KR102209788B1 - Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same - Google Patents

Abstract

The present invention provides a metal film oxidizing agent; Polyethylene glycol containing a sulfonyl group; And an etchant composition comprising water, and a method of manufacturing an array substrate for a liquid crystal display, comprising using the composition.

Description

Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same

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

In the case of flat panel displays such as LCD, PDP and OLED, especially TFT-LCD, a single film made of copper or copper alloy, and furthermore, copper or copper is used to reduce wiring resistance and increase adhesion with silicon insulating film while becoming larger. The adoption of a multilayer of two or more layers of alloys/other metals, alloys of other metals, or metal oxides has been widely studied. For example, a copper/molybdenum film, a copper/titanium film, or a copper/molybdenum-titanium film can form the source/drain wires constituting the gate wires and data lines of a TFT-LCD, which will contribute to the large screen of the display. I can. Accordingly, there is a need to develop a composition having excellent etching properties capable of etching a metal film including the copper-based film as described above.

As the above-described etching composition, an etching solution based on hydrogen peroxide and amino acid, an etching solution based on hydrogen peroxide and phosphoric acid, and an etching solution based on hydrogen peroxide and polyethylene glycol are known.

For example, Korean Patent Laid-Open Publication No. 10-2011-0031796 discloses an etchant comprising A) hydrogen peroxide (H ₂ O ₂ ) B) persulfate, C) a water-soluble compound having an amine group and a carboxyl group, and water.

Republic of Korea Patent Publication No. 10-2012-0044630 discloses a copper-containing metal film etching solution containing A) hydrogen peroxide, B) phosphoric acid, C) a cyclic amine compound, D) sulfate, E) boronic acid and F) water, and have.

Republic of Korea Patent Publication No. 10-2012-0081764 discloses an etching solution containing A) ammonium hydroxide, B) hydrogen peroxide, C) a fluorine-containing compound, D) a polyhydric alcohol and E) water.

However, the above etchants do not sufficiently satisfy the conditions required in this field in terms of CD loss, taper, pattern straightness, metal residue, storage stability, and number of processed sheets for a metal film including a copper-based film. have.

Republic of Korea Patent Publication No. 10-2011-0031796 Republic of Korea Patent Publication No. 10-2012-0044630 Republic of Korea Patent Publication No. 10-2012-0081764

An object of the present invention is to provide an etchant composition for a metal film having excellent work safety, excellent etching rate, and processing capability of a large amount of substrates in order to solve the problems of the prior art as described above.

In particular, an object of the present invention is to provide an etchant composition for a metal film having excellent side etching control and a method of manufacturing an array substrate for a liquid crystal display using the same.

The present invention provides a metal film oxidizing agent; Polyethylene glycol containing a sulfonyl group; And it provides an etchant composition comprising water.

In the present invention, the polyethylene glycol containing the sulfonyl group may be any one selected from compounds represented by the following Formulas 1 and 2:

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ may be hydrogen, a C ₁ to C ₁₂ linear or branched alkyl group, preferably a methyl group, an ethyl group, a propyl group, or a butyl group, most preferably hydrogen or a methyl group.

In addition, n in Formula 1 “G 2” may be an integer that satisfies a weight average molecular weight of 300 to 1000, preferably an integer that satisfies 400 to 800.

In addition, the present invention a) forming a gate electrode on the substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer on the gate insulating layer; d) forming source/drain electrodes on the semiconductor layer; And e) forming a pixel electrode connected to the source/drain electrode, wherein the a), d) or e) step comprises forming a metal film, and the metal It provides a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming an electrode by etching a film with the etchant composition of the present invention.

The metal film etchant composition of the present invention contains polyethylene glycol containing a sulfonyl group, thereby providing an effect of treating a large amount of substrates. In particular, it facilitates side etching control.

In addition, the etchant composition for a metal film comprising a copper-based film according to an embodiment of the present invention contains a low content of hydrogen peroxide, thereby providing excellent work safety and an effect of economically disposing of the etchant, while providing excellent etching speed. Has.

In addition, the manufacturing method of an array substrate for a liquid crystal display device using the etchant composition of the present invention is to prepare an array substrate for a liquid crystal display device having excellent driving characteristics by forming an electrode having an excellent etching profile on an array substrate for a liquid crystal display device. Makes it possible.

Hereinafter, the present invention will be described in detail. Since the following detailed description is a description of an embodiment of the present invention, even if there is a limited expression, it does not limit the scope of the rights determined from the claims.

Etching solutions of the prior art do not sufficiently satisfy the conditions required in this field in terms of CD loss, taper, pattern straightness, metal residue, storage stability, and number of processed sheets for a metal film including a copper-based film. In particular, there is a problem in that the desired shape cannot be realized because the etching control performance of the side etching formed by etching is poor.

In general, in the etchant composition, polyethylene glycol serves to increase the uniformity of etching by lowering the surface tension. However, with the conventional etchant composition, the etch control performance of side etching was insufficient.

Therefore, the present inventors have made diligent efforts to improve the etch control performance of the side etching of the etchant, and it has been confirmed that when polyethylene glycol containing a sulfonyl group is included in the etchant composition, the side etch control is remarkably improved. Finished.

That is, the present invention is a metal film oxidizer; Polyethylene glycol containing a sulfonyl group; And it relates to an etchant composition comprising water.

The etchant composition of the present invention may be used regardless of the quality of the etching film, but may be preferably used for etching a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or a multilayer film made of them.

The copper-based metal film refers to a copper film or a copper alloy film, the molybdenum-based metal film refers to a molybdenum film or a molybdenum alloy film, and the titanium-based metal film refers to a titanium film or a titanium alloy film.

The multilayer film may include, for example, a double layer of a molybdenum-based metal film/copper-based metal film having a copper-based metal film as a lower film and a molybdenum-based metal film as an upper film; A copper-based metal film/molybdenum-based metal film double layer and a molybdenum-based metal film/copper-based metal film/molybdenum-based metal film having a molybdenum-based metal film as a lower film and a copper-based metal film as an upper film, or Like a copper-based metal film/molybdenum-based metal film/copper-based metal film, a multilayer of three or more layers in which a copper-based metal and a molybdenum-based metal film are alternately stacked is included.

In addition, the multilayer film is, for example, a copper-based metal film as a lower film, a titanium-based metal film as an upper film, a titanium-based metal film/copper-based metal film as a double film, a titanium-based metal film as a lower film, and a copper-based metal film as an upper film. Copper-based metals and titanium-based metals such as copper-based metal film/titanium-based double film and titanium-based metal film/copper-based metal film/titanium-based metal film or copper-based metal film/titanium-based metal film/copper-based metal film It includes a multilayer of three or more layers in which the films are alternately stacked.

In the multilayer film, the interlayer bonding structure may be determined in consideration of a material constituting a film disposed above or below the multilayer film, or adhesion with the films.

In the above, the copper, molybdenum, or titanium alloy film refers to a metal film made of an alloy using copper, molybdenum, or titanium as a main component according to the characteristics of the film. For example, the molybdenum alloy film contains molybdenum as a main component, and at least one selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In) It means a film made of an alloy formed including.

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

First, the metal film oxidizing agent of the present invention will be described.

The metal film oxidizing agent of the present invention serves to oxidize a multilayer film containing a metal.

With respect to the total weight of the composition of the present invention, the metal film oxidizer may contain 1 to 40% by weight, and the amount of the metal film oxidizer may be appropriately adjusted according to the type and characteristics of the oxidizing agent.

The metal film oxidizing agent is not particularly limited, and may be typically at least one selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, halogen acid, and halide salt. The metal oxide refers to an oxidized metal, for example, Fe ^{3 +} , Cu ^{2 +,} etc., and the metal oxide also includes a compound that dissociates into the Fe ^{3 +} , Cu ^{2 +} etc. in a solution state, and Sulfate includes ammonium persulfate, persulfate alkali metal salt, oxone, and the like, and halide includes chlorate, perchlorate, bromate, perbromate, and the like.

According to a preferred embodiment of the present invention, hydrogen peroxide may be used as the metal film oxidizing agent, and the hydrogen peroxide is a main component that oxidizes copper, molybdenum, and titanium. The hydrogen peroxide is preferably contained in an amount of 1 to 25% by weight, preferably 1 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. When the above-described range is satisfied, a decrease in etching rates of copper, molybdenum, and titanium is prevented, an appropriate amount of etching may be implemented, and an excellent etching profile may be obtained. However, outside the above-described range, the layer to be etched may not be etched, or over-etching may occur, resulting in loss of patterns and loss of functions as a metal wiring.

Next, polyethylene glycol containing the sulfonyl group will be described.

In general, polyethylene glycol contained in the etchant composition inhibits the activity of metal ions, such as copper ions, by enclosing metal ions, such as copper ions, dissolved in the etchant after etching a metal film, thereby decomposing hydrogen peroxide. It serves to suppress When the activity of metal ions, for example, copper ions is lowered in this way, the process can be stably performed while the etchant is used, and the number of substrates processed is increased.

In the present invention, the polyethylene glycol contained in the etchant composition contains a sulfonyl group. That is, the etchant composition of the present invention contains polyethylene glycol containing a sulfonyl group, and the polyethylene glycol containing a sulfonyl group may be any one selected from compounds represented by the following Chemical Formulas 1 and 2:

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ may be hydrogen, a C ₁ to C ₁₂ straight or branched chain alkyl group, preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and most preferably hydrogen or a methyl group.

In addition, n in Formula 1 “G 2” may be an integer that satisfies a weight average molecular weight of 300 to 1000, preferably an integer that satisfies 400 to 800.

If the weight average molecular weight of Formulas 1 and 2 exceeds 1000, the viscosity of the etchant composition is excessively increased and the etching rate is lowered. Therefore, it is preferable to satisfy the above range. In addition, when the weight average molecular weight is less than 300, the selectivity of the side bonding of the metal of the metal film of polyethylene glycol containing a sulfonyl group, for example, copper (Cu) of the copper film is insufficient, and the control effect of side etching is insufficient. there is a problem.

Specifically, the role of the polyethylene glycol containing the sulfonyl group represented by Chemical Formulas 1 and 2 in the etchant composition of the present invention will be described as a mechanism.

The polyethylene glycol of Formulas 1 and 2 necessarily contains a sulfonyl group at one end of the polyethylene glycol. The polyethylene glycol residue of the polyethylene glycol containing the sulfonyl group of the present invention is bonded to the photoresist, and the sulfonyl group is bonded to the metal of the metal film, for example, the copper oxide in the form of oxidation on the copper (Cu) surface of the copper film. . Therefore, by selectively forming a protective film on the surface of the metal of the metal film in the side portion, for example, the copper (Cu) surface of the copper film, it is protected from side etching by an oxidizing agent, thereby remarkably improving the side etching control.

Accordingly, the polyethylene glycol containing a sulfonyl group of the present invention serves to increase a margin in the process by reducing the loss of a critical dimension (CD) of a metal of a metal film, for example, copper of a copper film.

By such a mechanism, the etchant composition containing polyethylene glycol containing a sulfonyl group of the present invention has better control of side etching than the generally used etchant composition containing polyethylene glycol, so that the desired type of etching is preferably performed. Can be implemented.

The content of the polyethylene glycol containing the sulfonyl group is 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of the composition. If the content of the polyethylene glycol containing the sulfonyl group is less than 0.1% by weight, the number of processed sheets and etching uniformity may be reduced, and the decomposition of hydrogen peroxide may be accelerated. If it exceeds 10% by weight, foam This can cause a lot of disadvantages.

Meanwhile, according to a preferred embodiment of the present invention, based on the total weight of the etchant composition of the present invention, 1 to 40% by weight of the metal film oxidizer; 0.1 to 10% by weight of polyethylene glycol containing the sulfonyl group; And the remaining amount of water.

And the etchant composition of the present invention may further include any one or more selected from a nitrogen atom-containing compound, a fluorine-containing compound, and an acid containing a sulfur (S) atom or a phosphorus (P) atom.

In particular, the etchant composition may be preferably used for etching a copper-based metal film/molybdenum metal film or a copper-based metal film/titanium metal film. However, the use of the composition is not limited to the double layer.

The nitrogen atom-containing compound contained in the etchant composition of the present invention serves to improve the etch rate and the number of processed sheets of the etchant. As the nitrogen atom-containing compound, those known in the art may be used without limitation, and representatively, a compound containing an amino group and a carboxylic acid group in the molecule may be used, and the compound containing an amino group and a carboxylic acid group in the molecule may include a carboxylic acid and an amino group. And alpha amino acids containing one carbon atom therebetween. Representative examples include monovalent amino acids such as glycine, glutamic acid, glutamine, isoleucine proline, tyrosine and arginine, and polyvalent amino acids such as iminodiacetic acid, nitrilodriacetic acid, and ethylene glycol tetraacetic acid. In addition, the nitrogen atom-containing compounds may be used alone or in combination of two or more.

The nitrogen atom-containing compound may be included in an amount of 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. When the nitrogen atom-containing compound is included in the above-described range, the etching rate of the etching solution and the number of processed sheets may be improved.

The fluorine-containing compound contained in the etchant composition of the present invention serves to remove etching residues and serves to etch the titanium-based metal film.

The fluorine-containing compound is preferably a compound capable of dissociating into fluorine ions or polyatomic fluorine ions. The compound capable of dissociating into the fluorine ion or the polyatomic fluoride ion may be one or two or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, sodium bifluoride, and potassium bifluoride.

The fluorinated compound may be contained in an amount of 0.1 to 5% by weight, more preferably 0.1 to 2% by weight, based on the total weight of the composition. If the above-described range is satisfied, it is preferable because the etching residue is prevented and the etching of the glass substrate or the lower silicon film is not caused. However, outside the above-described range, stains may occur in the substrate due to non-uniform etching characteristics, the lower layer may be damaged due to an excessive etching rate, and it may be difficult to control the etching rate during processing.

The acid containing the sulfur (S) atom or phosphorus (P) atom contained in the etchant composition of the present invention can be used without limitation, components known in the art such as sulfuric acid, sulfonic acid, phosphoric acid, and phosphonic acid. Can be preferably used. The phosphoric acid provides hydrogen ions to the etching solution, thereby promoting the etching of copper of hydrogen peroxide. In addition, the solubility in water is increased by bonding with oxidized copper ions to form phosphate, thereby removing residues of the metal film after etching.

The acid may be included in an amount of 0.01 to 10% by weight, more preferably 0.01 to 1% by weight, based on the total weight of the composition. When the content of the acid satisfies the above range, it is possible to avoid the risk of excessive etching of the metal layer due to acid and corrosion of the lower layer, and there is no problem that the etching rate of the metal layer is lowered because the acid content is too low. Function can be performed.

The water used in the present invention means deionized water and is used for semiconductor processing, and preferably, water of 18㏁/cm or more is used.

The etchant composition of the present invention may further include at least one of an etch control agent, a surfactant, a metal ion sequestering agent, a corrosion inhibitor, and a pH adjuster in addition to the above-mentioned components.

The etchant composition of the present invention is a specific example,

Hydrogen peroxide may be used as the metal film oxidizing agent, and may further include a nitrogen atom-containing compound along with polyethylene glycol and water including a sulfonyl group.

In addition, it may further include at least one selected from the group consisting of a fluorinated compound and an acid containing a sulfur (S) atom or a phosphorus (P) atom.

According to a preferred embodiment of the present invention, the etchant composition comprises 1 to 25% by weight of hydrogen peroxide based on the total weight of the composition; 0.1 to 10% by weight of polyethylene glycol containing a sulfonyl group; And a residual amount of water, 0.1 to 10% by weight of a nitrogen atom-containing compound, 0.1 to 5% by weight of a fluorine-containing compound, and 0.01 to 10% by weight of an acid containing a sulfur (S) atom or a phosphorus (P) atom. At least one selected from the group consisting of may further include.

In particular, the etchant composition may be preferably used for etching a copper-based metal film or a copper-based metal film/molybdenum metal film or a copper-based metal film/titanium-based metal film. However, the use of the composition is not limited to the film quality.

It is preferable that the components constituting the etchant composition of the present invention have a purity for semiconductor processing.

The present invention also includes the steps of: a) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer on the gate insulating layer; d) forming source/drain electrodes on the semiconductor layer; And e) forming a pixel electrode connected to the source/drain electrode, wherein the a), d) or e) step comprises forming a metal film, and the metal It relates to a method of manufacturing an array substrate for a liquid crystal display device, comprising the step of forming an electrode by etching a film with the etchant composition of the present invention.

Since the array substrate for a liquid crystal display manufactured by the above method includes an electrode having an excellent etching profile, it has excellent driving characteristics.

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

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention more specifically, 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.

Example 1-6 and Comparative Example 1 ~4: Etchant Preparation of the composition

An etchant composition was prepared by mixing the components shown in Table 1 below in the corresponding amount.

division Metal film oxidizer Polyethylene glycol containing a sulfonyl group Glycine Ammonium fluoride Phosphoric acid Triethylene glycol Deionized water Example 1 nitric acid 10 Formula 1-1 5 One X X X Balance Example 2 Ammonium persulfate 10 Formula 1-1 5 One X X X Balance Example 3 Hydrogen peroxide 10 Formula 1-1 5 One X X X Balance Example 4 Hydrogen peroxide 10 Formula 2-1 5 One X X X Balance Example 5 Hydrogen peroxide 10 Formula 1-1 5 One One X X Balance Example 6 Hydrogen peroxide 5 Formula 1-1 5 One One 0.1 X Balance Comparative Example 1 Hydrogen peroxide 10 X X One X X X Balance Comparative Example 2 Hydrogen peroxide 10 X X One One X X Balance Comparative Example 3 Hydrogen peroxide 10 X X One One 0.1 X Balance Comparative Example 4 Hydrogen peroxide 10 X X One One 0.1 5 Balance

(Unit: wt%)

Formula 1-1:

Formula 2-1:

Test example One: Etching speed And CD Ross Rating

(One) Cu Single-acting Etching

A copper film was deposited on the glass substrate by chemical vapor deposition. The thickness of the film was about 2000 to 2500 Å. Then, a photoresist was applied to form a single copper film on a selective area, and the photoresist was partially removed by a developer, and selectively exposed using a mask. A single Cu layer was etched using the etchant compositions of Examples 1 to 4 and Comparative Example 1. During the etching process, the temperature of the etchant composition was set to about 30°C and etching was performed for 100 seconds. By measuring EPD (End Point Detection, metal etching time point) with the naked eye, the etching rate (etching rage) over time was obtained. The profile cross-section of the etched Cu single layer was measured for CD loss using SEM (Hitachi, model name S-4700), and the results are shown in Table 2 below.

(2) Cu / Mo - Ti Double membrane Etching

An alloy film of molybdenum and titanium (50:50) and a copper film were continuously deposited on the glass substrate by chemical vapor deposition. The thickness of each film was about 300 to 400 Å for the molybdenum-titanium alloy film and about 2000 to 2500 Å for the copper film. Then, a photoresist was applied to form a copper/molybdenum-titanium double layer on a selective region, and the photoresist was partially removed by a developer by selectively exposing using a mask. The Cu/Mo-Ti double layer was etched using the etchant compositions of Examples 5 and 6 and Comparative Examples 2 to 4. During the etching process, the temperature of the etchant composition was set to about 30°C and etching was performed for 100 seconds. With the naked eye, EPD (End Point Detection, metal etching time) was measured to obtain an etching rage over time. The profile cross section of the etched Cu/Mo-Ti double layer was measured for CD loss using SEM (Hitachi, model name S-4700), and the results are shown in Table 2 below.

Test example 2: Evaluation of the number of processed sheets

A reference etch test was performed with the etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4, and 4,000 ppm of copper powder was added to the reference test etchant to completely dissolve. Thereafter, etching was performed again, a reference etching test was performed, and the rate of decrease of the etching rate was evaluated.

<Evaluation criteria>

○: Excellent (less than 10% etch rate decrease)

△: Good (Etch rate decrease rate 10% ~ 20%)

×: Defective (Etch rate reduction rate exceeds 20%)

division Test Example 1 Test Example 2 Etching speed (Å/sec) CD loss (㎛) Number of processing Example 1 145 2.1 ○ Example 2 167 1.8 ○ Example 3 125 1.7 ○ Example 4 125 2.3 ○ Example 5 128 1.7 ○ Example 6 142 2.0 ○ Comparative Example 1 121 3.8 × Comparative Example 2 123 4.8 × Comparative Example 3 140 4.2 × Comparative Example 4 145 4.0 △

Referring to Table 1 of the measurement results, it can be seen that Examples 1 to 6 have significantly less CD loss than Comparative Examples 1 to 4. That is, it can be seen that the polyethylene glycol containing the sulfonyl group of the present invention controls the side etching.

Specifically, the CD loss of Examples 3 and 5 was the least, showing the best side-etching control effect, followed by the side-etching effect in the order of Example 2, Example 6, and Example 4. In the etch rate, Example 2 was the best.

When comparing the average value of the CD loss, Comparative Examples 1 to 4 had an average CD loss value of about 4.2 µm, and the average value of the CD loss of Examples 1 to 6 was about 1.9 µm. A lot appeared. In particular, in Comparative Example 4, even though triethylene glycol, which is generally used, was included, the CD loss was significantly inferior to Examples 1 to 6 at 4 μm.

Therefore, it can be seen that the side etching control of the etchants that do not contain polyethylene glycol containing a sulfonyl group is significantly inferior.

In addition, in terms of the number of treated sheets, all of Examples 1 to 6 were excellent, whereas Comparative Examples 1 to 3 were all poor except for Comparative Example 4, and Comparative Example 4 also had a lower number of treated sheets than Examples 1 to 6.

In conclusion, it can be seen that the etchant composition of the present invention is superior to the conventional etchant composition.

Claims (10)

1 to 40% by weight of the oxidizing agent of the metal film based on the total weight of the composition; 0.1 to 10% by weight of polyethylene glycol containing a sulfonyl group; And the remaining amount of water,
Polyethylene glycol containing the sulfonyl group is any one selected from compounds represented by the following Chemical Formulas 1 and 2,
An etchant composition, characterized in that it is used for etching a copper-based metal film, a molybdenum-based metal film, a titanium-based metal film, or a multilayer film made of them.
[Formula 1]
.

[Formula 2]

In Formula 1 and Formula 2,
R ₁ is hydrogen, a straight chain or branched chain alkyl group of C ₁ to C ₁₂ , and n is an integer that satisfies the weight average molecular weight of 300 to 1000. delete The method according to claim 1,
The metal film oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, halogen acid and halide. delete The method according to claim 1,
At least one selected from the group consisting of 0.1 to 10% by weight of a nitrogen atom-containing compound, 0.1 to 5% by weight of a fluorine-containing compound, and 0.01 to 10% by weight of an acid containing a sulfur (S) atom or a phosphorus (P) atom Etching liquid composition, characterized in that it further comprises. The method of claim 5,
1 to 25% by weight of hydrogen peroxide is included as the oxidizing agent based on the total weight of the composition; The nitrogen atom-containing compound is an amino acid, the sulfur (S) atom or the phosphorus (P) atom-containing acid is phosphoric acid, and the fluorine-containing compound is composed of ammonium fluoride, sodium fluoride, potassium fluoride, sodium bifluoride, and potassium bifluoride. An etchant composition comprising at least one selected from the group. The method according to claim 1,
The C ₁ ~ C ₁₂ straight or branched chain alkyl group is a methyl group, an ethyl group, a propyl group, or a butyl group, n is an etchant composition, characterized in that the weight average molecular weight is an integer satisfying 400 ~ 800. delete The method according to claim 1,
The etchant composition, wherein the multilayer film is a copper-based metal film/molybdenum metal film, or a copper-based metal film/titanium metal film. a) forming a gate electrode on the substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source/drain electrodes on the semiconductor layer; And
e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the source/drain electrode,
The step a), d) or e) comprises forming a metal film, and etching the metal film with the etchant composition of any one of claims 1, 3, 5 to 7, and forming an electrode. Method of manufacturing an array substrate for a liquid crystal display device.