KR102433337B1 - Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same - Google Patents

Abstract

The present invention relates to an etchant composition for a copper-based metal film comprising a primary alcohol having 3 to 6 carbon atoms, hydrogen peroxide, a fluorine-containing compound, an azole compound, an organic acid, a phosphoric acid or a phosphate compound, and water, and a method for manufacturing an array substrate for a liquid crystal display using the same With respect to this, the etchant composition has excellent exothermic stability to improve stability in the etching process.

Description

Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same

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.

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. The etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask, and typically dry etching using plasma or wet etching using an 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 that causes RC signal delay, and in particular, in the case of TFT-LCD (thin film transistor-liquid crystal display), increasing the panel size and realizing 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, the development of a low-resistance material is essential. Therefore, chromium (Cr, resistivity: 12.7×10 ^-8 Ωm), molybdenum (Mo, resistivity: 5×10 ^-8 Ωm), aluminum (Al, resistivity: 2.65×10 ^-8 Ωm), which have been mainly used in the prior art, and these It is difficult to use alloys for gates and data wires used in large TFT LCDs.

Under this background, interest in a copper-based metal film such as a copper film and a copper molybdenum film and an etchant composition thereof as a new low-resistance metal film is increasing. An etching composition for copper and copper/molybdenum or copper/molybdenum alloy electrodes of a display device is disclosed. However, since there is a limit to improving the exothermic stability through the glycol used in the prior literature, there was a disadvantage including instability during the process progress.

In addition, in the case of an etchant composition for a copper-based metal film, various types are currently used, but the performance such as thermal stability required by the user is not satisfied, so the development of a new etchant composition is required.

Republic of Korea Patent Publication No. 10-2010-0035250

The etchant compositions for the copper-based metal film known to date do not sufficiently satisfy the needs of users. In particular, the hydrogen peroxide-based etchant composition has excellent etching properties for the copper-based metal film, but as the concentration of copper ions eluted into the etchant increases, overheating occurs due to the chain decomposition reaction of hydrogen peroxide, so there is a disadvantage in the process. has

Accordingly, an object of the present invention is to provide an etchant composition for a copper-based metal film that has significantly improved stability, in particular, thermal stability, so that an etching process can be stably performed.

Another object of the present invention is to provide an etchant composition for a copper-based metal film having an excellent number of treatments.

Another object of the present invention is to provide a method for etching a copper-based metal film using the etching solution composition and a method for manufacturing an array substrate for a liquid crystal display device.

In order to achieve the above object,

The present invention provides an etchant composition for etching a copper-based metal layer comprising a compound of Formula 1, hydrogen peroxide, a fluorine-containing compound, an azole compound, an organic acid, phosphoric acid or phosphate, and water.

[Formula 1]

HO-R

R is a linear or branched alkyl group having 3 to 6 carbon atoms.

In addition, the present invention comprises the steps of (1) forming a copper-based metal film on a substrate;

(2) selectively leaving a photoreactive material on the copper-based metal layer; and

(3) etching the exposed copper-based metal film with the etchant composition of the present invention; provides a method of etching a copper-based metal film comprising a.

In addition, the present invention comprises the steps of (1) forming a gate wiring on a substrate;

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

(3) forming a semiconductor layer on the gate insulating layer;

(4) forming source and drain electrodes on the semiconductor layer; and

(5) In the 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,

The step (1) 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 (4) comprises forming a copper-based metal film on a semiconductor layer, and etching the copper-based metal film with the etchant composition of the present invention to form source and drain electrodes. A method of manufacturing a substrate is provided.

In addition, the present invention provides an array substrate for a liquid crystal display manufactured by the manufacturing method of the present invention.

The etchant composition of the present invention has very excellent exothermic stability, thereby improving process stability.

In addition, the etchant composition of the present invention has a very excellent effect of the number of treatments.

Furthermore, when the etchant composition according to the present invention is used to etch copper or copper alloy wiring with low resistance, a large-screen, high-brightness circuit can be realized, and an environmentally friendly array substrate for a liquid crystal display can be manufactured.

In addition, when manufacturing an array substrate for a liquid crystal display using the etchant composition according to the present invention, the gate wiring and the source/drain wiring can be etched at once, so that the process is greatly simplified and the process yield can be maximized.

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

The present invention relates to an etchant composition for etching a copper-based metal layer comprising a compound of Formula 1, hydrogen peroxide, a fluorine-containing compound, an azole compound, an organic acid, phosphoric acid or phosphate, and water.

[Formula 1]

HO-R

R is a linear or branched alkyl group having 3 to 6 carbon atoms.

The copper-based metal film of the present invention includes copper as a component of the film, and in particular, the copper-based metal film may be characterized as having a thickness of 5,000 angstroms or more.

The copper-based metal film may include a single film of copper or a copper alloy; Alternatively, it is a concept including a multilayer film including 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.

Here, the alloy film is a concept including a nitride film or an oxide film.

Examples of the multilayer film include a copper/molybdenum film, a copper/molybdenum alloy 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 is, for example, one or more selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In), etc. It means a layer made of an alloy of metal and molybdenum.

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

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

compound of formula 1

The compound represented by Formula 1 included in the etchant composition of the present invention may be represented as follows.

[Formula 1]

HO-R

R is a linear or branched alkyl group having 3 to 6 carbon atoms.

In addition, the compound of Formula 1 is preferably 1-propanol or 1-butanol.

The compound represented by Formula 1 included in the etchant composition of the present invention inhibits the decomposition reaction of hydrogen peroxide by enclosing copper ions dissolved in the etchant after etching the copper-based metal film to suppress the activity of copper ions. do If the activity of copper ions is lowered in this way, the temperature increase due to the decomposition of hydrogen peroxide can be suppressed while the copper etchant is used, so that the process can be performed stably.

That is, the compound of Formula 1 used in the etchant composition of the present invention serves to suppress the decomposition of the fruit water by chelating the copper cation, thereby improving the exothermic stability. The glycol compound used in the existing etchant composition showed a limit in exothermic stability, and thus showed instability during the etching process, but in the present invention, by using the compound of Formula 1 instead of the glycol compound, the above problems are improved can do.

In addition, in the compound of Formula 1, if R is less than 3 carbon atoms, problems may occur in the content and stability of the etchant composition due to volatility, and if it exceeds 6 carbon atoms, solubility decreases and does not dissolve in water, so it cannot be used as an etchant composition .

The compound of Formula 1 is included in an amount of 0.1 to 10 wt%, preferably 1 to 5 wt%, based on the total weight of the etchant composition of the present invention.

When the compound of Formula 1 is included in an amount of less than 0.1 wt%, the decomposition of hydrogen peroxide is accelerated, which may cause an exothermic problem, and when it is included in an amount exceeding 10 wt%, the etching rate of the copper-based metal layer is lowered.

hydrogen peroxide ( H ₂ O ₂ )

Hydrogen peroxide (H ₂ O ₂ ) included in the etchant composition of the present invention is a main oxidizing agent that affects the etching of the copper-based metal layer.

The hydrogen peroxide is included in an amount of 3 to 25 wt%, preferably 5 to 23 wt%, based on the total weight of the etchant composition of the present invention.

When the hydrogen peroxide is contained in an amount of less than 3 wt%, sufficient etching is not achieved due to insufficient etching power of a single film of the copper-based metal film, or a multilayer film including the copper-based metal film and the molybdenum-based metal film, or the etching rate is slowed down. This happens. In addition, when included in an amount exceeding 25% by weight, thermal stability due to an increase in copper ions may be greatly reduced, and it may be difficult to control the process because the etch rate may be increased as a whole.

fluoride compound

The fluorine-containing compound included in the etchant composition of the present invention means a compound capable of dissociating in water to generate fluorine (F) ions.

The fluorine-containing compound is an auxiliary oxidizing agent that affects the etching rate of the molybdenum-based film when etching a multilayer film made of a copper-based metal film and a molybdenum-based metal film, and the molybdenum-based film may be preferably a molybdenum alloy film.

In addition, it serves to remove residues that are inevitably generated in the solution for simultaneously etching the multilayer film.

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

For example, hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH ₄ F), borate fluoride (NH ₄ BF ₄ ), ammonium bifluoride (NH ₄ FHF), potassium fluoride (KF), potassium hydrogen fluoride (KHF) ₂ ), aluminum fluoride (AlF ₃ ), and hydroboric acid (HBF ₄ ) It contains at least one selected from the group consisting of. In addition, it is more preferable to include ammonium fluoride (NH ₄ F) without an HF group that may not cause damage to the lower oxide semiconductor layer (SiO ₂ ).

The fluorine-containing compound is included in an amount of 0.01 to 5 wt%, preferably 0.1 to 3 wt%, based on the total weight of the etchant composition of the present invention.

When the fluorine-containing compound is included in an amount of less than 0.01 wt %, the etching rate of the molybdenum alloy film may be slowed, and etching residues may be generated. In addition, when it contains more than 5 wt%, the etching performance of the molybdenum alloy film is improved, but since the etching rate is overall faster, an undercut phenomenon or etching damage of the lower layer (n+ a-Si:H, a-Si:G) may occur. have.

azole compound

The azole compound included in the etchant composition of the present invention controls the etching rate of the copper-based metal film, reduces the CD Loss of the pattern, and increases the margin in the process by reducing the etching profile fluctuation according to the number of treatments. is an ingredient that

The azole compound is, for example, a pyrrole-based, a pyrazole-based, an imidazole-based, a triazole-based, a tetrazole-based, a pentaazole-based, and an oxa-based compound. It contains at least one selected from the group consisting of sol (oxazole), isoxazole (isoxazole), diazole (thiazole) and isodiazole (isothiazole), preferably tetrazole (tetrazole) Including, specifically, it is most preferable to include 5-methyltetrazole (5-methyltetrazole) or 5-aminotetrazole (5-aminotetrazole).

The azole compound is included in an amount of 0.1 to 5 wt%, preferably 0.5 to 2 wt%, based on the total weight of the etchant composition of the present invention.

When the azole compound is included in an amount of less than 0.1 wt %, CD loss may be excessively generated, and an etch profile change according to over-etching and the number of treated sheets may appear significantly. In addition, if it is included in excess of 5 wt%, the etching rate of copper may be too slow, resulting in loss of process time.

organic acid

The organic acid contained in the etchant composition of the present invention serves to make the environment of the etchant easy to etch the copper-based metal layer by appropriately adjusting the pH.

The type of the organic acid is not particularly limited, and includes, for example, at least one selected from the group consisting of acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, malonic acid, pentanoic acid, lactic acid and oxalic acid.

The organic acid is included in an amount of 1 to 10% by weight, preferably 2 to 5% by weight, based on the total weight of the etchant composition of the present invention.

When the organic acid is included in an amount of less than 1% by weight, the exothermic phenomenon is not improved, and when it is included in an amount exceeding 5% by weight, a problem occurs in that the viscosity of the etchant is increased.

Phosphoric acid or phosphate compound

The phosphoric acid or phosphate compound included in the etchant composition of the present invention serves to increase the etch rate by adjusting the pH, and to make the taper profile of the pattern good.

If the etchant composition of the present invention does not include phosphoric acid or a phosphate compound, the etch rate may be very low, resulting in a poor etch profile.

The phosphoric acid compound is at least one selected from the group consisting of phosphoric acid, phosphorous acid, and phosphinic acid. It is not particularly limited as long as it is selected from two substituted salts, and first or second ammonium phosphate dibasic, first or second sodium phosphate dibasic and first or second potassium phosphate (potassium phosphate) dibasic) may be at least one selected from the group consisting of. And it is preferable to include at least one selected from the group consisting of phosphoric acid, phosphorous acid, and ammonium phosphate dibasic.

The phosphoric acid or phosphate compound is included in an amount of 0.3 to 10 wt%, preferably 0.5 to 5 wt%, based on the total weight of the etchant composition of the present invention.

If the phosphoric acid or phosphate compound is included in an amount of less than 0.3 wt %, an etching profile may be deteriorated. In addition, when included in more than 10 wt%, the etching rate of the copper or copper alloy film is too fast, or the etching rate of the molybdenum or molybdenum alloy film is too slow may occur.

In addition, the etchant composition of the present invention may further include a water-soluble compound including a nitrogen (N) atom and a carboxyl group (-COOH) in one molecule.

The water-soluble compound containing a nitrogen (N) 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 from changing when a large number of substrates are etched. give.

In general, in the case of an etchant composition using hydrogen peroxide, hydrogen peroxide self-decomposes during storage, so the storage period is not long, and there is a risk that the container may explode. However, when a water-soluble compound including a nitrogen (N) atom and a carboxyl group in one molecule is included in the etchant composition, the decomposition rate of hydrogen peroxide is reduced by nearly 10 times, which is advantageous in 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 film is formed and etched after being oxidized to black may occur in many cases. However, when the compound is added, this phenomenon can be prevented can

The water-soluble compound containing a nitrogen (N) atom and a carboxyl group in one molecule is preferably alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid ), nitrilotriacetic acid and at least one selected from the group consisting of sarcosine, among which it is preferable to include iminodiacetic acid. These can be used individually or in mixture of 2 or more types.

The water-soluble compound including a nitrogen (N) atom and a carboxyl group in one molecule may be included in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of the etchant composition of the present invention.

When the water-soluble compound containing a nitrogen (N) atom and a carboxyl group is contained in an amount of less than 0.5 wt% in one molecule, a passivation film is formed after etching a large amount of substrates (about 500 sheets), making it difficult to obtain a sufficient process margin. In addition, when included in excess of 10% by weight, the etching rate of molybdenum or molybdenum alloy is slowed, so that in the case of a copper molybdenum film or a copper molybdenum alloy film, a residue problem of the molybdenum or molybdenum alloy film may occur.

In addition, the etchant composition of the present invention may further add conventional additives in addition to the above-described components, and the additive may include at least one selected from the group consisting of a metal ion sequestering agent and a corrosion inhibitor. In addition, the additive is not limited thereto, and in order to further improve the effect of the present invention, various other additives known in the art may be selected and added.

The components of the etchant composition of the present invention can be prepared by a conventionally known method, and it is preferable to use them with purity for semiconductor processing.

Water included in the 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 it is preferable to use deionized water. In addition, it is preferable to use deionized water having a specific resistance value of 18 ㏁·cm or more, which shows the degree of removal of ions in the water.

The etchant composition of the present invention may be characterized in that the pH is 1.5 to 4. If the pH is out of the above range, an etching defect may occur, and a phenomenon in which etching may not be performed may occur.

Also, the present invention

(1) forming a copper-based metal film on a substrate;

(2) selectively leaving a photoreactive material on the copper-based metal layer; and

(3) etching the copper-based metal film exposed with the etchant composition of the present invention; relates to a method of etching a copper-based metal film comprising a.

In the method of etching a copper-based metal film of the present invention, the photoreactive material is preferably a conventional photoresist material, and may be selectively left by a conventional exposure and development process.

In addition, the copper-based metal film includes copper as a component of the film, and 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 may include a single film of copper or a copper alloy; Alternatively, it is a concept including a multilayer film including 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.

Here, the alloy film is a concept including a nitride film or an oxide film.

Examples of the multilayer film include a copper/molybdenum film, a copper/molybdenum alloy 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, copper The 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 is, for example, one or more selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In), etc. It means a layer made of an alloy of metal and molybdenum.

In particular, the copper-based metal film may be a multilayer film composed of a copper or copper alloy film and a molybdenum or molybdenum alloy film.

Also, the present invention

(1) forming a gate wiring on a substrate;

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

(3) forming a semiconductor layer on the gate insulating layer;

(4) forming source and drain electrodes on the semiconductor layer; and

(5) forming a pixel electrode connected to the drain electrode;

The step (1) 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 (4) comprises forming a copper-based metal film on a semiconductor layer, and etching the copper-based metal film with the etchant composition of the present invention to form source and drain electrodes. It relates to a method of manufacturing an array substrate.

In addition, the copper-based metal film includes copper as a 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 may include a single film of copper or a copper alloy; Alternatively, it is a concept including a multilayer film including 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.

Here, the alloy film is a concept including a nitride film or an oxide film.

Examples of the multilayer film include a copper/molybdenum film, a copper/molybdenum alloy 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, copper The 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 is, for example, one or more selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In), etc. It means a layer made of an alloy of metal and molybdenum.

In particular, the copper-based metal film may be a multilayer film composed of a copper or copper alloy film and a molybdenum or molybdenum alloy film.

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

In addition, the present invention relates to 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 through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

< etchant Composition Preparation>

Example 1 to 6 comparative example 1 to 3.

10 kg of each of the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were prepared according to the composition shown in Table 1 below, and the remaining amount of water was included so that the total weight of the etchant composition was 100% by weight.

(Unit: % by weight) division H ₂ O ₂ AF CA phosphoric acid 5-ATZ ethanol 1-propanol 1-butanol TEG Example 1 8 0.2 5 0.7 0.1 - One - - Example 2 8 0.2 5 0.7 0.1 - 2 - - Example 3 8 0.2 5 0.7 0.1 - 3 - - Example 4 8 0.2 5 0.7 0.1 - 5 - - Example 5 8 0.2 5 0.7 0.1 - - 2 - Example 6 8 0.2 5 0.7 0.1 - - 5 - Comparative Example 1 8 0.2 5 0.7 0.1 - - - - Comparative Example 2 8 0.2 5 0.7 0.1 2 - - - Comparative Example 3 8 0.2 5 0.7 0.1 - - - 2

AF: ammonium fluoride

CA: citric acid

5-ATZ: 5-aminotetrazole

TEG: triethyene glycol

Experimental example One. etchant Evaluation of exothermic stability of the composition

The exothermic stability according to Cu dissolution of the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 3 was evaluated.

After dissolving a certain amount of Cu (5000 ppm) in each solution for evaluation, temperature monitoring was performed while standing in a constant temperature bath at a constant temperature (35° C.), and the results are shown in Table 2 below.

division maximum
fever temperature
(℃) time (h) Example 1 40.3 11.7 Example 2 38.7 12.6 Example 3 37.5 13.4 Example 4 36.8 14.6 Example 5 37.1 9.4 Example 6 36.9 11.1 Comparative Example 1 Exothermic heat during Cu melting process Comparative Example 2 50.3 8.6 Comparative Example 3 68.8 12.2

The results in Table 2 show the maximum temperature and the maximum temperature generation time.

It was confirmed that the etchant compositions of Examples 1 to 6 of the present invention did not exceed a maximum of 40°C.

On the other hand, it was confirmed that the etchant composition of Comparative Example 1 generated exotherm during the dissolution process of Cu, and the etchant composition of Comparative Examples 2 and 3 exhibited a very high exothermic temperature than the etchant composition of Examples.

Therefore, when the copper-based metal film is etched using the etchant composition of the present invention, it can be confirmed from the above results that the exothermic stability of the etchant can be remarkably improved, thereby improving the stability during the process.

Claims (18)

With respect to the total weight of the etchant composition,
0.1 to 10 wt% of a compound of Formula 1, 3 to 25 wt% of hydrogen peroxide, 0.01 to 5 wt% of a fluorine-containing compound, 0.1 to 5 wt% of an azole compound, 1 to 10 wt% of an organic acid, 0.3 to 10 wt% of a phosphoric acid or phosphate compound And an etchant composition for etching a copper-based metal film comprising the remaining amount of water such that the total weight of the etchant composition is 100% by weight,
The compound of Formula 1 is to include at least one selected from the group consisting of 1-propanol and 1-butanol,
The organic acid includes citric acid,
The copper-based metal film has a thickness of 5000 Å or more,
Even when copper ions are contained in the composition at a concentration of 5000 ppm, the etchant composition for etching a copper-based metal film, characterized in that the thermal stability is improved.
[Formula 1]
HO-R
R is a linear or branched alkyl group having 3 to 6 carbon atoms. delete The method according to claim 1, wherein the fluorine-containing compound includes at least one selected from the group consisting of hydrogen fluoride, sodium fluoride, ammonium fluoride, fluoroborate, ammonium bifluoride, potassium fluoride, potassium hydrogen fluoride, aluminum fluoride, and hydroboric acid. An etchant composition for etching a copper-based metal film, characterized in that The method according to claim 1, wherein the azole compound is at least one selected from the group consisting of pyrrole-based, pyrazole-based, imidazole-based, triazole-based, tetrazole-based, pentaazole-based, oxazole-based, isoxazole-based, diazole-based and isodiazole-based compounds. An etchant composition for etching a copper-based metal film, comprising: delete The method according to claim 1, wherein the phosphoric acid or phosphate compound is at least one selected from the group consisting of phosphoric acid, phosphorous acid, phosphinic acid, first or second ammonium phosphate, first or second sodium phosphate, and first or second potassium phosphate. An etchant composition for etching a copper-based metal film, comprising: delete The etchant composition for etching a copper-based metal film according to claim 1, wherein the etchant composition further comprises a water-soluble compound including a nitrogen atom and a carboxyl group in one molecule. The method according to claim 8, wherein the water-soluble compound containing a nitrogen atom and a carboxyl group in one molecule comprises at least one selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid and sarcosine. An etchant composition for etching a copper-based metal film, characterized in that. The etchant composition for etching a copper-based metal film according to claim 8, wherein the water-soluble compound including a nitrogen atom and a carboxyl group in one molecule is included in an amount of 0.5 to 10% by weight based on the total weight of the etchant composition. The method according to claim 1, wherein the copper-based metal film is a single film of copper or a copper alloy; Or for etching 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 etchant composition. The etchant composition for etching a copper-based metal film according to claim 1, wherein the etchant composition has a pH of 1.5 to 4. delete The etchant composition for etching a copper-based metal film according to claim 1, wherein the etchant composition further comprises at least one selected from the group consisting of a metal ion sequestrant and a corrosion inhibitor. (1) forming a copper-based metal film on a substrate;
(2) selectively leaving a photoreactive material on the copper-based metal layer; and
(3) etching the copper-based metal film exposed with the etchant composition of any one of claims 1, 3, 4, 6, 8 to 12 and 14;
The copper-based metal layer is a copper-based metal layer etching method, characterized in that the thickness of 5000 Å or more. (1) forming a gate wiring on a substrate;
(2) forming a gate insulating layer on the substrate including the gate wiring;
(3) forming a semiconductor layer on the gate insulating layer;
(4) forming source and drain electrodes on the semiconductor layer; and
(5) forming a pixel electrode connected to the drain electrode;
In the step (1), a copper-based metal film is formed on a substrate, and the copper-based metal film is etched with the etchant composition of any one of claims 1, 3, 4, 6, 8 to 12 and 14 to form a gate wiring. comprising steps,
In step (4), a copper-based metal film is formed on the semiconductor layer, and the copper-based metal film is etched with the etchant composition of any one of claims 1, 3, 4, 6, 8 to 12 and 14 to form source and drain electrodes. comprising the step of forming
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 5000 Å or more. The method of claim 16 , 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 16 .