type surfactant include glycerol, triethylene glycol, and polyethylene glycol, and one or more of them may be selected and used. In addition, it is more preferable to use triethylene glycol among them.

The polyalcohol-type surfactant is included in an amount of 1 to 5% by weight, more preferably 1.5 to 3% by weight, based on the total weight of the composition. When the content is less than 1% by weight based on the above-mentioned basis, there may be problems in that the etching uniformity is lowered and the decomposition of hydrogen peroxide is accelerated. On the other hand, if it exceeds 5% by weight, there is a disadvantage in that a lot of bubbles are generated.

(G) water

The water included in the etchant composition of the present invention is not particularly limited, but it is preferable to use deionized water for semiconductor processing. desirable.

The water is included in the remaining amount so 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 include at least one selected from an etch control agent, a metal ion sequestrant, a corrosion inhibitor, a pH control agent, and other additives, but not limited thereto, in addition to the above-mentioned components. . 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.

It is preferable that the etchant composition for a copper-based metal film of the present invention has a purity for a semiconductor process, and each component can be prepared by a commonly known method.

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

Step d) comprises 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. It provides a manufacturing method of

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

The copper-based metal film 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); Alternatively, 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. Here, the alloy film is a concept including a nitride film or an oxide film.

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

Further, 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, a double film such as a copper/titanium film, or a triple film.

The copper / molybdenum film means comprising 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 including 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 has, for example, molybdenum as a main component, and neodymium (Nd), tantalum (Ta), indium (In), palladium (Pd), niobium (Nb), nickel (Ni), chromium (Cr), magnesium ( Mg), tungsten (W), protactinium (Pa), titanium (Ti), and the like may refer to an alloy-type layer including at least one metal selected from the group consisting of.

In particular, in the present invention, as a copper-based metal film, a multilayer film made of a copper or copper alloy film and a molybdenum or molybdenum alloy film can be preferably applied.

That is, the etchant composition of the present invention may etch a multilayer film including a copper or copper alloy film and a molybdenum or molybdenum alloy film as an example.

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

In addition, the present invention 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 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 technical 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 6 and Comparative Examples 1 to 4 including the remaining amount of water in the composition and content shown in Table 1 below were prepared, respectively.

(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 5 in practice 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

main)

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

Experimental example One. etching Profile test

Each of the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), SEMES), and the temperature of the etchant composition was set to about 33 ° C. did. The total etching time may vary depending on the etching temperature, but in the LCD etching process, it was usually performed for about 50 to 80 seconds.

After inserting the substrate and starting spraying, when the etching time of 50 to 80 seconds is over, it is taken out and washed with deionized water, and then 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: manufactured by Hitachi, model name S-4700). The results are shown in Table 2 below.

<Evaluation criteria>

○: good

△: Normal

Х: bad

Unetch: Unetched

Experimental example 2. According to the number of processed one-sided etching (side etch) change and taper angle test

Each of the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), SEMES), and the temperature of the etchant composition was set to about 33 ° C. did. The total etching time may vary depending on the etching temperature, but in the LCD etching process, it was usually performed for about 50 to 80 seconds.

After inserting the substrate and starting spraying, when the etching time of 50 to 80 seconds is over, it is taken out and washed with deionized water, and then 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: manufactured by Hitachi, model name S-4700). The results are shown in Table 2 below.

The side etch cross-section of each copper-based metal film etched in the etching process was inspected using SEM (made by Hitachi, model name S-4700).

The side etch refers to the distance between the tip of the photoresist and the tip of the lower metal measured after etching. If the amount of one-sided etch is changed, the signal transfer speed is changed during TFT driving, which may cause staining. Therefore, it is desirable to minimize the amount of change in one-sided etching. In this test, in the case of the etchant composition satisfying the condition that the variation in one-sided etching is within ±0.1 μm, it was determined that it can be used continuously in the etching process.

In addition, the taper angle refers to the slope of the copper (Cu) slope. If the taper angle is too high, cracking occurs due to poor step coverage during subsequent film deposition, so it is important to maintain an appropriate taper angle. In general, when the initial taper angle increases by 15° or more or exceeds 70°, the defect rate may increase in the next process, so the used etchant composition is replaced with a new etchant composition. In this test, when the condition that the amount of change in the taper angle according to the Cu ion concentration is within ±12° is satisfied, the etchant composition can be used continuously in the etching process, and an experiment was conducted.

Experimental example 3. According to the number of transactions etchant Exothermic temperature test of the composition

Each of the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), SEMES), and the temperature of the etchant composition was set to about 33 ° C. did. The total etching time may vary depending on the etching temperature, but in the LCD etching process, it was usually performed for about 50 to 80 seconds.

The temperature of the composition was measured at a copper ion concentration of 7,000 ppm in the etchant composition by inserting the substrate and starting spraying, and is shown in Table 2 below.

Experimental example 4. residue measurement

Each of the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were put into the experimental equipment of the spray etching method (model name: ETCHER (TFT), SEMES), and the temperature of the etchant composition was set to about 33 ° C. did. The total etching time may vary depending on the etching temperature, but in the LCD etching process, it was usually performed for about 50 to 80 seconds.

After inserting the substrate and starting spraying, when the etching time of 50 to 80 seconds is over, it is taken out and 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, the residue, a phenomenon in which the metal film is not etched on the part not covered with the photoresist, was measured using a scanning electron microscope (SEM; model name: S-4700, manufactured by HITACHI), and the results are shown in Table 2 below. shown in

<Residue Evaluation Criteria>

No residue: X

Residue generation: ○

division etching
profile number of transactions
according to (300ppm->7,000ppm)
One-sided etching change (㎛) number of transactions
according to (300ppm->7,000ppm)
Taper angle change (°) 7,000ppm
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, the etchant compositions of Examples 1 to 6 all exhibited good etching properties. In detail, when the copper-based metal film was etched using the etchant compositions of Examples 1 to 6, the etch profile and straightness were excellent, and Mo and Ti residues were not generated. In addition, it was confirmed that the unilateral etch change amount according to the number of treatments satisfies the condition of ±0.1 μm. It was confirmed that the temperature after dissolving copper ions at a concentration of 7,000 ppm was also stable at around 35 °C.

On the other hand, in the case of the etchant composition not containing sodium triphosphate (Comparative Example 1 and Comparative Example 4), the etch rate was too slow and the etch profile was poor. In addition, the unilateral etch change amount did not satisfy the condition of ±0.1 μm, and the temperature at a copper ion concentration of 7,000 ppm rapidly increased to 50°C and 60°C, respectively.

In particular, in the case of the composition of Comparative Example 1, although it contains sodium phosphate, a single phosphate, it can be seen that the evaluation result is not excellent.

In Comparative Example 3, in which the content of sodium triphosphate exceeds the range of the present invention, the exothermic temperature evaluation showed a stable result at 30° C., but the etch rate was too fast and the evaluation result of the unilateral etch 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; In the method of manufacturing an array substrate for a liquid crystal display comprising:
Step a) includes forming a copper-based metal film on a substrate, etching the copper-based metal film with an etchant composition for a copper-based metal film to form a gate wiring, and step d) is a copper-based metal film on a semiconductor layer 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 the copper-based metal film is based on 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) having a nitrogen atom and a carboxyl group in one molecule 0.5 to 5% by weight of a water-soluble compound, (E) 0.1 to 5% by weight of sodium triphosphate, (F) 1 to 5% by weight of a polyalcohol-type surfactant, and (H) the balance of water;
The method of manufacturing an array substrate for a liquid crystal display device, characterized in that the copper-based metal film has a thickness of 5,000 Å or more. The method according to claim 1,
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 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) an etchant composition for a copper-based metal film comprising a residual amount of water, wherein the copper-based metal film has a thickness of 5,000 Å or more. 5. The method according to claim 4,
The copper-based metal film may include a single film of copper or a copper alloy; Or at least one film selected from a copper film and a copper alloy film and a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film, characterized in that the multilayer film comprising a multilayer film, characterized in that the etchant composition for a copper-based metal film . 5. The method according to claim 4,
The fluorine compound is hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH ₄ F), ammonium bifluoride (NH ₄ F ₂ ), borate fluoride (NH ₄ BF ₄ ), ammonium hydrogen fluoride (NH ₄ FHF), An etchant composition for a copper-based metal film, characterized in that at least one selected from potassium fluoride (KF), potassium hydrogen fluoride (KHF ₂ ), aluminum fluoride (AlF ₃ ), and tetrafluoroboric acid (HBF _{4 ).} 5. The method according to claim 4,
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 sarcosine (sarcosine) etchant composition for a copper-based metal film, characterized in that at least one selected from the group consisting of. 5. The method according to claim 4,
The polyalcohol-type surfactant is an etchant composition for a copper-based metal film, characterized in that at least one selected from glycerol, triethylene glycol, and polyethylene glycol. delete